Citation
Distribution, movement, and extraction of arsenic in selected Florida soils

Material Information

Title:
Distribution, movement, and extraction of arsenic in selected Florida soils
Creator:
Thomas, John E ( John Edward ), 1952-
Publication Date:
Language:
English
Physical Description:
xviii, 278 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Arsenic ( jstor )
Bison ( jstor )
Cattle ( jstor )
Plumes ( jstor )
Prairies ( jstor )
Soil horizons ( jstor )
Soil samples ( jstor )
Soils ( jstor )
Surfactants ( jstor )
Tobacco chewing ( jstor )
Arsenic -- Environmental aspects -- Florida ( lcsh )
Dissertations, Academic -- Soil and Water Science -- UF ( lcsh )
Soil and Water Science thesis, Ph. D ( lcsh )
Soil pollution -- Florida ( lcsh )
Soil remediation -- Florida ( lcsh )
Dudley Farm ( local )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1998.
Bibliography:
Includes bibliographical references (leaves 267-276).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by John E. Thomas.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
029245972 ( ALEPH )
41228933 ( OCLC )

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DISTRIBUTION, MOVEMENT, AND EXTRACTION
OF ARSENIC
IN SELECTED FLORIDA SOILS


















By

JOHN E. THOMAS


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

1998


































Copyright 1998

by

JOHN E. THOMAS















ACKNOWLEDGMENTS


I would like to express my deep appreciation to the

faculty and staff of the University of Florida's Department of

Soil and Water Science. The roll call of the people who

assisted in this project is indeed a long one. First and

foremost, I express my gratitude to Dr. L.-T. Ou for the

microbiology training I received and his understanding as I

pursued this degree while working full-time for him. I

especially want to extend my acknowledgment to Dr. R. D. Rhue,

the chairman of my committee, for his timely advice and help.

Thanks also go to the members of my advisory committee: Dr.

D. Chynoweth, Dr. E. Hanlon, Dr. W. Harris, and Dr. B. McNeal

whose patience and helpful words of guidance were sorely

needed. Dr. A. Al-Agley, Dr. M. Collins, and Dr. L. Ma are

appreciated for their generosity in supplying equipment and

technical expertise. Bill Reve and Martin Sandquist deserve my

gratitude for their assistance in completing this project. I

also wish to express my appreciation to Florida Park Service

personnel, including Howard Adams, Jack Gillem, Butch Hunt,

Sally Morrison, and Jim Riemer. Lastly, I wish to acknowledge

the patience, love, and encouragement I received from my wife,

Pamela.
















TABLE OF CONTENTS



ACKNOWLEDGMENTS . . ... iii

LIST OF TABLES . .. ix

LIST OF FIGURES . . ... xii

ABSTRACT . ... .xvii

CHAPTERS

1 INTRODUCTION . . 1

Purpose and Statement of Problem . 1
Cattle Dipping Vats . 1

2 OVERVIEW OF ARSENIC . .. 16

Arsenic Sources and Toxicology .. 16
Arsenic and Regulatory Laws ... 19
Chemistry of Arsenic . 21
Oxidation states of arsenic .. 26
Reduction-oxidation equilibria of arsenic 28
Precipitation reactions of arsenic 31
Arsenic Compounds in Soil ... 31
Abiotic Interactions of Arsenic ... 33
Biotic Interactions of Arsenic .. 37
Remediation Techniques for
Arsenic-Contaminated Soil ... 40
Physical remediation techniques 41
Chemical remediation techniques 44
Biological remediation techniques 45

3 CATTLE DIPPING VAT SITES . .. 47

Introduction . ... 47
Materials and Methods . .. 49
Results and Discussion . .. 58
Confirmed Vat Sites ............ 62
Payne's Prairie Bison Pen vat .. 62
Payne's Prairie Williston Road vat 75
Dudley Farm vat . 87











University of Florida Foundation
vat . ... 97
Jackson's Gap vat . .. 102
Payne's Prairie South Rim vat .. .105
Payne's Prairie U.S. 441 vat .. .105
Tuscawillow vat . .. 110
Marion County vat . .. 110
Reported Vat Sites . 113
Blackwater River State Forest vat 116
Cecil Webb vat . 116
Jay Livestock Market vat .. .122
Lake Arbuckle vat . .. .126
Lake Kissimmee vat . .. 129
Myakka River vat . .. .129
Okaloosa-Walton Community College
vat . .. 133
Tosohatchee vat . 137
St. Marks Wildlife Refuge vat .. .137
Walker Ranch vat . .. .141
Conclusions . .. 145

4 BIOLOGICAL VOLATILIZATION OF ARSENIC ... .149

Introduction . .. 149
Materials and Methods . .. .150
Results and Discussion . .. .154
Conclusions . ... 159

5 COLUMN STUDIES ON THE MOBILITY OF ARSENIC 161

Introduction . ... 161
Materials and Methods . .. .163
Results and Discussion . .. .174
Differential Pressure Column Studies 174
Mechanically Pumped Column Study 190
Conclusions . .. 195

6 SURFACTANT EXTRACTION OF ARSENIC FROM SOIL 198

Introduction . ... 198
Materials and Methods . .. .203
Results and Discussion . .. .206
Conclusions . .. 218

7 CONCLUSION . . .. 220

APPENDICES

A RAW DATA FOR CONFIRMED VAT SITES .. .228

B RAW DATA FOR REPORTED VAT SITES .. .249











REFERENCE LIST . ... . 267

BIOGRAPHICAL SKETCH .... . 277















LIST OF TABLES


Table _

1-1. Cattle fever, ticks and vats in the
United States . 7

2-1. Estimated U.S. demand for arsenic (metric tons) 18

2-2. Toxicity data of selected arsenical compounds 18

2-3. U.S.E.P.A. allowable aqueous concentrations 20

2-4. Different systems describing electronegativities
(E.N.) of selected elements 27

2-5. Reduction potentials of selected As compounds. 30

2-6. Metal-arsenate solubility product constants 32

3-1. Operational parameters for metal analysis by flame
or hydride generation ... .. 54

3-2. Operational parameters for arsenic analysis by
graphite furnace ... .. 55

3-3. Spectral interference by aluminum in the analysis
of arsenic at wavelength 193.6 nm using a
graphite furnace atomic absorption
spectrometer with deuterium background
correction . . 56

3-4. Soil map units and taxonomic classes for confirmed
cattle dipping vat sites ... 61

3-5. Selected characteristics of soil 10 meters south
of the Bison Pen vat . .. 66

3-6. Selected metal concentrations in soil 10 meters
south of the Bison Pen . ... .68

3-7. Selected characteristics of soils sampled at
Williston Road vat site . ... .80









3-8. Selected metal concentrations in soil from
Williston Road vat site . .. 83

3-9. Selected characteristics of soil 2.3 meters
east of the Dudley Farm vat .. .91

3-10. Selected metal concentrations in soil 2.3 meters
east of the Dudley Farm vat ... .96

3-11. Selected characteristics of soil 0.9 meters
north of the excavated U.F. vat .. 100

3-12. Selected metal concentrations in soil 0.9 meters
north of U.F. vat . 101

3-13. Soil map units and taxonomic classes for reported
cattle dipping vat sites ... .117

5-1. Selected soil column characteristics. ... 176

5-2. Flow rate variations after sequential elution of
differential pressure columns ... 187

A-1. Selected site data for Payne's Prairie Bison
Pen cattle dipping vat ... .230

A-2. Selected site data for 10205 S.W. Williston
Road cattle dipping vat ... .234

A-3. Selected site data for Dudley Farm cattle
dipping vat . .. .247















LIST OF FIGURES


Figure page

1-1. Schematic plan for the construction of a concrete
cattle dipping vat. . 2

2-1. Arsenic nomenclature and structures. ... 22

2-2. Other examples of arsenic compounds. ... 24

2-3. Oxidation-reduction stability diagram
for As . . ... 29

3-1. Map of roads and vats south of Gainesville, FL 59

3-2. Map of roads and vats west of Gainesville, FL. 60

3-3. Photograph of the Payne's Prairie Bison Pen vat .63

3-4. U.S.G.S. topographical map of the Payne's Prairie
Bison Pen vat site . 64

3-5. Soil survey map of the Payne's Prairie Bison Pen
vat site . ... 65

3-6. Argillic horizon depth and associated As
concentrations at the Payne's Prairie
Bison Pen vat site . 70

3-7. "Geo-Eas" contour map of As plume at the Payne's
Prairie Bison Pen vat site ... 71

3-8. Two-dimensional "Surfer" contour map of As plume
at the Payne's Prairie Bison Pen vat site .72

3-9. Three-dimensional "Surfer" map of the As plume
across the argillic horizon at the Payne's
Prairie Bison Pen vat site .. .73

3-10. Three-dimensional map of the As plume on the
argillic horizon along with surface topography
at the Payne's Prairie Bison Pen vat site .74

3-11. Photograph of the S.W. 10205 Williston Road vat 76

ix









3-12. Soil survey map of the S.W. 10205 Williston Road
vat site . . 77

3-13. Photograph of the Williston Road vat's transect
lane . 79

3-14. Soil horizons at the Williston Road vat site
in terms of: a) a two-dimensional map of
three horizons, b) the Aquod Bh horizon and
Aqualf surface horizon with the As plume,
and c) the argillic horizon with its As
plume ....... . 81

3-15. Contour maps of As on Aquod's Bh horizon and
Aqualf's surface horizon of the Williston
Road vat using: a)the laboratory analysis
versus b)the field test ...... 85

3-16. Arsenic on argillic horizon's contour maps of
the Williston Road vat using: a) laboratory
analysis versus b)the field test 86

3-17. Photograph of the Dudley Farm vat ... .88

3-18. Soil survey map of the Dudley Farm vat site 90

3-19. Surface map of the Dudley Farm site with
arsenic plume ... 92

3-20. Topographical map of the Dudley Farm vat site .93

3-21. Field test strips and laboratory analysis
results for the Dudley Farm vat soil
by depth . . 95

3-22. U.S.G.S. topographical map of the U.F. Foundation
excavated vat site .... .... 98

3-23. Soil survey map of the U.F. Foundation
excavated vat site . 99

3-24. Soil survey map of the Payne's Prairie
Jackson's Gap vat site ... .103

3-25. U.S.G.S. topographical map of the Payne's
Prairie Jackson's Gap vat site .... 104

3-26. Soil survey map of the Payne's Prairie
South Rim vat site . ... 106

3-27. U.S.G.S. topographical map of the Payne's
Prairie South Rim vat site ..... 107









3-28. Soil survey map of the Payne's Prairie U.S. 441
vat site . . 108

3-29. U.S.G.S. topographical map of the Payne's Prairie
U.S. 441 vat site . .. 109

3-30. Soil survey of the Tuscawillow vat site .. 111

3-31. U.S.G.S. topographical map of the Tuscawillow
vat site. . ... 112

3-32. Soil survey map of the Marion County vat site 114

3-33. U.S.G.S. topographical map of the Marion County
vat site . .. 115

3-34. Topographical map of the Blackwater River State
Forest vat site . ... 119

3-35. Soil survey map of the Blackwater River State
Forest vat site . ... 120

3-36. Topographical map of the Cecil Webb vat site 121

3-37. Soil survey map of the Cecil Webb vat site 123

3-38. Topographical map of the Jay Livestock Market
vat site . .. 124

3-39. Soil survey map of the Jay Livestock Market
vat site . ... 125

3-40. Topographical map of the Lake Arbuckle vat site 127

3-41. Soil survey map of the Lake Arbuckle vat site 128

3-42. Topographical map of the Lake Kissimmee vat site 130

3-43. Soil survey map of the Lake Kissimmee vat site 131

3-44. Topographical map of the Myakka River vat site 132

3-45. Soil survey map of the Myakka River vat site 134

3-46. Topographical map of the Okaloosa-Walton Community
College vat site . ... 135

3-47. Soil survey map of the Okaloosa-Walton Community
College vat site . 136

3-48. Topographical map of the Tosohatchee vat site .138









3-49. Soil survey map of the Tosohatchee vat site 139

3-50. Topographical map of the St. Marks Wildlife Refuge
vat site . ... 140

3-51. Soil survey map of the St. Marks Wildlife Refuge
vat site . ... 142

3-52. Topographical map of the Walker Ranch vat site 143

3-53. Soil survey map of the Walker Ranch vat site .144

4-1. Subsurface volatile As gas flux and rainfall
for 1996 at the Payne's Prairie Bison Pen
vat site . .. 156

4-2. Subsurface volatile As gas flux and rainfall
for three months in 1997 at the Williston
Road vat site . .. .156

4-3. Cumulative volatile As evolved from contaminated
subsurface soil from the Bison Pen site under
various oxic conditions . .. .158

4-4. Volatilization of As by Fusarium sp. under various
oxic conditions with and without a soil
column scrubber. . ... 158

5-1. Schematic cross-section of apparatus used for the
aerobic, unsaturated, differential pressure
column . ... 165

5-2. Schematic cross-section of apparatus used for
the low oxic, unsaturated, differential
pressure column . ... 167

5-3. Schematic cross-section of apparatus used for
the ponded, saturated, differential
pressure column . ... 169

5-4. Effluent from an aerobic, unsaturated column of
Payne's Prairie Bison Pen vat "E" soil
(45-60 cm depth)sequentially eluted with
50 mM potassium chloride, nitrate, and
phosphate solution . ... .177

5-5. Effluent from a micro-aerobic, unsaturated column
of Payne's Prairie Bison Pen vat "E" soil
(45-60 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and
phosphate solutions . ... .178









5-6. Iron and arsenic in effluent from an aerobic,
unsaturated column of Payne's Prairie Bison
Pen vat "Bt" soil (152-165 cm depth)
sequentially eluted with 50 mM potassium
chloride, nitrate, and phosphate solutions. 183

5-7. Aluminum and arsenic in effluent from an
aerobic, unsaturated column of Payne's
Prairie Bison Pen vat "Bt" soil
(152-165 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and
phosphate solutions . ... .185

5-8. Iron and arsenic in effluent from a ponded,
saturated column of S.W. Williston Road
vat "A" soil (15-30 cm depth) sequentially
eluted with 50 mM potassium chloride, nitrate,
and phosphate solutions ... .186

5-9. Aluminum and arsenic in effluent from a ponded,
saturated column of S.W. Williston Road
vat "A" soil (15-30 cm depth) sequentially
eluted with 50 mM potassium chloride, nitrate,
and phosphate solutions ... .189

5-10. Chloride and arsenic in effluent from a pumped,
saturated column of Payne's Prairie Bison Pen
vat "A" soil (0-5 cm depth) initially saturated
with 30 mM potassium chloride then eluted
with solution of sodium arsenate (4.86 g/L). 191

5-11. Phosphate and arsenate log-log isotherms for
Payne's Prairie Bison Pen vat "A" soil
(0-5 cm depth) . 193

5-12. Comparison of calculated and experimental break-
through of arsenic in the Payne's Prairie
Bison Pen "A horizon" soil column. ... .196

6-1. Chemical structures of a)hexadecyltrimethyl ammonium
bromide (HdtABr); b) 3-[3-cholamidopropyl)-
dimethylammonia]-l-propane sulfonate (CHAPS);
c) sodium dodecylsulfate (SDS); and d) [16-
pyrimidinium crown-4]4+ . .. 200

6-2. Extraction of arsenic from Payne's Prairie vat soil
using HdtABr, hexadecyltrimethylammonium
bromide (a cationic surfactant) .. .207


xiii









6-3. Extraction of arsenic from Payne's Prairie Bison Pen
vat soil using CHAPS, 3-[(3-cholamidopropyl)-
dimethylammonia]-l-propanesulfonate
(a zwitterionic surfactant). ... 208

6-4. Extraction of arsenic from Payne's Prairie Bison
Pen vat soil using sodium dodecylsulfate
(an anionic surfactant) with [16-pyrimidinium
crown-4]4 . . 209

6-5. Comparison of extraction efficiency for the "Bt"
horizon of Payne's Prairie vat soil using
sodium dodecylsulfate (NaSDS) with and
without the chelating agent [16-pyrimidinium
crown-4]4+. . .. 213

6-6. Effect of chelate to soil weight ratio on the
extraction of arsenic from Payne's Prairie
Bison Pen "Bt" horizon soil samples using
30 mM sodium dodecylsulfate ... 215

6-7. Effect of chelate to soil weight ratio on the
extraction of arsenic from Payne's Prairie
Bison Pen vat "E" soil samples using
30 mM sodium dodecylsulfate ... 216

6-8. Timed trial study of chelate/SDS extraction
of arsenic from Payne's Prairie Bison Pen
vat site soil samples. . ... 217

A-1. Sampling map for Payne's Prairie Bison Pen
vat site . . 229

A-2. Sampling map for 10205 S.W. Williston Road
vat site . ... 233

A-3. Sampling map for Dudley Farm vat site .. .246

B-l. Woodward-Clyde Consultants' arsenic survey map of
Blackwater State Forest cattle dipping
vat site . ... 250

B-2. Woodward-Clyde Consultants' arsenic survey map of
Cecil Webb cattle dipping vat site 251

B-3. Woodward-Clyde Consultants' arsenic survey map of
Dudley Farm cattle dipping vat site.
Arsenic detected in soil samples 0-30 cm
below surface. . ... 252









B-4. Woodward-Clyde Consultants' arsenic survey map of
Dudley Farm cattle dipping vat site. Arsenic
detected in soil samples 91-122 cm below
surface. . ... 253

B-5. Woodward-Clyde Consultants' arsenic survey map of
Dudley Farm cattle dipping vat site. Arsenic
detected in soil samples deeper than 122 cm
below surface. . ... 254

B-6. Woodward-Clyde Consultants' arsenic survey map of
Jackson's Gap cattle dipping vat site 255

B-7. Woodward-Clyde Consultants' arsenic survey map of
Jay Livestock Market cattle dipping vat site.
Arsenic detected in soil samples 0-30 cm
below surface . .. 256

B-8. Woodward-Clyde Consultants' arsenic survey map of
Jay Livestock Market cattle dipping vat site.
Arsenic detected in soil samples 61-76 cm
below surface . ... .257

B-9. Woodward-Clyde Consultants' arsenic survey map of
Lake Arbuckle cattle dipping vat site 258

B-10. Woodward-Clyde Consultants' arsenic survey map of
Lake Kissimmee cattle dipping vat site 259

B-11. Woodward-Clyde Consultants' arsenic survey map of
Myakka River State Preserve cattle dipping
vat site . . 260

B-12. Woodward-Clyde Consultants' arsenic survey map of
Okaloosa-Walton Community College cattle
dipping vat. Arsenic detected in soil
samples 0-61 cm below surface ...... 261

B-13. Woodward-Clyde Consultants' arsenic survey map of
Okaloosa-Walton Community College cattle
dipping vat. Arsenic detected in soil
samples 152-183 cm below surface ... .262

B-14. Woodward-Clyde Consultants' arsenic survey map of
Okaloosa-Walton Community College cattle
dipping vat. Arsenic detected in soil
samples 274-305 cm below surface ... .263

B-15. Woodward-Clyde Consultants' arsenic survey map of
Tosohatchee cattle dipping vat site 264









B-16. Woodward-Clyde Consultants' arsenic survey map of
St. Marks Wildlife Refuge cattle dipping
vat site . .. 265

B-17. Woodward-Clyde Consultants' arsenic survey map of
Walker Ranch cattle dipping vat site 266


xvi














Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

DISTRIBUTION, MOVEMENT, AND EXTRACTION
OF ARSENIC
IN SELECTED FLORIDA SOILS

By

John E. Thomas

May 1998


Chairperson: R. Dean Rhue
Major Department: Soil and Water Science

Arsenic (As), as a soil contaminant in Florida, can often

be traced to the extensive use of cattle dipping vats to

eradicate ticks. These vats held 5700 liters of arsenical

solution, which was to be disposed of on-site yearly. With

over 3400 sites in Florida, this represented a pervasive

anthropogenic introduction of a potentially toxic contaminant.

Of these 3400 vats, ninety-four were located in Alachua

County, Florida. Out of nine sites studied, the maximum soil

As concentrations at three selected sites ranged from 100 to

767 mg/kg. The differences in As concentrations at these

sites were attributed to a number of factors including

variations in soil, hydrology, and vat history.


xvii








Effects of physicochemical soil properties on retention

of As were investigated. Particle-size analysis suggested

that soils with higher clay contents retained more arsenic.

Contaminated soils with higher iron and aluminum content also

exhibited higher As concentrations. Ground-penetrating radar

was utilized at a Payne's Prairie vat site to locate the

argillic horizon. Locating of the As plumes was effected by

analysis of hand-augured soil borings. A Fusarium fungal

culture was isolated from near this Payne's Prairie site that

was capable of volatilizing As.

Soil gas collections near the surface overlying the zone

of highest As concentration at two sites were shown to be

essentially free of arsenic, though subsurface soil gas

collections at two vat sites revealed gaseous As.

Mobilization studies were conducted on contaminated soil

columns eluted with various anions under variable oxic

conditions. Other studies involved surfactant extractions. A

cationic surfactant, cetyl trimethyl ammonium bromide, was

compared to a zwitterionic surfactant, 3-[(3-cholamidopropyl)-

dimethylammonia]-l-propane sulfonate. Efficiencies of both

extractants were below that of an anionic surfactant, sodium

dodecyl sulfate, after arsenic has been completed with a

cationic macrocycle, [16-pyrimidium crown-4]".


xviii















CHAPTER 1
INTRODUCTION


Purpose and Statement of Problem


The primary area of interest in this study was focused

upon arsenic (As)- contaminated soils in Florida that resulted

from the extensive long-known use of cattle dipping for the

purpose of tick eradication. The investigation was divided

into four objectives. First was evaluation of the extent of

As contamination at selected cattle dipping vat sites. A

second objective was the assessment of physical and chemical

properties that affect retention and mobility of As at these

sites. Third was an attempt to fit the movement of As in soil

to a one-dimensional transport model that included a

retardation factor. A final objective involved the

examination of biotic as well as chemical extraction methods

that affect the release of As from soil.


Cattle Dippina Vats


In Florida, as in many other southern states, one source

of soil contamination by As can be ascribed to the extensive

use of cattle dipping vats to eradicate ticks. Vats became

the preferred method of eradication by virtue of the





























































Figure 1-1. Schematic plan for the construction of concrete
cattle dipping vat.











thoroughness, speed, and simplicity of the dipping operation.1

Typically, the vats were 7.6-9.1 meters (25-30 feet) long and

0.8 to 1.1 meters (2.5-3.5 feet) wide according to plans

supplied by the United States Department of Agriculture

(U.S.D.A.) and the Federal Bureau of Animal Industries (Figure

1-1).2'3,4 Florida alone had over 3400 cattle dipping vats

which typically contained 5700 to 7600 liters of 0.14 to 0.22

percent total As solution.3'4 The vats were expected to be

emptied or replenished yearly. Disposal of the toxic waste

was by one of two procedures. The first "approved practice is

to run the waste bath into a pit properly guarded by a fence,

where it will gradually seep away under the surface and do no

harm, provided only that seepage cannot be carried to a well,

stream or spring from which any person or domestic animal may

drink".3 This procedure was recommended in 1919 by the

U.S.D.A. During the era of this recommendation, Florida had

a much lower population and much less urban development, so

the potential for harm was much reduced compared to today.

The second method of waste disposal, proposed in 1913, was to

form an insoluble precipitate. The clear liquid was to be

pumped or syphoned out onto the ground, since it contained

little As. The precipitate was to be "taken out and buried if

so desired" and it, too, was judged to be non-poisonous.5 The

procedure to "render harmless the arsenic" called for

measuring the number of gallons of solution left in the vat.

For each 378 liters, 2.7 kilograms of slaked lime was to be









4

added. Slaked lime is made by calcining calcium carbonate

from limestone, marble or seashells to form an anhydrous

calcium oxide (quicklime) that can be subsequently reacted

with water. After addition of the slaked lime, the vat

solution was to stand for several hours. Then, for each 378

liters in the vat, 2.7 kilograms of copperas was to be added.

Copperas, ferrous sulfate (FeSO,.7HO), is a strong reducing

agent. After ten to twelve hours, "the arsenic unites with

the copperas (iron) and will have fallen to the bottom of the

vat as an insoluble, harmless precipitate or sediment."5

Since ferrous sulfate is quickly converted to the ferric form

under basic conditions and arsenite [As (III)] is reduced to

arsenate [As (V)], the precipitate would most likely be

FeAsO,, barring complexation with other metals and anions in

the vat solution.

An interesting side note is that, at a 1992 U.S.E.P.A.

workshop, the Bechtel Corporation and Artech Systems Inc.

presented the "Cashman Process" in which acid leach of

arsenical flue dust was treated with iron and gypsum

(CaS0.2H 0) to form ferric arsenate. A long-term stability

test over a period of several months was performed on a 3

meter thick pile of residues, by collecting the run-off. An

estimate of 4 to 8 million years was given for all the As to

leach out of such piles.6 In this case, as in the cattle

dipping precipitation/burial method, underlying assumptions

were made concerning 1) low carbon input, 2) persistence of a









5
highly oxic environment and 3) low microbial activity. For

the cattle dipping vat residues, in particular, these

assumptions are suspect.

Another area of possible contamination from cattle

dipping vats involves the use of pesticides other than As.

From 1906 to the mid-1940s, As was the preferred tickicide by

both state and federal programs. In fact, for 60 years it was

the only product officially approved by the U.S.D.A. However,

in 1946, an "outbreak" occurred in Florida associated with

reappearance of the cattle-fever-carrying tick species

Boophilus microplus. At this time, Florida officials began

using 0.5% DDT with 0.03% gamma benzene hexachloride. In the

cattle dipping vats, this mixture was known as "Dip 30". In

1960, dioxathion was permitted, coumaphous in 1968 and

toxaphene in 1972.1 Other contaminants found at vat sites

include DDD, DDE, dieldrin, lindane, chlordane, toluene and

methlyene chloride.3

Hindsight shows that the history of the cattle dipping

vat parallels a history of As contamination of Florida soils.

However, in defense of the tick eradication program, it should

be emphasized that the economic devastation upon southern

cattlemen by Boophilus annulatus, the cattle-fever tick, was

debilitating, being on the order of $130,500,000 in 1906

dollars. In 1996, the program would have cost more than a

billion dollars.1 In light of factors such as economic

impetus, sparse population, and scant chemical and









6
environmental knowledge (by today's standards), the tick

eradication program appears justified given the historical

perspective. A time table (Table 1-1)7-15 for cattle fever,

cattle ticks and cattle vats reveals a treatment period that

spans more than 50 years, with variable success in pestilence

control.











Table 1-1. Cattle fever, ticks and vats in the


7

United States


Time Description Reference
1785 North Carolina passed a law restricting 1

cattle movement, which was suspected to

have been caused by Boophilus annulatus

and piroplasmosis.

1796 Dr. Pease observed an outbreak of 5

disease among Lancaster, PA, cattle

following passage of South Carolina

cattle.

1814 Virginia refused passage of South 7

Carolina cattle suspected of being

disease carriers.

1868 Texas cattle shipped up the Mississippi 5

River to Cairo, IL and then by rail into

Illinois and Indiana caused enormous

losses in cattle.

1883- Dr. D.E. Salmon determined the boundary 5

1885 line of permanently infected territory.



1889 Theobald Smith described the cow tick as 5,7

carrier of peculiar microorganism that

cause cattle fever. This was the first

instance in which a disease was shown to

be insect-borne.











Table 1-1. --continued

Time Description Reference
1889- T. Smith and F.L. Kilborne confirmed the 7

1892 role of Boophilus annulatus in the

epidemiology of Babesia bigemina.
1896 Dr. C. Curtice advocated cattle fever 1

tick eradication and outlined suggested

methods.

1897 The Interstate Association of the 7

Livestock Sanitary Board (now known as

the U.S. Animal Health Association) met

in Fort Worth, TX, to discuss dipping

experiments and quarantine lines.
1899 Dr. Curtice, State Veterinarian of North 5

Carolina, instigated a tick eradication

program in that state.
1903 Beaumont crude petroleum was shown to 7

provide Twelve counties in North

Carolina were released from quarantine

due to a successful tick eradication

program, the best tick control of any

preparation tested.
1906 Twelve counties in North Carolina were 5

released from quarantine due to

successful tick eradication program.











Table 1-1. --continued

Time Descriotion Reference
1906 U.S. Congress appropriated $82,500 to 1

initiate a tick eradication program.



1907 =700,000 sq. miles (1,813,000 km2) 1

remained under federal quarantine.

Approximately, the line passed through

Virginia, N. Carolina, Tennessee,

Missouri, Oklahoma, Texas and

California. Florida and 14 other

southern states were under federal

quarantine.


1910 Arsenic dips replaced straight crude 1

petroleum dips.



1911 Four-fifths of the formerly quarantined 1,5

area was released from quarantine. In

general, the program was proceeding from

the West and North, moving towards the

Southeast.



1914 Fifty dipping vats were documented to 8

exist in Florida.











Table 1-1. --continued

Time Description Reference
1915 Eighty-eight dipping vats were reported 8

to be constructed state-wide, with eight

in Alachua County, FL. A.L. Jackson of

Payne's Prairie was listed as the owner

of one vat. All vats had been built

with private funds except for one vat

built by the University of Florida.
1916 Broward and Dade counties and part of 9

Palm Beach county were declared free of

cattle tick by the federal Secretary of

Agriculture. A large dipping vat and

non-infectious feeding pens were

established at Jacksonville, FL to

facilitate shipping cattle out-of-state

under a Federal certificate of dipping.
1917 State legislature passed a "Local Option 10

Tick Eradication Bill" allowing counties

that voted favorably to start a tick

eradication program.
1917 Open-range policy and re-infestation 10

from non-dipping areas, as well as a

lack of public interest and funds,

caused the program to fail.











1-1. --continued


ime Description Reference
1923 The Florida State legislature passed a 10

compulsory cattle-dipping law and

created the State Live Stock Sanitary

Board. The law allowed for partial

compensation to owners for dipping their

herds, as well as a one half mill levy

to carry out the work.
1924 Dipping began in Gadsden and Escambia 10,11

counties under the new law.

Repercussions involved state dipmen

wounded in battles with cattlemen, and

15 dipping vats in Escambia county were

dynamited.
1926 Georgia built a 240 mile fence along the 10,11

Florida border to prevent the movement

of tick-infested cattle. This fence

remained in place for 5 years and

extended from the Chattacoochee River to

the St. Mary's River.
1927 A more effective cattle dipping policy 1

was initiated by the Florida

Legislature. Instead of arresting

cattlemen who did not dip their herds,

the cattle were rounded up, dipped, and


Table











Table 1-1. --continued

Time Description Reference
1927 held at the owner's expense. Upon 1

refusal to pay, the cattle were sold and

any unexpended balance was returned to

the owners.

1930 Alachua county was scheduled to start 12

dipping =March 1.
1931 The Orange county program was declared 1

successful, yet re-infestation occurred.
1937 The U.S. Bureau of Entomology and Plant 1

Quarantine and the U.S. Bureau of

Biological Survey issued a report

stating that:

1) The Boophilus annulatus (var.

australis) tick existed in Florida

2) This tropical variety could use deer

as well as cattle as a host, though no

other wild animals in swamps appeared to

act as hosts.

3) All deer would have to be removed if

a tick program were to be successful.



The Florida Legislature passed laws

allowing deer removal from Orange,

Osceola, Highlands, and Glades counties.











1-1. --continued


Time Description Reference
1938 Overcoming a court injunction, deer 7

removal began. Approximately 20,000

deer are slaughtered.



1941 Boophilus annulatus microplus, a cattle- 1

fever tick, was found on 4 of 22 deer.

Deer removal continued in Orange,

Osceola, Highlands and Glades counties.



1943 Deer in Big Cypress Swamp, and in 14

Collier and Hendry counties, were

exempted from slaughter because they

were on Seminole Indian Reservation.

Forty-two of these deer were inspected

and found to be tick-free. Florida was

released from Federal quarantine on Dec.

1, 1943.



1945 A fever tick re-infestation was found in 14

Highlands County, FL. Infested areas

of Glades, Highlands, Okeechobee and

parts of Osceola and Polk counties were

placed under federal quarantine.


Table











Table 1-1. --continued

Time Description Reference
1946 A Florida state official charged vats 1

with 0.5% DDT plus 0.03% gamma benzene

hexachloride (BHC). The mixture was

sold as "Dip 30".
1948 On Oct. 1, Glades, Highlands, Okeechobee 14

and parts of Osceola and Polk counties

were released from federal quarantine.

On Oct. 20, Volusia county was found to

be infested, with then spread to

Putnam, Flagler, Brevard, Osceola, Lake,

St. John's, Alachua, Orange, Madison and

Jackson counties in Florida as well as

Brantley county in Georgia. All this

was due to heavy movement of cattle from

Volusia county.
1950 Florida was released from Federal 14

quarantine on Dec. 1, but dipping

continued due to a re-infestation threat

associated with close proximity of

Florida to tick-infested countries and

islands of the West Indies.
1951 Florida state officials started using 14

Toxaphene and DDT-BHC as tickicides.

Arsenic dips remained the only ones











1-1. --continued


Time Description Reference
recognized by Bureau of Animal 14

Industries for official work under Dept.

of Agriculture regulations.
1957 On April 23, southern cattle tick 15

(Boophilus annulatus microplus) was

found on 4 ranches in southern

Okeechobee county and 1 ranch in

county. More than 100 ranches in 10

counties were placed under quarantine,

even though the ticks were found to be

non-infectious. Counties affected

included Palm Beach, Hendry, Broward,

St. Lucie, Glades, Highlands, Martin,

Taylor, Dade and Okeechobee. An

eradication program was undertaken by

the Florida Livestock Board and the

Agricultural Research Service.
1958 A limited outbreak of B. microplus 1

apparently was successfully eradicated.
1960 The last reported outbreak of Boophilus 1

microplus re-infestation occurred in

Florida. No ticks of this variety have

been found since 1961.


Table















CHAPTER 2
OVERVIEW OF ARSENIC


Arsenic Sources and Toxicology


Arsenic occurs naturally in the atmosphere water7,

sediment18, soil19 and various organisms20. It ranks 20th in

abundance among the chemical elements20 and occurs in =245

mineral species6. Arsenic is present at an average

concentration of 2 to 5 mg/kg in the earth's crust and is

primarily associated with igneous and sedimentary rocks.21

Re-distribution can occur through natural means such as

weathering, biological activity and volcanic activity.

Anthropogenic inputs can also occur from smelting operations,

fossil fuel combustion, glass and electronics manufacturing,

wood preservatives and agricultural uses.6

Environmental contamination from As compounds introduced

by man is due primarily to the use of arsenic compounds as

pesticides and wood preservatives. Arsenite and arsenate, the

As (III) and As (V) oxides, respectively, account for = two-

thirds of the arsenic compounds utilized, with

organoarsenicals comprising the remainder.22 Atmospheric

contamination by As compounds has been associated with

smelting operations and the burning of fossil fuels.20









17

As shown in Table 2-1, although certain areas for As

usage are declining, there remains an overall increase in

demand for As. With this increase in usage comes an increase

in the possibility of environmental contamination. Arsenic is

an element that is toxic at high levels and is considered

carcinogenic at low levels.23'24 The toxicity of As is highly

dependent on its chemical formulation. Table 2-2 illustrates

the toxicological variation among selected arsenical compounds

as well as biological half-lives of the various species.24

Since toxicity data are specific to individual organisms, the

animal tested is listed along with the numerical value. It

should be noted that the 50% lethal doses are median values.

One conclusion that can be drawn from Table 2-2 is that there

are no large differences in the toxicology of inorganic

arsenicals. However, methylated As compounds are far less

toxic than inorganic compounds. It has been hypothesized that

the methylation of inorganic arsenic by organisms is a

detoxification mechanism.20 In contrast, studies on the

toxicologic effects of dimethylarsinic acid (DMA) reveal

damage to DNA and indicate mutagenicity.25

Toxicologists and nutritional experts are well aware that

detrimental as well as beneficial effects are caused not by

the "element" itself but by specific compounds incorporating

the element. As illustrated in Table 2-2, As can be

classified both as highly toxic, when in the inorganic form,













Table 2-1. Estimated U.S. demand for arsenic (metric tons)

1971 1981 1991
Agricultural 15,600 8,900 5,000
Chemicals
Glass 2,000 1,000 1,900
Industrial Chemicals 970 9,100 14,300
Nonferrous Alloys and 570 600 1,000
Electronics
Other 500 400 400
Total 19,640 20,000 21,600




Table 2-2. Toxicity data of selected arsenical compounds

Arsenic Compound LD, (mg/kg) Biological
Half-Life(hours)

Arsenite 34.5 28.6 (hamster)
(arsenic trioxide) (mouse)
Arsenite 4.5 (rat) 30 (human)
(sodium arsenite)
Arsenate 14-18 (rat) 50.4 (human)
(sodium arsenate)
Monomethylarsonic Acid 1,800 7.4 (hamster)
(MA) (mouse)
Dimethylarsinic Acid 1,200 5.6 (hamster)
(DMA) (mouse)
Trimethylarsine 8,000 3.7 (hamster)
(TMA) (mouse)
Trimethylarsine Oxide 10,600 5.3 (hamster)
(TMAO) (mouse)
Arsenobetaine 10,000 6.1 (hamster)
(mouse)









19
and as innocuous to humans when present as certain

organoarsenicals. Such is the case for seafood, where As is

present as arsenobetaine and yet safe at 500 times the

U.S.E.P.A. acceptable level for human drinking water.20'26'27


Arsenic and Regulatory Laws


The concept of allowable limits for As being set by

regulatory agencies is based on "total concentration" rather

than "species concentration". This is due to the fact that

the arduous and time-consuming task of quantifying the

multitude of arsenical species present is simply not

economically feasible. Even though regulatory decisions

concerning allowable concentrations of As may not vary based

on speciation; there are regulatory variations based upon the

background matrix (air, soil, water, food, etc.) and the

intended usage of that matrix. There are also differing

regulatory laws among various agencies setting limits on

allowable arsenic concentrations. An example of the variance

due to usage can be exemplified by the aqueous limits set by

U.S.E.P.A. (Table 2-3).26'27

Currently, in the United States, there is no limit set

on As contamination allowable in soil, except as a 5 ppm

upper limit for the U.S.E.P.A. Toxicity Characteristic

Leaching Procedure (TCLP).28 The United Kingdom also has set

a limit of 10 mg/kg for domestic gardens and 40 mg/kg for



























Table 2-3. U.S.E.P.A. allowable aqueous concentrations


Matrix Usage Allowable Concentration

_______________________________ (pg/l)
Human Drinking Water 50
Livestock Drinking Water 200
Irrigation Water for Crops 100









21

parks and playing fields.29 The Netherlands standard for As

contamination in soil is set at 30 mg/kg.29


Chemistry of Arsenic


Arsenic is a member of Group Va of the periodic table.

It has an atomic number of 33 and atomic weight of 74.92.30

Arsenic exhibits properties that enable it to form alloys with

metals and to form predominantly covalent bonds with hydrogen,

oxygen, sulfur, and carbon.21 Similarities between the

chemical behavior of phosphorus (P) and arsenic are a result

of similar electronic orbital configurations. The electronic

configuration for As can be described as [Ar]3d104s24p3.

Arsenic, like phosphorus, will readily undergo catenation to

form a series of cyclic compounds of formula (RAs), where n =

3 to 6. It can also form RAsAsR compounds. Akin to P, the

stereochemistry of arsenic can be influenced by dn-dn and dn-

pn interactions that foreshorten bond lengths as well as

producing bond angles distorted by the presence of lone pairs

of electrons.31 The supposition has been made that the

toxicity of arsenic arises from its similar chemical behavior

to phosphorus and its ability to form covalent bonds with

sulfur, which inactivates many enzymatic systems.21 Some of

the more important environmental and agricultural arsenical

species are depicted in Figures 2-1 and 2-2. As illustrated

by these structures, As can have coordination numbers
















HO
HO --As:
/
HO

Arsenous Acid
(Arsenite Salts)












HO

CH3 -As= O

HO

Methylarsonic Acid


HO
HO --As 0
/
HO

Arsenic Acid
(Arsenate Salts)











HO

CH3 --As = 0


CH,

Dimethylarsinic Acid
(Cacodylic Acid)


Figure 2-1. Arsenic nomenclature and structures.
















H
H As:

H

Arsine















CH,

CH, -As:
/
CH,

Trimethylarsine


CH,

HO As:
/
CH,

Dimethylarsine












AsO(OH)






NH,

Arsanilic Acid


Figure 2-1.


continued











AsO(OH)




NO.

OH


3-Nitro-4-Hydroxyphenolarsonic Acid
(Roxarsone)




AsO(OH);






NO,

4-Nitrophenylarsonic Acid
(Nitrarsone)




AsO(OH),






NHCONH.


p-Ureidobenzenearsonic Acid
(Carbarsone)


Figure 2-2. Other examples of arsenic compounds.


















NH3 0


NH,- Fe -- As CH3


NH3 OH

Ferric Methanearsonate
(Neo-Arsozin)


0 0/- +NH3--R


CH +NH-
CH, 0- +NH,-R


where R = t-decyl or t-octyl


t-Octyl or t-Decyl Ammonium Methanearsonate
(AMA or Super-Dal-E-Rad)


Figure 2-2. --continued









26

of 3, 4 and 5. Arsenic can have coordination numbers of 2 and

6 as well.30


Oxidation States of Arsenic


The oxidation states of arsenic include +5, +3 and 0.

Some confusion exists in the literature as to whether or not

to include -3 as one of the oxidation states as well.20 The

most common method for determining oxidation states is to

assign the charge distribution in chemical bonds based on the

relative electronegativities of the pertinent atoms.31 Linus

Pauling first defined electronegativity as "the power of an

atom in a molecule to attract electrons to itself."32 As

illustrated in Table 4, the value assigned to an atom's

electronegativity is dependent on the model chosen for

estimation. L. Pauling based his electronegativity scale on

thermochemical data.31 R.T. Sanderson based his scale on size

and charge of the atom, to arrive at an estimation of relative

electron density.31 R.S. Milliken suggested using an average

of the atom's ionization energy and electron affinity (values

in Table 4 were derived from the subsequent work of H. Jaffe

and co-workers).31 A.L. Allred and E.G. Rochow derived their

scale based on the electrostatic force exerted on valence

electrons by the nucleus.31 Basically, the larger

electronegativity values dictate that a larger partial

negative charge be assigned to that atom. Under the Pauling




















Table 2-4. Different systems describing electronegativities
(E.N.) of selected elements.3


Element Pauling Sanderson Allred- Milliken-Jaffea
Rochow

E.N. E.N. E.N. E.N. Orbital
or
Hybrid
As 2.18 2.53 2.20 1.59 sp

2.58 sp3

C 2.55 2.47 2.50 1.75 p

2.48 sp3

2.75 sp2

3.29 sp
0 3.44 3.46 3.50 3.04 p

4.63 20%s

4.93 sp3

5.54 sp2
S 2.58 2.66 2.44 2.28 p

3.21 sp3

H 2.20 2.31 2.20 2.21 s


a) Electronegativities
comparison purposes.


adjusted to Pauling's scale for









28

and Allred-Rochow scales, it is clear that As is considered to

be positively charged with respect to C, O and S. However,

the problem becomes muddled in the case of H. Further

confusion can arise if the electronegativities are assigned

using one of the two remaining systems. For the sake of

consistency and simplicity, the values given by Pauling will

be used throughout the remainder of this dissertation in

assigning oxidation states. This necessitates that As be

regarded as electropositive in relation to C, O, S and H. As

such, the only oxidation states assigned to As will be +5, +3

or 0.


Reduction-Oxidation Equilibria of Arsenic


The oxidation state of aqueous As is highly dependent on

the pH of the system as illustrated in Figure 2-3.18 Typical

mineral soils or sediments can have pH values in the range 5

to 9 with an Eh values of -300 (water-logged) to +900 (well-

aerated) millivolts (mV). Some of the reduction potentials of

As compounds are given in Table 2-5.18 It is interesting to

note that only the reduction of elemental As to arsine has a

negative EO; this means that reduced conditions would be

required in a sterile, pure, aqueous system to produce this

gas.
















6 -




As04
2 -


0 -, ;. :


-2





-6

Reduced H20

-8


-10


-12 -
AsH3

-14
0 2 4 6 8 10 12 14

pH

Figure 2-3. Oxidation-reduction stability diagram
for As.













Table 2-5. Reduction potentials of selected As compounds.


Reaction E volts (25C)


H3AsO, + 3HK + 2e- AsO' + 3HO 0.550

H3AsO4 + 2H* + 2e- HAsO, + 2HKO 0.560

H,AsO4- + 3H* + 2e- HAsO, + 2H20 0.666

HAsO,4 + 4HK + 2e- HAsO, + 2HKO 0.881

HAsO4- + 3H' + 2e- AsOG- + 2H20 0.609

AsO,43 + 4H' + 2e- AsO,- + 2H2O 0.977

As203, + 6H' + 6e- = 2As + 3HKO 0.234

As2O,,^ + 10H+ + 10e- = 2As + 5HKO 0.429

As20,,s + 4H+ + 4e- -:As,03^. + 2HO 0.721

AsO' + 2H' + 3e- = As + HO 0.254

HAsO 3 + 3H' + 3e- As + 2HKO 0.248

AsO + 4H' + 3e- As + 2H20 0.429

As04-3 + 8HK + 5e- As + 2HO 0.648

2H3AsO + 4H+ + 4e- As.03,, + 5HO 0.580

2H2AsO,4 + 6H+ + 4e- As-O,^ + 5HO 0.687

2HAsO,-- + 8H + 4e- = As-O,,,, + 5HKO 0.901

2AsO4-3 + 10H + 4e- =As'O3 + 5HO 1.270

As + 3HI + 3e- = AsH,, -0.608










Precipitation Reactions of Arsenic


Pure systems are rarely, if ever, encountered in a

natural environmental setting, but the effect of precipitation

reactions as well as sorption-desorption equilibria must be

considered when determining the fate and transport of As. A

compilation of the negative log of the solubility product

equilibrium constants (pK,) are given in Table 2-6 for

selected metal arsenical complexes.18'34 The relatively high

values for pK,, indicate that arsenate can form practically

insoluble metallic salts. Other practically insoluble

compounds bearing As may be formed as well; for instance,

under conditions where sulfides are stable, As will

precipitate with sulfur. One example is the formation of

orpiment (AsS3) under conditions when the pH=4 and -3
Another example is the formation of realgar (As,S,) at pH=4 and

-4
literature for these systems.35


Arsenic Compounds in Soil


As mentioned previously, As is ranked 20th among the

chemical elements in abundance20 and can be found in more than

245 minerals.6 Although arsenite and arsenate are considered

to be the most common forms of As compounds in the

environment, organo-arsenicals can be found in soil pore

waters as well. The presence of many arsenical compounds in

















Table 2-6. Metal-arsenate solubility product constants.


Compound pKa Reference
AlAsO, 15.80 18

Ba,(AsO,) 21.62 34
BaHAsO4 HO 24.64 34

Ca (AsO,) 18.48 34
Cd,(AsO,) 32.66 18

Co,(AsO,) 28.11 18

Cu (AsO4) 35.12 18
CrAsOQ 20.11 18
FeAsO, 20.24 18

Mg3(AsO,) 30.32 34
Mn (AsOj) 28.72 18

Ni;(AsO1) 25.51 18
Pb,(AsO,) 35.39 18

Sr (AsO,) 18.79 34
Zn,(AsO4) 27.40 18
a) pK,, represents the negative log of the solubility product

equilibrium constant.








33

soil is due to the intervention of various organisms. Man

introduces organo-arsenicals as feed additives (arsanilic

acid, 3-nitro-4-hydroxyphenol arsenic acid and 4-

nitrophenylarsenic acids), as post-emergence grass herbicides

(mono- and disodium salts of methanearsonic acids), as

insecticides (calcium and lead salts of arsenate), as

fungicides (sodium arsenite, ferric methanearsonate and 10,10-

oxybisphenoxarsine), and as desiccants/defoliants

(dimethylarsinic acid and t-octyl or t-decyl ammonium

methanearsonate).21, 38-41 Molds, yeasts, fungi, algae and

bacteria have all been reported in various reviews to produce

organo-arsenicals, predominantly by methylation of arsenic

oxides and hydroxides.18'20'21'37 Volatile species of dimethyl-

and trimethylarsine, as well as AsH3, have been formed under

both aerobic and anaerobic conditions in soils.18'20'21'37 Most

of these compounds are depicted in Figures 2-1 and 2-2.


Abiotic Interactions of Arsenic


As amply demonstrated in the preceding paragraphs,

arsenic can be found in a multitude of compounds, all of which

will interact with soil to various degrees. Some generalities

can be drawn in regards to the interactions of As with soil.

Autoradiography, electron microscopy, and electron probe

microanalysis have each been used to measure the location of

added arsenate on soil components. Sorption is a function of

interlayer spacing in a clay lattice in conjunction with the









34

amount of hydroxyaluminum on the surface of the clay.19

Arsenic retention has also been reported to be proportional to

soil sesquioxide content and to decrease as amorphous iron and

aluminum are removed. Organo-arsenicals, similar to inorganic

As and P, will sorb to iron hydroxides in clay with increasing

sorption in the order cacodylate < arsenate = methylarsonate.

Adsorption has been shown to be a function of arsenical

species concentration, iron content and clay type. For

methanearsonate, the sorptive capacity of clays is given as

kaolinite > vermiculite > montmorillonite. The greater

adsorptive capacity of 1:1 type clays kaolinitee) was

attributed to greater number of exposed hydroxyl groups of

these minerals.42

Another study revealed that this generalization holds

for arsenate only in the pH range of 1 to 9. At pH >9, the

adsorptive capacity of montmorillonite exhibited a minima and

subsequently increased while that for kaolinite continued to

decrease. The increase in sorptive capacity was explained by

noting that the montmorillonite contained calcite as a small

impurity. Calcite has been shown to reach a maxima of

sorptive capacity for arsenate at pH = 11.43. This study

reached the conclusion that, the finer the soil texture, the

higher the clay and/or the iron content, the more the sorption

of arsenicals will occur.19

Interaction of humic acid with As has been reported as

well as the conclusion that, at certain pH values, these









35
interactions may outweigh the sorption of As to hydrous

oxides.20 Other investigators concluded that sorption of As

to metals may be a greater influence on immobilization than

organic matter.21

Accumulation of As by metal hydrous oxides in

"rhizosphere soil" has been suggested as possible by the

oxidative effect of wetland plant roots. Oxidation of the

rhizosphere could cause iron oxyhydroxides to precipitate, and

the oxyhydroxides, in turn, would sorb As.44

Manganese oxide/hydroxides will also form complexes with

various As species. Studies of pore water in sediments and

flooded soils have shown that the As concentration correlates

better to dissolved Fe than to Mn. The conclusion was that,

as Mn(IV) is reduced to Mn(II), the released As is resorbed by

the iron oxides/hydroxides. As such, iron content can still

be considered to be the controlling factor in the release of

As.20,45

Arsenic can also be released from soil through

competitive reactions for sorption sites by P. Seventy-seven

percent of As present in a soil was displaced by KHPO4 in an

experiment designed to simulate phosphate additions to an

orchard soil.46 Another study involving fourteen different

extracting solvents on four different soils concluded that the

order of effectiveness was: deionized distilled water = 1 N

NH4C1 = 0.5 M CH3COONH, = 0.5 M NHNO, < 0.5 M (NHI,)S04 < 0.5

M NH4F = 0.5 M NaHCO, = 0.5 M (NH,);CO, < 0.5 M KHzPO, < 0.5 N









36
HzSO4 = 0.1 N NaOH. No solvent removed more than 80% of the

total As from any of the four soils, even after 18 hours of

shaking.47

One soil washing procedure that has been reported to

remove more As involved use of a surfactant and a chelating

agent. Four surrogate contaminated soils with average pH of

8.5 were washed with chelating agent (ethylene diaminetetra-

acetic acid) water and surfactant-water solutions. This

system was effective in removing 93% of the spiked As.48

The removal efficiency of As by leaching with water through

soil is highly dependent on the soil type with an order of

sand < silt loam < clay. Organoarsenicals tend to leach in

much the same manner as arsenate. However, one study has

indicated, that in sandy loam and clay columns, the leaching

of cacodylic acid was more rapid than for the sodium salts of

methylarsonate.19

The rate of leaching for inorganic As is dependent on

its oxidation state. During laboratory elution of a sandy

column under oxidizing conditions, As (III) eluted at five to

six times greater rate and at about eight times greater

quantity than As (V). These differences were considered to be

related to the weaker interaction of As (III) to Fe (III) in

comparison to As (V) and Fe (III). In reducing conditions, As

(V) and As (III) leached at similar rates. This behavior was

attributed to the reduction of iron, the reduction of arsenic,

or both.20










Biotic Interactions of Arsenic


Redox reactions, as well as methylation/demethylation

reactions, are often facilitated by micro-organisms in the

soil. Several review articles have been published dealing

with microbial transformations of As.18,19,20,21

One of the major transformations of As is through

bacterial oxidation. Microbial-mediated oxidation of arsenite

to arsenate in cattle dipping fluids was suggested in a 1909

Australian article.20 It remained a matter of dispute whether

this change was brought about biotically or abiotically. In

1911, an agent for the United States Bureau of Animal Industry

reported independently finding the same phenomenon and showed

the change occurred through the growth of microorganisms in

the dipping baths, with other factors being of little

importance.49 Confirmation of bacterial oxidation of arsenite

was obtained by a South African group that isolated a pure

culture capable of bringing about such change. The bacteria,

named Bacillus arsenoxyduns, was eventually lost.20

The oxidation of arsenite to arsenate has been suggested

as a detoxification mechanism, since bacteria are about ten

times more sensitive to arsenite than arsenate.21 Even in the

early 1900's, it was recognized that the cattle fever tick was

approximately two times more susceptible to arsenite than

arsenate.49 In fact, a simple field test for arsenite

concentration in cattle dipping fluids was developed based on








38

titrating with iodine until the starch indicator changed

color.50 Knowing the amount of arsenite in the dip was

extremely important in light of the fact that it is more toxic

to cattle than arsenate.

Conversely, the concentration of arsenite may be

increased, rather than decreased, in the dipping vats by

evaporation or by biotic reduction of arsenate. The influence

of bacterial reduction of arsenate in cattle dipping fluids

was described in 1915 as a development that occurred after the

rapid growth of oxidizing bacteria, but only if dipping was

done in sufficient amounts and over short intervals. It was

conjectured that the bath became so rich in nutrients that it

finally formed a favorable medium for the growth of reducing

organisms, which could flourish and counteract the action of

oxidizing microorganisms. It was hypothesized that the

oxidizing organisms worked slowly, but steadily; whereas the

reducing organisms worked sporadically, briefly, and only

during sufficiently rich nutrient conditions.49 Although

there seems to be no literature reporting the isolation of

such a reducing bacterium from cattle dipping fluids, an

anaerobic (also microaerophilic) bacteria has been isolated

from a freshwater marsh sediment that is capable of using As

(V) as an electron acceptor and lactate as the electron

donor.51 This particular strain showed a time lag before

growth was evident that was dependent on the amount of 02

present. Oxygen at 1, 3 and 5% induced a lag time of 40








39
hours, while a culture kept at 15% 02 required 95 hours. This

bacterial growth pattern leads to the speculation that, as the

aforementioned cattle dipping fluids became enriched with

nutrients, the oxidizing bacteria would flourish to the point

of depleting the oxygen level in the bath. Then, the reducing

bacteria could quickly grow and, subsequently, the rapid rise

in arsenite concentration would be observed.

Reduction of arsenate to arsenite may also lead to biotic

methylation and subsequent formation of a volatile arsine

species. In anaerobic conditions, a Methanobacterium strain

produced dimethylarsine and fungal strains of Penicillium and

Aspergillus converted sodium methylarsonate, sodium cacodylate

and arsenous acids to trimethylarsine. A wood rotting fungus,

Lenzites trabea, produced a garlic-smelling volatile As

compound (probably trimethylarsine) from a medium containing

arsenic trioxide.21 The volatile arsenic compounds are stable

in anaerobic conditions, but rapidly oxidize in the presence

of oxygen if the concentration of methylarsines is above 0.05

0.10 milligram per liter. At lower concentrations, these

volatile arsenical species are stable enough to migrate from

the area.18

Demethylation of methylated As species has also been

shown to occur. Some of the same species that form volatile

alkylarsines are also capable of using methane arsonic acid as

a carbon source for growth. Species that can do both include

Flavorbacterium, Aeromona, and Norcardia.20 Other species








40

that can utilize methanearsonate as a carbon source include

Achromobacter, Pseudomonas, Alcaligenes and Enterobacter.21

An Alcaligenes species that was isolated from soil produced

only arsenate. Another study showed that dimethylarsinic acid

degraded to arsenate in soil in aerobic conditions, but not in

anaerobic conditions.18

The general rule is that biomethylation is favored in

anaerobic or reducing conditions and that carbon cleavage of

organo-arsenicals occurs predominantly with aerobic or

oxidizing conditions. Like most general rules, exceptions can

be found. For example, one study showed that a mixed

bacterial fungal population could release trimethylarsine in

aerobic or anaerobic conditions.18 Another organism,

Aspergillus fumigatus, was reported to produce a volatile form

of arsenic from As(III) in aerobic conditions.44

Methylation and volatilization have been suggested as

possible means to remediate As contaminated sites. This

combination is, by no means the only procedure capable of

cleaning a site.44


Remediation Techniques for Arsenic-Contaminated Soil


There is a plethora of remedial treatments for

contaminated sites. These remedial methods can be placed

within the three headings of in-situ, prepared-bed and in-tank

reactors. In each of these categories the processes may be

physical29, chemical29, biological44 or any combination of








41
these approaches. The aim is to achieve separation, volume

reduction, immobilization, and detoxification, if possible.

Not all remediation techniques apply to As-contaminated sites;

however, a brief summary of the techniques that apply follows:


Physical remediation techniques


Excavation. Excavation is a simple prepared-bed method

that aims to transfer contaminants elsewhere or to prepare

them for further treatment. Disadvantages include determining

the volume of contamination, the requiring of large amounts of

clean fill material, and an increase in groundwater pollution

due to disturbing of the soil column. There are also problems

involving traffic, noise, dust and surface water pollution.

Entombment. Entombment is another prepared-bed method,

wherein a collection is made of one or more contaminants that

are placed on a single site and a tomb is then constructed to

avoid dispersion. Disadvantages include the associated

contamination of the collection area, the need to physically

move the contaminants with its concurrent problems, and the

need for construction of an effective structure.

Cover. This technique is widely used in the United

Kingdom and applies to both in situ and prepared-bed methods.

The cover material can be anything from asphalt, or concrete,

to clean soil. Disadvantages are that the area under the

cover is still contaminated and lateral migration can occur

with the influence of surface and ground water.








42

Soil Washing. Separation and volume reduction can be

accomplished using this in-tank method. It is particularly

well suited for remediation of non-volatile organic and

metals. The washing procedure does not work as well with soil

that contains an appreciable amount of clay or organic matter;

however, the main disadvantage is that the washing fluid

becomes highly toxic and usually hard to treat.

Soil Flushing. While soil washing is an in-tank

procedure, soil flushing does not require excavation. It is

an in situ method that also aims to separate and reduce the

volume of contaminants. Solutions used to flush the soil

include water, acidic and basic solutions, surfactants, and

various solvents. The same problems exist for soil flushing

as for soil washing.

Soil Vacuum Extraction. This is an air-stripping

technique that applies to both in situ and prepared-bed

methods. This method extracts contaminants by moving clean

air through unsaturated soil. This air movement causes mass

migration from soil water into the soil air. Disadvantages

are the need for a volatile or semi-volatile contaminant, and

the air-movement restriction problems inherent with non-

homogeneous and/or saturated soils.

Electro-kinetic Reclamation. This is an in situ method

which requires that the soil be electrically charged using

direct current along with the insertion of a water-circulation










system at one or both electrodes. Charged contaminants in

such a system cause water movement to the oppositely charged

electrode. The moving water also carries non-charged

contaminants, usually to the cathode. Drawbacks include a

strong dependence on soil composition and moisture content as

well as limits on the amount of electric charge and the length

of time required to complete the process.

Particle Size Separation. With this method, size

separation is carried out by gravity via an in-tank method.

It requires that the contaminants, such as arsenic, are

associated with the finest soil particles. Drawbacks include

the complexity of the operation and problems with subsequently

treating the fine particles.

Rotary Kiln. This is an in-tank process that is

successful in volume reduction and detoxification.

Disadvantages are that it produces fly ash, a highly

particulate emission that can be as toxic, or more so, than

the original material. It also is limited to small particles

and thus usually needs to have prior size reduction done on

the contaminated material.

Pyrolysis. This is an in-tank process that is utilized

for volume reduction and detoxification of contaminated soil

that cannot undergo regular incineration in a rotary kiln.

The principal disadvantage is that it can only handle small

quantities at a time.








44

Cement Solidification. This is an in situ or in-tank

method of storage and immobilization. It is accomplished by

mixing Portland cement with the contaminated soil.

Disadvantages include incompatibility with large amounts of

dissolved sulphate salt or metallic anions such as arsenate,

along with difficulty in hardening over a short time if the

soil has a high amount of organic matter, silt or clay. Long-

term effects of this method have not been adequately studied.

Vitrification. This is an in situ or in-tank method that

is used to immobilize and store contaminants by fusing them

into a glass-like substance. The main disadvantage is the

high energy requirement, particularly with soils of high water

content.


Chemical remediation techniques


Precipitation. This technique can be done as an in situ,

prepared-bed or in-tank method. The premise is separation,

possible volume reduction and/or immobilization by the

formation of insoluble precipitates. This method was

recommended by the Florida State Board of Health, Veterinary

Division, for the As dipping-vat program. The arsenic was to

be precipitated as a ferric salt in basic conditions, and then

buried. Unfortunately, subsequent microbial action reduces

the iron and frees the As species for migration. The main

drawback to this method is a lack of testing on long-term

stability of the precipitates.










Carbon Adsorption. This procedure can be used as an in

situ or a prepared-bed technique, or as a complimentary

technique in conjunction with other methods such as pyrolysis.

It is most effective with contaminants of high molecular

weight, high boiling point, low solubility, and low polarity.

The primary drawback is the lack of knowledge of long-term

stability.

Ion Exchange. This is an in situ or prepared-bed method

emphasizing separation and immobilization of contaminants.

Disadvantages include the limitation of applicable inorganic

contaminants in suitable soils and the requirement of

convenient pH control.


Biological remediation techniques


Bioleaching. This technique can be performed as in situ,

in-tank or in prepared beds. Bioleaching may affect arsenical

compounds directly by increasing mobility of As through

reduction to inorganic As (III) or through reduction of

associated ions (i.e., iron or sulfur). Bioleaching may occur

indirectly by microbial production of organic acids, such as

malic acid, or by microbial production of inorganic acids,

such as sulfuric acid. These acids could in turn mobilize As

via dissolution or ionic displacement mechanisms. Impediments

to bioleaching may derive from soil composition, soil pH,

nutrient requirements, bioavailability of the As compounds,

and competition by indigenous microorganisms. Another








46

drawback is the need to remediate large volumes of

contaminated liquid resulting from the bioleaching process.

Volatilization. This remediation method occurs naturally

in situ. It may also be carried out in a prepared bed or in-

tank. Volatilization of As can be mediated by bacteria,

algae, actinomycetes or fungi or by a mixture of organisms.

This technique exhibits all of the drawbacks exemplified by

the bioleaching process, except that the large volume of

contaminated liquid is replaced by a large volume of highly

toxic gas.

Bioaccumulation and Biosorption. This technique involves

the sorption of As onto microbial biomass or direct

accumulation of As within soil microorganisms. The

remediation may occur in situ, in-tank or in prepared beds.

Drawbacks include soil composition, pH, nutrient requirements,

microbial competition, and bioavailability of the contaminant.

Additional problems arise in regards to biosorption stability

and subsequent separation of bioaccumulated As.














CHAPTER 3
CATTLE DIPPING VAT SITES


Introduction


A number of difficulties arose during the process of

selecting which cattle dipping vat sites were to be

investigated. Among the problems encountered was the fact

that there is no public record of vat locations. The vats

have been unused for cattle dipping for over thirty years.

During this time period, Florida has been developed

extensively and many vats are no longer even in existence.

Often the vats have been buried, paved or constructed over, so

that physical evidence of their presence has been virtually

obliterated. In addition, there was initially a problem

involving liability for the cost of remediating these sites,

if contamination were found. During the 1996 legislative

session, the State of Florida passed a bill (House Bill #1073

and Senate Bill #956) releasing property owners whose land

contained a cattle dipping vat from liability for costs,

damages or penalties associated with the discharge,

evaluation, containment, assessment or remediation of any

substances that were used in the cattle-fever tick eradication

program, retroactive to 1909.52 However, at the onset of this








48

research project in 1992, the liability for remediation costs

rested solely with the owner of the property. With estimates

of such costs ranging from $130,000 to $800,000 per site (not

including cost of annual operation and maintenance),4 private

property owners were not willing to admit even having a vat,

much less allow an investigation of the site. One of the

first criteria for site selection thus became the need for

vats to be located on state property. Other factors included

proximity to the University of Florida in Gainesville,

accessibility to the vat and to the surrounding land and, if

possible, availability of anecdotal accounts of the location

and the history of use for the vat site. The latter criterion

is, in fact, the key to locating many of these vats. It must

be remembered that cattlemen who utilized these vats when they

were in their thirties would now be in their sixties. They

thus constitute a location resource that is steadily

disappearing. Some other assumptions and facts also can aid

in locating vats; for instance:

a) a water source was needed (each vat held =5700 liters);

b) vats needed to be drained; therefore, the location would be

at higher elevation in relation to surrounding terrain,

although in some cases only by a matter of centimeters;

c) the Florida sun is an extreme condition that could be

alleviated if the vat were located under tree cover;

d) no cow was expected to travel more than 1.6 kilometers








49

(three miles) to the nearest vat; hence, it can be assumed

that vats are no farther than 3.2 kilometers apart;

e) the number of vats per Florida county were recorded, often

with the original owner's name;

f) tax rolls should also reveal the original owner of the

cattle, since the taxman was invariably present at major

dipping operations; and

g) holding areas such as auction houses and railway heads

invariably had vats nearby.

All of these assumptions can be utilized to find cattle

dipping vat sites. Clearly, the easiest way to locate a vat

is still through anecdotes from the people involved in using

them.


Materials and Methods


Those vats that were located during the course of this

study usually came from anecdotal accounts, primarily by the

Payne's Prairie park staff (Butch Hunt, Jack Gillem, Jim

Weimer, and Howard Adams). Other sources included previous vat

surveys by Woodward-Clyde, Inc., and sources located on the

University of Florida campus.19

All vat sites near the University of Florida were

visually confirmed and the surrounding soil was sampled for As

contamination, if the site was accessible. Only one confirmed

vat site for this study was not in Alachua County. This site








50
was located in adjacent Marion County with the owner amenable

to a cursory examination of the vat, which had been filled

with soil. A total of nine vats were investigated at least to

the extent of 1) obtaining latitude and longitude using

global positioning satellite technology, 2) placement on

topographical and soil survey maps and 3) if permitted by the

landowner, selected soil sampling and analysis for As

contamination. Ten other vat sites were investigated by the

Woodward-Clyde consulting firm and the results were reported

to the Florida Department of Environmental Protection.4

The global positioning survey was accomplished using a

Magellan Model GPS 2000 unit (Magellan Systems Corp., San

Diego, CA). Topographical maps were supplied by the U.S.

Geological Survey, Denver, CO. Soil map units, taxonomic

classes, and soil survey maps were obtained from the U.S.D.A.

Natural Resource Conservation Service.53-62 Vat locations were

superimposed on a road map using latitudes and longitudes by

the program "ArcView GIS version 3.0".63

Soil samples were selected on the basis of topography

and tested on-site for As. The on-site As soil test was a

modification of water analysis procedure for the "EM Quant

Arsenic Test Kit" (EM Science, Gibbstown, NJ). The test was

rapid, though more qualitative than quantitative. The kit came

with zinc dust, 30% HC1 and 100 indicator strips as well as a

graduated color chart to estimate the concentration of As.








51
The original procedure called for placing 5 mL of water into

a 50 mL tube. This procedure was modified to substitute a 0.5

g soil sample (delivered via scoop) and 5 mL of a 500 mg/L P

solution (from KH2PO4). A few drops of isopropanol were added

to suppress foaming, if required. A small scoop of zinc dust

(=0.4 g) was added and the contents thoroughly mixed. An

indicator strip containing mercuric (II) bromide was inserted

into a septa cap and the cap was attached to the culture tube

after 0.2 mL 30% HC1 was added. A syringe needle (18 gauge)

was put through the cap to relieve excess pressure. The

arsine gas generated would react with the indicator strip

turning it from light yellow to orange-tan to dark chocolate

brown, depending on the amount of As in the soil.

The pH of the soil was measured by mixing 2:1 water:soil,

stirring, and then allowing the slurry to equilibrate for ten

minutes. The pH was measured using a combination electrode

and an Accumet pH meter model #910 from Fisher Scientific,

Inc., Norwalk, CT.64

Percent moisture in the soil samples was determined by

drying a known weight of field-moist soil for 24 hours at

105C. The dried sample was weighed and percent moisture

calculated on a dry weight basis.65

Soil organic matter was measured using a modified

Walkley-Black method. This involved a sulfuric/chromic acid

digestion followed by sodium hydroxide titration using

diphenylamine as an indicator.66








52

Particle size distribution of the soil samples was

determined using sodium metaphosphate solution to suspend the

clay. An aliquot of the suspension was taken at a prescribed

depth, dried and determined by weighed to measure the amount

of clay. Sand was separated from silt by wet sieving, dried

and determined by weighing. Percent silt in the soil was

determined by difference [100-(% sand + % clay)].67

Soils were digested for metal analysis using U.S.E.P.A.

method #3050 or #3051. The former is a HNO3/HC1/HO digestion

on a hot plate, while the latter is a HNO3 digestion using

pressurized teflon bombs and a microwave oven as a heating

source. Both methods yield results termed "Total Recoverable"

metals, although method #3050 yields slightly higher results

than method #3051.68,69 All reagents were analytical grade and

obtained from Fisher Scientific Supply Co. (Orlando, FL). The

digestion instrumentation for method # 3051 was a CEM MDS-2000

microwave unit.

The digestates were analyzed for aluminum (Al), iron

(Fe), manganese (Mn) and arsenic (As) by one of four methods.

Al, Fe and Mn were either determined by inductively coupled

argon plasma spectrometry (ICAP) or by flame atomic absorption

spectrophotometry. The As was determined by either a cold

vapor hydride method according to instructions supplied by the

Perkin-Elmer Corporation or by graphite furnace as in

U.S.E.P.A. method #SW846-7060.70 The instrumentation used for








53

these analyses included a multi-channel Jarrell-Ash

Inductively Coupled Argon Plasma unit model 161-E,

a Perkin-Elmer (Franklin, MA) Atomic Absorption Spectrometer

(AAS) model #2380, a Perkin-Elmer Graphite Furnace (GF) model

HGA-400 and a Perkin-Elmer Hydride System MHS-10 (Norwalk,

CT). Spectrophotometer conditions for the flame and hydride

vapor atomic adsorption analysis are given in Table 3-1.

Operational parameters for the graphite furnace are shown in

Table 3-2.

Background correction for the graphite furnace utilized

a deuterium lamp. This type of correction compensates for

smoke; however, it is inadequate for spectral interference.

A spectral interference "occurs when an absorbing wavelength

of an element present in the sample but not being determined

falls within the bandwidth of the adsorption line of the

element of interest".71 For As analysis by graphite furnace

using deuterium lamp background correction, the spectral

interference is caused by aluminum.72 Fortunately, the

spectral interference caused by aluminum absorption exhibits

a strong linear correlation (R2=0.996) with the apparent As

concentration (Table 3-3). Since the aluminum can be measured

by nitrous oxide flame AAS, the contribution of aluminum to

the apparent As signal can be calculated and subtracted from

the measured As concentration to obtain the true, or the

corrected As concentration. After correction for aluminum




















Table 3-1. Operational parameters for metal analysis by flame
or hydride generation.


Element Slit Width Wavelength Standard Range

(nm) (nm) (mg/L)
Arsenic 0.7 193.6 0.002-0.02
Aluminum 0.7 309.3 5-100
Iron 0.2 248.3 0.3-10
Manganese 0.2 279.5 0.1-10


I Perkin-Elmer 2380 Atnmic~ Absorntion 8nectrnmeinr


















Table 3-2. Operational parameters for arsenic analysis by
graphite furnace.


Perkin-Elmer 2380 Atomic Absorption Spectrometer

Wavelength = 193.7 nm
Slit Width = 0.7 nm
Integration Time = 5 s
Absorption Mode = Peak Height
Background Correction = Deuterium Lamp
Pyrolyzed Graphite Tube with L'vov Platform
Perkin Elmer HGA-400 Graphite Furnace
Program: Step Temp. (C) Ramp (s) Hold (s) Other

1 100 20 30
2 1300 10 10
3 2300 0 5 Stop Flow

Read
4 2500 1 3
Perkin-Elmer AS-40 Autosampler

Sample Injection Volume = 10 pl
Modifier Injection Volume = 10 4l
Matrix Modifier = 5% Ni(NO3); in 0.1 N HNO3























Table 3-3. Spectral interference by aluminum in the analysis
of arsenic at wavelength 193.6 nm using a graphite furnace
atomic absorption spectrometer with deuterium background
correction.




Aluminum Concentration Apparent Arsenic

(mg/L) Concentration ( g/L)
10 2.59

25 13.7

50 39.5

100 84.1
250 189.
500 349.








57

interference, the As concentration as measured by graphite

furnace agreed well with the values obtained by hydride

generation, which was free from this particular interference.

The cold vapor hydride system was operated in accordance

with the Perkin-Elmer MHS-10 mercury/hydride system manual.73

In general, 10 mL of acidic sample solution was placed in a

reaction flask and the flask was purged with argon. The

reductant, 3% NaBH4 in 1% NaOH, was added for no more than 15

seconds. The resulting gas, AsH3, was swept from the reaction

vessel into a heated T-shaped quartz cell and the maximum peak

height for absorbance at a wavelength of 193.6 nm was measured

and recorded. All reagents were of analytical grade and

purchased from Fisher Scientific Supply Co. (Orlando, FL).

For sites where the arsenic contaminant plume was

delineated in the soil, soil samples were collected using

either a 2.5 cm soil probe or a 10 cm bucket auger (Forestry

Suppliers, Inc., Jackson, MS). The soil samples were

transferred to plastic bags, labeled and stored in the

laboratory at 80C until digestion and analysis. All soil

samples for this phase were digested and analyzed for As

within two weeks of collection.

The contaminant plumes were plotted using "Geo-Eas

1.0.1,66 and/or "Surfer v.5".74 Depths to the argillic horizons

were determined by soil probe and measuring tape.

Topographical measurements were performed using a








58

Lietz/Sokkisha C3a Automatic Level from Florida Level and

Transit Co., Jacksonville, FL.

To better determine the subsurface topography of the

argillic horizon at one of the sites, ground-penetrating radar

(GPR) was employed. The GPR unit, a Geophysical Systems model

3102, was run at 400 nm/s with attenuation of 100 and with a

frequency of 500 MHZ at 16 scans/s. Output was interpreted

using the Radan III program.75

All photographs of the vats were taken using a Ricoh RDC-

2E digital camera from Ricoh Corporation, Sparks, NV. Color

prints were produced by an Epson Stylus Color 800 printer.


Results and Discussion



This discussion section of the vat site studies was

broken into two major sections, confirmed (personally

investigated) and reported (investigated by state-contracted

consultants). In order to facilitate future investigations of

the confirmed vat sites, the locations were overlayed by GIS

on road maps (Figures 3-1 and 3-2). A summary of confirmed

vat sites with the soil map units and taxonomic class revealed

that seven out of nine sites were located on Ultisols (Table

3-4). The only two vat sites not on an Ultisol were located

at the Payne's Prairie State Preserve South Rim location and













N


W E

S


.i- ,
-. ..Gpihesville
.US 441
Bison
va


Pen --
t


Williston \441 vat '
S Road vat.i v
4- ... 1Rim ntJackpon Gapva
Y-- Ri$m vet
l_ / illiston
i road
Micanopy
S TiicCT suullow


-, 'I*Manon
\ vat
Mcri


T q4'-T i-


I I''-^
;4unty .i



L
^ u. .


Figure 3-1. Map of roads and vats south of Gainesville, FL.


_il


a i


i


-T












N




S


4I

S-- pr .inggs

"__ Alacho










Ne erry
----I

2 hi

:.^"Li


aB -- 4 *- -

'U.F. Fuaitation Vat j

-us4
i'. '%-.

_**- _" ^ .1.- I


t -I-_* _
'11p

S, --G inesville
S.,- US 441


Figure 3-2. Map of roads and vats west of Gainesville, FL.








Table 3-4. Soil map units and taxonomic classes for confirmed cattle dipping vat sites.


Site Soil Map Unit Taxonomic Class

Bison Pen vat Millhopper sand Loamy, siliceous, hyperthermic Grossarenic
Paleudults
US 441 vat Lochloosa fine Loamy, siliceous, hyperthermic Aquic Arenic
sand Paleudults
Marion County vat Blichton sand Loamy, siliceous, hyperthermic Arenic Plinthic
Paleaquults
Dudley Farm vat Bonneau fine Loamy, siliceous, thermic Arenic Paleudults
sand
UF Foundation vat Lochloosa fine Loamy, siliceous, hyperthermic Aquic Arenic
sand Paleudults
Tuscawillow vat Kanapaha sand Loamy, siliceous, hyperthermic Grossarenic
Paleaquults
Jackson Gap vat Millhopper sand Loamy, siliceous, hyperthermic Grossarenic
Paleudults
South Rim vat Tavares sand Hyperthermic, uncoated Typic Quartzipsamments

Williston Road vat Pottsburg sand Sandy, siliceous, thermic Grossarenic Haplaquods

Monteocha loamy Sandy, siliceous, hyperthermic Ultic Haplaquods
sand

Wauberg sand Loamy, siliceous, hyperthermic Arenic Albaqualfs









62

bordered by Williston Road. All raw data for the confirmed

sites that had transects were tabulated in Appendix A.


Confirmed Vat Sites


Payne's Prairie Bison Pen Vat Site


The first site that was investigated was located on the

Payne's Prairie State Preserve =46 meters from the

Gainesville-Hawthorne railway. The vat was largely intact,

although partially filled with loose concrete, branches,

decomposing leaves and other detritus (Figure 3-3). The

topographical map shows that the vat was located on the side

of a hill (Figure 3-4). The soil survey map, which is

superimposed on an aerial photograph (Figure 3-5), reveals

that the site is wooded and heavily shaded. The name for this

site was derived from the holding pens for bison and cattle

that were once located nearby. The train rails and the

holding pens have since been removed from this site, but the

vat itself is still largely intact. The soil immediately to

the south (downhill) of the vat was mapped as a Millhopper

sand.53 Selected soil characteristics, including particle size

distribution, organic matter content, pH and As concentrations

are given in Table 3-5. The argillic horizon that is common

to the Millhopper sand played an important part in delineation

of the contaminant plume at this site. The As contaminant

plume was found on the southern side of the vat with the























































Figure 3-3. Photograph of the Payne's Prairie Bison Pen vat.
























































Figure 3-4. U.S.G.S. topographical map of the Payne's
Prairie Bison Pen vat site.





















































Figure 3-5. Soil survey map of the Payne's Prairie
Bison Pen vat site. Map unit designations:
8B Millhopper sand, 20B Tavares sand, 25 Pomona sand,
31B Blichton sand, 54 Emeralda fine sandy loam,
and 56 Wauberg sand.














Table 3-5. Selected characteristics of soil 10 meters south of the Bison Pen vat.


Soil Depth Horizon Dominant Particle Size Organic pH Arsenic
Taxonomic (cm) Munsell Distribution (%) Matter (%) (mg As/
Class Color Silt Sand Clay kg soil)
Silt Sand Clay

Udult 0-30 Ap 10YR 4/1 4.3 95.0 0.7 0.8 5.7

30-91 El 10YR 7/1 3.3 95.8 0.9 0.6 5.8 --

91-122 E2 10YR 7/2 4.0 95.3 0.7 0.4 5.4 0.8

122- E3 10YR 6/4 3.4 95.8 0.8 0.3 5.6 21.5

152

152- Bt 10YR 5/3 2.3 84.4 13.3 0.2 5.3 72.2

178

178- Btg 10YR 4/2 1.4 78.4 20.2 0.1 5.3 1.8










highest concentration of As in this plume being found 12.2

meters south of the center of the vat. This particular soil

sample from the Bt horizon contained 110 mg As/kg dry soil.

The location of the contaminant plume in relation to the vat

was expected, since anyone who had to empty the vat would

naturally do so to the downhill side of the vat. Transects

were laid out at 4.6 meter intervals east-west and at 6.1

meter intervals north-south. The north-south transects

extended to 12.2 meters uphill from the vat and 61.0 meters

downhill from the vat. The east-west transects measured a

maximum of 13.7 meters in east or west direction from the

center of the vat, though not all transects were of equal

total length. Transect length was determined by taking soil

samples from the top of the argillic horizon, which were

analyzed for As. Vertical soil sampling showed that the As

concentration is greatest on and directly above the Bt horizon

(Table 3-6). At this vat site, the arsenic did not penetrate

down to the lower, gleyed argillic horizon (Btg). It is

important to note that this soil sits directly on top of the

Hawthorn formation, which is almost impermeable to water.

Since the upper argillic was readily distinguished from the E

horizons by texture as well as by As content, it was chosen as

the diagnostic horizon for delineating this contaminant plume.

To delineate the contaminant plume, thirty-six samples

were taken from the top of the argillic horizon using a ten

centimeter soil auger and analyzed for metals (Figure 3-6).






















Table 3-6. Selected metal concentrations in soil 10 meters south of the Bison Pen vat.


Horizon Arsenic Iron Aluminum Manganese
(mg As/kg soil) (mg Fe/kg soil) (mg Al/kg soil) (mg Mn/kg soil)

Ap --- 365 960 9.4

El --- 238 690 7.5

E2 0.8 203 660 6.3

E3 21.5 170 560 4.1

Bt 72.2 129 770 1.7

Btg 1.8 183 970 2.0








69

Data for the depth, and for the nothing and eating coordinates as

well as the As concentrations, were used as input to the U.S.E.P.A.

program "Geo-EAS". The "Geo-EAS" program correctly stopped the

contaminant contour at the edge of the vat (Figure 3-7). However,

it is interesting to note that the U.S.E.P.A. program also

generated a single point at 100 nothing and 45 eating outside the

plume contour. Since it was set to draw contours at increments of

20 gg As/g soil, it ignored a point at 120 nothing and 45 eating

that yielded an arsenic concentration of 12.2 ig As/g soil. When

the plume contour was generated using "Surfer version 5.0" a

dumbbell shape was shown using contour levels of 20 mg As/kg soil

(Figure 3-8). The biggest obvious drawback of the "Surfer" program

was closure of the contours nearest to the vat where it actually

had no data to confirm this depiction. On the other hand, the

"Surfer" program has the advantage of allowing the user to

superimpose the contour map of the contaminant plume on top of a

three-dimensional grid representing the argillic horizon (Figure

3-9). In addition, the topographic map of the surface may be

superimposed over the argillic horizon and plume depictions (Figure

3-10).

The argillic horizon's three-dimensional representation was

generated using ground-penetrating radar (GPR). A ten-cm bucket

auger was used to "ground-truth" the GPR readings at

thirty-six locations. The depths measured by GPR and by soil probe

were linearly correlated, with a regression coefficient of R2 =

0.989. One source of error in these measurements was that the









0174
<0.7

0170 A
1.14 -



87.5
0170

0152 0138 0145
1.41 97.8 19.6

0145 0138 0142 0151 0133 0147 0163
<0.7 <0.7 33.0 110. 29.6 17.9 4.29

0130 C130 0135
<0.7 22.1 8.28

096 C146 0132 0135
<0.7 <0.7 12.2 <0.7

0122 0114 0117 0124
<0.7 7.13 25.8 <0.7

0114 0112 0109 0109
<0.7 <0.7 1.11 0.76


112 100 0103 0104
<0.7 <0.7 <0.7 <0.7

C 92
2.89
2Depth (cm)

O91
<0.7 Arsenic (ug/g)
(corrected for Al)

0 86
<0.7
Figure 3-6. Argillic horizon depth and associated As
concentrations at the Payne's Prairie Bison Pen vat.










240
<0.7

220 L .
1.14

200


180 y


160 \

10 <0.7 07 \33. 0. 9. 17.9 4 29
140

o <0.7 22. 5<0. 8.28
Z 120

<0.7 <0.7 12.2 <0.7 \
100 0 r

<0.7 7.13 25.8 \

80
<0.7 <0.7 1.11 0.76
60

<0.7 <0.7 <0.7 <0.7

40 -
2.89

20 -
<0.7
<0.7
0 ......._____ (<:7__ .
0 15 30 45 60 75 90

Easting


Figure 3-7. "Geo-Eas" contour map of As plume
at the Payne's Prairie Bison Pen vat site.










220.00-



200.00-



180.00-



160.00-



140.00-



120.00-



100.00-



80.00-



60.00-



40.00-



20.00-


oo
( \


0. 00
0.00 20.00 40.00 60.00


- Arsenic
mg/kg soil


80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5


Figure 3-8. Two-dimensional "Surfer" contour map of As plume
at the Payne's Prairie Bison Pen vat site. All distances measured
in meters.











Arsenic
mg/kg soil


80

75

70

65

60

55

50

45


.4, ~~


Figure 3-9. Three-dimensional "Surfer" map of the As plume
across the argillic horizon at the Payne's Prairie Bison Pen vat
site. All distances shown in meters.












Arsenic
mg/kg soil



80

75

70

65

60

55

50

45
4,-,


r~f~K



.5- -


Figure 3-10. Three-dimensional map of As plume on the argillic
horizon along with surface topography at the Payne's Prairie Bison
Pen vat site. All distances measured in meters.


--- _
.--

h~L, --








75

heavy brush on-site made surface contact with the radar unit

difficult to maintain. Overall, the GPR allowed the argillic

horizon to be mapped to a three-dimensional grid. Once the

"dumbbell"-shaped contaminant plume was overlayed on this grid, it

was easy to see that the "crests" and "valleys" of the argillic

horizon actually determined the shape of the plume.


Payne's Prairie Williston Road Vat


Another vat at Payne's Prairie State Preserve that had its

contaminant plume shape heavily influenced by the argillic

horizon was located at 10205 S.W. Williston Road, Gainesville, FL.

This vat was 90% intact, although there is currently a tree growing

through the side of the vat (Figure 3-11). The soil survey map53

(Figure 3-12) shows an area that is wooded; however, there is

evidence (small or missing trees) that at one time it was at least

partially clear-cut. Presently, the area has heavy (< 1 meter

height) brush to dense thickets (>3 meter height). The heavy

undergrowth prevented use of ground penetrating radar at this

location, since good contact with the surface could not have been

maintained. The contaminant As plume was mapped solely by soil

sampling with either a 10-cm bucket auger or a 2.5 cm soil probe

(Forestry Suppliers, Inc., Jackson, MS). The first 50 m were

"bush-hogged" to allow for easy access. The soils found at this

site were actually similar inclusions to those mapped, but did not

match

the taxonomy rigorously. This area near the vat was mapped as
























































Figure 3-11. Photograph of the S.W. 10205 Williston Road vat.





















































Figure 3-12. Soil survey map of the S.W. 10205
Williston Road vat site. Map unit designations:
3B Arredondo fine sand, 7B Kanapaha sand,
8B Millhopper sand, 19 Monteocha loamy sand,
20B Tavares sand, 28 Chipley sand, 50 Sparr fine sand,
52 Ledwith muck, and 59 Pottsburg sand.








78

Pottsburg sand.53 Between 60 and 70 meters, the soil was described

in the soil survey report as a Monteocha loamy sand.53 The

transects then extended into an area mapped as Wauberg sand. The

soil actually found at this site did not match the taxonomy given

for the map units. Inclusions of similar soil were identified.

The soil mapped as Pottsburg sand was taxonomically an Aquod and

the soil mapped as Wauberg sand was an Aqualf. The transects for

the Aqualf had to be performed along lanes cut by machete, since

this was where the dense thicket began (Figure 3-13). The particle

size distribution for the Aquod and Aqualf soils as well as organic

matter content, pH and As concentrations are given in Table 3-7.

The surface, spodic and argillic horizons of all three soils were

plotted in a three-dimensional grid (Figure 3-14A). What is not

clearly shown in this area plot is how the Pottsburg and Monteocha

soil map units overlap. In this transitional phase, the two spodic

horizons do not intersect each other as one would surmise from the

plot. The spodic horizon of the Aquod actually overlaid the Bh

horizon of the soil mapped as Monteocha sand, and was separated

from it by an E horizon located between the organic horizons. In

fact, the Monteocha soil was never clearly identified as a separate

soil in the field, although it is delineated on the soil survey

map. The As contaminant plume's shape was influenced not only by

the soil horizons composition, but also by the contours of these

soil horizons. This is similar to the situation found at the

Payne's Prairie Bison Pen Vat site. The maximum concentration





























































Figure 3-13. Photograph of the Williston Road vat's transect
lane. Flag marks soil with greatest As concentration at this
site.









Table 3-7. Selected characteristics of soils sampled at Williston Road vat site. These soils
were located within the Pottsburg sand and Wauberg sand map units in the Alachua county soil
survey and represent inclusions of similar soils.


Soil Depth Horizon Dominant Particle Size Organic pH Arsenic
Taxonomic (cm) Munsell Distribution (%) Matter (%) (mg As/
Class Color Silt Sand Clay kg soil)
^_____ _____ _____ Silt Sand Clay jk__soil)

Aquod 0-15 Ap 10YR 5/1 0.6 98.0 1.4 0.75 4.8 --

15-79 E 10YR 6/1 0.7 97.6 1.7 0.18 5.2 1.24

79-113 Bhl 10YR 2.5/2 3.5 94.2 2.3 1.01 5.4 11.8

113-135 Bh2 10YR 3/2 2.9 95.6 1.5 0.84 6.0 12.9

135-147 Bt 10YR 4/2 8.3 84.4 7.3 0.49 6.4 12.4

147- Btg 10YR 4/1 1.7 82.2 16.1 0.24 7.2 --

Aqualf 0-30 Al 10YR 2.5/1 8.0 87.8 4.2 3.38 5.9 51.2

30-46 A2 10YR 2.5/2 2.7 95.6 1.7 1.02 6.2 75.1

46-114 Bw 10YR 3/3 3.3 95.6 1.1 0.45 6.4 60.1

114- Bt 10YR 4/2 2.8 75.0 22.2 0.37 6.4 99.6

a Soil sample was taken 12 meters northeast of vat.
b Soil sample was taken 68 meters northeast of vat.











Surface


S1.50 Spodic Horizon

0.5D Argillic Horizon


-0.5




Aqualf soil Aquod soil

Arsenic
/ ug/g soil
.-- Aquod Bh and Aqualf Surface Horizons
s /-80
.' ..'-.--- --- -' '---- 75


"a' ?""" _' ........_ 55
o^ --' __- ~ -65
60





















were ra nl Ar






Figure 3-14. Soil horizons at the Williston Road vat site in terms
of: a) a two-dimensional map of three horizons, b) the Aquod Bh
horizon and Aqualf surface horizon with the As plume, and
c) the argillic horizon with its As plume. All As concentrations
were based on laboratory analysis. All distances are in meters.









82
of arsenic (Table 3-8) was found on top of the argillic

horizon for the Aqualf soil; however, at this site, the

arsenic had moved a greater distance from the vat (Figure 3-

14C). The greatest amount of arsenic was located 80 m from

the vat, almost twice as far as found at the Bison Pen vat

site. The vat was located at coordinates of 15 by 40-50 on

the grid map of Figure 3-14. The highest concentration of

arsenic found in the Bh horizon was located directly above the

spot on the argillic horizon that had the maximum amount of

arsenic. The maximum concentration of As (99.6 mg/kg dry

soil) in the argillic horizon was higher than the maximum

concentration (30.1 mg As/kg soil) found in the spodic

horizon. It was at this site that the As field test was first

used extensively to delineate the contaminant plume. A

typical scenario involved one person using a machete to blaze

a transect, a second person measuring distance, sampling soil

and keeping the transect straight (as well as parallel to the

other transects), and a third person conducting the field test

for arsenic. The transects were made only as long as

absolutely necessary according to the field test results.

This site required seven days for the three-man team to

delineate the arsenic plume. The soil was sampled at the

blackest section of the surface or spodic horizon and at the

top of the argillic horizon. Only the upper Bh horizon was

sampled in the area where overlaying spodic horizons were

found. For comparison, the contour map of the field test was




Full Text
Northing
229
80
70
60
50
40
30
20
10
0
1^=1 I
o
o
o

o
o
o
o
o



o
o







o




o
o
o




o
o
o




o
o
o




o
o
o




o
o
0
o
o

o
o
o
0
o
o

o
o
o
o o o
0 10
Easting
O O O
20 30
O Elevation only
Elevation and Sampled
Figure A-l. Sampling map for Payne's Prairie Bison pen vat
site. All distances are in meters.


276
103. Chattopadhhyay, A. and E. London, Fluorimetric
Determination of Critical Micelle Concentration
Avoiding Interference from Detergent Charge,
Analytical Biochemistry, 1984, 139, 408-412.
104. Parades, S., M. Tribout, and L. Seppulveda, Enthalpies
of Micellization of Quarternary Tetradecyl- and
Cetyltrimethyl ammonium", Journal of Physical
Chemistry, 1984, 88, 1871-1875.
105. Oades, J.M., Chapter 3 An Introduction to Organic
Matter in Mineral Soils, In: Minerals in Soil
Environments, 2nd edition, Dixon, J.B. and S.B. Weed,
(Eds), Soil Science Society of America, 1989, 127-135.


26
of 3, 4 and 5. Arsenic can have coordination numbers of 2 and
6 as well.30
Oxidation States of Arsenic
The oxidation states of arsenic include +5, +3 and 0.
Some confusion exists in the literature as to whether or not
to include -3 as one of the oxidation states as well.20 The
most common method for determining oxidation states is to
assign the charge distribution in chemical bonds based on the
relative electronegativities of the pertinent atoms.31 Linus
Pauling first defined electronegativity as "the power of an
atom in a molecule to attract electrons to itself."32 As
illustrated in Table 4, the value assigned to an atom's
electronegativity is dependent on the model chosen for
estimation. L. Pauling based his electronegativity scale on
thermochemical data.31 R.T. Sanderson based his scale on size
and charge of the atom, to arrive at an estimation of relative
electron density.31 R.S. Milliken suggested using an average
of the atom's ionization energy and electron affinity (values
in Table 4 were derived from the subsequent work of H. Jaffe
and co-workers).31 A.L. Allred and E.G. Rochow derived their
scale based on the electrostatic force exerted on valence
electrons by the nucleus.31 Basically, the larger
electronegativity values dictate that a larger partial
negative charge be assigned to that atom. Under the Pauling


35
interactions may outweigh the sorption of As to hydrous
oxides.20 Other investigators concluded that sorption of As
to metals may be a greater influence on immobilization than
organic matter.21
Accumulation of As by metal hydrous oxides in
"rhizosphere soil" has been suggested as possible by the
oxidative effect of wetland plant roots. Oxidation of the
rhizosphere could cause iron oxyhydroxides to precipitate, and
the oxyhydroxides, in turn, would sorb As.44
Manganese oxide/hydroxides will also form complexes with
various As species. Studies of pore water in sediments and
flooded soils have shown that the As concentration correlates
better to dissolved Fe than to Mn. The conclusion was that,
as Mn(IV) is reduced to Mn(II), the released As is resorbed by
the iron oxides/hydroxides. As such, iron content can still
be considered to be the controlling factor in the release of
As.20'45
Arsenic can also be released from soil through
competitive reactions for sorption sites by P. Seventy-seven
percent of As present in a soil was displaced by KH,P04 in an
experiment designed to simulate phosphate additions to an
orchard soil.46 Another study involving fourteen different
extracting solvents on four different soils concluded that the
order of effectiveness was: deionized distilled water = 1 N
NH4C1 ~ 0.5 M CHjCOONH, ~ 0.5 M NH4NO, < 0.5 M (NH4)2S04 < 0.5
M NH4F 0.5 M NaHCOj 0.5 M (NH,)2C03 < 0.5 M KH,P04 < 0.5 N


114
Figure 3-32. Soil survey map of the Marion County vat
site. Map unit designations: ArB Arredondo sand, BcB
Blichton sand, BoC Boardman loamy sand, FeC Fellowship
loamy sand, FgC Fellowship gravelly loamy sand, FmB
Flemington loamy sand, KeB Kendrick loamy sand, LoB
Lochloosa fine sand, SpB Sparr fine sand, WgB Wacahoota
gravelly sand, and ZuC Zuber loamy sand.


165
Figure 5-1. Schematic cross-section of apparatus used
for the aerobic, unsaturated, differential pressure column.


201
concentration (CMC), the hypothesis is that the arsenical
anion would be in the palisade area of the micelle. It was
theorized that this would prevent re-formation of arsenic-soil
bonds. The zwitterionic surfactant was expected to behave in
similar fashion, since a zwitterion is an ion that carries
both positive and negative charges. The negative charge for
the CHAPS surfactant is on the outside of the micelle, the
positive charge recessed inward and the center of the micelle
contains the non-polar tail of the surfactant. The non-polar
tail of CHAPS contains hydroxyl groups, allowing for hydrogen
bonding to the oxyanionic arsenic. This attraction as well as
coulombic attraction between the positively-charged portion of
the zwitterionic surfactant and the negatively-charged
arsenical ion was hypothesized to be an effective scavenger.
The outer negative charge on the micelle was expected to
repulse the negative charge found on the soil particle; hence
preventing re-adsorption of As. Obviously, if the negative
outer charge repulses arsenical anions, then extraction
efficiency would be low.
The final surfactant system involved an anionic
surfactant, sodium dodecylsulfate (SDS) (Figure 6-lc). Since
this surfactant and the contaminant both exhibit negative
charges, the extraction efficiency would be expected to be
negligible, unless the charge is reversed on one of the
components. Complexation of the arsenical anions by a highly-
charged chelator would accomplish this goal. In fact, this


142
Figure 3-51. Soil survey map of the St. Marks Wildlife Refuge
vat site. Map unit designations: 7 Otela fine sands,
11 Shadeville fine sand, 12 Shadeville-Seaboard fine sand,
27 Moriah-Pilgrims fine sands, and 48 Otela-Ortega sands.


129
Lake Kissimmee Vat
The Lake Kissimmee vat was located in the Kissimmee
State Park in Polk County, Florida. The topographical map
revealed the surrounding area to be marshy, although the vat
site itself is on slightly higher ground (Figure 3-42). The
soil survey report has the vat site mapped as Smyrna and
Myakka fine sands (Figure 3-43).57 The main difference
between these two soil series is depth to the spodic horizon.
The Myakka typically has the spodic horizon starting at 64 cm,
whereas the Smyrna has a shallow spodic horizon at 30 cm. In
either case, the maximum arsenic concentration would probably
be found in these spodic horizons. The lowest horizon in both
of these soil series was given as "C" with single grained sand,
loose and very strongly acidic. This implied that As would
not be retained once it had migrated through the spodic
horizons. The shallow water table, indicated by the
prevalence of marsh on the topographical map, probably has
dispersed the arsenic contamination over a large area. The
preliminary survey showed a range of <0.7 to 76 mg As/kg soil.
The latter value was at 73 cm depth, which corresponded to
within the spodic horizons of these soil series.
Mvakka River Vat
This vat was located near a camp ground in Manatee
County, Florida (Figure 3-44). The soil series was mapped as


Figure 3-14. Soil horizons at the Williston Road vat site in terms
of: a) a two-dimensional map of three horizons, b) the Aquod Bh
horizon and Aqualf surface horizon with the As plume, and
c) the argillic horizon with its As plume. All As concentrations
were based on laboratory analysis. All distances are in meters.


185
Time (Hours)
Figure 5-7. Aluminum and arsenic in effluent from an
aerobic, unsaturated column of Payne's Prairie Bison Pen
vat "Bt" soil (152-165 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and phosphate solutions.
Aluminum Effluent Concentration (ug/L)


SC-r
256
detected in soil samples 0-30 cm below surface.


158
Figure 4-3. Cumulative volatile As evolved from
contaminated subsurface soil from the Bison Pen site
under various oxic conditions.
Figure 4-4. Volatilization of As by Fusarium sp.
under various oxic conditions with and without a soil
column scrubber.


155
were observed at both the Bison Pen and Williston Road sites
(Figures 4-1 and 4-2). Control samples taken at both sites
did not show the presence of volatile As species. For the
Bison Pen vat site, Spearman rank non-parametric correlation
test showed no relationship between arsenic volatilized and
rainfall when all twelve datum pairs of arsenic concentration
(ng mL1) and rainfall (cm) were used (Figure 4-1). On the
other hand, when the two months of excessive rainfall (>25 cm)
were excluded, then a slight correlation was found. The rank
correlation coefficient was 0.612 at a significance level of
0.06.84 Since the Williston Road vat site had only three datum
pairs of As concentration (ng mL-1) and rainfall (cm) no
statistical analysis was performed (Figure 4-2). The
Williston Road vat study does confirm that subsurface As
volatilization was not an isolated event, however. Possible
explanations for the low Spearman rank correlation found
between As volatilization and rainfall with the Bison Pen vat
site data include: 1) that, with non-excessive rainfall, there
was an influx of nutrients that stimulated As production,
while excessive rainfall may have limited volatile As species
by converting the gaseous arsenicals to another form; or 2)
that the excessive rainfall caused oxygen depletion in the
system, which adversely affected the rate of volatile arsenic
formation.


77
Figure 3-12. Soil survey map of the S.W. 10205
Williston Road vat site. Map unit designations:
3B Arredondo fine sand, 7B Kanapaha sand,
8B Millhopper sand, 19 Monteocha loamy sand,
20B Tavares sand, 28 Chipley sand, 50 Sparr fine sand,
52 Ledwith muck, and 59 Pottsburg sand.


5-6.
Iron and arsenic in effluent from an aerobic,
unsaturated column of Payne's Prairie Bison
Pen vat Bt" soil (152-165 cm depth)
sequentially eluted with 50 mM potassium
chloride, nitrate, and phosphate solutions. 183
5-7. Aluminum and arsenic in effluent from an
aerobic, unsaturated column of Payne's
Prairie Bison Pen vat Bt" soil
(152-165 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and
phosphate solutions 185
5-8. Iron and arsenic in effluent from a ponded,
saturated column of S.W. Williston Road
vat A" soil (15-30 cm depth) sequentially
eluted with 50 mM potassium chloride, nitrate,
and phosphate solutions 186
5-9. Aluminum and arsenic in effluent from a ponded,
saturated column of S.W. Williston Road
vat A soil (15-30 cm depth) sequentially
eluted with 50 mM potassium chloride, nitrate,
and phosphate solutions 189
5-10. Chloride and arsenic in effluent from a pumped,
saturated column of Payne's Prairie Bison Pen
vat A" soil (0-5 cm depth) initially saturated
with 30 mM potassium chloride then eluted
with solution of sodium arsenate (4.86 g/L). 191
5-11. Phosphate and arsenate log-log isotherms for
Payne's Prairie Bison Pen vat A soil
(0-5 cm depth) 193
5-12. Comparison of calculated and experimental break
through of arsenic in the Payne's Prairie
Bison Pen A horizon" soil column 196
6-1. Chemical structures of a)hexadecyltrimethyl ammonium
bromide (HdtABr); b) 3-[3-cholamidopropyl)-
dimethylammonia]-1-propane sulfonate (CHAPS);
c) sodium dodecylsulfate (SDS); and d) [16-
pyrimidinium crown-4]4+ 200
6-2. Extraction of arsenic from Payne's Prairie vat soil
using HdtABr, hexadecyltrimethylammonium
bromide (a cationic surfactant) 207
xiii


14
Table 1-1. continued
Time
Description
Reference
1946
A Florida state official charged vats
with 0.5% DDT plus 0.03% gamma benzene
hexachloride (BHC). The mixture was
sold as "Dip 30".
1
1948
On Oct. 1, Glades, Highlands, Okeechobee
and parts of Osceola and Polk counties
were released from federal quarantine.
On Oct. 20, Volusia county was found to
be infested, with then spread to
Putnam, Flagler, Brevard, Osceola, Lake,
St. John's, Alachua, Orange, Madison and
Jackson counties in Florida as well as
Brantley county in Georgia. All this
was due to heavy movement of cattle from
Volusia county.
14
1950
Florida was released from Federal
quarantine on Dec. 1, but dipping
continued due to a re-infestation threat
associated with close proximity of
Florida to tick-infested countries and
islands of the West Indies.
14
1951
Florida state officials started using
Toxaphene and DDT-BHC as tickicides.
Arsenic dips remained the only ones
14


99
Figure 3-23. Soil survey map of the U.F. Foundation
excavated vat site. Map unit designations: 5B Fort Meade
fine sand, 7B Kanapaha sand, 8B Millhopper sand, 13 Pelham
sand, 14 Pomona sand, 29B Lochloosa fine sand, and 31C
Blichton sand.


5
highly oxic environment and 3) low microbial activity. For
the cattle dipping vat residues, in particular, these
assumptions are suspect.
Another area of possible contamination from cattle
dipping vats involves the use of pesticides other than As.
From 1906 to the mid-1940s, As was the preferred tickicide by
both state and federal programs. In fact, for 60 years it was
the only product officially approved by the U.S.D.A. However,
in 1946, an "outbreak" occurred in Florida associated with
reappearance of the cattle-fever-carrying tick species
Boophilus microplus. At this time, Florida officials began
using 0.5% DDT with 0.03% gamma benzene hexachloride. In the
cattle dipping vats, this mixture was known as "Dip 30". In
1960, dioxathion was permitted, coumaphous in 1968 and
toxaphene in 1972.1 Other contaminants found at vat sites
include DDD, DDE, dieldrin, lindane, chlordane, toluene and
methlyene chloride.3
Hindsight shows that the history of the cattle dipping
vat parallels a history of As contamination of Florida soils.
However, in defense of the tick eradication program, it should
be emphasized that the economic devastation upon southern
cattlemen by Boophilus annulatus. the cattle-fever tick, was
debilitating, being on the order of $130,500,000 in 1906
dollars. In 1996, the program would have cost more than a
billion dollars.1 In light of factors such as economic
impetus, sparse population, and scant chemical and


87
movement of arsenic in gaseous form to occur; hence, the plume
migrated further. It will be demonstrated later in this
dissertation that subsurface volatilization of As did occur at
both of these sites. As such, it may be a contributing factor
in the movement of arsenic through the soil.
Dudley Farm Vat
In contrast to the Williston Road Vat site, the Dudley
Farm Vat site had a plume which was laterally confined on one
side by a large limestone formation. However, this vat site
had a plume depth that was significantly greater than found at
the two other sites previously discussed. Lateral dimensions
of the plume had been previously mapped by the firm of
Woodward-Clyde Consultants (Tallahassee, FL).4 This vat
remained in good shape, with the most damage occurring from
the collapse of the splash wall (Figure 3-17) The in-ground
walls were intact and the vat still contained water. This
water was tested for As, but concentrations were below the
analytical detection limit of 8.0 /g As/mL solution. Water
from a well located 46 meters east of the vat was sampled and
analyzed, but no As was detected. The Woodward-Clyde
Consultants had already delineated the arsenic plume at this
site for the Florida Department of Environmental Protection.19
The surface and subsurface data for this site were depicted on
site maps in Appendix B. The soil around the vat was mapped


253
or- or-2
V-b
1 r
O'"--7 or-} -0?-3-
I :j
J
J I = i
5_LifJ G L^lJ [Hi
I t_£ i j<0.7i ]o.ay| ¡ : !
. .*=!*?. T
a '2r e 'S'
Of-3?K-IC Of-PgM-l*
d* ¡fer*
or--9 ;r-:o
I 1
zr-2; CP-2*
s 2 I 3 i
[30* ?E)!3
S 5,
w
::
3f-:i :'-:i >
3r-3:-s
TT:
e.*-r :
J I i;
>"-3C or-;.i
Sampled 0.5 ft.
(8) Sampled 0.5 and 2.0 ft.
[#]Sampled 0.5 and 4.0 ft.
EI3Arsenic in mg/kg
Figure B-4. Woodward-Clyde Consultants1 arsenic survey map
of Dudley Farm cattle dipping vat site. Arsenic detected
in soil samples at 91-122 cm below surface.


Table A-2. continued
Easting
Northing
Surface
Elevation
(meters)
Argillic
Depth
(meters)
50
80
0.552
50
85
0.491
-1.105
50
90
0.475
50
95
0.469
-0.864
50
100
0.421
50
105
0.415
-0.838
50
110
0.411
50
115
0.396
-0.940
50
120
0.408
50
125
0.390
-1.041
55
65
0.792
55
70
0.683
-1.092
55
75
0.600
55
80
0.500
-0.902
55
85
0.475
55
90
0.475
-0.635
55
95
0.479
55
100
0.439
-0.584
55
105
0.466
55
110
0.427
-0.965
60
65
0.844
60
70
0.668
60
75
0.549
-0.991
60
80
0.500
60
85
0.472
-0.914
60
90
0.491
60
95
0.463
-0.889
Arqlllic Arsenic Concentration (mq/kq)
Field Results Laboratory Analysis
37.5 14.7
6.25 12.1
5 3.85
12.5 0
1.25 0.52
1.25 0.03
8.75 2.36
12.5 2.21
3.75 1.11
0 0
0 0
0 0
1.25
Iron (mg/kg)
Argillic Horizon
Aluminum (mg/kg) Manganese (mg/kg)
1830
17500 1
2640
21900 1
1400
14200 1
1120
11000 0
5140
25500 2
3470
27500 2
2640
23900 2
1270
10800 1
2790
27400 1
3520
26200 1
3470
25900 2
2440
11000
16600 1
67400 3
11000
67400
239


Table A-l. Selected site data for Payne's Prairie Bison Pen cattle dipping vat.
Surface
Argillic
Arsenic
Aluminum
Elevation
Depth
Easting
Northing
(meters)
(meters)
(mg/kg)
(mg/kg)
0
67 06
2.554
-1.417
0
60.96
2.426
-1.544
0
54.86
2.283
-1.347
0
48.76
2.222
-1.277
0
42.66
1.939
-1.361
0
36.56
1.756
-1.291
0
30.46
1.536
-1.277
0
24.36
1.323
-1.080
0
18.26
1.079
-0.954
0
12.61
0.707
-0.911
0
6.1
0.381
-0.883
0
0
0.055
-0.799
4.57
67.06
2.566
-1.375
4.57
60.96
2.576
-1.403
4.57
54.86
2.240
-1.333
<0.7
436.7
4.57
48.76
2.082
-1.319
<0.7
171.8
4.57
42.66
1.935
-1.235
<0.7
145.5
4.57
36.56
1.701
-1.263
<0.7
482.2
4.57
30.46
1.490
-1.122
<0.7
953.8
4.57
24.36
1.289
-1.122
<0.7
517.8
4.57
18.26
1.045
-1.066
4.57
12.61
0.695
-1.080
4.57
6.1
0.424
-1.080
4.57
0
0.079
-1.066
9.14
67.06
2.932
-1.199
9.14
60.96
2.356
-1.165
1.41
572.2
9.14
54.86
2.228
-1.188
32.97
924
9.14
48.76
2.100
-1.245
22.15
427.7
9.14
42.66
1.841
-1.188
<0.7
301.4
230


CHAPTER 6
SURFACTANT EXTRACTION OF ARSENIC FROM SOIL
Introduction
Extraction by solvents was reviewed in the previous
chapter. Another type of remediation technique for treating
As contaminated soil involves the use of surfactants with or
without a chelating agent. In general, if the process is
completed in situ, it is referred to as soil surfactant
flushing. The ex situ method, whereby the soil is excavated
prior to treatment, is termed soil surfactant washing.98 If
the process is to be done in situ, then the site must be
carefully selected, since soil flushing engenders mobilization
of the contaminant. Generally, the surfactant mixture is
applied via an injection well and the surfactant-contaminated
solution is removed by a recovery well. An unsuitable site
subjected to this treatment may make remediation more
difficult. On the other hand, ex situ treatment confines the
contaminant within its system; however, it does require
excavation of a considerable amount of soil. This may not be
a practical alternative in many cases.
Other practicalities to be considered involve recovery of
the surfactant for recycling, extraction efficiency of the
198


APPENDIX A
RAW DATA FOR CONFIRMED VAT SITES
This appendix contains elevation and metal analysis for
the transects that were performed on the Alachua County cattle
dipping vat sites by John E. Thomas.
228


Relative Concentration (C/CO)
196
Pore Volumes
Figure 5-12. Comparison of calculated and experimental
break-through of arsenic in the Payne's Prairie Bison Pen
"A horizon" soil column.


a pop o/¡va te pp&PErr aouNDAPr
JOW-28
OW-27
CW-26 *
OW-24*
0.87 ^
\
\
GW-25
^MW-1
\
0W-2j\
IV-23,
3C-:
3W-I7,
OW-6a
cv- ;s {
<0.7:
OW-4
<0.70
JQW-6
^
GW-5
CW-4_ <0.70
0.73 #
OW-2
[6.5 | Arsenic in mg/kg
Background
larripltd 0.5 ft.
^ Sampled 0.5 and 2.5 ft.
ffil Sampled 0.5, 2.0 and 4.0 ft
Civ-J
&
Figure B-13. Woodward-Clyde Consultants' arsenic survey map
of Okaloosa-Walton Community College cattle dipping vat site
Arsenic detected in soil samples at 152-183 cm below surface


19
and as innocuous to humans when present as certain
organoarsenicals. Such is the case for seafood, where As is
present as arsenobetaine and yet safe at 500 times the
U.S.E.P.A. acceptable level for human drinking water. 20,26,27
Arsenic and Regulatory Laws
The concept of allowable limits for As being set by
regulatory agencies is based on "total concentration" rather
than "species concentration". This is due to the fact that
the arduous and time-consuming task of guantifying the
multitude of arsenical species present is simply not
economically feasible. Even though regulatory decisions
concerning allowable concentrations of As may not vary based
on speciation; there are regulatory variations based upon the
background matrix (air, soil, water, food, etc.) and the
intended usage of that matrix. There are also differing
regulatory laws among various agencies setting limits on
allowable arsenic concentrations. An example of the variance
due to usage can be exemplified by the aqueous limits set by
U.S.E.P.A. (Table 2-3) .26,27
Currently, in the United States, there is no limit set
on As contamination allowable in soil, except as a 5 ppm
upper limit for the U.S.E.P.A. Toxicity Characteristic
Leaching Procedure (TCLP).28 The United Kingdom also has set
a limit of 10 mg/kg for domestic gardens and 40 mg/kg for


218
of the contaminants, regardless of whether the contaminants
are metals (e.g. As, Zn, Cd, Cr, Cu, Pb) or organics (e.g.
acetone, chlorobenzene, xylene, anthracene, and
pentachlorophenol). If the medium to fine sand portion ( <2
mm size fraction) is removed in the soil washing, then more
94
than 90% of the contaminants are simultaneously removed.
For the soil fraction smaller than 2 mm in size, the
surfactant/chelation technique was found to be a suitable
method for the remediation of arsenical contamination in soil.
Conclusions
For samples from the E horizon of the Payne's Prairie
Bison Pen vat site, the anionic surfactant/chelation system of
sodium dodecylsulfate with [16-pyrimidinium crown-4]+4 proved
the most effective in removing As from soil. The cationic
surfactant, hexadecyltrimethylammonium bromide (HdtABr), did
not have as high an extraction efficiency as the zwitterionic
surfactant, 3-[3-cholamidopropyl)-dimethyl ammonia)-1-propane
sulfonate (CHAPS).
For soil samples from the Bison Pen vat site "Bt horizon,
the cationic and zwitterionic surfactants were essentially
equivalent in their low recovery of As. It was also found
that NaSDS alone could not effectively remove As from a
contaminated soil. However, the anionic surfactant/chelator
system of NaSDS with a high positively charged macrocycle
proved to be much more efficient than the other surfactant


18
Table 2-1. Estimated U.S. demand for arsenic (metric tons)
1971
1981
1991
Agricultural
Chemicals
15,600
8,900
5,000
Glass
2,000
1,000
1,900
Industrial Chemicals
970
9,100
14,300
Nonferrous Alloys and
Electronics
570
600
1,000
Other
500
400
400
Total
19,640
20,000
21,600
Table 2-2. Toxicity data of selected arsenical compounds
Arsenic Compound
LD50 (mg / kg)
Biological
Half-Life(hours)
Arsenite
(arsenic trioxide)
34.5
(mouse)
28.6 (hamster)
Arsenite
(sodium arsenite)
4.5 (rat)
30 (human)
Arsenate
(sodium arsenate)
14-18 (rat)
50.4 (human)
Monomethylarsonic Acid
(MA)
1,800
(mouse)
7.4 (hamster)
Dimethylarsinic Acid
(DMA)
1,200
(mouse)
5.6 (hamster)
Trimethylarsine
(TMA)
8,000
(mouse)
3.7 (hamster)
Trimethylarsine Oxide
(TMAO)
10,600
(mouse)
5.3 (hamster)
Arsenobetaine
10,000
(mouse)
6.1 (hamster)


6
environmental knowledge (by today's standards), the tick
eradication program appears justified given the historical
perspective. A time table (Table 1-1)7-15 for cattle fever,
cattle ticks and cattle vats reveals a treatment period that
spans more than 50 years, with variable success in pestilence
control.


DISTRIBUTION, MOVEMENT, AND EXTRACTION
OF ARSENIC
IN SELECTED FLORIDA SOILS
By
JOHN E. THOMAS
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1998


119
Figure 3-34. Topographical map of the Blackwater River
State Forest vat site.


169
Figure 5-3. Schematic cross-section of apparatus used
for the ponded, saturated, differential pressure column.


APPENDIX B
RAW DATA FOR REPORTED VAT SITES
This appendix contains sampling maps of arsenic analysis
for other cattle dipping vat sites as performed by Woodward-
Clyde Consultants for the Florida Department of Environmental
Protection.4
249


110
plants and algae. Five mL of water were tested using the As
field test. The As concentration was at the lowest
colorimetric detection limit of 0.1 mg As/L water. Soil
samples taken at the 60 cm depth for both 0.99 m west and 0.58
m east of the vat exceeded the limits (>37.5 mg As/kg soil) of
the colorimetric test. Soil samples 3.7 meters west of the
vat and at depths of 3 0 and 4 3 cm tested at 17.5 mg As/kg
soil. No further assessment was made on the soil at this
site.
Tuscawillow Vat
This site had a vat which remained in good structural
shape with standing water. It was located outside the
Micanopy city limits, adjacent to the Tuscawillow Prairie.
This vat was fenced and on private property, so only the
location and condition of the vat could be confirmed from the
public roadside. The soil map (Figure 3-30) shows a small
stand of trees that surround the vat. The soil map gives the
location as occupied by soil belonging to the Kanapaha series.
Topography around the vat is low-lying and nearly level
(Figure 3-31).
Marion County Vat
The final vat investigated was located in nearby Marion
County. This vat was privately owned. The owner was gracious
in allowing us to complete a cursory examination of


186
Figure 5-8. Iron and arsenic in effluent from a
ponded, saturated column of S.W. Williston Road
vat "A" soil (15-30 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and phosphate solutions.
Iron Effluent Concentration (ug/L)


84
placed adjacent to the contour map of the laboratory analysis
for Aquod Bh and Aqualf surface horizons as well as for the
argillic horizon (Figures 3-15 and 3-16, respectively). The
field test had an upper limit of 37.5 mg As/kg soil. Any soil
containing As above this level would yield a colorimetric
response (black) that gave no indication of the actual As
concentration. Since the field test was based on a crude
colorimetric comparison, the concentrations found were
somewhat rough estimates. However, the field test was
performed on a 1:10 dilution while the laboratory analysis
involved a 1:100 dilution during the digestion procedure.
Because of this, the overall shape of the plume as shown by
the field test may be a more accurate depiction; whereas, the
concentrations given by the laboratory analysis would
certainly be more accurate.
The greater movement of the As plume at this site,
compared to the Bison Pen Vat site, is probably due to the
presence of the Bh horizons, which were absent at the first
site. The greater migration of the arsenic plume at the
second site might be due to the spodic horizon inhibiting the
downward flux of arsenic by causing a perched watertable which
would have allowed the arsenic to travel laterally.
Alternatively, the influx of organic compounds down to the
argillic horizon may have facilitated volatilization of the As
by stimulating microorganism growth and thus, allowed lateral


219
systems tested. In fact, if the soil weight to
surfactant/chelate weight ratio were adjusted, it is possible
to achieve 100% extraction efficiency for both the E and the
Bt horizon soils from the Bison Pen vat site. A timed trial
using the surfactant/chelate system revealed that there was no
significant difference between mixing times of one hour and
twenty-four hours.
Although the extraction efficiency is not a problem with
the surfactant/chelate system, several issues need to be
resolved before it is implemented on a commercial scale.
First, the cost of the macrocycle will be high, since it is
not yet commercially available. Secondly, biodegradability of
the surfactant/chelate mixture must be demonstrated. Lastly,
removal of the surfactant and chelating agent from the waste
stream has yet to be worked out.


Table 3-6. Selected metal concentrations in soil 10 meters south of the Bison Pen vat.
Horizon
Arsenic
(mg As/kg soil)
Iron
(mg Fe/kg soil)
Aluminum
(mg Al/kg soil)
Manganese
(mg Mn/kg soil)
Ap

365
960
9.4
El

238
690
7.5
E2
0.8
203
660
6.3
E3
21.5
170
560
4.1
Bt
72.2
129
770
1.7
Btg
1.8
183
970
2.0


144
Figure 3-53. Soil survey map of the Walker Ranch vat site.
Map unit designations: 6 basinger fine sand, 13 gentry fine
sand, 15 Hontoon muck, 16 Immokalee fine sand, 26 Oldsmar
fine sand, 27 Ona fine sand, 38 Rivera fine sand, 40 Samsula
muck, and 42 Smyrna fine sand.


141
area to be mapped as Otela fine sand and Shadeville-Seaboard
fine sands (Figure 3-51).61 The Otela series consists of
typically moderately well-drained Grossarenic Paleudults. The
Btg" horizon of this soil series usually has fine prominent
red mottles. The maximum arsenic concentration would be
expected to be located in these mottles. The Shadeville-
Seaboard series may or may not have an argillic horizon. The
Shadeville portion has sandy clay loam over fractured, porous
limestone bedrock. If the arsenic does migrate through the
"Bt" horizon, it may eventually reach the water table through
porous bedrock. The Seaboard series would not be any better
at retaining arsenic since it consists of fine sand over a
fractured porous limestone bedrock. Regardless of which soil
series the site contains, it appears that the arsenic could
have reached the water table. The arsenic sampling survey
showed <0.7 to 16 mg/kg outside the vat and 71 mg/kg inside
the vat.
Walker Ranch Vat
The Walker Ranch vat, located in Osceola County, FL, was
located in an area that was topographically shown as marshy
(Figure 3-52) The soil survey report has the site mapped as
the Immokalee series (Figure 3-53).62 The Immokalee soil
series is found on nearly level, poorly-drained locations. It
has a spodic horizon that usually begins around 94 cm deep.


126
migrate beneath this building. The consulting firm did not
report arsenic levels above 9 mg/kg. This soil series
typically has reddish sandy clay loam starting at 20 cm and
extending to 200 cm. Although the area is considered to be
well-drained, the sandy clay loam has sand particles coated
and bridged with clay which would inhibit the movement of
arsenic. It is quite possible that the maximum arsenic
concentration at this site lies under a metal building and was
inaccessible to sampling by the consulting firm.
Lake Arbuckle Vat
The Lake Arbuckle vat site was located in Polk County,
Florida, in an area bordering the Blue Jordan Swamp (Figure 3-
40) The soil series are mapped as Immokalee or Astatula
(Figure 3-41).57 The Astatula series consists of uncoated
Typic Quartzipsamments. The only confirmed site mapped as
this soil series was located at the south rim of the Payne's
Prairie State Preserve. It was determined at this site that
the uncoated Typic Quartzipsamments were not capable of
retaining arsenic. On the other hand, the Immokalee soil
series has several spodic horizons. Based on prior experience
at the Williston Road vat, it has been shown that the Bh
horizon can retain arsenic. Since the range of As in the
consulting firm's survey extended from 0.73 to 73 mg/kg, it
can be assumed that the soil series is more likely to be
similar to Immokalee than Astatula.


154
using Perkin-Elmer Hydride System model MHS-10. Operating
conditions for the graphite furnace and the hydride generation
system were described previously in Chapter 3.
Results and Discussion
Volatile As gas emissions from the soil surface at both
the Dudley Farm vat site and the Payne's Prairie Bison Pen vat
site were not detected. Collection of gaseous arsenical
species was attempted by continuously purging the air in a
sample collection box situated over the area of greatest
subsurface As contamination (110 mg kg-1 soil at the Bison Pen
vat site and 767 mg kg1 at the Dudley Farm vat site) At a
gas flow rate of 49.6 L hr1, the 13.5 L collection box was
fully purged every 11.2 minutes. These results conflicted
with findings reported by Braman.83 The differences were
attributed to variation in arsenic's time of application and
its depth of placement. Braman applied sodium arsenite to the
soil and grass surface, and immediately placed a bell jar over
the applied area for sampling.83 In contrast, the soil at
these cattle dipping vat sites was contaminated more than
thirty years ago. Additionally, the majority of As
contamination was not located on the soil surface at the
sampling points, but rather at a depth greater than 100 cm for
both vat sites.
To ascertain that As was being volatilized at these two
sites, subsurface probes were installed. Volatile As species


204
into a 35 mL screw-top glass culture tube. The soil samples
came from the "Bison Pen" vat in Payne's Prairie State
Preserve. One set of soil samples was from the E horizon
located at a depth of 45-60 cm, and other soil samples were
from the Bt horizon at 145-160 cm depth. All of these samples
were taken 3 meters downhill from, and south of, the vat. The
amount of As in the soil had been determined as 1.1 ug/g for
the E horizon and 55.1 ug/g for the Bt horizon. The first set
of experiments involved the anionic surfactant, sodium
dodecylsulfate (NaSDS), and the highly positive charged
macrocycle, [16-pyrimidium crown -4]4+. To a known weight of
soil was added either a) a constant volume (25 mL) of [16
pyrimidium crown -4]4+ in deionized distilled water (5.0 g/100
mL) with 0, 5, 10 or 30 mM NaSDS; b) various volumes (2, 7, 15
and 2 5 mL) of the 6.0 g/100 mL crown solution and enough
deionized, distilled water (DDIW) to bring the volume to 25 mL
with 30 mM NaSDS; or c) constant amounts of crown and
surfactant at the highest concentration with the weight of
soil being varied. These tubes were capped using teflon tape
and teflon-lined septa caps and the tubes were placed on a
rotary mixer. After 24 hours, the tubes were removed and
opened. To those tubes that had a constant amount of crown
solution, various amounts of aqueous sodium dodecylsulfate
solution (1.44 g/25 mL)were added. Other experiments had the
chelating agent and the anionic surfactant mixed together
prior to adding soil, with the shaking time varied. No


216
Figure 6-7. Effect of chelate to soil weight ratio on the
extraction of arsenic from Payne's Prairie Bison Pen vat "E"
soil samples using 30 mM sodium dodecylsulfate.


Figure 3-40. Topographical map of the Lake Arbuckle
vat site.


271
46.Woolson, E.A., J.H. Axley, and P.C. Kearny, "The
Chemistry and Phytotoxicity of Arsenic in Soils: II.
Effects of time and phosphorus", Soil Science Society
of America Proceedings, 1973, 37, 254-259.
47. Johnston, S.E. and W.M. Barnard, "Comparative
Effectiveness of Fourteen Solutions for Extracting
Arsenic from Four Western New York Soils", Soil Science
Society of America Journal, 1979, 43, 304-308.
48. Wilson, D.J. and A.N. Clarke, "Soil Surfactant
Flushing/Washing Chapter 10" In: Hazardous Waste
Site Soil Remediation: Theory and Application of
Innovative Technologies", Wilson, D.J. and Clarke, A.N.
(Eds), Marcel Dekker, Inc., 1994, 493-551.
49. Chapin, R.M., "Studies on the Changes in the Degree of
Oxidation of Arsenic in Arsenical Dipping Baths",
Bulletin of the United States Department of
Agriculture, 1915, 259, 1-12.
50. Melvin, A.D., "Laboratory and Field Assay of Arsenical
Dipping Fluids", Bulletin of the United States
Department of Agriculture, 1914, 76, 1-17.
51. Laverman, A.M., J.S. Blum, J.K. Schaeffer, E.J.P.
Phillips, D.R. Lovely, and R.S. Oremland, "Growth of
Strain SES-3 with Arsenate and Other Diverse Electron
Acceptors", Applied and Environmental Microbiology,
1995, Vol. 61, No. 10, 3556-3561.
52. Parks, B., Tallahassee Report, Florida Agriculture,
Florida Farm Bureau, 1996, vol. 55, no. 6.
53. USDA Soil Conservation Society, Soil Survey of Alachua
County Florida, 1985.
54. USDA Soil Conservation Society, "Soil Survey of Marion
County Florida, 1979.
55. USDA Soil Conservation Society, Soil Survey of Santa
Rosa County Florida, 1980.
56. USDA Soil Conservation Society, Soil Survey of
Charlotte
County Florida", 1984.
57.USDA Soil Conservation Society, Soil Survey of Polk
County Florida", 1990.


B-16.
B-17.
Woodward-Clyde Consultants' arsenic survey map of
St. Marks Wildlife Refuge cattle dipping
vat site
Woodward-Clyde Consultants1 arsenic survey map of
Walker Ranch cattle dipping vat site . .
265
266
xvi


37
Biotic Interactions of Arsenic
Redox reactions, as well as methylation/demethylation
reactions, are often facilitated by micro-organisms in the
soil. Several review articles have been published dealing
18 19 20 21
with microbial transformations of As. ' '
One of the major transformations of As is through
bacterial oxidation. Microbial-mediated oxidation of arsenite
to arsenate in cattle dipping fluids was suggested in a 1909
Australian article.20 It remained a matter of dispute whether
this change was brought about biotically or abiotically. In
1911, an agent for the United States Bureau of Animal Industry
reported independently finding the same phenomenon and showed
the change occurred through the growth of microorganisms in
the dipping baths, with other factors being of little
importance.49 Confirmation of bacterial oxidation of arsenite
was obtained by a South African group that isolated a pure
culture capable of bringing about such change. The bacteria,
named Bacillus arsenoxyduns, was eventually lost.20
The oxidation of arsenite to arsenate has been suggested
as a detoxification mechanism, since bacteria are about ten
times more sensitive to arsenite than arsenate.21 Even in the
early 1900's, it was recognized that the cattle fever tick was
approximately two times more susceptible to arsenite than
49
arsenate. In fact, a simple field test for arsenite
concentration in cattle dipping fluids was developed based on


67
highest concentration of As in this plume being found 12.2
meters south of the center of the vat. This particular soil
sample from the Bt horizon contained 110 mg As/kg dry soil.
The location of the contaminant plume in relation to the vat
was expected, since anyone who had to empty the vat would
naturally do so to the downhill side of the vat. Transects
were laid out at 4.6 meter intervals east-west and at 6.1
meter intervals north-south. The north-south transects
extended to 12.2 meters uphill from the vat and 61.0 meters
downhill from the vat. The east-west transects measured a
maximum of 13.7 meters in east or west direction from the
center of the vat, though not all transects were of equal
total length. Transect length was determined by taking soil
samples from the top of the argillic horizon, which were
analyzed for As. Vertical soil sampling showed that the As
concentration is greatest on and directly above the Bt horizon
(Table 3-6) At this vat site, the arsenic did not penetrate
down to the lower, gleyed argillic horizon (Btg). It is
important to note that this soil sits directly on top of the
Hawthorn formation, which is almost impermeable to water.
Since the upper argillic was readily distinguished from the E
horizons by texture as well as by As content, it was chosen as
the diagnostic horizon for delineating this contaminant plume.
To delineate the contaminant plume, thirty-six samples
were taken from the top of the argillic horizon using a ten
centimeter soil auger and analyzed for metals (Figure 3-6).


REFERENCE LIST
1. Graham, O.H. and J.L. Hourrigan, "Eradication Programs
for the Arthropod Parasites of Livestock", Journal of
Medical Entomology, 1977, vol. 13, no. 6, 629-658.
2. Scott, J.M., "Beef Cattle in Florida", State of Florida
Department of Agriculture, July 1929, Bulletin No. 28,
143-147.
3. Ellenberger, W.P. and R.M. Chapin, "Cattle Fever Ticks
and Methods of Eradication", United states Department
of Agriculture, 1919, Farmer's Bulletin #1057, 1-32.
4. Woodward-Clyde Consultants, "Cattle Dip Vat Assessment
Program A Summary Report Prepared for Florida
Department of Environmental Protection", January 1995.
5. Dawson, C.F., "Cattle Tick Eradication", State Board of
Health of Florida, Publication #103, March 1913, 162-
214.
6. Abstract Proceedings on Workshop on Removal, Recovery,
Treatment and Disposal of Arsenic and Mercury, United
States Environmental protection Agency document 600/R-
2/105, August 1992.
7. George, J.E., "Cattle Fever Tick Eradication Programme
in the U.S.A." In: The Eradication of Ticks,
Proceedings of the Expert Consultation on the
Eradication of Ticks with Special Reference to Latin
America, Mexico City, Mexico, June, 1987, 1-7.
8. In Florida Health Notes, State Board of Health Florida,
Annual Report #27, 1915, 206-217.
9. In Florida Health Notes, State Board of Health Florida,
Annual Report #28, 1916, 220-232.
10. In Florida Review, Bureau of Immigration, Dept, of
Agriculture, Vol. 1, #10, 1926, 1-16.
11. Dacy, George H., Four Centuries of Florida Ranching,
Britt Printing Co., Louis, Mo., 1940, 275-293.
267


Arsenic
mg/kg soil
Figure 3-10. Three-dimensional map of As plume on the argillic
horizon along with surface topography at the Paynes Prairie Bison
Pen vat site. All distances measured in meters.


121
Figure 3-36. Topographical map of the Cecil Webb vat site.


62
bordered by Williston Road. All raw data for the confirmed
sites that had transects were tabulated in Appendix A.
Confirmed Vat Sites
Payne's Prairie Bison Pen Vat Site
The first site that was investigated was located on the
Payne's Prairie State Preserve -46 meters from the
Gainesville-Hawthorne railway. The vat was largely intact,
although partially filled with loose concrete, branches,
decomposing leaves and other detritus (Figure 3-3). The
topographical map shows that the vat was located on the side
of a hill (Figure 3-4) The soil survey map, which is
superimposed on an aerial photograph (Figure 3-5), reveals
that the site is wooded and heavily shaded. The name for this
site was derived from the holding pens for bison and cattle
that were once located nearby. The train rails and the
holding pens have since been removed from this site, but the
vat itself is still largely intact. The soil immediately to
the south (downhill) of the vat was mapped as a Millhopper
sand.53 Selected soil characteristics, including particle size
distribution, organic matter content, pH and As concentrations
are given in Table 3-5. The argillic horizon that is common
to the Millhopper sand played an important part in delineation
of the contaminant plume at this site. The As contaminant
plume was found on the southern side of the vat with the


Table A-2. -
Easting Northing
40 135
45 130
40 140
40 125
50 65
50 85
50 90
50 95
50 100
50 105
50 110
50 115
50 120
50 125
55 65
55 70
55 75
55 80
55 85
55 90
55 95
55 100
55 105
55 110
60 65
60 70
60 75
60 80
60 85
60 90
60 95
continued
Surface
Elevation
(meters)
0.317
0.351
0.299
0.341
1.097
0.491
0.475
0.469
0.421
0.415
0.411
0.396
0.408
0.390
0.792
0.683
0.600
0.500
0.475
0.475
0.479
0.439
0.466
0.427
0.844
0.668
0.549
0.500
0.472
0.491
0.463
Surface or
Spodic
Horizon
Depth
(meters)
Horizon's Arsenic Concentration (ma/kq)
Field Results Laboratory Analysis
-0.178 1.25 0.22
-0.356 0 0
-0.203 21.2 13.6
-0.178 25 11.2
-0.152 6.25 5.5
-0.178 2.5 0.23
-0.178 0 0
-0.154 0 0.14
-0.305 0 1.01
-0.152 2.5 1.79
-0.102 3.75 1.27
-0.102 0 0.06
-0.127 0 0.89
-0.102 0 0.61
-0.127 1.25 0.36
Surface or Spodic Horizon
Iron (mg/kg)
Aluminum (mg/kg) Manganese (mg/kg)
820
1500 0
800
1300 23
620
3800 2
680
3900 1
980
2900 1
570
1800 1
1520
2200 1
460
4200 35
440
10700 7
1300
5000 12
1230
4700 5
930
6600 1
1940
10100 40
2090
9000 22
2550
K>
7900 4


194
and the intercept corresponds to log10 of the distribution
coefficient (Kd) For phosphate Kd = 14.5 and n = 0.36 for
this soil, while the arsenate values were 8.49 and 0.44,
respectively. The Kd value found for arsenate was within the
range reported in the literature of 1.9 to 18.0, based on 37
different studies. The median was reported as 6.7 with a
standard deviation of 0.52.96
If the Freundlich constant, n, was assumed to be equal to
unity, then the distribution coefficient could be considered
as a gauge of anion adsorption. Another useful aspect of
assuming n=l is that the Freundlich equation is reduced to a
linear equation without the necessity of taking the log of the
expression. For this simplified expression, a retardation
equation can then be derived.97 This equation relates
retardation to the distribution coefficient as: R = 1 + (pb
Kd) /sat, where R is the retardation factor, pb is the bulk
density (g/cm3) Kd is the distribution coefficient, and 03at
is the porosity (cm3/cm3T) For the soil used in this column
study, R equals 93.4. Since the pore velocity was 23.4 cm/min
and the length of the soil column was 5.0 cm, this meant that
the break-through time for a non-absorbed analyte was 0.213
minutes. For arsenate, with its retardation factor of 93.4,
the break-through time was calculated as 19.9 minutes. In
terms of pore volumes, this was calculated as 4.07. The
column effluents were collected as fractions consisting of 0.4
pore volumes. The analyzed fractions showed that break-


8
Table 1-1. continued
Time
Description
Rpfprprlrp
1889-
T. Smith and F.L. Kilborne confirmed the
7
1892
role of BooDhilus annulatus in the
epidemiology of Babesia biaemina.
1896
Dr. C. Curtice advocated cattle fever
tick eradication and outlined suggested
methods.
1
1897
The Interstate Association of the
Livestock Sanitary Board (now known as
the U.S. Animal Health Association) met
in Fort Worth, TX, to discuss dipping
experiments and quarantine lines.
7
1899
Dr. Curtice, State Veterinarian of North
Carolina, instigated a tick eradication
program in that state.
5
1903
Beaumont crude petroleum was shown to
provide Twelve counties in North
Carolina were released from quarantine
due to a successful tick eradication
program, the best tick control of any
preparation tested.
7
1906
Twelve counties in North Carolina were
released from quarantine due to
successful tick eradication program.
5


9
Table 1-1. continued
Time
Description
Reference
1906
U.S. Congress appropriated $82,500 to
initiate a tick eradication program.
1
1907
-700,000 sg. miles (1,813,000 km2)
remained under federal guarantine.
Approximately, the line passed through
Virginia, N. Carolina, Tennessee,
Missouri, Oklahoma, Texas and
California. Florida and 14 other
southern states were under federal
guarantine.
1
1910
Arsenic dips replaced straight crude
petroleum dips.
1
1911
Four-fifths of the formerly quarantined
area was released from quarantine. In
general, the program was proceeding from
the West and North, moving towards the
Southeast.
1,5
1914
Fifty dipping vats were documented to
exist in Florida.
8


76
Figure 3-11. Photograph of the S.W. 10205 Williston Road vat.


34
19
amount of hydroxyaluminum on the surface of the clay.
Arsenic retention has also been reported to be proportional to
soil sesquioxide content and to decrease as amorphous iron and
aluminum are removed. Organo-arsenicals, similar to inorganic
As and P, will sorb to iron hydroxides in clay with increasing
sorption in the order cacodylate < arsenate = methylarsonate.
Adsorption has been shown to be a function of arsenical
species concentration, iron content and clay type. For
methanearsonate, the sorptive capacity of clays is given as
kaolinite > vermiculite > montmorillonite. The greater
adsorptive capacity of 1:1 type clays (kaolinite) was
attributed to greater number of exposed hydroxyl groups of
these minerals.42
Another study revealed that this generalization holds
for arsenate only in the pH range of 1 to 9. At pH >9, the
adsorptive capacity of montmorillonite exhibited a minima and
subsequently increased while that for kaolinite continued to
decrease. The increase in sorptive capacity was explained by
noting that the montmorillonite contained calcite as a small
impurity. Calcite has been shown to reach a maxima of
sorptive capacity for arsenate at pH = 11.43. This study
reached the conclusion that, the finer the soil texture, the
higher the clay and/or the iron content, the more the sorption
of arsenicals will occur.19
Interaction of humic acid with As has been reported as
well as the conclusion that, at certain pH values, these


Table 3-9. Selected characteristics of soil 2.3 meters east of the Dudley Farm vat.
Soil
Taxonomic
Class
Depth
(cm)
Horizon
Dominant
Munsell
Color
Particle Size
Distribution (%)
Organic
Matter (%)
PH
Arsenic
(mg As/
kg soil)
Silt
Sand
Clay
Udult
0-36
Ap
10YR 3/2
5.4
91.2
3.4
1.79
5.4
74.5
36-66
E
10YR 5/2
4.2
91.2
4.6
0.63
7.1
108 .
66-112
Btl
10YR 6/3
5.2
82.2
12.6
0.36
7.1
73.7
112-147
Bt2
10YR 6/2
5.4
78.4
16.2
0.23
7.0
356.
147-197
Bt3
10YR 6/2
3.9
68.4
27.7
0.25
5.4
525.
197-
Btg
10YR 6/1
4.3
68.4
27.3
0.22
5.3
767.


116
Blackwater River State Forest Vat
The Blackwater River vat is located in Santa Rosa County,
Florida. Due to the scale of the topographical map (Figure 3-
34), it is not possible to accurately place the vat on the
soil survey map (Figure 3-35).55 The possible soil series are
mapped as Orangeburg, Bonifay or Troup. All of these soils
are Paleudults. The argillic horizon depth may vary from 36
cm (Orangeburg) to 119 cm (Bonifay) to 140 cm (Troup) An
actual sampling of the soil at this site is the only way to
confirm the soil series. Regardless of which of these three
soil series is found, the highest As concentration will be
found in or on the Bt" horizon. The sampling plan executed by
the consulting firm was performed at pre-set depth intervals
determined prior to visiting the site. It is quite likely
that the highest concentration in the soil profile was missed,
since the soil structure at the site was ignored in favor of
simplicity and consistency. The highest As concentrations
found at this site were 340, 370 and 320 mg As/kg soil. The
general movement of the plume appears to be southwest from the
drip pad.
Cecil Webb Vat
The Cecil Webb vat was located in Charlotte County, FL.
The topographical map showed the vat site as level with a
preponderance of wet areas surrounding it (Figure 3-36).


Table A-2. continued
Surface
Argillic
Araillic Arsenic
Concentration (ma/ka) -
Easting
Northing
Elevation
(meters)
Depth
(meters)
Field Results
Laboratory Analysis
Iron (mg/kg)
20
65
0.494
-0.965
3.75
3.99
8280
25
65
0.457
30
65
0.445
-1.118
12.5
5.2
2930
35
65
0.512
40
65
0.695
-1.422
3.75
9.22
2940
45
65
0.835
15
70
0.335
20
70
0.207
20
70
0.421
25
70
0.341
-0.991
12.5
3.77
3640
35
70
0.808
40
70
0.866
45
70
1.006
-1.397
31.2
6.18
2020
5
75
0.372
-1.143
1.25
0.46
3900
15
75
0.293
-1.168
1.25
0
2440
20
75
0.265
-1.143
12.5
3.87
2860
30
75
0.207
-1.067
15
4.85
7440
25
75
0.262
35
75
0.643
40
75
0.677
-1.245
31.2
6.43
730
45
75
0.762
0
80
0.238
-1.041
1.25
0.04
4230
5
80
0.396
10
80
0.116
-1.016
12.5
0
2090
15
80
0.280
20
80
0.171
-0.940
12.5
3.87
3920
20
80
0.122
25
80
0.189
35
80
0.485
-1.118
17.5
8.17
3130
40
80
0.518
45
80
0.570
-0.864
37.5
99.6
1640
0
85
0.177
5
85
0.085
-0.572
15
7.21
11800
Argillic Horizon
Aluminum (mg/kg) Manganese (mg/kg)
52000 4
22800 2
25400 1
26600
5
18400 2
30900 2
24300 2
24200 3
26800 2
8500 0
31200 2
20900 13
32600 4
29100 2
13100 0
68400 2
236


240
220
200
180
160
i
140
120
100
80
60
40
20
0
re 3
-e
<0.7
o
1.14
o d>
17.9 4.29
O O O O
<0.7 <0.7 12.2 <0.7
/
0 cf
<0.7 7.13 25.8 \
O
O
<0.7 <0.7 1.11 0.76
O O O O
<0.7 <0.7 <0.7 <0.7
O
2.89
O
<0.7
<0,7
1 1 - 1
15
30
45
60
75
90
Easting
7. "
yne'
Geo-Eas" contour map of As plume
s Prairie Bison Pen vat site.


93
Figure 3-20. Topographical map of the Dudley Farm vat site.


Figure 3-47. Soil survey map of the Okaloosa-Walton
Community College vat site. Map unit designations
17 Lakeland snad, 31,33 Troup sand, and 36 Pits.


40
that can utilize methanearsonate as a carbon source include
Achromobacter, Pseudomonas, Alcaligenes and Enterobacter.21
An Alcaligenes species that was isolated from soil produced
only arsenate. Another study showed that dimethylarsinic acid
degraded to arsenate in soil in aerobic conditions, but not in
anaerobic conditions.18
The general rule is that biomethylation is favored in
anaerobic or reducing conditions and that carbon cleavage of
organo-arsenicals occurs predominantly with aerobic or
oxidizing conditions. Like most general rules, exceptions can
be found. For example, one study showed that a mixed
bacterial fungal population could release trimethylarsine in
aerobic or anaerobic conditions.18 Another organism,
Aspergillus fumigatus, was reported to produce a volatile form
of arsenic from As(III) in aerobic conditions.44
Methylation and volatilization have been suggested as
possible means to remediate As contaminated sites. This
combination is, by no means the only procedure capable of
cleaning a site.44
Remediation Techniques for Arsenic-Contaminated Soil
There is a plethora of remedial treatments for
contaminated sites. These remedial methods can be placed
within the three headings of in-situ, prepared-bed and in-tank
reactors. In each of these categories the processes may be
physical29, chemical29, biological44 or any combination of


10
Table 1-1. continued
Time
Description
Reference
1915
Eighty-eight dipping vats were reported
to be constructed state-wide, with eight
in Alachua County, FL. A.L. Jackson of
Payne's Prairie was listed as the owner
of one vat. All vats had been built
with private funds except for one vat
built by the University of Florida.
8
1916
Broward and Dade counties and part of
Palm Beach county were declared free of
cattle tick by the federal Secretary of
Agriculture. A large dipping vat and
non-infectious feeding pens were
established at Jacksonville, FL to
facilitate shipping cattle out-of-state
under a Federal certificate of dipping.
9
1917
State legislature passed a "Local Option
Tick Eradication Bill" allowing counties
that voted favorably to start a tick
eradication program.
10
1917
Open-range policy and re-infestation
from non-dipping areas, as well as a
lack of public interest and funds,
caused the program to fail.
10


42
Soil Washing. Separation and volume reduction can be
accomplished using this in-tank method. It is particularly
well suited for remediation of non-volatile organics and
metals. The washing procedure does not work as well with soil
that contains an appreciable amount of clay or organic matter;
however, the main disadvantage is that the washing fluid
becomes highly toxic and usually hard to treat.
Soil Flushing. While soil washing is an in-tank
procedure, soil flushing does not require excavation. It is
an in situ method that also aims to separate and reduce the
volume of contaminants. Solutions used to flush the soil
include water, acidic and basic solutions, surfactants, and
various solvents. The same problems exist for soil flushing
as for soil washing.
Soil Vacuum Extraction. This is an air-stripping
technique that applies to both in situ and prepared-bed
methods. This method extracts contaminants by moving clean
air through unsaturated soil. This air movement causes mass
migration from soil water into the soil air. Disadvantages
are the need for a volatile or semi-volatile contaminant, and
the air-movement restriction problems inherent with non-
homogeneous and/or saturated soils.
Electro-kinetic Reclamation. This is an in situ method
which requires that the soil be electrically charged using
direct current along with the insertion of a water-circulation


172
column studies involved replacement of the chloride ion with
a different anion, the pore volume of the column was
calculated by finding the volume which passed through the
column from the time when the chloride influx solution was
replaced to the time when the chloride concentration was only
half of its original concentration on the effluent curve.
Intact soil cores were taken adjacent to the area from
which the soil column was filled. These cores were sampled by
pounding two stacked brass rings into the soil and removing by
careful excavation. Each ring measured 3.0 cm height by 5.4
cm internal diameter. The rings were separated and loose soil
was removed from the core by shaving with a flat-blade
spatula. The o-ring in the plexiglass pressure cell (Soil
Moisture Equipment Co., Santa Barbara, CA) was lubricated with
Cellu-Solve grease (Fisher Scientific, Orlando, FL) and the
core was inserted so that good contact between the porous
porcelain plate and the soil was maintained. The bottom of
the cell was injected with deionized water by syringe. The
cell was placed in a water bath and allowed to saturate by
capillary action. Saturation was confirmed by adding one drop
of water to the top of the cell and, subsequently, having one
drop of water exit the bottom. Total weight of the cell was
recorded for saturated conditions. The soil was dried at
104C overnight and the dry soil weight recorded.
The retention of As and P was investigated as well,
using adsorption isotherms. Isotherm determinations were


13
Table 1-1. continued
Time
DescriDtion
Reference
1938
Overcoming a court injunction, deer
removal began. Approximately 20,000
deer are slaughtered.
7
1941
Boophilus annulatus microplus, a cattle-
fever tick, was found on 4 of 22 deer.
Deer removal continued in Orange,
Osceola, Highlands and Glades counties.
1
1943
Deer in Big Cypress Swamp, and in
Collier and Hendry counties, were
exempted from slaughter because they
were on Seminole Indian Reservation.
Forty-two of these deer were inspected
and found to be tick-free. Florida was
released from Federal quarantine on Dec.
1, 1943.
14
1945
A fever tick re-infestation was found in
Highlands County, FL. Infested areas
of Glades, Highlands, Okeechobee and
parts of Osceola and Polk counties were
placed under federal quarantine.
14


195
through occurred between 3.85 and 4.25 pore volumes. It is
obvious (Figure 5-12) that, as a first approximation, this
method of calculating the retardation factor is acceptable.
Conclusions
In general, differential pressure column studies indicate
that the removal of As from soil is best accomplished with low
oxic conditions. For the "E" horizon from the Bison Pen vat
site, the total amount of As removed with low oxic levels was
almost triple the concentration of As eluted under aerobic
conditions.
Of the three anions investigated, phosphate was much more
effective then chloride or nitrate in releasing As from the
soil. Phosphate has homologous chemistry with As and could
readily displace the As from the soil chemically. Phosphate
is also a necessary macro-nutrient and may stimulate microbial
growth, especially after potassium, nitrogen, and carbon
sources have been supplied. This increased biotic activity
can, under low oxic conditions or at anaerobic micro-sites,
cause reduction of iron and solubilization of humic/fulvic
complexes. Both would cause an increase in the amount of As
in the effluent from a soil column. Several unsuccessful
attempts were made to maintain a sterile column, to elucidate
the biotic versus chemical displacement of As in soil.
Both the chloride and nitrate anions were ineffective in
displacing As from soil. In fact, it appeared that nitrate


261
APPR0X1UA It PROPERTY BOUNDARY
aOW-28
V <0.70
165 |Arsenic
in
mg/ kg
Background
sample
0.
5 ft.
^ Sampled
0.
5 and 2.5 ft.
(|§| Sampled
0.
5, 2.0 and 4.0 ft.
Figure B-12. Woodward-Clyde Consultants' arsenic survey map
of Okaloosa-Walton Community College cattle dipping vat site.
Arsenic detected in soil samples at 0-61 cm below surface.


112
Figure 3-31. U.S.G.S. topographical map of the
Tuscawillow vat site.


32
Table 2-6. Metal-arsenate solubility product constants.
Compound
pK.,a
Reference
AlAsO,,
15.80
18
Ba, (AsO,),
21.62
34
BaHAsO, -H,0
24.64
34
Ca, (AsO.,) ,
18.48
34
Cd, (AsO.)
32.66
18
Co, (AsO,)
28.11
18
Cu, (AsO,)
35.12
18
CrAsO,
20.11
18
FeAso,
20.24
18
Mg, (AsO,),
30.32
34
Mn, (AsO,)
28.72
18
Ni, (AsO,)
25.51
18
Pb, (AsO,)
35.39
18
Sr, (AsO,),
18.79
34
Zn, (AsO,).
27.40
18
a) pKsp represents the negative log of the solubility product
equilibrium constant.


21
parks and playing fields.29 The Netherlands standard for As
contamination in soil is set at 30 mg/kg.29
Chemistry of Arsenic
Arsenic is a member of Group Va of the periodic table.
It has an atomic number of 33 and atomic weight of 74.92.30
Arsenic exhibits properties that enable it to form alloys with
metals and to form predominantly covalent bonds with hydrogen,
oxygen, sulfur, and carbon.21 Similarities between the
chemical behavior of phosphorus (P) and arsenic are a result
of similar electronic orbital configurations. The electronic
configuration for As can be described as [ Ar ] 3d104s24p3.
Arsenic, like phosphorus, will readily undergo catenation to
form a series of cyclic compounds of formula (RAs)n where n =
3 to 6. It can also form R2AsAsR compounds. Akin to P, the
stereochemistry of arsenic can be influenced by dn-dn and dn-
pn interactions that foreshorten bond lengths as well as
producing bond angles distorted by the presence of lone pairs
of electrons.31 The supposition has been made that the
toxicity of arsenic arises from its similar chemical behavior
to phosphorus and its ability to form covalent bonds with
sulfur, which inactivates many enzymatic systems.21 Some of
the more important environmental and agricultural arsenical
species are depicted in Figures 2-1 and 2-2. As illustrated
by these structures, As can have coordination numbers


88
Figure 3-17. Photograph of the Dudley Farm vat


156
Time (Month)
Figure 4-1. Subsurface volatile As gas flux and
rainfall for 1996 at the Payne's Prairie Bison Pen
vat site.
2.0
1.5
fO
M
4J
C ~
Q) f-q
o E
C \
O CTt
o cL.O
o
-H
C
o
0.5
0.0
Arsenic
(ng As/mL gas)
Rainfall
(centimeters)
Time (Month)
Figure 4-2. Subsurface volatile As gas flux
and rainfall for three months in 1997 at
the Williston Road vat site.
30.0
25.0
20.0
15.0
10.0
5.0
0.0
Rainfall (centimeters) Rainfall (centimeters)


221
waste. Arsenic in soil may be present as the chemically
stable species such as H3As04, H2As04~, HAs04=, and As203. The
effect of the biota on As in soil means that the species may
be present as an organo-complex or even a gaseous compound.
The problems presented by such a large number of
potentially hazardous sites and the complexity of the
chemistry, as well as the biochemistry, of As requires a far-
reaching approach. This dissertation may be summarized by
categorizing these problems into four objectives.
The first objective was to evaluate the extent of the
arsenic contamination at selected cattle dipping vat sites.
Before this evaluation could take place, the vats had to be
located. The tick eradication program terminated more than
thirty years ago and, since no formal record of vat locations
had been made, it was found that personal anecdotes were the
primary source for locating these vats. A secondary problem
with these investigations was engendered by the question of
liability. Although the operation of these vats and the
disposal of the waste were mandated by both the federal and
state governments, there are currently no laws allocating
funds for the remediation of these sites. This meant that the
vast majority of the vats that were found were sited on
government property, since few private owners would admit to
having a vat site where the remediation costs could be quite
prohibitive.


184
addition occurred before the elution of As from the soil. The
lag in As elution upon release of iron from the soil may be
explained by re-adsorption of the arsenical anions by the
aluminum oxides and hydroxides that are present in the Bt
horizon. Elution of aluminum by this column occurred with
chloride and nitrate, but was negligible in the case of
phosphate (Figure 5-7). Given these column conditions and for
this soil sample, there appeared to be no correlation between
the arsenic and aluminum concentrations in the leachate
solutions. In contrast, the release of iron preceded the
release of As from this soil.
A similar elution pattern of iron release before As
release was observed in the fourth column investigation,
although the effect was not as dramatic (Figure 5-8). The
fourth column study was done using ponded and saturated column
conditions using an A" horizon that contained 3.3% organic
matter. Since the organic matter content was three times
greater than for any soil previously tested, the decision was
made to forego the addition of a second carbon source, such as
glucose. One of the drawbacks of this column design was its
susceptibility to atmospheric pressure fluctuations. The
amount of ponding on the column would vary from 0.64 cm to 2
cm and the flow rate through influence of the differential
pressure column would vary with temperature and barometric
pressure. Generally, the longer a column was maintained, the
slower its flow rate (Table 5-2) An exception to this


212
extraction system. The decrease in extraction efficiency was
exceptionally sharp for the zwitterionic surfactant system
(Figure 6-3) It is hypothesized that not only would the
positively charged portion of the zwitterionic surfactant be
electrostatically attracted to the negatively charged face of
clay, but the negatively charged sulfate tail of the
zwitterion would be adsorbed at the positively charged edges
of the clay particles.9 With such an aptitude for adsorption,
an increase in clay content would have a greater adverse
effect on the zwitterionic surfactant than on the other
extractants.
By far the most efficient extraction system consisted of
a chelating agent in conjunction with an anionic surfactant
(Figure 6-4). Without the chelating agent, extraction
efficiency dropped to less than ten percent, regardless of
whether the surfactant concentration was above or below the
CMC level (Figure 6-5). It is hypothesized that, since the
surfactant and the contaminant are both carrying negative
charges, it is probable that the amount of contaminant that
was extracted from the soil was largely due to ionic
displacement of the arsenical oxyanion by the anionic
surfactant.
In contrast, the extraction efficiency can approach 100%
if the chelator/surfactant solution to soil ratio were high
enough. For the Bt horizon soil samples, essentially 100%
extraction efficiency was achieved using 30 mM SDS with a


272
58.
USDA Soil Conservation
County Florida", 1958.
Society,
Soil
Survey
of
Manatee
59.
USDA Soil Conservation
County Florida", 1989.
Society,
Soil
Survey
of
Walton
60.
USDA Soil Conservation
County Florida, 1979.
Society,
Soil
Survey
of
Orange
61.
USDA Soil Conservation
County Florida, 1991.
Society,
"Soil
Survey
of
Wakulla
62.
USDA Soil Conservation
County Florida, 1979.
Society,
"Soil
Survey
of
Osceola
63. Environmental Systems Research Institute, Inc.,
ArcView GIS Version 3.0", 380 New York Street,
Redlands, CA, 1996.
64. Page, A.L. (Ed), Methods of Soil Analysis, Part 2,
Chemical and Microbiological Properties", 2nd edition,
American Society of Agronomy and Soil Science Society
of America, Inc. Publishers, Madison, WI, USA, 1982,
208-209.
65. Klute, A., (ed.), Methods of Soil Analysis, Part I,
Physical and Microbiological Methods", 2nd edition,
American Society of Agronomy and Soil Science Society
of America, Inc. Publishers, Madison, WI, USA, 1986,
508-511.
66. University of Georgia, College of Agriculture
Experimental Station, Reference Soil Test Methods for
the Southeastern Region of the United States, Southern
Cooperative Series Bulletin 289, Sept. 1983, 35-37.
67. Klute, A., (ed.), Methods of Soil Analysis, Part 1,
Physical and Mineralogical Methods", 2nd edition,
American Society of Agronomy and Soil Science Society
of America, Inc. Publishers, Madison, WI, USA, 1986,
399-404.
68. U.S. Environmental Protection Agency, "Test Methods for
Evaluating Solid Wastes", SW-846, 3rd edition, Office
of Solid Waste and Emergency Response, Washington,
D.C., 1992.
69. Binstock, D.A., P.M. Grohse and A. Gaskill,
Development and validation of a method for determining
elements in solid waste by microwave digestion,
Analytical Chemistry, 1991, 74, 360-366.


130
Figure 3-42. Topographical map of the Lake Kissimmee
vat site.


25
NH3 O
NH3 Fe As CH3
NH3 OH
Ferric Methanearsonate
(Neo-Arsozin)
o- +nh3
R
where R = t-decyl or t-octyl
0- +NH3 R
t-Octyl or t-Decyl Ammonium Methanearsonate
(AMA or Super-Dal-E-Rad)
Figure 2-2. continued


Table 3-13. Soil map units and taxonomic classes for reported cattle dipping vat sites.
Site/County
Mapped Soil Name
Taxonomic Class
Blackwater River
/Santa Rosa
Bonifay
Loamy, siliceous, thermic Grossarenic Plinthic
Paleudults
Orangeburg
Fine-loamy, siliceous, thermic Typic Paleudults
Troup
Loamy, siliceous, hyperthermic Arenic Paleudults
Cecil Webb
/Charlotte
Pineda
Loamy, siliceous, hyperthermic Arenic
Glossaqualfs
Jay Livestock Market
/Santa Rosa
Red Bay
Fine-loamy, siliceous, thermic Rhodic Paleudults
Lake Arbuckle
/Polk
Astatula
Hyperthermic, uncoated Typic Quartzipsamments
Immokalee
Loamy, siliceous, thermic Arenic Paleudults
Lake Kissimmee
/Polk
Myakka
Sandy, siliceous, hyperthermic Aerie Haplaquods
Smyrna
Sandy, siliceous, hyperthermic Aerie Haplaquods
Myakka River
/Manatee
EauGallie
Sandy, siliceous, hyperthermic Grossarenic
Argiauolls
Okaloosa-Walton
Community College
/Walton
Lakeland
Thermic, coated Typic Quartzipsamments
Troup
Loamy, siliceous, hyperthermic Arenic Paleudults


168
conditions within the system. A schematic of the column and
suction apparatus is shown in Figure 5-3.
The differential pressure columns had solution delivered
by using differential pressure between the inlet and outlet of
the column. Flow rate for this type of column is
susceptible to temperature and barometric pressure changes.
Whenever available, an incubator was used to maintain a
constant temperature of 25C. If an incubator was not
available, the ambient temperature was recorded and will be
noted with the results for that particular column study. No
attempts were made to control fluctuations in flow due to
changes in barometric pressure.
All columns were flushed with 50 mM potassium chloride
(pH = 5.71) followed by 50 mM potassium nitrate (pH = 5.91)
and, finally, the columns were flushed with 50 mM potassium
phosphate buffer (3.402 g KH,PO, and 4.331 g K2HP04 in 1.0 L
distilled deionized water, pH = 6.86). The unsaturated
columns had 0.8 g glucose per 1.0 L of eluant; whereas no
glucose was added to the eluant for the saturated, ponded
column. The soil in this column was judged to have an
adequate amount of organic matter already present to insure
good microbial activity.
After collection, all effluent fractions were weighed,
filtered through a 0.45 m membrane filter, preserved with 0.1
mL HN03 and refrigerated at 4C until analyzed.


Table A-l.
continued
Surface
Argillic
Arsenic
Elevation
Depth
Easting
Northing
(meters)
(meters)
(mg/kg)
22.85
36.56
1.591
-1.547
22.85
30.46
1.390
-1.453
22.85
24.36
1.122
-1.477
22.85
18.26
0.802
-1.407
22.85
12.61
0.604
-1.314
22.85
6.1
0.317
-1.290
22.85
0
0.101
-1.267
Aluminum
(mg/kg)
232


LIST OF TABLES
Table Bags
1-1. Cattle fever, ticks and vats in the
United States 7
2-1. Estimated U.S. demand for arsenic (metric tons) . 18
2-2. Toxicity data of selected arsenical compounds ... 18
2-3. U.S.E.P.A. allowable aqueous concentrations .... 20
2-4. Different systems describing electronegativities
(E.N.) of selected elements 27
2-5. Reduction potentials of selected As compounds. . 30
2-6. Metal-arsenate solubility product constants .... 32
3-1. Operational parameters for metal analysis by flame
or hydride generation 54
3-2. Operational parameters for arsenic analysis by
graphite furnace 55
3-3. Spectral interference by aluminum in the analysis
of arsenic at wavelength 193.6 nm using a
graphite furnace atomic absorption
spectrometer with deuterium background
correction 56
3-4. Soil map units and taxonomic classes for confirmed
cattle dipping vat sites 61
3-5. Selected characteristics of soil 10 meters south
of the Bison Pen vat 66
3-6. Selected metal concentrations in soil 10 meters
south of the Bison Pen 68
3-7. Selected characteristics of soils sampled at
Williston Road vat site 80
vii


23
H.
H
/
As:
H
Arsine
CH,
\
HO As:
/
CH,
Dimethylarsine
CH,
CH,
/
As:
CH,
AsO(OH),
NH
Trimethylarsine
Arsanilic Acid
Figure 2-1. continued


135
Figure 3-46. Topographical map of the Okaloosa-Walton
Community College vat site.


90
Figure 3-18. Soil survey map of the Dudley Farm vat site.
Map unit designations: 3B Arredondo fine sand,
8B Millhopper sand, 29B Lochloosa sand,33B Norfolk loamy
fine sand, and 39B Bonneau fine sand.


122
The soil survey report has the soil mapped as Pineda series
(Figure 3-37).56 These soils are deep, poorly drained
Alfisols with an arenic horizon in the subsurface. Based on
the study done at the Williston Road vat, it would be expected
that the As plume has traveled =¡100 meters from the vat. The
hydrology at this site would largely determine the distance
the contaminant plume has migrated. The mixed horizon of
"B2tg & A12" would contain the highest concentration of
arsenic. Although the sandy intrusions into this horizon may
allow the arsenic to pass through it, the slightly sticky,
sandy loam should retain enough arsenic to allow a plume to be
delineated. The typical depth for this horizon is given as 91
to 137 cm. The consulting firm that did the preliminary
survey did found 140 mg As/kg soil in the only sample taken,
at the 122 cm depth. All other samples ranged from <0.7 to
7.0 mg/kg at the pre-determined sampling depths of 15 and 76
cm.
Jay Livestock Market Vat
The Jay Livestock Market vat, located in Santa Rosa
County, Florida, was described as nearly level to gently
sloping (Figure 3-38) and well-drained. This soil series was
mapped as Red Bay sandy loam soil (Figure 3-39).55 The soil
at this site was highly disturbed and the vat had been
removed. Its reported position was in front of a metal
building. The direction of drainage would cause the plume to


79
Figure 3-13. Photograph of the Williston Road vat's transect
lane. Flag marks soil with greatest As concentration at this
site.


92
Arsenic
ug/g soil
80
75
70
65
60
Figure 3-19. Surface map of the Dudley Farm site with arsenic plume
All distances are measured in meters.


106
Figure 3-26. Soil survey map of the Payne's Prairie South
Rim vat site. Map unit designations: 3B Arredondo fine sand,
8B Millhopper sand, 14 Pomona sand, 16 Surrency sand, 19
Monteocha loamy sand, 20B Tavares sand, 21 Newnan sand,
31B,C,D Blichton sand, and 50 Sparr fine sand.


Table 3-10. Selected metal concentrations in soil 2.3 meters east of the Dudley Farm vat.
Horizon
Arsenic
(mg As/kg soil)
Iron
(mg Fe/kg soil)
Aluminum
(mg Al/kg soil)
Manganese
(mg Mn/kg soil)
Ap
74.5
119.1
333.3
5.2
A
108.
170.6
356.8
2.8
Bw
73.7
109.4
507.0
2.1
Btl
356.
231.8
650.2
0.7
Bt2
525.
299.4
1704.2
0.5
Btg
767.
766.3
1239.4
0.2


Percent Arsenic Recovery
208
60
50
40
30
20
10
0
-10
0 5 10 15 20 25 30 35
Surfactant Concentration (millimole/liter)
Figure 6-3. Extraction of arsenic from Payne's Prairie
Bison Pen vat soil using CHAPS, 3-[(3-cholamidopropyl)-
dimethylammonium]-1-propanesulfonate (a zwitterionic
surfactant).


Arsenic
mg/kg soil
Figure 3-9. Three-dimensional "Surfer" map of the As plume
across the argillic horizon at the Payne's Prairie Bison Pen vat
site. All distances shown in meters.


103
Figure 3-24. Soil survey map of the Payne's Prairie
Jackson's Gap vat site. Map unit designations: 3B
Arredondo fine sand, 8B Millhopper sand, 14 Pomona sand,
16 Surrency sand, 19 Monteocha loamy sand, 20B Tavares
sand, 21 Newnan sand, 31B,C,D Blichton sand, and 50 Sparr
fine sand.


Copyright 1998
by
JOHN E. THOMAS


200
1 +
CH,(CH2)15NCH,Br
CHj
O
II +
C CHjtCHA-p-OSO Na
II
0
Figure 6-1. Chemical structures of a)hexadecyltrimethyl
ammonium bromide (HdtABr); b) 3-[3-cholamidopropyl)-
dimethylammonia]-1-propane sulfonate (CHAPS); c) sodium
dodecylsulfate (SDS); and d) [16-pyrimidinium crown-4]4+.


12
Table 1-1. continued
Time
Description
Reference
1927
held at the owner's expense. Upon
refusal to pay, the cattle were sold and
any unexpended balance was returned to
the owners.
1
1930
Alachua county was scheduled to start
dipping March 1.
12
1931
The Orange county program was declared
successful, yet re-infestation occurred.
1
1937
The U.S. Bureau of Entomology and Plant
Quarantine and the U.S. Bureau of
Biological Survey issued a report
stating that:
1) The Booohilus annulatus (var.
australis) tick existed in Florida
2) This tropical variety could use deer
as well as cattle as a host, though no
other wild animals in swamps appeared to
act as hosts.
3) All deer would have to be removed if
a tick program were to be successful.
The Florida Legislature passed laws
allowing deer removal from Orange,
Osceola, Highlands, and Glades counties.
1


36
H2S04 = 0.1 N NaOH. No solvent removed more than 80% of the
total As from any of the four soils, even after 18 hours of
shaking.47
One soil washing procedure that has been reported to
remove more As involved use of a surfactant and a chelating
agent. Four surrogate contaminated soils with average pH of
8.5 were washed with chelating agent (ethylene diaminetetra-
acetic acid) water and surfactant-water solutions. This
system was effective in removing 93% of the spiked As.48
The removal efficiency of As by leaching with water through
soil is highly dependent on the soil type with an order of
sand < silt loam < clay. Organoarsenicals tend to leach in
much the same manner as arsenate. However, one study has
indicated, that in sandy loam and clay columns, the leaching
of cacodylic acid was more rapid than for the sodium salts of
methylarsonate.19
The rate of leaching for inorganic As is dependent on
its oxidation state. During laboratory elution of a sandy
column under oxidizing conditions, As (III) eluted at five to
six times greater rate and at about eight times greater
guantity than As (V). These differences were considered to be
related to the weaker interaction of As (III) to Fe (III) in
comparison to As (V) and Fe (III). In reducing conditions, As
(V) and As (III) leached at similar rates. This behavior was
attributed to the reduction of iron, the reduction of arsenic,
20
or both.


65
Figure 3-5. Soil survey map of the Payne's Prairie
Bison Pen vat site. Map unit designations:
8B Millhopper sand, 20B Tavares sand, 25 Pomona sand,
31B Blichton sand, 54 Emeralda fine sandy loam,
and 56 Wauberg sand.



258
Figure B-9. Woodward-Clyde Consultants' arsenic survey map
of Lake Arbuckle cattle dipping vat site.


30
Table 2-5. Reduction potentials of selected As compounds.
Reaction E, volts (25C)
H3As04
+ 3H+ + 2e- AsO* + 3H20
0.550
H3As04
+ 2H+ + 2e- =£= HAs02 + 2H20
0.560
H2As04-
+ 3H* + 2e- =i= HAsO, + 2H;0
0.666
HAs04-
+ 4H+ + 2e-=i=HAs02 + 2H20
0.881
HAs04-
+ 3H* + 2e- AsO,- + 2H20
0.609
As04-3
+ 4H* + 2e- AsO," + 2H,0
0.977
As203 ( s )
+ 6H* + 6e" 2As + 3H20
0.234
*-S2<-)5|s|
+ 10H* + 10e- 2As + 5H20
0.429
^s25(s)
+ 4H* + 4e- As203|s| + 2H20
0.721
AsO+ +
2H* + 3e- As + H,0
0.254
HAsO, 4
- 3H* + 3e- =?= As + 2H;0
0.248
As02" +
4H+ + 3e- =£= As + 2H,0
0.429
As04"3 -
t- 8H* + 5e- As + 2H20
0.648
2H3As04
+ 4H* + 4e~ As,03(s| + 5H20
0.580
2H2As04
- + 6H+ + 4e* =i= As,03(s) + 5H,0
0.687
2HAs04-
2 + 8H+ + 4e- ^ As203|s| + 5H20
0.901
2As04-3
+ 10H+ + 4e" =£= As203 + 5H20
1.270
As + 3H+ + 3e~ AsH3(gl
-0.608


22
HO
\
HO As:
/
HO
H\
HO As 0
/
HO
Arsenous Acid
(Arsenite Salts)
Arsenic Acid
(Arsenate Salts)
HO
HO
CH3 As = 0
CH3 As = 0
HO
ch3
Methylarsonic Acid
Dimethylarsinic Acid
(Cacodylic Acid)
Figure 2-1. Arsenic nomenclature and structures.


39
hours, while a culture kept at 15% 02 required 95 hours. This
bacterial growth pattern leads to the speculation that, as the
aforementioned cattle dipping fluids became enriched with
nutrients, the oxidizing bacteria would flourish to the point
of depleting the oxygen level in the bath. Then, the reducing
bacteria could quickly grow and, subsequently, the rapid rise
in arsenite concentration would be observed.
Reduction of arsenate to arsenite may also lead to biotic
methylation and subsequent formation of a volatile arsine
species. In anaerobic conditions, a Methanobacterium strain
produced dimethylarsine and fungal strains of Penicillium and
Aspergillus converted sodium methylarsonate, sodium cacodylate
and arsenous acids to trimethylarsine. A wood rotting fungus,
Lenzites trabea, produced a garlic-smelling volatile As
compound (probably trimethylarsine) from a medium containing
arsenic trioxide.21 The volatile arsenic compounds are stable
in anaerobic conditions, but rapidly oxidize in the presence
of oxygen if the concentration of methylarsines is above 0.05
- 0.10 milligram per liter. At lower concentrations, these
volatile arsenical species are stable enough to migrate from
the area.18
Demethylation of methylated As species has also been
shown to occur. Some of the same species that form volatile
alkylarsines are also capable of using methane arsonic acid as
a carbon source for growth. Species that can do both include
Flavorbacterium, Aeromona, and Norcardia.20
Other species


20
Table 2-3. U.S.E.P.A. allowable aqueous concentrations
Matrix Usage
Allowable Concentration
(Mg/1)
Human Drinking Water
50
Livestock Drinking Water
200
Irrigation Water for Crops
100


Arsenic Effluent Concentration (ug/L)
178
Time (Hours)
Figure 5-5. Effluent from a micro-aerobic, unsaturated
column of Payne's Prairie Bison Pen vat "E" soil (45-60
cm depth) sequentially eluted with 50 mM potassium chloride,
nitrate, and phosphate solutions.
Iron Effluent Concentration (ug/L)


94
holes, minus the soil samples (10 g each), which were kept
for laboratory analysis. Lateral movement exceeded vertical
movement of the contaminant. The As field test was done on
samples taken 1.8 meters east of the vat. Results of the
laboratory analysis and the field test are presented
graphically in Figure 3-21. The greatest As concentration was
356 fxg As/g soil at a depth of 1.2 meters. This is the depth
where soil clay content noticeably increases. It is
interesting to note that As concentration tended to increase
and decrease in waves" as the depth increases. One hypothesis
that would explain this finding invokes the idea that the vats
were to be emptied on an annual basis and that the waves"
provide physical evidence of the dumping pattern. Since no
records were kept on the vat's operation, such hypotheses
cannot be tested. Drilling verified the presence of As to a
depth of 6.8 meters. The depth increments used in Figure 3-21
do not represent all of the soil horizons sampled at this
site. If As is analyzed by soil horizon (Table 3-10) then it
is apparent that, similar to the previous vats investigated,
presence of the argillic horizon is associated with an
increase in the amount of As detected in the soil. Unlike the
previous vat sites, the Dudley Farm's argillic horizon did not
appear to constitute a barrier to the downward migration of
As.


274
83. Braman, R.S., "Arsenic in the environment". In:
Woolson, E.A. (ed.) Arsenical pesticides, American
Chemical Society Symposium Series 7, American Chemical
Society, Washington, D.C., 1975, 108-123.
84. Eisensmith, S.P., S.D. Fisher, and A. Srivasta,
Spearman's Rank Correlation Test In: Freed, R.D.
(ed.) MSTAT-C: Microprocessor Statistical Program,
Version 2.0", 1992.
85. McGeehan, S.L. and D.V. Naylor, Sorption and Redox
Transformation of Arsenite and Arsenate in Two Flooded
Soils", Soil Science Society of America Journal,
1994, 58, 337-342.
86. Peryea, F.J., Phosphate-Induced Release of Arsenic
from Soils Contaminated with Lead Arsenate, Soil
Science Society of American Journal, 1991, 55, 1301-
1306.
87. Nielsen, D.R. and J.W. Biggar, "Miscible Displacement
in Soils: I. Experimental Information, Soil Science
Society of America Proceedings, 1961, 25(1), 1-5.
88. Page, A.L. (ed.) "Methods of Soil Analysis, Part 2,
Chemical and Microbiological Properties, 2nd edition,
American Society of Agronomy and Soil Science Society
of America, Inc. Publishers, Madison, WI, USA, 1982,
459-460.
89. Klute, A. (ed.) Methods of Soil Analysis, Part 1,
Physical and Mineralogical Methods", 2nd edition,
American Society of Agronomy and Soil Science Society
of America, Inc. Publishers, Madison, WI, USA, 1986,
635-662.
90. Zhou, M., Comparison of P Retention Characteristics
between Bh and Bt Horizons from Selected Florida
Soils", Masters Thesis, University of Florida, 1994,
13-14.
91. Murphy, J. and J.P Riley, A modified single solution
method for the determination of phosphate in natural
waters", Analytical Chemica Acta, 1962, 27, 31-36.
Liveesey, N.T., and P.M. Huang, "Adsorption of Arsenate
by Soils and its Relation to Selected Chemical
Properties and Anions, Soil Science, 1981, 131(2), 88-
94.
92.


31
Precipitation Reactions of Arsenic
Pure systems are rarely, if ever, encountered in a
natural environmental setting, but the effect of precipitation
reactions as well as sorption-desorption equilibria must be
considered when determining the fate and transport of As. A
compilation of the negative log of the solubility product
equilibrium constants (pKsc) are given in Table 2-6 for
selected metal arsenical complexes.18,34 The relatively high
values for pKsp indicate that arsenate can form practically
insoluble metallic salts. Other practically insoluble
compounds bearing As may be formed as well; for instance,
under conditions where sulfides are stable, As will
precipitate with sulfur. One example is the formation of
orpiment (As2S3) under conditions when the pH=4 and -3 Another example is the formation of realgar (As^S,) at pH=4 and
-4 literature for these systems.35
Arsenic Compounds in Soil
As mentioned previously, As is ranked 20th among the
chemical elements in abundance20 and can be found in more than
245 minerals.6 Although arsenite and arsenate are considered
to be the most common forms of As compounds in the
environment, organo-arsenicals can be found in soil pore
waters as well. The presence of many arsenical compounds in


3-12. Soil survey map of the S.W. 10205 Williston Road
vat site 77
3-13. Photograph of the Williston Road vat's transect
lane 79
3-14. Soil horizons at the Williston Road vat site
in terms of: a) a two-dimensional map of
three horizons, b) the Aquod Bh horizon and
Aqualf surface horizon with the As plume,
and c) the argillic horizon with its As
plume 81
3-15. Contour maps of As on Aquod's Bh horizon and
Aqualf's surface horizon of the Williston
Road vat using: a)the laboratory analysis
versus b)the field test 85
3-16. Arsenic on argillic horizon's contour maps of
the Williston Road vat using: a) laboratory
analysis versus b)the field test 86
3-17. Photograph of the Dudley Farm vat 88
3-18. Soil survey map of the Dudley Farm vat site ... 90
3-19. Surface map of the Dudley Farm site with
arsenic plume 92
3-20. Topographical map of the Dudley Farm vat site . 93
3-21. Field test strips and laboratory analysis
results for the Dudley Farm vat soil
by depth 95
3-22. U.S.G.S. topographical map of the U.F. Foundation
excavated vat site 98
3-23. Soil survey map of the U.F. Foundation
excavated vat site 99
3-24. Soil survey map of the Payne's Prairie
Jackson's Gap vat site 103
3-25. U.S.G.S. topographical map of the Payne's
Prairie Jackson's Gap vat site 104
3-26. Soil survey map of the Payne's Prairie
South Rim vat site 106
3-27. U.S.G.S. topographical map of the Payne's
Prairie South Rim vat site 107
x


64
Figure 3-4. U.S.G.S. topographical map of the Payne's
Prairie Bison Pen vat site.


82
of arsenic (Table 3-8) was found on top of the argillic
horizon for the Aqualf soil; however, at this site, the
arsenic had moved a greater distance from the vat (Figure 3-
14 C) The greatest amount of arsenic was located 80 m from
the vat, almost twice as far as found at the Bison Pen vat
site. The vat was located at coordinates of 15 by 40-50 on
the grid map of Figure 3-14. The highest concentration of
arsenic found in the Bh horizon was located directly above the
spot on the argillic horizon that had the maximum amount of
arsenic. The maximum concentration of As (99.6 mg/kg dry
soil) in the argillic horizon was higher than the maximum
concentration (30.1 mg As/kg soil) found in the spodic
horizon. It was at this site that the As field test was first
used extensively to delineate the contaminant plume. A
typical scenario involved one person using a machete to blaze
a transect, a second person measuring distance, sampling soil
and keeping the transect straight (as well as parallel to the
other transects), and a third person conducting the field test
for arsenic. The transects were made only as long as
absolutely necessary according to the field test results.
This site required seven days for the three-man team to
delineate the arsenic plume. The soil was sampled at the
blackest section of the surface or spodic horizon and at the
top of the argillic horizon. Only the upper Bh horizon was
sampled in the area where overlaying spodic horizons were
found. For comparison, the contour map of the field test was


7
Table 1-1. Cattle fever, ticks and vats in the United States
Time
Description
Reference
1785
North Carolina passed a law restricting
cattle movement, which was suspected to
have been caused by Roonhilus annulatus
and piroplasmosis.
1
1796
Dr. Pease observed an outbreak of
disease among Lancaster, PA, cattle
following passage of South Carolina
cattle.
5
1814
Virginia refused passage of South
Carolina cattle suspected of being
disease carriers.
7
1868
Texas cattle shipped up the Mississippi
River to Cairo, IL and then by rail into
Illinois and Indiana caused enormous
losses in cattle.
5
1883-
Dr. D.E. Salmon determined the boundary
5
1885
line of permanently infected territory.
1889
Theobald Smith described the cow tick as
carrier of peculiar microorganism that
cause cattle fever. This was the first
instance in which a disease was shown to
be insect-borne.
5,7


51
The original procedure called for placing 5 mL of water into
a 50 ml tube. This procedure was modified to substitute a 0.5
g soil sample (delivered via scoop) and 5 mL of a 500 mg/L P
solution (from KH P0;) A few drops of isopropanol were added
to suppress foaming, if reguired. A small scoop of zinc dust
(0.4 g) was added and the contents thoroughly mixed. An
indicator strip containing mercuric (II) bromide was inserted
into a septa cap and the cap was attached to the culture tube
after 0.2 mL 30% HC1 was added. A syringe needle (18 gauge)
was put through the cap to relieve excess pressure. The
arsine gas generated would react with the indicator strip
turning it from light yellow to orange-tan to dark chocolate
brown, depending on the amount of As in the soil.
The pH of the soil was measured by mixing 2:1 water:soil,
stirring, and then allowing the slurry to equilibrate for ten
minutes. The pH was measured using a combination electrode
and an Accumet pH meter model #910 from Fisher Scientific,
Inc., Norwalk, CT.64
Percent moisture in the soil samples was determined by
drying a known weight of field-moist soil for 24 hours at
105C. The dried sample was weighed and percent moisture
calculated on a dry weight basis.65
Soil organic matter was measured using a modified
Walkley-Black method. This involved a sulfuric/chromic acid
digestion followed by sodium hydroxide titration using
diphenylamine as an indicator.66


ACKNOWLEDGMENTS
I would like to express my deep appreciation to the
faculty and staff of the University of Florida's Department of
Soil and Water Science. The roll call of the people who
assisted in this project is indeed a long one. First and
foremost, I express my gratitude to Dr. L.-T. Ou for the
microbiology training I received and his understanding as I
pursued this degree while working full-time for him. I
especially want to extend my acknowledgment to Dr. R. D. Rhue,
the chairman of my committee, for his timely advice and help.
Thanks also go to the members of my advisory committee: Dr.
D. Chynoweth, Dr. E. Hanlon, Dr. W. Harris, and Dr. B. McNeal
whose patience and helpful words of guidance were sorely
needed. Dr. A. Al-Agley, Dr. M. Collins, and Dr. L. Ma are
appreciated for their generosity in supplying equipment and
technical expertise. Bill Reve and Martin Sandquist deserve my
gratitude for their assistance in completing this project. I
also wish to express my appreciation to Florida Park Service
personnel, including Howard Adams, Jack Gillem, Butch Hunt,
Sally Morrison, and Jim Riemer. Lastly, I wish to acknowledge
the patience, love, and encouragement I received from my wife,
iii
Pamela.


63
Figure 3-3. Photograph of the Payne's Prairie Bison Pen vat.


123
Figure 3-37. Soil survey map of the Cecil Webb vat site.
Map unit designations: 13 Boca fine sand, 33 Oldsmar sand,
44, 63 Malabar fine sand, 49 Felda fine sand, 53 Myakka
fine sand, and 73 Pineda fine sand.


Table 3-4. Soil map units and taxonomic classes for confirmed cattle dipping vat sites.
Site
Soil Map Unit
Taxonomic Class
Bison Pen vat
Millhopper sand
Loamy, siliceous, hyperthermic Grossarenic
Paleudults
US 441 vat
Lochloosa fine
sand
Loamy, siliceous, hyperthermic Aquic Arenic
Paleudults
Marion County vat
Blichton sand
Loamy, siliceous, hyperthermic Arenic Plinthic
Paleaquults
Dudley Farm vat
Bonneau fine
sand
Loamy, siliceous, thermic Arenic Paleudults
UF Foundation vat
Lochloosa fine
sand
Loamy, siliceous, hyperthermic Aquic Arenic
Paleudults
Tuscawillow vat
Kanapaha sand
Loamy, siliceous, hyperthermic Grossarenic
Paleaquults
Jackson Gap vat
Millhopper sand
Loamy, siliceous, hyperthermic Grossarenic
Paleudults
South Rim vat
Tavares sand
Hyperthermic, uncoated Typic Quartzipsamments
Williston Road vat
Pottsburg sand
Sandy, siliceous, thermic Grossarenic Haplaquods
Monteocha loamy
sand
Sandy, siliceous, hyperthermic Ultic Haplaquods
Wauberg sand
Loamy, siliceous, hyperthermic Arenic Albaqualfs


Table 3-11. Selected characteristics of soil 0.9 meters north of the excavated U.F. vat.
These soils were located within the Lochloosa fine sand map units in the Alachua county soil
survey and represent inclusions of similar soils.
Soil
Taxonomic
Class
Depth
(cm)
Horizon
Dominant
Munsell
Color
Particle Size
Distribution (%)
Organic
Matter (%)
PH
Arsenic
(mg As/
kg soil)
Silt
Sand
Clay
Udult
0-23
Ap
10YR 4/4
3.7
89.4
6.9
0.3
6.2
26.9
23-121
El
10YR 5/4
4.0
92.6
3.4
0.1
6.2
7.7
121-149
E2
10YR 4/3
3.5
93.8
2.7
0.0
6.3
2.7
149-170
Bt
10YR 5/3
4.4
80.8
14.8
0.0
6.6
33.8
170-
Btg
10YR 4/2
4.0
77.8
18.2
0.0
6.7
24.3
o
o


191
Total Volume Collected (mL)
Figure 5-10. Chloride and arsenic in effluent from a
pumped, saturated column of Payne's Prairie Bison Pen
vat "A" soil (0-5 cm depth) initially saturated with
30 mM potassium chloride, then eluted with solution of
sodium arsenate (4.86 g/L).
Chloride Concentration (mM)


69
Data for the depth, and for the northing and easting coordinates as
well as the As concentrations, were used as input to the U.S.E.P.A.
program "Geo-EAS''. The Geo-EAS" program correctly stopped the
contaminant contour at the edge of the vat (Figure 3-7) However,
it is interesting to note that the U.S.E.P.A. program also
generated a single point at 100 northing and 45 easting outside the
plume contour. Since it was set to draw contours at increments of
20 ig As/g soil, it ignored a point at 120 northing and 45 easting
that yielded an arsenic concentration of 12.2 i¡g As/g soil. When
the plume contour was generated using Surfer version 5.0" a
dumbbell shape was shown using contour levels of 20 mg As/kg soil
(Figure 3-8). The biggest obvious drawback of the Surfer program
was closure of the contours nearest to the vat where it actually
had no data to confirm this depiction. On the other hand, the
"Surfer program has the advantage of allowing the user to
superimpose the contour map of the contaminant plume on top of a
three-dimensional grid representing the argillic horizon (Figure
3-9) In addition, the topographic map of the surface may be
superimposed over the argillic horizon and plume depictions (Figure
3-10) .
The argillic horizon's three-dimensional representation was
generated using ground-penetrating radar (GPR). A ten-cm bucket
auger was used to ground-truth" the GPR readings at
thirty-six locations. The depths measured by GPR and by soil probe
were linearly correlated, with a regression coefficient of R2 =
0.989.
One source of error in these measurements was that the


211
the As proved to be more difficult to remove from the soil
matrix. For these soil samples, the extraction efficiencies
at maximum surfactant concentration ranged from 3.3%
(zwitterionic surfactant) to 7.3% (cationic surfactant) to
58.1% (anionic surfactant with chelating agent) for the given
soil:solution ratio with the surfactant above the CMC level.
The overall drop in extraction efficiencies for each
surfactant system when comparing E to Bt horizon soil samples
was probably due to the increase in the negative charge of the
soil particles. The particle fractions found in the E horizon
soil samples were 95.8% sand, 3.4% silt and 0.8% clay; whereas
the Bt horizon soil samples had particle fractions consisting
of 91.4% sand, 5.3% silt and 3.3% clay. This increase of 2.5%
clay should yield a concurrent increase in overall negative
charge of the soil. This negative charge would attract not
only the iron and aluminum cations (with which arsenic
oxyanions will preferentially complex), but would also attract
and hold the positively charged components of these extraction
systems.105 This adsorption phenomenon could account for
shifts in the slope of the curves as well as some of the
decrease in extraction efficiencies. Another probable reason
for the drop in extraction efficiencies involves the increase
in iron and aluminum concentrations that occurs with increase
in clay content. An increase in competition by cations
available to complex the arsenical anions implies that there
should be a decrease in efficiency for any surfactant


Figure 3-27. U.S.G.S. topographical map of the Payne'
Prairie South Rim vat site.


Table 3-13. continued
Site/County
Mapped Soil Name
Taxonomic Class
Tosohatchee
/Orange
Malabar
Loamy, siliceous, hyperthermic Arenic
Ochraqualfs
Pineda
Loamy, siliceous, hyperthermic Arenic
Glossaqualfs
St. Marks Wildlife
Refuge
/Wakulla
Otela
Loamy, siliceous, thermic Grossarenic Paleudalfs
Seaboard
Thermic, coated Lithic Quartzipsamments
Shadeville
Loamy, siliceous, thermic Arenic Hapludalfs
Walker Ranch
Immokalee
Loamy, siliceous, thermic Arenic Paleudults
CO


BG-1
257
DOCK
0
ca rnc PENS
JA Y- 1 7
I 5., I JA Y- 16
'JA>
>. A Y-19 -
[6.5 | Arsenic in mg/kg
Background sample
-(j>- Sampled 0.5 ft.
^ Sampled 0.5 and 2.5 ft.
Sampled 0.5, 2.0 and 4.0 ft.
RAMP
.JA Y15
. JAY-14
c
JA Y-10
I s-' !
RAMP
-$rJAY-9
Drainage
H ^*r-s
JA Y6
JA Y11
&
CID
I JA Y5
nrM Y~4
I z- i
. JA Y-J
&
JAY-2
%
LH]
JA Y-J
-&
Figure B-8. Woodward-Clyde Consultants arsenic survey map
of Jay Livestock Market cattle dipping vat site. Arsenic
detected in soil samples 61-76 cm below surface.


268
12. In Florida Review, Department of Agriculture, Vol. 4,
#25, 1930, 4.
13. Knapp, J.V.; "Existence of tropical variety of cattle
fever tick (Boophilus annulatus, Var. Australis)
complicates tick eradication in Florida." Journal of
American Veterinary Medical Association 96, 1940, 607-
608.
14. United States Bureau of Animal Industry, Annual Reports
of the Department of Agriculture, Washington, D.C.,
1942-1952, 32-97.
15. Cooperative Economic Insect Reports Plant Protection
and Quarantine Programs, Animal and Plant Health
Service, United States Department of Agriculture,
Hyattsville, Md., Vol. 7, #21, 1957, 401.
16. Chilvers, D.C. and P.J. Peterson, "Global Cycling of
Arsenic", In: Lead, Mercury, Cadmium and Arsenic in
the Environment, Hutchison, T.C. and K.M. Meema (Eds),
John Wiley and Sons Ltd., New York, 1987, 279-301.
17. Sanders, J.G., "Arsenic Cycling in Marine Systems",
Marine Environmental Research, 1980, 3, 257-266.
18. Lemmo, N.V., S.D. Faust, T. Belton, and R. Tucker,
"Assessment of the chemical and biological significance
of arsenical compounds in a heavily contaminated
watershed. Part I. The fate and speciation of
arsenical compounds in aquatic environments A
literature review", Journal of Environmental Sciences
and Health, 1983, A18, 335-387.
19. Woolson, E.A., In: Topics in Environmental Health:
Biological and Environmental Effects of Arsenic,
Fowler, A.B. (ed.), Elsevier: Amsterdam, 1983, 6, 51.
20. Cullen, W.R. and K.J. Reimer, "Arsenic Speciation in
the Environment", Chemical Reviews, 1989, 89, 713-764.
21. Tamaki, S. and W.T. Frankenberger, "Environmental
Biochemistry of Arsenic", Reviews of Environmental
Contamination and Toxicology, 1992, 124, 79-110.
22. Persson, J.A. and K. Irgum, "Determination of Dimethyl-
arsine Acid in Seawater in the Sub-ppb Range by
Electro-thermal Atomic Absorption Spectrometry after
Preconcentration on an Ion-Exchange Column", Analytica
Chimica Acta, 1982, 138, 111-119.


55
Table 3-2. Operational parameters for arsenic analysis by
graphite furnace.


197
had a slight repressive effect on the elution of As from soil
columns.
Elution of As from the soil columns was either preceded
by or accompanied by the elution of iron, though no
relationship was found between the release of aluminum and the
As concentration in the effluent. In fact, only the "Bt"
horizon from the Bison Pen vat site and the "A horizon from
the Williston Road site released enough aluminum to be
detected.
Using the A" horizon from the Bison Pen vat site, it was
shown that a one-dimensional transport model based on the
Freundlich relationship could be used to predict the break
through of As from a soil column. The assumptions made in
calculating a retardation factor were justified by the
accuracy of the prediction.
Further research should include evaluation of the
transport model in order to predict the break-through of As
from soil columns eluted with solutions containing As and
organic compounds similar to those found in some of the
formulations for cattle dipping mixtures. It would also be of
interest to speciate the arsenic, iron, and aluminum being
eluted from these columns. Other guestions include: 1) to
what extent biotic influences versus chemical mechanisms play
a part in the extent of As elution from soil columns upon
phosphate addition, and 2) how much As would be eluted by a
mixture of anions such as nitrate and phosphate.


179
demonstrated that the cations, NH4+ and Ca+2, had no effect on
phosphate displacement of arsenate.86 These researchers
suggested that the dissolved phosphate controlled As
solubility through specific anion exchange, and that the
solubility of the phosphate was determined by meta-stable
phosphate minerals.86 As previously noted, the rather harsh
treatment of soils in these studies would inhibit, if not
preclude altogether, their biotic viability.
The above arguments for an anionic displacement mechanism
are very convincing and should not be ignored. However, in
these column studies on the Bison Pen vat site E horizon
soil, biological activity was a contributing factor to the
release of As from the soil upon the addition of phosphate
anions, since iron was released to the effluent concurrently.
It should be noted, at this point, that the column system had
been supplied with potassium, nitrogen, and carbon (as
glucose) before the nutrient, phosphate, was added. These
column studies demonstrated that iron was released from the
soil concurrent with the release of As (Figure 5-4 and 5-5) .
Bacterial reduction of iron oxides has long been known to be
important in increasing the nutrient availability of iron and
in determining the movement of iron in soil.85 It has been
suggested that the As will adsorb preferentially to oxalate-
extractable amorphous A1 and Fe compounds.86 Other researchers
have demonstrated a high correlation existed between aluminum
and iron minerals with the adsorption of As.84
The results of


213
Surfactant Concentration (millimole/liter)
Figure 6-5. Comparison of extraction efficiency for the
"Bt" horizon of Payne's Prairie Bison Pen vat soil using
sodium dodecylsulfate (NaSDS) with and without the chelating
4 +
agent [16-pyrimidinium crown-4]


41
these approaches. The aim is to achieve separation, volume
reduction, immobilization, and detoxification, if possible.
Not all remediation techniques apply to As-contaminated sites;
however, a brief summary of the techniques that apply follows:
Physical remediation techniques
Excavation. Excavation is a simple prepared-bed method
that aims to transfer contaminants elsewhere or to prepare
them for further treatment. Disadvantages include determining
the volume of contamination, the requiring of large amounts of
clean fill material, and an increase in groundwater pollution
due to disturbing of the soil column. There are also problems
involving traffic, noise, dust and surface water pollution.
Entombment. Entombment is another prepared-bed method,
wherein a collection is made of one or more contaminants that
are placed on a single site and a tomb is then constructed to
avoid dispersion. Disadvantages include the associated
contamination of the collection area, the need to physically
move the contaminants with its concurrent problems, and the
need for construction of an effective structure.
Cover. This technique is widely used in the United
Kingdom and applies to both in situ and prepared-bed methods.
The cover material can be anything from asphalt, or concrete,
to clean soil. Disadvantages are that the area under the
cover is still contaminated and lateral migration can occur
with the influence of surface and ground water.


164
diameter. The column contained fused glass frits at both
ends. The glass frits were either coarse 40-60 micron mesh
or medium" 10-15 micron mesh (Aldrich, Inc., Milwaukee, WI) .
A glass frit sandwiched between two silicone rubber o-rings
was inserted into a cap to which a short length of 0.64 cm
Tygon tubing had been attached. A piece of column of
approximately 5 cm in length was wrapped with Teflon tape and
pushed into the end of the column until it was tight against
the inner silicone o-ring. The column was packed full of
soil, making sure that good contact occurred between soil and
frit. The water content was adjusted using boiled, deionized
water. A second cap end was prepared in identical manner.
The two 5 cm column segments were joined together and fastened
using transparent tape. In order to insure good aeration,
0.16 cm diameter holes were drilled into the body of the tube
(about 1.27 cm apart) in a diamond pattern (Figure 5-1).
The second column also consisted of material from the E
horizon taken from the Bison Pen vat site, but this column
experiment was conducted under anaerobic, unsaturated
conditions. The column for this experiment was also made from
HDPE, but was a single piece with no holes drilled into the
body of the column. Soil with the desired moisture content
was sealed into the column by pressing the end caps,
containing o-rings and glass frits, tightly onto the ends of
the column after wrapping with Teflon tape. Nitrogen gas was


153
contaminated soil with pre-moistened ambient air or
industrial-grade nitrogen. Samples of autoclaved soil and of
live" soil had water content adjusted with deionized sterile
water, and of live soil adjusted instead with 1 mL sterile 20%
agueous glucose solution, were examined in duplicate. The
evolved volatile As gas was collected on 0.65 g activated
coconut charcoal (ORBA-32 tube by Supelco, Inc.).
A fungus was isolated from the Bison Pen vat soil by
sequential 1:10 dilutions into a media of
thiamine/succinic/glucose solution following Cox and
Alexander.81 The fungus was identified from its microchondial
structure as a Fusarium species.82 One hundred milliliters of
media with 0.02 g Na2HAs04.7H20 were inoculated with this
fungus. Volatile As was swept from the flask by flushing
with pre-moistened ambient air or industrial grade nitrogen.
The As fumes were collected on 0.65 g activated coconut
charcoal.
All samples (0.65 g charcoal or 0.5 g soil) were digested
using HN03 acid in Teflon bombs in accordance with U.S.E.P.A.
method #3051.68 All digests were diluted to 100 mL prior to
analysis. Analysis for As was accomplished using a Perkin-
Elmer Atomic Absorption Spectrophotometer model 2380 equipped
with a graphite furnace model HGA-400 and an autosampler model
AS-40. Deuterium lamp background correction was employed. Due
to unknown interferences, all charcoal samples had to analyzed
by the method of standard additions. Results were confirmed


BIOGRAPHICAL SKETCH
John E. Thomas was born on August 16, 1952 in Paoli, PA.
He graduated from Juniata College in Huntingdon, PA, with a
B.S. in chemistry in 1973. His first project after graduation
was on a newly developed automobile exhaust catalyst control
with W.R. Grace, Inc. Following this experience, he returned
to college and received a M.S. degree from the University of
Florida's Department of Chemistry in 1978. His major area of
study involved X-ray crystallographic structure determination
of lanthanide and actinide complexes. In the following years,
he worked for the U.S.D.A. on insect pheromone separation and
synthesis; for Water and Air Research Co. as a private
consultant; for the University of Florida (U.F.) Department of
Food Science and Human Nutrition on registration of pesticide
use for minor crops; for the U.F. Department of Agronomy on
no-tillage systems; and, finally, for the U.F. Department of
Soil and Water Science on projects ranging from metal
transport in soil after sludge application to bioremediation
of chemicals such as tetraethyllead, aldicarb, 1,3-
dichloropropene, carbofuran, fenamiphos, and methyl bromide.
In 1992, he started work on a Doctor of Philosophy degree
under the direction of Dr. R. D. Rhue in the Soil and Water
Science Department, investigating soil and groundwater arsenic
277


159
the media for the low oxic levels. In contrast, with higher
oxygen content, the fungus was distributed throughout the
media. For the high oxic cases, arsenic species produced may
not have had the opportunity to evolve from the agueous
solution before being converted to nonvolatile species.18
Stability diagrams for As in aqueous systems at pH 4.0 to 10.0
show that, regardless of the value for pE, arsenic acid is the
only stable ionic species.20 This suggests that conversion
kinetics determine the amount of gaseous As evolved.
Conclusions
No volatile As was emitted from surface soil of the
Dudley Farm or Payne's Prairie Bison Pen vat sites. However,
gaseous arsenic was collected from the subsurface at the
Payne's Prairie Bison Pen vat site and at the Williston Road
vat site. A slight correlation was found to exist between the
amount of rainfall and the amount of gaseous As produced.
In laboratory studies, contaminated Bison Pen vat soil
was found to emit more gaseous As in high oxic conditions than
in low oxic conditions. A Fusarium species was isolated from
this soil that could volatilize As, though it exhibited a
different pattern of As emission than the soil samples. The
fungus volatilized more As in low oxic conditions than in high
oxic levels. This was attributed to the formation of a fungal
mat at the surface of the liquid media in low oxic conditions.
Presumably, this mat allowed the residence time of the


33
soil is due to the intervention of various organisms. Man
introduces organo-arsenicals as feed additives (arsanilic
acid, 3-nitro-4-hydroxyphenol arsenic acid and 4-
nitrophenylarsenic acids), as post-emergence grass herbicides
(mono- and disodium salts of methanearsonic acids), as
insecticides (calcium and lead salts of arsenate), as
fungicides (sodium arsenite, ferric methanearsonate and 10,10-
oxybisphenoxarsine), and as desiccants/defoliants
(dimethylarsinic acid and t-octyl or t-decyl ammonium
methanearsonate).21' 38-41 Molds, yeasts, fungi, algae and
bacteria have all been reported in various reviews to produce
organo-arsenicals, predominantly by methylation of arsenic
oxides and hydroxides.18'20'21,37 Volatile species of dimethyl-
and trimethylarsine, as well as AsH3, have been formed under
both aerobic and anaerobic conditions in soils.18'20'21'37 Most
of these compounds are depicted in Figures 2-1 and 2-2.
Abiotic Interactions of Arsenic
As amply demonstrated in the preceding paragraphs,
arsenic can be found in a multitude of compounds, all of which
will interact with soil to various degrees. Some generalities
can be drawn in regards to the interactions of As with soil.
Autoradiography, electron microscopy, and electron probe
microanalysis have each been used to measure the location of
added arsenate on soil components. Sorption is a function of
interlayer spacing in a clay lattice in conjunction with the


Table A-2. continued
Surface
Argillic
Araillic Arsenic
Concentration (ma/ka) -
Argillic Horizon
Easting
Northing
Elevation
(meters)
Depth
(meters)
Field Results
Laboratory Analysis
Iron (mg/kg)
Aluminum (mg/kg)
Manganese
45
100
0.427
-0.965
21.2
16.9
1400
11100
0
5
105
0.116
-1.029
1.25
1.36
4840
36200
2
15
105
0.073
-1.105
1.25
0.37
2200
20200
1
20
105
0.067
25
105
0.037
-0.737
15
3.85
2300
21300
0
30
105
0.448
-0.864
12.5
5.35
1280
12600
0
35
105
0.436
40
105
0.366
-0.940
21.2
8.96
1010
8900
0
45
105
0.390
20
110
0.064
-1.118
0.41
6200
41600
1
25
110
0.018
30
110
0.411
35
110
0.393
-0.940
17.5
4.12
2020
16100
0
40
110
0.341
-0.838
2.5
3.28
2350
20100
1
45
110
0.390
-0.914
2.5
7.95
2000
22900
1
25
115
0.034
-0.914
3.75
1.72
2670
26200
1
30
115
0.430
-0.838
1.25
0.39
1200
13500
1
35
115
0.363
40
115
0.347
45
115
0.396
25
120
0.000
30
120
0.424
35
120
0.338
-0.914
1.25
0.69
4890
35800
1
40
120
0.347
-0.813
2.5
2.8
2280
18200
1
45
120
0.390
-0.889
1.25
5.97
2910
24400
1
25
125
0.018
-1.016
1.25
1.54
3920
38300
1
30
125
0.472
40
130
0.287
-0.991
0
0.22
1050
10900
0
45
125
0.378
40
135
0.317
45
130
0.351
-0.864
0
0.25
1720
18800
1
40 140 0.299
40 125 0.341
238


146
vats). An organic horizon in the soil was also shown to be
capable of containing appreciable amounts of As. The
eluviated sand horizons held the least amount of As. The Bh
horizon contained held less As than found in the upper surface
of the argillic horizons; however, if low organic matter and
low clay content were found in the soil, then the arsenic
contaminant plume was exceedingly difficult to delineate. It
has been suggested for these sites that, if the clay contents
were concentrated, then the As "trail'' could be determined.
These observations, coupled with the development of a
guick field test for arsenic in soil, suggest that a more
appropriate protocol for evaluating the arsenic contamination
at these cattle dipping vat sites may be available. It simply
is not efficient to spend days of manual labor digging holes
at pre-determined depths and distances with no regard for
environmental conditions on-site or to spend days waiting for
laboratory analysis of these soil samples for arsenic. It
would be time better spent if the soil survey and topography
maps were consulted prior to the first visit to the vat site.
Once the mapped soil series is known, the probable depths
for sampling can be more accurately planned. For example, in
all of the cases studied to date, the horizon with the highest
concentration of As was found to be the argillic, if it was
present. If iron-bearing (red) nodules with a clay coating are
in the soil, then the As will concentrate in this coating,
assuming that it contacts the contaminant plume. The same


85
Figure 3-15. Contour maps of As on Aquod's Bh horizon and Aqualf's
surface horizon of the Williston Road vat using: a) the laboratory
analysis versus b) the field test. All distances are in meters.


251
: i)
$
Cw-PCN- 2 CW-P£N-3 CW-PEN-4
| <0*70 1 I Cw-PEN-I
I CW-PEN-5
(oVj
CW-PEN-6
I CVr-PCN-7
I cO." 0 I
CW-PEN-9 CW-PCN-'0
| 0.^0 | | <0.% |
CW-PCN- i 1
r^n
CW-PCN-<2
Cw-PCN-13
Sampled 0.5 ft.
() Sampled 0.5 and 2.0 ft.
E3IArsenic in mg/kg
Temporary Monitoring Well
W-PCN-16
r^n
Figure B-2. Woodward-Clyde Consultants' arsenic survey map
of Cecil Webb cattle dipping vat site.


147
concentration effect occurs if red redoximorphic features
occur in the soil within the plume. If a spodic horizon is
present, the plume will migrate a considerable distance from
the vat. Arsenic will also leave a trail within these spodic
horizons. If the soil is an uncoated Quartzipsamment, the
arsenic plume will leave very little trace of its passage.
However, if it is a coated Quartzipsamment, the plume's trail
should be detectable, although the As concentrations may be
low. All of these soil features are mentioned in accompanying
descriptions in the soil surveys.5362
The direction of the plume's migration will be the same
as the direction of water flow. Equally obvious is the
observation that, if you were to empty a vat of its contents,
then the direction you'd toss the dip solution is downhill
from the vat. The topographical map can give an a priori
basis for speculating on the direction of groundwater flow.
However, only actual on-site sampling and inspection can
confirm the soil series and direction of groundwater flow.
Prior knowledge of probable soil and water conditions, in
conjunction with the arsenic field test kit, make it quite
possible to establish the direction and migration distance of
a plume in most soils within a single day. Furthermore, a
team of three people should be able to fully delineate an
arsenic plume in a worst case scenario (i.e., a spodosol with
a high water table) in less than a week, if the contaminant
can be found at all.


163
Materials and Methods
A total of five column studies were conducted. Four
columns were set up in a manner similar to that described by
Nielson and Biggar.87 These column experiments are referred
to as "differential pressure columns since solution was
generally inputted and removed from the column under suction.
Water flow occurred as a result of both suction and gravity
gradients. A fifth column study was conducted by pumping
solution through a water-saturated column at a constant flow
rate. All soils used for the differential pressure columns
were collected from As contaminated cattle dipping vat sites.
The soils were stored in plastic bags in a 4C refrigerator
until used. No soil was stored longer than three months, to
ensure microbial viability.
All of the contaminated soils had their As concentrations
determined by nitric acid digestion and graphite furnace
atomic absorption spectrometry as described in the third
chapter of this dissertation.
The first column consisted of a sample of the E horizon
taken from the Bison Pen vat site. It was located 12.5 m
south of the vat and at a depth of 45-60 cm below the surface.
Total recoverable As in this sample was 21.5 mg/kg soil. This
column was aerobic and utilized unsaturated water flow. The
column was constructed from high density polyethylene (HDPE)
and measured approximately 10 cm in length by 1.5 cm in


Table A-2
continued
Easting Northing
55 30
40 35
45 35
50 35
55 35
40 40
45 40
50 40
55 40
40 45
45 45
50 45
55 45
40 50
45 50
50 50
55 50
15 55
20 55
25 55
30 55
35 55
40 55
45 55
50 55
55 55
15 60
20 60
25 60
30 60
35 60
40 60
45 60
Surface
Elevation
(meters)
1.670
1.698
1.268
1.524
1.676
1.448
1.237
1.472
1.576
1.158
1.198
1.362
1.426
1.027
1.152
1.170
1.210
0.972
0.994
0.951
0.927
0.988
0.988
1.109
1.128
0.981
0.792
0.683
0.823
0.671
0.628
0.863
0.930
Argillic
Depth
(meters)
-1.194
-1.041
-1.270
-1.397
-1.295
-1.321
-1.575
-1.321
-0.940
-1.295
Argillic Arsenic Concentration (mq/kq)
Field Results Laboratory Analysis
1.25 0.95
3.75 0
3.75 0.54
3.75
0.57
1.25
8.75
6.25
21.2
6.25 2.55
21.2 4.44
3.75
5.33
Argillic Horizon
Iron (mg/kg)
Aluminum (mg/kg) Manganese (mg/kg)
3560
30000 1
2010
12900 0
3900
22000 1
1440
11800 1
3950
30200 1
2740
22400 1
5020
37400 2
2920
23600 1
2460
23100 1
3000
210
28900 1
K>
2800 3 ¡d
210
2800
235


128
Figure 3-41. Soil survey map of the Lake Arbuckle vat site.
Map unit designations: 15 Tavares fine sand, 21 Immokalee
fine sand, 25 Placid and Myakka fine sands, 30 Pompano fine
sand, 35 Hontoon muck, 36 Basinger mucky fine sand,
77 Satellite sand, and 83 Archbold sand.


30
35
40
45
50
55
30
35
40
45
50
55
30
35
40
45
50
55
40
45
50
55
40
45
50
55
40
45
50
55
40
45
A-2. Selected site data for 10205 S.W. Williston Road cattle dipping vat.
Northing
0
0
0
0
0
0
5
5
5
5
5
5
10
10
10
10
10
10
15
15
15
15
20
20
20
20
25
25
25
25
30
30
Surface
Elevation
(meters)
2.003
1.960
2.015
2.060
2.100
2.198
1.914
1.920
1.939
2.015
2.045
2.045
1.832
1.939
2.051
2.112
2.094
2.100
2.042
2.009
2.006
2.054
1.939
1.878
1.856
1.890
1.945
1.628
1.704
1.695
1.347
1.359
Argillic
Depth
(meters)
-1.397
-1.448
-1.549
-1.499
-1.499
-1.626
-1.397
-1.372
-1.397
-1.118
Argillic Arsenic Concentration (mq/kq) Argillic Horizon
Field Results Laboratory Analysis Iron (mg/kg) Aluminum (mg/kg) Manganese (mg/kg)
0.11
0.59
1.25
1.25
1.25
0.625
12.5
1.24
12.4
8.36
1.37
3.46
1190
608
470
610
3450
1300
910
4100
4300
10000
7400
6500
234


LIST OF FIGURES
Figure page
1-1. Schematic plan for the construction of a concrete
cattle dipping vat 2
2-1. Arsenic nomenclature and structures 22
2-2. Other examples of arsenic compounds 24
2-3. Oxidation-reduction stability diagram
for As 29
3-1. Map of roads and vats south of Gainesville, FL . 59
3-2. Map of roads and vats west of Gainesville, FL. . 60
3-3. Photograph of the Payne's Prairie Bison Pen vat . 63
3-4. U.S.G.S. topographical map of the Payne's Prairie
Bison Pen vat site 64
3-5. Soil survey map of the Payne's Prairie Bison Pen
vat site 65
3-6. Argillic horizon depth and associated As
concentrations at the Payne's Prairie
Bison Pen vat site 70
3-7. Geo-Eas" contour map of As plume at the Payne's
Prairie Bison Pen vat site 71
3-8. Two-dimensional "Surfer" contour map of As plume
at the Payne's Prairie Bison Pen vat site . 72
3-9. Three-dimensional Surfer" map of the As plume
across the argillic horizon at the Payne's
Prairie Bison Pen vat site 73
3-10. Three-dimensional map of the As plume on the
argillic horizon along with surface topography
at the Payne's Prairie Bison Pen vat site . 74
3-11. Photograph of the S.W. 10205 Williston Road vat . 76
IX


180
these column studies suggested that as iron was released from
the soil under these conditions, then As is also mobilized.
The effluents in these studies were analyzed for aluminum;
however, none was detected in the leachate, even though
aluminum was present in this soil horizon at a total content
of 960 mg Al/kg soil.
Several attempts at clarifying the roles of the biotic
and the abiotic release mechanisms were made by trying to
maintain a sterile soil column. The soil and column material
were autoclaved three times for 1-hour periods. The solutions
were autoclaved and received either 10% chloroform or a
mixture of ampicillin/tetracycline. Effluents were tested for
microbial activity by streaking on an L-plate (200 mL
deionized water + 1 g Yeast extract + 2 g Tryptone + 1 g NaCl
+ 4 g agar). In all cases, biological growth occurred on the
agar plates, so no column remained sterile for any appreciable
time.
More success was achieved by placing the column in a
purging nitrogen gas, instead of in the ambient atmosphere.
These conditions are described as micro-aerobic or low oxic
since: 1) the gas manufacturer (Liquid Air, Jacksonville, FL)
claimed the N2(gl had less than 250 ppm 02; 2) no oxygen
scrubber was employed; and 3) the tubing and column were not
impermeable to 02lgl. Given these conditions, elution of the
micro-aerobic unsaturated column with 50 mM potassium chloride
yielded a leachate that typically contained an As


139
Figure 3-49. Soil survey map of the Tosohatchee vat site.
Map unit designations: 7 Candler-Urban land complex,
13 Felda fine sand, and 30 Pineda fine sand.


167
Figure 5-2. Schematic cross-section of apparatus used
for the low oxic, unsaturated, differential pressure column.


183
Time (Hours)
Figure 5-6. Iron and arsenic in effluent from an
aerobic, unsaturated column of Payne's Prairie Bison Pen
vat "Bt" soil (152-165 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and phosphate solutions.
Graph A is different scaling than Graph B.
Iron (ug/L)


132
Figure 3-44. Topographical map of the Myakka River vat site


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I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor ^f Philosophy.
Qul_
R. Dean Rhue, Chair
Professor of Soil and
Water Science
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy. ^
U/>
William Harris
Professor of Soil and
Water Science
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.

Edward Hanlon
Professor of Soil and
Water Science
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Brian McNeal
Professor of Soil and
Water Science
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
a dissertation for the degree of Doctor of Philosophy.
David Chynoweth
as
IS
Professor of Agricultural
and Biological
Engineering


CHAPTER 2
OVERVIEW OF ARSENIC
Arsenic Sources and Toxicology
Arsenic occurs naturally in the atmosphere16, water17,
sediment18, soil19 and various organisms20. It ranks 20th in
abundance among the chemical elements20 and occurs in 245
mineral species6. Arsenic is present at an average
concentration of 2 to 5 mg/kg in the earth's crust and is
primarily associated with igneous and sedimentary rocks.21
Re-distribution can occur through natural means such as
weathering, biological activity and volcanic activity.
Anthropogenic inputs can also occur from smelting operations,
fossil fuel combustion, glass and electronics manufacturing,
wood preservatives and agricultural uses.6
Environmental contamination from As compounds introduced
by man is due primarily to the use of arsenic compounds as
pesticides and wood preservatives. Arsenite and arsenate, the
As (III) and As (V) oxides, respectively, account for two-
thirds of the arsenic compounds utilized, with
organoarsenicals comprising the remainder.22 Atmospheric
contamination by As compounds has been associated with
smelting operations and the burning of fossil fuels.20
16


3-28. Soil survey map of the Payne's Prairie U.S. 441
vat site 108
3-29. U.S.G.S. topographical map of the Payne's Prairie
U.S. 441 vat site 109
3-30. Soil survey of the Tuscawillow vat site .... Ill
3-31. U.S.G.S. topographical map of the Tuscawillow
vat site 112
3-32. Soil survey map of the Marion County vat site 114
3-33. U.S.G.S. topographical map of the Marion County
vat site 115
3-34. Topographical map of the Blackwater River State
Forest vat site 119
3-35. Soil survey map of the Blackwater River State
Forest vat site 120
3-36. Topographical map of the Cecil Webb vat site . 121
3-37. Soil survey map of the Cecil Webb vat site . 123
3-38. Topographical map of the Jay Livestock Market
vat site 124
3-39. Soil survey map of the Jay Livestock Market
vat site 125
3-40. Topographical map of the Lake Arbuckle vat site 127
3-41. Soil survey map of the Lake Arbuckle vat site 128
3-42. Topographical map of the Lake Kissimmee vat site 130
3-43. Soil survey map of the Lake Kissimmee vat site 131
3-44. Topographical map of the Myakka River vat site 132
3-45. Soil survey map of the Myakka River vat site . 134
3-46. Topographical map of the Okaloosa-Walton Community
College vat site 135
3-47. Soil survey map of the Okaloosa-Walton Community
College vat site 136
3-48. Topographical map of the Tosohatchee vat site 138
xi


3-49. Soil survey map of the Tosohatchee vat site . 139
3-50. Topographical map of the St. Marks Wildlife Refuge
vat site 140
3-51. Soil survey map of the St. Marks Wildlife Refuge
vat site 142
3-52. Topographical map of the Walker Ranch vat site 143
3-53. Soil survey map of the Walker Ranch vat site . 144
4-1. Subsurface volatile As gas flux and rainfall
for 1996 at the Payne's Prairie Bison Pen
vat site 156
4-2. Subsurface volatile As gas flux and rainfall
for three months in 1997 at the Williston
Road vat site 156
4-3. Cumulative volatile As evolved from contaminated
subsurface soil from the Bison Pen site under
various oxic conditions 158
4-4. Volatilization of As by Fusarium sp. under various
oxic conditions with and without a soil
column scrubber 158
5-1. Schematic cross-section of apparatus used for the
aerobic, unsaturated, differential pressure
column 165
5-2. Schematic cross-section of apparatus used for
the low oxic, unsaturated, differential
pressure column 167
5-3. Schematic cross-section of apparatus used for
the ponded, saturated, differential
pressure column 169
5-4. Effluent from an aerobic, unsaturated column of
Payne's Prairie Bison Pen vat E" soil
(45-60 cm depth)sequentially eluted with
50 mM potassium chloride, nitrate, and
phosphate solution 177
5-5. Effluent from a micro-aerobic, unsaturated column
of Payne's Prairie Bison Pen vat E" soil
(45-60 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and
phosphate solutions 178
Xll


TABLE OF CONTENTS
ACKNOWLEDGMENTS iii
LIST OF TABLES ix
LIST OF FIGURES X
ABSTRACT xvii
CHAPTERS
1 INTRODUCTION 1
Purpose and Statement of Problem 1
Cattle Dipping Vats 1
2 OVERVIEW OF ARSENIC 16
Arsenic Sources and Toxicology 16
Arsenic and Regulatory Laws 19
Chemistry of Arsenic 21
Oxidation states of arsenic 26
Reduction-oxidation equilibria of arsenic 28
Precipitation reactions of arsenic ... 31
Arsenic Compounds in Soil 31
Abiotic Interactions of Arsenic 33
Biotic Interactions of Arsenic 37
Remediation Techniques for
Arsenic-Contaminated Soil 40
Physical remediation techniques . 41
Chemical remediation techniques . 44
Biological remediation techniques 45
3 CATTLE DIPPING VAT SITES 47
Introduction 47
Materials and Methods 49
Results and Discussion 58
Confirmed Vat Sites 62
Payne's Prairie Bison Pen vat 62
Payne's Prairie Williston Road vat ... 75
Dudley Farm vat 87
iv


00
0 0
0 0
0 0
0 0
0 0
0 0-
0 0-
0 0
0 0-
0 0-
0 0-
0
3-8
Payi
rs.
72
00
Arsenic
mg/kg soil
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
Two-dimensional "Surfer" contour map of As plume
's Prairie Bison Pen vat site. All distances measured


97
University of Florida Foundation Vat
In contrast to the Dudley Farm site, the U.F. Foundation
vat is highly disturbed to the point of virtual non-existence.
The vat itself, as well as a nearby barn, have been removed
from the site. The hole where the vat was located has been
back-filled with soil. Occasional pieces of concrete rubble
and a report prepared for the U.F. Foundation by CH2M Hill
Engineering (Gainesville, FL) are the only gross physical
evidence of where the vat was located.76 On the other hand,
chemical analysis of the soil revealed the presence of organic
contaminants such as Toxaphene and DDT along with its
associated degradation products. Arsenic was also found by
CH2M Hill up to a maximum of 37.6 mg As/kg soil. The concrete
rubble, along with the CH2M Hill report, place the vat at the
top of a hillside (Figure 3-22) The soil survey map (Figure
3-2 3) and actual soil sampling with a 10-cm bucket auger
indicated that the soil classification was actually a similar
soil inclusion to Lochloosa fine sand. The soil physical
characteristics showed that the clay content increases sharply
at a depth of 149 centimeters (Table 3-11). Similar to the
previous vat sites, the increase in clay content was reflected
by an increase in the As concentration (Table 3-12) The
argillic horizon at this site exhibited strong redoximorphic
features. A red mottle was separated from the surrounding Bt
soil and acid digested. Subseguent metal analysis revealed


CHAPTER 3
CATTLE DIPPING VAT SITES
Introduction
A number of difficulties arose during the process of
selecting which cattle dipping vat sites were to be
investigated. Among the problems encountered was the fact
that there is no public record of vat locations. The vats
have been unused for cattle dipping for over thirty years.
During this time period, Florida has been developed
extensively and many vats are no longer even in existence.
Often the vats have been buried, paved or constructed over, so
that physical evidence of their presence has been virtually
obliterated. In addition, there was initially a problem
involving liability for the cost of remediating these sites,
if contamination were found. During the 1996 legislative
session, the State of Florida passed a bill (House Bill #1073
and Senate Bill #956) releasing property owners whose land
contained a cattle dipping vat from liability for costs,
damages or penalties associated with the discharge,
evaluation, containment, assessment or remediation of any
substances that were used in the cattle-fever tick eradication
program, retroactive to 1909.52 However, at the onset of this
47


133
EauGallie fine sand, an Alfic Haplaquod (Figure 3-45).58
Arsenic would be expected to be found in the spodic horizon
and, at its maximum concentration, in the top of the Bt2g'
horizon. However, the preliminary survey gave a maximum
arsenic concentration of 880 mg/kg in the A horizon at only
one sampling point. Whether this value came from disturbed
soil or typographical error, it is clearly anomalous.
Excluding this one point, the range of As for this site was
<0.7 to 52 mg/kg. However, it should be noted that at
sampling depths of 15 cm and 45 cm, neither the spodic
(expected at 71 cm) nor the Bt2g (mapped at 127 cm) horizons
would have been analyzed for arsenic.
0k9lQosa-Waltop Community College Vat
Near the town of Defuniak Springs in Walton County,
Florida, the Okaloosa-Walton Community College has a vat site.
The vat structure has been removed and the site fenced off
from the rest of the campus. The area is highly developed
(Figure 3-46) The soil survey report has the area mapped as
either Lakeland or Troup sand (Figure 3-47).59 The Troup soil
series consists of well-drained moderately permeable
Grossarenic Paleudults. Some arsenic should be retained in the
Bt2" horizon where the sand particles are coated and bridged
with clay. On the other hand, the Lakeland series is
described as excessively drained, with rapidly permeable soils
containing 5 to 10 percent silt plus clay in the 2.5 to 101-cm


Percent Arsenic Recovery
207
0 12 3 4
Surfactant Concentration (millimole/liter)
Figure 6-2. Extraction of arsenic from Payne's Prairie
Bison Pen vat soil using HdtABr, hexadecyltrimethylammonium
bromide (a cationic surfactant).


59
Figure 3-1. Map of roads and vats south of Gainesville, FL.
/-fce/,


157
The data in Figure 4-1 suggest that the arsenic was being
volatilized in situ at the Payne's Prairie Bison Pen site. In
laboratory studies, a lesser amount of arsenic was volatilized
under low oxic (0 = 250 ppm) than under high oxic (ambient
air) conditions with and without glucose (Figure 4-3). The
addition of glucose apparently had no effect under low oxic
conditions. In contrast, arsenic volatilization was
stimulated by glucose addition under high oxic conditions.
Hyphae were found to develop throughout the soil samples in
the high oxic/glucose flasks.
A Fusarium species that was isolated from the soil was
placed in arsenic media under both high and low oxic
conditions (Figure 4-4). To test the hypothesis that re
adsorption by overlaying soil was inhibiting the release of
volatile arsenic to the atmosphere, ten grams of 0-5 cm
surface soil were packed into small plastic columns and placed
in line after the inoculated fungal media flask, but before
the charcoal collection tube, for two of the high oxic
samples. Initially, the soil appeared to reduce the amount of
arsenic reaching the carbon trap; however, the student's t-
test revealed that there was no statistical difference in the
means with or without the soil columns. In comparing the
effects of the oxygen levels, it was found that low levels
stimulated the release of volatile arsenic species by the
Fusarium species. This was attributed to the formation of a
fungal mat on the surface of


160
volatile As to be shortened to such an extent that the amount
of conversion of the gas to a non-volatile species was
reduced. Alternatively, it may be that other microorganisms
in the soil, as well as the Fusarium species, are causing the
gaseous arsenic to form.
Further research needs to investigate whether all vat
sites have subsurface arsenical gas being formed and whether
any sites have this gas being emitted at present from the
surface. Another research area, which has potential, is the
isolation and identification of other soil microorganisms that
can volatilize As.


Figure 3-25. U.S.G.S. topographical map of the Payne
Prairie Jackson's Gap vat site.


24
AsO(OH),
OH
3-Nitro-4-Hydroxyphenolarsonic Acid
(Roxarsone)
AsO(OH),
N02
4-Nitrophenylarsonic Acid
(Nitrarsone)
NHCONHj
p-Ureidobenzenearsonic Acid
(Carbarsone)
Figure 2-2. Other examples of arsenic compounds.


189
Figure 5-9. Aluminum and arsenic in effluent from a
ponded, saturated column of S.W. Willistn Road
vat "A" soil (15-30 cm depth) sequentially eluted with
50 mM potassium chloride, nitrate, and phosphate solutions.
Aluminum Effluent Concentration (ug/L)


LK-PEN-
<0.7
LX-PEN-2
<0.7
LK-PEN-3
<0.7
259
LK-PEN-4
<0.7
IK-PEN-3 DF-PCN-6
<0.7 <0.7
LK-PEN-7 LK-PEN-8
<0.7 <0.7
Or-f>tN-g -K-PEN 10
<0.7 tn
IXPCM 11 LKPCM12
fa??! LK-PEN13
<0.7
LK-PEN-U LX-PEN-15
fui CE]
LKPEN-17 LK-PEN-18
dti
LKPEN-16
7
Figure B-10. Woodward-Clyde Consultants' arsenic survey map
of Lake Kissimmee cattle dipping vat site.


Percent Arsenic Recovery
209
Figure 6-4. Extraction of arsenic from Payne's Prairie
Bison Pen vat soil using sodium dodecylsulfate (an anionic
surfactnt) with [16-pyrimidinium crown-4]+4.


Arsenic Effluent Concentration (ug/L)
177
1200
200
0 -
2000
0 500 1000 1500 2000 2500 3000 3500
Time (Hours)
Figure 5-4. Effluent from an aerobic, unsaturated column
of Payne's Prairie Bison Pen vat "E" soil (45-60 cm depth)
sequentially eluted with 50 mM potassium chloride, nitrate,
and phosphate solutions.
Iron Effluent Concentration (ug/L)


105
Pavne's Prairie South Rim Vat
This site is located within Payne's Prairie on Tavares
sand. The As field test was used to analyze soil down to a
depth of 249 cm. At no point along this soil core was arsenic
detected above background soil levels. Although some small
redoxymorphic features were present, no elevated As
concentrations were detected within these red mottles. This
vat remains in relatively good shape, although when it was
investigated there was no standing water in it. The bottom of
the vat contained plant detritus; hence, no visible cracks in
the vat could be discerned. The soil map (Figure 3-26) shows
the area to be heavily wooded. There is a depression located
within a hundred meters of the vat, although this is not
clearly depicted on the topographical map (Figure 3-27).
Pavne's Prairie US 441 Vat
The last vat located inside Payne's Prairie State Preserve
to be included in this dissertation is located along U.S.
Highway 441. The soil map (Figure 3-28) listed the soil as
Sparr fine sand. The topographic map (Figure 3-29) depicts
the vat as being located on the edge of a sharp slope. There
was a dry well located halfway down this slope and, at the
bottom of the slope, some very old pier pilings. It was
conjectured that this site might have been a docking area
before Lake Alachua (Payne's Prairie) was drained. The vat
structure remains in good shape, with murky water containing


I
\
I
2'6"
Figure 1-1. Schematic plan for the construction of concrete
cattle dipping vat.


263
APPROXtUA ,T PROPER!'*' BOJNOARY
OW-27
\
OW-26
*
r.GW-28
OW-24*
\ OW-25
QMW-t
0W-2j\
OW-25,
4.au .
OW-18 ow-rs ~20 ow-21 \
> 0 r
PENCE
k^OW-22
BG-t
OW-16
GW-15
OW-1 J* 0.76
07/-14
CW-7
&
CW-6
|6.5 | Arsenic in mg/kg
Background sample
Sampled 0.5 ft.
^ Sampled 0.5 and 2.5 ft.
(ffil Sampled 0.5, 2.0 and 4.0 ft.
Figure B-14. Woodward-Clyde Consultants arsenic survey map
of Okaloosa-Walton Community College cattle dipping vat site.
Arsenic detected in soil samples at 274-305 cm below surface.


Sampled 0.5 ft.
(8) Sampled 0.5 and 2.0 ft.
HUI Arsenic in mg/kg
Temporary Monitoring Well
/ \
r i
I i
l_od. rsn i
0l-N3d-cW l-N3d-dd
CD cp qra
5l-K3d-dd l-N3d-rid Cl-N3d-dd
IS
cl-N3d~dd
^ [?a [po
ll-N3 ED ITJl
8-Kid-dd -H3d-dri
9-N3d-dd S-M3d-dd
4p [p]
f-K3d-dd C-N3d-dd I-N3d-dd
cp
l-K3*-dd
Figure B-6. Woodward-Clyde Consultants' arsenic survey map
of Jackson's Gap cattle dipping vat site.


75
heavy brush on-site made surface contact with the radar unit
difficult to maintain. Overall, the GPR allowed the argillic
horizon to be mapped to a three-dimensional grid. Once the
dumbbeir-shaped contaminant plume was overlayed on this grid, it
was easy to see that the crests" and valleys" of the argillic
horizon actually determined the shape of the plume.
Pavne's Prairie Williston Road Vat
Another vat at Payne's Prairie State Preserve that had its
contaminant plume shape heavily influenced by the argillic
horizon was located at 10205 S.W. Williston Road, Gainesville, FL.
This vat was 90% intact, although there is currently a tree growing
through the side of the vat (Figure 3-11). The soil survey map53
(Figure 3-12) shows an area that is wooded; however, there is
evidence (small or missing trees) that at one time it was at least
partially clear-cut. Presently, the area has heavy (< 1 meter
height) brush to dense thickets (>3 meter height). The heavy
undergrowth prevented use of ground penetrating radar at this
location, since good contact with the surface could not have been
maintained. The contaminant As plume was mapped solely by soil
sampling with either a 10-cm bucket auger or a 2.5 cm soil probe
(Forestry Suppliers, Inc., Jackson, MS). The first 50 m were
bush-hogged to allow for easy access. The soils found at this
site were actually similar inclusions to those mapped, but did not
match
the taxonomy rigorously. This area near the vat was mapped as


This dissertation was submitted to the Graduate Faculty
of the College of Agriculture and to the Graduate School and
was accepted as partial fulfillment of the requirements for
the degree of Doctor of Philosophy.
May,1998
tSean, College/if
Agriculture
Dean, Graduate School


102
that aluminum (1577 mg/kg) and iron (1697 mg/kg) were higher
than for the surrounding soil. Of particular interest is the
fact that the As analysis detected 68.2 mg As/kg, which is
more than double the amount found in the Bt soil matrix. This
was a strong indication that the arsenic was associated with
the ferric and aluminum oxides/hydroxides evident in these
redoximorphic features.
Jackson's Gao vat
This vat was located in the Payne's Prairie State
Preserve. It was similar to the previous (U.F. Foundation)
vat in that the only gross physical evidence of its prior
existence was the concrete rubble and a report from a
consulting firm. The consulting firm of Woodward-Clyde, Inc.
evaluated the contamination at this site in 1994 and published
its findings in a report for the Florida Department of
Environmental Protection.4 Based on their prioritization
scheme, this site was rated last in terms of relative hazard
out of the twelve sites that they investigated. The rationale
for this rating was based on restricted access, a low level of
contamination, and other risk assessment factors. The
location relative to Gainesville is shown in Figure 3-6. The
soil map (Figure 3-24) and the topographical map (Figure 3-25)
are the only additional data supplied in this dissertation.
The soil was mapped as a Millhopper sand, with no further
study being done at this site.


86
Figure 3-16. Arsenic on argillic horizon's contour maps of the
Williston Road vat using: a) laboratory analysis versus b) the field
test. All distances are in meters.


CHAPTER 7
CONCLUSION
The presence of more than 3400 cattle dipping vats in
Florida was considered to be a cause of concern. The primary
reason for the concern was because these vats were expected to
be emptied yearly onto the soil as raw waste or as a
precipitated iron complex. Considering that the tick
eradication program ran from 1906 to the early 1960s, there
was considerable anthropogenic introduction of As into the
Florida environment. This contamination occurred in fourteen
other states as well.
Overall, the U.S. demand for As products increased by ten
percent from 1971 to 1991, even though the tick eradication
program ended ten years earlier. The toxicity of these As
compounds is highly dependent on the speciation and may range
from an LD50 of 4.5 mg kg-1 for arsine to more than 10,000 mg
kg-1 for arsenobetaine. Although there is such a great range
in toxicity, the U.S. government has set a maximum limit of 50
/ig L-1 total As in drinking water, regardless of species. For
soil, there currently is no limit on As concentration other
than for soil leachate. As determined by the U.S.E.P.A. toxic
contaminant leaching procedure, the leachate must contain less
than 5 mg L"1 for the soil to be considered as non-hazardous
220


Table A-3. Selected site data for Dudley Farm cattle dipping vat.
Easting
Northing
0-5 cm Surface
Arsenic (mg/Jcg)
131.23
0.00
0
98.43
0.00
1.9
114.83
16.40
1
82.02
16.40
0.2
131.23
32.81
4.5
114.83
32.81
4.3
98.43
32.81
4.2
114.83
49.21
10.3
98.43
49.21
6.1
82.02
49.21
0.6
131.23
65.62
6.3
114.83
65.62
17.7
98.43
65.62
43.5
114.83
82.02
3.6
98.43
82.02
0
82.02
82.02
0.2
131.23
98.43
2.5
98.43
98.43
7.7
114.83
114.83
3.1
82.02
114.83
2.2
65.62
114.83
1.4
131.23
131.23
0.6
98.43
131.23
0.5
65.62
131.23
3.1
32.81
131.23
1.3
0.00
131.23
0.9
98.43
147.64
0.6
65.62
147.64
19
32.81
147.64
1.4
0.00
147.64
0
65.62
164.04
0
32.81
164.04
0
247


Table A-2. continued
Easting Northing
45 0
50 0
55 0
30 5
35 5
40 5
45 5
50 5
55 5
30 10
35 10
40 10
45 10
50 10
55 10
40 15
45 15
50 15
55 15
40 20
45 20
50 20
55 20
40 25
45 25
50 25
55 25
40 30
45 30
50 30
55 30
Surface
Elevation
(meters)
2.060
2.100
2.198
1.914
1.920
1.939
2.015
2.045
2.045
1.832
1.939
2.051
2.112
2.094
2.100
2.042
2.009
2.006
2.054
1.939
1.878
1.856
1.890
1.945
1.628
1.704
1.695
1.347
1.359
1.512
1.670
Surface or
Spodic
Horizon
Depth
(meters)
Horizon's Arsenic Concentration (ma/kq)
Field Results Laboratory Analysis
Surface or Spodic Horizon
Iron (mg/kg) Aluminum (mg/kg) Manganese (mg/kg)
-1.168
-1.118
-1.245
-1.168
-1.041
16.2
1.25
16.2
31.2
0.62
1.25
21.2
2.08
0.07
0.69
1.24
0.42
0
5.04
0.02
1190
760
210
230
340
8600
4400
1800
1400
2200
1200
3200
240


Depth (Meters)
Figure 3-21. Field test strips and laboratory analysi
results for Dudley Farm vat soil by depth.


Table 3-8. Selected metal concentrations in soil from Williston Road vat site.
Aquod soil
Horizon8
Arsenic
(mg As/kg soil)
Iron
(mg Fe/kg soil)
Aluminum
(mg Al/kg soil)
Manganese
(mg Mn/kg soil)
Ap

111.2
1854.
6.55
E
1.24
169.8
2488.

Bhl
11.8
658.6
11103.
5.24
Bh2
12.9
412.7
7230.

Bt
12.4
2060.
2864 .
2.62
Aqualf soil
Horizon6
Arsenic
(mg As/kg soil)
Iron
(mg Fe/kg soil)
Aluminum
(mg Al/kg soil)
Manganese
(mg Mn/kg soil)
A
51.2
372.
2863.
7.86
A2
75.1
500.
1761.
7.86
Bw
60.1
336.
1455.
2.62
Btg
99.6
1191.
9507.
2.62
a Soil sample was taken 12 meters northeast of vat.
b Soil sample was taken 68 meters northeast of vat.


Recovery of Arsenic
217
0 5 10 15 20 25 30
Time (Hours)
Figure 6-8. Timed trial study of chelate/SDS extraction of
arsenic from Payne's Prairie Bison Pen vat site soil samples.


57
interference, the As concentration as measured by graphite
furnace agreed well with the values obtained by hydride
generation, which was free from this particular interference.
The cold vapor hydride system was operated in accordance
with the Perkin-Elmer MHS-10 mercury/hydride system manual.73
In general, 10 mL of acidic sample solution was placed in a
reaction flask and the flask was purged with argon. The
reductant, 3% NaBH4 in 1% NaOH, was added for no more than 15
seconds. The resulting gas, AsH3, was swept from the reaction
vessel into a heated T-shaped guartz cell and the maximum peak
height for absorbance at a wavelength of 193.6 nm was measured
and recorded. All reagents were of analytical grade and
purchased from Fisher Scientific Supply Co. (Orlando, FL).
For sites where the arsenic contaminant plume was
delineated in the soil, soil samples were collected using
either a 2.5 cm soil probe or a 10 cm bucket auger (Forestry
Suppliers,
Inc.
, Jackson, MS).
The
soil samples
were
transferred
to
plastic
bags, labeled
and stored in
the
laboratory
at 8
C until
digestion
and
analysis. All
soil
samples for this phase were digested and analyzed for As
within two weeks of collection.
The contaminant plumes were plotted using "Geo-Eas
1.0.I"66 and/or Surfer v.5".74 Depths to the argillic horizons
were determined by soil probe and measuring tape.
Topographical measurements were performed using a


150
As can be accomplished either aerobically or anaerobically.
Under anaerobic conditions, bacteria such as Methanobacterium,
Pseudomonas, and Alcaligenes have been cited as the causative
agents.20 The volatilization of As by bacteria under aerobic
conditions has been demonstrated for Staphylococcus aureus and
E. coli.20 Other microorganisms, besides bacteria, have been
shown to convert As to the volatile methylated species.
Fungi, such as Candida humicola, Gliocladium roseum and
Penicillium sp. have been shown to produce volatile
, , on ,
trimethylarsine aerobically. Under aerobic conditions, soil
treated with arsenate has been shown to evolve 1.5% of the As
as unidentified volatile species.78
A study was conducted to establish the amount and
location of volatile As species at an arsenic-contaminated
cattle dipping vat site. Laboratory studies were undertaken
to establish the relationship of oxic conditions in subsurface
soils to the volatilization of As. Other experiments were
conducted to isolate and identify the causative agent.
Materials and Methods
Two vat sites, at the Williston Road and the Payne's
Prairie Bison Pen, were investigated for volatilization of As
below the soil surface. The Bison Pen vat site and the Dudley
Farm vat site were studied for surface emissions of arsenical
gases. All three of these sites were described in Chapter
3 of this dissertation.


205
difference in extraction efficiency was noted between these
two methods for equivalent shaking times. The amount of SDS
solution was calculated to give 0 and 5 mM (below the critical
micelle concentration, CMC), and to give 10 and 30 mM (above
CMC) in the final solution. The CMC of sodium dodecylsulfate
is generally accepted as -8.2 mM. DDIW was added, when
necessary, to achieve a final volume of 29.4 mL in all tubes.
To the tubes that had various amounts of crown solution, there
was added enough aqueous sodium dodecylsulfate to yield 30 mM
as a final concentration. After mixing on the rotary shaker
for a pre-set time, the tubes were centrifuged at 1500 RPM for
10 minutes. Five mL of the supernatant then were removed by
Class A pipette and placed in a teflon digestion bomb. All
samples were digested by microwave after the addition of 5 mL
of HN03 according to U.S.E.P.A. method #3051, and analyzed by
graphite furnace.68 Instrument model numbers and operation
conditions were described in Chapter 3.
The CMC effect on As extraction efficiency was tested
in a similar fashion for two surfactants, CHAPS and HdtABr.
A stock aqueous solution of CHAPS (18 mg/mL) was diluted to
yield 0.0, 5.0 mM (below the CMC), 10.0, 30.0 mM (above the
CMC) in 2 9.4 mL and added to 0.5 g soil.103 For HdtaBr, the
aqueous solution (0.3 mg/mL) was diluted to 0.0, 0.75 mM
(below the CMC), 1.0, 3.0 mM (above the CMC) in 29.4 mL and
added to 0.5 g soil.104 Samples were mixed, centrifuged,
digested, and analyzed using the methods described previously.


45
Carbon Adsorption. This procedure can be used as an in
situ or a prepared-bed technique, or as a complimentary
technique in conjunction with other methods such as pyrolysis.
It is most effective with contaminants of high molecular
weight, high boiling point, low solubility, and low polarity.
The primary drawback is the lack of knowledge of long-term
stability.
Ion Exchange. This is an in situ or prepared-bed method
emphasizing separation and immobilization of contaminants.
Disadvantages include the limitation of applicable inorganic
contaminants in suitable soils and the requirement of
convenient pH control.
Biological remediation techniques
Bioleachina. This technique can be performed as in situ,
in-tank or in prepared beds. Bioleaching may affect arsenical
compounds directly by increasing mobility of As through
reduction to inorganic As (III) or through reduction of
associated ions (i.e., iron or sulfur). Bioleaching may occur
indirectly by microbial production of organic acids, such as
malic acid, or by microbial production of inorganic acids,
such as sulfuric acid. These acids could in turn mobilize As
via dissolution or ionic displacement mechanisms. Impediments
to bioleaching may derive from soil composition, soil pH,
nutrient requirements, bioavailability of the As compounds,
and competition by indigenous microorganisms. Another


181
concentration of 100-300 /ig/L (Figure 5-5) This is two to
six times more than the U.S.E.P.A. limit for drinking water,
and two to six times the effluent concentration under aerobic
conditions.27 Upon switching the eluant anion from chloride
to nitrate, there was a decrease in the amount of leachate As.
After 5800 hours of operation; however, the air conditioning
in the laboratory became non-functional. The column thus was
subjected to a 10C temperature increase from 22 to 32C. It
is believed that this increase in temperature was responsible
for an increase in biological activity which, in turn, was
directly related to an increase in iron and arsenic for the
column's effluent. When the ambient temperature returned to
22C at 6975 hours, there was a decrease in the As
concentration of the leachate once more.
When the eluting anion was changed from nitrate to
phosphate, it resulted in a large increase in the iron and
arsenic concentrations in the column effluent. This is
similar to the behavior observed for the high oxic,
unsaturated column; however, the maximum As concentration was
roughly 2-fold greater under aerobic conditions than for the
low oxic conditions. In contrast, the iron concentration was
nearly seven times greater for the low oxic column's leachate
than for leachate from the high oxic column. It is
hypothesized that the variation in iron release was due to
greater biological reduction of iron from ferric to ferrous (a
more mobile species) under the less oxic conditions. The


53
these analyses included a multi-channel Jarrell-Ash
Inductively Coupled Argon Plasma unit model 161-E,
a Perkin-Elmer (Franklin, MA) Atomic Absorption Spectrometer
(AAS) model #2380, a Perkin-Elmer Graphite Furnace (GF) model
HGA-400 and a Perkin-Elmer Hydride System MHS-10 (Norwalk,
CT). Spectrophotometer conditions for the flame and hydride
vapor atomic adsorption analysis are given in Table 3-1.
Operational parameters for the graphite furnace are shown in
Table 3-2.
Background correction for the graphite furnace utilized
a deuterium lamp. This type of correction compensates for
smoke; however, it is inadequate for spectral interference.
A spectral interference "occurs when an absorbing wavelength
of an element present in the sample but not being determined
falls within the bandwidth of the adsorption line of the
element of interest.71 For As analysis by graphite furnace
using deuterium lamp background correction, the spectral
interference is caused by aluminum.72 Fortunately, the
spectral interference caused by aluminum absorption exhibits
a strong linear correlation (R2=0.996) with the apparent As
concentration (Table 3-3). Since the aluminum can be measured
by nitrous oxide flame AAS, the contribution of aluminum to
the apparent As signal can be calculated and subtracted from
the measured As concentration to obtain the true, or the
corrected As concentration. After correction for aluminum


134
Figure 3-45. Soil survey map of the Myakka River vat site.
Lower right quadrant map unit designations: 16 Delray complex
20 EauGallie fine sand, 26 Floridans-Immokalee-Okeelanta
association, and 22 Felda fine sand.


152
Subsurface soil gas samples were collected by passing 30
mL of gas through ORBA-32 tubes six times a month for one year
at the Payne's Prairie Bison Pen vat site and for three months
at the Williston Road vat site. A subsurface gas sampling
apparatus was constructed from 501 stainless steel 0.64 cm
diameter tubing with the sampling ports covered by Gore-Tex
(expanded TFE polymer on loosely woven polyester cloth
manufactured by W.L. Gore, Inc.) The sampling apparatus was
based on design specifications from Magnussen et al.
Subsurface gas sampling probes were installed at the Payne's
Prairie Bison Pen vat site to a depth of 132 cm, with as
little disturbance to the last 60 cm of soil as possible.
Control sampling tubes were installed at this site to an egual
depth and at an equal distance from the vat, but on the
northern, uphill side where no As had been detected in the
soil. The second vat site along Williston Road had a set of
subsurface sampling probes placed 67 meters northeast of the
center of the vat to a depth of 76 cm, with as little
disturbance to the last 30 cm of soil as possible. Subsurface
control probes for the Williston Road vat site were installed
twenty-five meters southwest of the hot subsurface probes.
The control probes were entrenched to a depth of 76 cm;
however, the soil around the control probes contained no
detectable As.
Manifold experiments on the Bison Pen vat soils were
conducted by flushing flasks containing 100 g arsenic-


265
LPlb Tj
SU-PN-I SU-PEN-2
rm Q3
SU-PfLN-
<0*7
SU-PtN-5
C3
SU-PVi-
02
SU-PN-
<£L7
SU-PEN-8
<0*7
SU-PCN-9 34-PCN-IO
GS CD
SM-PCN-M
<3X7
SU-PEN-12
<0*7
SU-PtN-lJ
cm
gj-PCN-14
cm
SU-PN-I5
S3
SU-P£N-17 SM-PEN-18
SW-PCN-
<0*7
Figure B-16. Woodward-Clyde Consultants' arsenic survey map
of St. Marks Wildlife Refuge cattle dipping vat site.


89
as a Bonneau fine sand (Figure 3-18). As shown in Table 3-9,
these soils tend to be slightly acidic, with organic matter
content greatest for the surface (0-36 cm) soil. The soils
from the lower depth contained redoxymorphic features and red
concretions. The surface topography was mapped (Figure 3-19)
and As was analyzed to a 5 cm depth. To the south of the vat
there is a sinkhole (Figure 3-20) that might have constituted
a problem if the arsenic contaminant plume had reached it.
Some As (0.8 yq/g soil) was detected on the road outside the
gate leading from the vat towards the sinkhole. This was
probably tracked there by humans or cattle, although transport
by erosion could not be excluded. More As (1.9 yg/g soil) was
found approximately 30 meters south of the vat. The probable
source of this contamination was from the copper-chromate-
arsenate (CCA) pressure-treated fence posts that were stacked
in a pile at this location. In general, the Woodward-Clyde
data and the surface soil analysis indicate that the arsenic
contaminant plume is moving to the west towards the
undeveloped pasture rather than towards the homestead to the
east or towards the sinkhole to the south. Vertical movement
of the As was investigated by utilizing a truck-mounted drill
unit. It was generously supplied by the Florida Department of
Environmental Protection test(D.E.P.) and operated by Mr. Lee
Booth of D.E.P.'s Waste Management Division. All holes were
back-filled with "Dolomite" mixed with soil taken from the


214
chelator to soil weight(g) ratio equal to 150 (Figure 6-6).
A lower rate of chelating agent to soil was required for the
E horizon soil sample (Figure 6-7). Indeed, a very low ratio
of 0.6 g chelator/g soil removed 100% of the arsenic found in
the E horizon soil samples.
To ascertain whether the maximum extraction efficiency
was attained in the allotted time for shaking, a timed trial
was done. It is apparent that the maximum extraction was
definitely obtained within a 24-hour shaking time (Figure 6-
8). In fact, analysis of the data by the student's t-test
revealed that the extraction efficiency from 1- through 24-
hour shaking times were essentially equivalent. Since the
maximum extraction efficiency for both Bt and E horizon soil
samples was reached at equivalent shaking times, the
implication is that the extraction kinetics were not diffusion
limited for the time length examined for these soil samples
and, thus, were not dependent on effective particle size below
2 mm. The surficial adsorption of arsenic was not completely
unexpected, since observation of a nodule by scanning electron
microprobe analysis using a Joel Superprobe 733 model revealed
a lack of As in the cracks and fissures of the nodule. The As
appeared to be located on the clay fraction that surrounded
the nodule. This observation has been made by other
investigators as well.18 It has been shown that the silt,
clay and humus fraction of soil contains a significant portion


225
Another column study that was performed involved an
attempt to simulate flow and concentration conditions found
when a cattle dipping vat solution was dumped onto a typical
Florida soil. It was found that under these conditions, a
simple one-dimensional transport model that employed
equilibrated sorption as defined by the Freundlich
relationship could be used to predict, within ten percent of
the correct pore volume, the break-through of arsenate from
the soil column.
The fourth objective was directly related to the third
goal, in that the removal of As from soil was the main thrust.
Both biological volatilization and direct chemical extraction
methods were investigated. Fungi, bacteria, and actinomycetes
are capable of volatilizing As. The studies described herein
are the first to document that a Fusarium species can
accomplish this feat. Fusarium is a wide-spread soil fungi,
so it may be quite common that one method of transporting As
from the immediate environment is by volatilization. It has
been shown that, at the two vat sites where subsurface probes
were installed, a volatile As species was being produced. It
is interesting to note that, at the two vat sites where a
surface gas collection box was utilized, there was no
detectable As being emitted from the soil surface. This
implied that the volatile As was being converted to a less
labile form before reaching the surface. The laboratory
experiments designed to explore this hypothesis were not


137
control section. This type of soil would not be expected to
retain arsenic in any appreciable amounts. Indeed, the
consulting firm's survey revealed a range of <0.7 to 4.90 mg
As/kg soil, although it should be noted that no samples were
taken within the fenced-off area.
Tosohatchee Vat
The Tosohatchee vat in Orange County, Florida, was found
on nearly level topography (Figure 3-48) The site was mapped
as either Pineda or Malabar soil series (Figure 3-49).60 The
main difference in these soils is the depth of the typical
argillic horizon. The Malabar soils have an argillic horizon
depth of 102-147 cm, in contrast to the Pineda soils having it
at 94-147 cm. In either case, the maximum concentration of
arsenic would be expected to be found in the argillic horizon.
The arsenic sampling survey reported that the maximum
concentration of arsenic (100 mg/kg) was found at 152 cm.
Given that the error in sampling depth was given as 15 cm and
that this soil may not be a typical example of the soil series
mapped, it is quite probable that the maximum concentration
was found in the argillic horizon.
St. Marks wildlife Refuge Vat
The St. Marks Wildlife Refuge was located in Wakulla
County, FL. The vat site was situated along the Seaboard
railway (Figure 3-50). The soil survey report revealed the


266
. WR-22
<0. 7 //P-3 ,
<0.7 '"K /f\ .'-K
^W-7 ^M-6
<0.7 <0.7 <0.7
<0.7 -ffe-
WR-.
<0.7
~%t-2 -Qm-,
<0.7
<0.7
WR-20 =
Arsenic mg/kg at 0.5 ft.
Arsenic mg/kg at 4 ft.
Figure B-17. Woodward-Clyde Consultants' arsenic survey map
of Walker Ranch cattle dipping vat site.


143
Figure 3-52. Topographical map of the Walker Ranch vat site


Common pE/pH range for soil
pH
Figure 2-3.
for As.
Oxidation-reduction stability diagram


170
The fifth column study that was conducted involved an
uncontaminated soil. This soil was from the Payne's Prairie
State Preserve Bison Pen vat site. Soil was sampled from the
0-5 cm depth 54.9 meters south of the vat. The soil was
analyzed for As; however, none was detected. The soil column
was taken as intact as possible by pushing a glass column into
the soil after surface litter had been removed. The glass
column (Sigma-Aldrich, Inc., Supelco Division, Bellefonte, PA)
measured 2.5 cm (internal diameter = i.d.), and the soil
column length was 5 cm. More intact soil cores were taken
using two brass rings (i.d. = 5.4 cm, height = 3 cm) that
could be stacked; hence, soil was sampled to a cumulative
depth of 6 cm. These latter two soil cores were used to
determine porosity and bulk density. All soil cores were
wrapped in plastic and stored at 4C until used. No soil core
was stored more than 3 months before usage.
The uncontaminated surface soil in the glass column was
connected to a Shimadzu LC-10AS liquid chromatograph pump
using 0.16 mm outer diameter plastic tubing and zero dead
volume connectors. The soil column was initially saturated
with 30 mM potassium chloride by pumping the solution in from
the bottom of the column at a rate of 0.01 mL/minute. The
column then was inverted after approximately two pore volumes
of eluant were flushed out. The column was flushed with 42.3
mL 30 mM KC1 at 3.27 mL/minute, with the flow going top to
bottom. At this time, the potassium chloride solution was


Table A-2. continued
Surface or
Spodic
Horizon's Arsenic
Concentration (ma/ka)
Surface or Spodic Horizon
Easting
Northing
Elevation
Depth
Field Results
Laboratory Analysis
Iron (mg/kg)
Aluminum (mg/kg)
Manganese (mg/kg)
(meters)
(meters)
15
65
0.494
-0.229
0
0
970
1700
56
20
65
0.494
-0.152
1.25
0
760
2400
4
40
65
0.695
-0.381
0
0.23
600
1200
16
45
65
0.835
15
70
0.335
20
70
0.207
20
70
0.421
25
70
0.341
-0.203
1.25
0.29
370
2100
66
35
70
0.808
40
70
0.866
45
70
1.006
-0.381
0
0.69
1030
2300
16
5
75
0.372
-0.102
1.25
0.43
1670
6300
4
15
75
0.293
-0.102
0
0.21
1550
8200
7
20
75
0.265
-0.152
2.5
1.37
1230
4900
2
30
75
0.207
-0.152
12.5
3.27
4310
7100
40
25
75
0.262
35
75
0.643
40
75
0.677
-0.254
16.2
10.7
1120
4900
6
45
75
0.762
-0.406
31.2
14.6
0
80
0.238
-0.076
2.5
1.66
2020
11900
38
5
80
0.396
10
80
0.116
-0.127
12.5
2.71
2330
9200
16
15
80
0.280
20
80
0.171
-0.127
2.5
2.2
1050
5300
10
20
80
0.122
25
80
0.189
35
80
0.485
-0.178
21.2
1.89
980
6700
8
40
80
0.518
45
80
0.570
-0.254
37.5
60.1
450
4500
1
0
85
0.177
5
85
0.085
-0.102
12.5
3.59
3080
9500
1 K
K>


11
Table 1-1. continued
Time
DescriDtion
Reference
1923
The Florida State legislature passed a
compulsory cattle-dipping law and
created the State Live Stock Sanitary
Board. The law allowed for partial
compensation to owners for dipping their
herds, as well as a one half mill levy
to carry out the work.
10
1924
Dipping began in Gadsden and Escambia
counties under the new law.
Repercussions involved state dipmen
wounded in battles with cattlemen, and
15 dipping vats in Escambia county were
dynamited.
10,11
1926
Georgia built a 240 mile fence along the
Florida border to prevent the movement
of tick-infested cattle. This fence
remained in place for 5 years and
extended from the Chattacoochee River to
the St. Mary's River.
10,11
1927
A more effective cattle dipping policy
was initiated by the Florida
Legislature. Instead of arresting
cattlemen who did not dip their herds,
the cattle were rounded up, dipped, and
1


CHAPTER 5
COLUMN STUDIES ON THE MOBILITY OF ARSENIC
Introduction
Mobility of As is dependent on several factors, including
its speciation and its oxidation state. Soil characteristics
also play an important role in such movement. The oxides and
hydroxides of aluminum, iron, and manganese are the primary
controlling determinants of As sorption by soil. Arsenite
undergoes similar sorption, but to a lesser extent. Sorption
may occur by ligand exchange or by electrostatic attraction.85
Ligand exchange may occur with surface hydroxide or aqueous
groups from hydrous metal oxides, from phyllosilicate edges,
and from calcite.86 Immobilization of As by metal oxides has
been considered to be a more dominant mechanism than
. . . 21
immobilization by organic matter.
The release of As once it has been adsorbed onto the
soil is also a well researched topic. Extractants such as
KN03, KH2P04, NH4N03, NHC1, NH4F, (NH4)2S04, (NH4)2C03, NaOH,
Na2HP04/NaH2P04, CH3COONH4, HC1, HN03 and H,S04 have all been
used to remove As from soil by column leaching or batch
extraction.47 Almost without exception, these studies were
performed on soils that had been treated in one manner or
161


131
Figure 3-43. Soil survey map of the Lake Kissimmee vat
site. Map unit designations: 13 Samsula muck, 17 Smyrna
and Myakka fine sands, 21 Immokalee sand, 25 Placid and
Myakka fine sands, 74 Narcoossee sand, and 87 Basinger
fine sand.


250
(TD n CpD
2i-n3 6-N3d-a8
[pj Cp3 ITT1
B-w3s-aa -N3d-aa 9-N3d-ae
nrn
;-N3d-ae
CpD qp rrn
f-Kk-aa r-N3a-aa j-fOd-M
cp
i-N3^-a
Figure B-l. Woodward-Clyde Consultants' arsenic survey map
of Blackwater State Forest cattle dipping vat site.


273
70. Perkin-Elmer Corp., Instructions for model 2380",
Absorption Spectrophotometer, Sept. 1987, 9-6.
71. Slavin, W., Graphite Furnace AAS A Source Book",
Perkin-Elmer Corp. Ridgefield, Ct., 1984, 75-79.
72. Perkin-Elmer Corp., MHS-10 Mercury/Hydride System
Operator's Manual, 761 Main Ave., Norwalk, CT, USA,
1978, 9-1.
73. U.S.E.P.A. Environmental Monitoring Systems Laboratory,
Geostatistical Environmental Exposure Assessment
Software System (Geo-EAS) Version 1.2.1" Las Vegas, NV,
USA, 1990.
74. Golden Software, Inc., Surfer Version 5.0", 809 14th
St., Golden, CO, USA, 1994.
75. Geophysical Survey Systems, Inc., Radan III", 13 Klein
Drive, North Salem, NH, USA, 1990.
76. CH,M Hill, Contamination Assessment Report and
Remedial Alternatives Evaluation for the San Felasco
Hammock Property Addition, Prepared for the University
of Florida Foundation, Inc., Gainesville, FL, USA,
September 1993.
77. Sandberg, G. and Allen, I.K., A proposed arsenic cycle
in an agronomic ecosystem, In: Woolson, E.A. (Ed)
"Arsenical pesticides, American Chemical Society
Symposium Series 7, American Chemical Society,
Washington, D.C., 1975, 124-127.
78. Woolson, E.A., Generation of alkylarsines from Soil",
Weed Science, 1977, 25, 412-416.
79. Rolston, D.E., Gas Flux", In: Klute, A. (ed.) Method
of soil analysis Part I., Physical and mineralogical
methods." American Society of Agronomy Soil Science
Society of America, 1986, 1103-1119.
80. Magnusson, T., A method of equilibration chamber
sampling and gas chromatography analysis of soil
atmosphere." Plant Soil, 1989, 39-47.
81. Cox, D.P. and M. Alexander, Effect of phosphate and
other anions on trimethyllarsine formation by Candida
humicola, Applied Microbiology, 1973, 25, 408-413.
Barron, G.L., The genera of hyphomycetes from soil",
Williams and Wilkins Co., Baltimore, MD, 1968, 165.
82 .


Table A-2. continued
Easting Northing
10 85
15 85
30 85
35 85
40 85
45 85
0 90
5 90
10 90
15 90
20 90
25 90
30 90
35 90
40 90
45 90
0 95
5 95
10 95
15 95
20 95
25 95
30 95
35 95
40 95
45 95
0 100
5 100
10 100
15 100
20 100
Surface
Elevation
(meters)
0.171
0.146
0.098
0.506
0.445
0.445
0.104
0.158
0.134
0.067
0.055
0.006
0.485
0.503
0.451
0.469
0.085
0.146
0.091
0.085
0.058
0.049
0.491
0.491
0.436
0.494
0.116
0.171
0.079
0.067
0.055
Surface or Spodic Horizon
Surface or
Spodic Horizon's Arsenic Concentration (mq/ka)
Horizon
Depth Field Results Laboratory Analysis Iron (mg/Jcg) Aluminum (mg/kg) Manganese (mg/kg)
(meters)
-0.127
-0.127
3.75
37.5
1.7
10.8
890
2520
7400
6000
-0.152
-0.102
-0.102
-0.076
37.5
1.25
1.25
18.7
13.8
0.21
0.36
7.75
1080
3380
2220
1480
3600
5500
8400
7600
-0.152
-0.127
-0.127
-0.102
12.5
37.5
1.25
7.45
13.8
0.33
2.46
3820
640
2420
1250
4900
2700
6700
7600
-0.102
-0.127
6.25
37.5
4.22
14.7
1450
2440
5500
6400
-0.178
-0.127
-0.152
-0.127
3.75
6.25
8.3
0.14
1100
1330
450
1600
4400
2700
3300
7900
243


Northing
246
250.00
200.00
150.00
100.00
50.00
0.00
0.00 50.00 100.00
Easting
Figure A-3. Sampling map for Dudley Farm vat site.
All distances are in meters.


3
thoroughness, speed, and simplicity of the dipping operation.1
Typically, the vats were 7.6-9.1 meters (25-30 feet) long and
0.8 to 1.1 meters (2.5-3.5 feet) wide according to plans
supplied by the United States Department of Agriculture
(U.S.D.A.) and the Federal Bureau of Animal Industries (Figure
1-1),2,3'4 Florida alone had over 3400 cattle dipping vats
which typically contained 5700 to 7600 liters of 0.14 to 0.22
percent total As solution.3,4 The vats were expected to be
emptied or replenished yearly. Disposal of the toxic waste
was by one of two procedures. The first "approved practice is
to run the waste bath into a pit properly guarded by a fence,
where it will gradually seep away under the surface and do no
harm, provided only that seepage cannot be carried to a well,
stream or spring from which any person or domestic animal may
drink".3 This procedure was recommended in 1919 by the
U.S.D.A. During the era of this recommendation, Florida had
a much lower population and much less urban development, so
the potential for harm was much reduced compared to today.
The second method of waste disposal, proposed in 1913, was to
form an insoluble precipitate. The clear liguid was to be
pumped or syphoned out onto the ground, since it contained
little As. The precipitate was to be "taken out and buried if
so desired" and it, too, was judged to be non-poisonous.5 The
procedure to "render harmless the arsenic" called for
measuring the number of gallons of solution left in the vat.
For each 378 liters, 2.7 kilograms of slaked lime was to be


Table A-2. continued
Easting Northing
20 85
25 85
25 85
35 85
40 85
45 85
0 90
5 90
10 90
15 90
20 90
25 90
30 90
35 90
40 90
45 90
0 95
5 95
10 95
15 95
20 95
25 95
30 95
35 95
40 95
45 95
0 100
5 100
10 100
15 100
20 100
25 100
30 100
Surface
Elevation
(meters)
0.049
0.055
0.058
0.506
0.445
0.445
0.104
0.158
0.134
0.067
0.055
0.006
0.485
0.503
0.451
0.469
0.085
0.146
0.091
0.085
0.058
0.049
0.491
0.491
0.436
0.494
0.116
0.171
0.079
0.067
0.055
0.073
0.454
Argillic
Depth
(meters)
-0.864
-0.914
-0.711
-0.800
-0.965
-0.864
-0.889
-0.762
-0.813
-0.787
-0.864
-1.041
-0.787
-0.813
-0.508
Argillic Arsenic Concentration (mq/kq)
Field Results Laboratory Analysis
37.5
37.5
2.5
21.2
2.5
37.5
37.5
18.7
6.25
18.7
21.2
2.5
1.25
3.75
37.5
33.1
28.1
0.4
12.1
0.39
26.2
65.1
13.8
1.32
4.01
7.73
5.18
0
0
9.21
Iron (mg/kg)
Argillic Horizon
Aluminum (mg/kg) Manganese (mg/kg)
4180
29400 1
2160
16300 1
1010
6800 0
7220
55200 1
3870
29900 1
2670
23600 1
2160
16900 0
5270
31200 1
2040
18800 0
2450
23300 1
2530
31000 1
2340
23100 1
2700
16100 1
2740
25800 0
6170
34000 1
6170
34000
237


3-8
Selected metal concentrations in soil from
Williston Road vat site 83
3-9. Selected characteristics of soil 2.3 meters
east of the Dudley Farm vat 91
3-10. Selected metal concentrations in soil 2.3 meters
east of the Dudley Farm vat 96
3-11. Selected characteristics of soil 0.9 meters
north of the excavated U.F. vat 100
3-12. Selected metal concentrations in soil 0.9 meters
north of U.F. vat 101
3-13. Soil map units and taxonomic classes for reported
cattle dipping vat sites 117
5-1. Selected soil column characteristics 17 6
5-2. Flow rate variations after sequential elution of
differential pressure columns 187
A-l. Selected site data for Payne's Prairie Bison
Pen cattle dipping vat 230
A-2. Selected site data for 10205 S.W. Williston
Road cattle dipping vat 234
A-3. Selected site data for Dudley Farm cattle
dipping vat 247
viii


58
Lietz/Sokkisha C3a Automatic Level from Florida Level and
Transit Co., Jacksonville, FL.
To better determine the subsurface topography of the
argillic horizon at one of the sites, ground-penetrating radar
(GPR) was employed. The GPR unit, a Geophysical Systems model
3102, was run at 400 nm/s with attenuation of 100 and with a
frequency of 500 MHZ at 16 scans/s. Output was interpreted
using the Radan III program.75
All photographs of the vats were taken using a Ricoh RDC-
2E digital camera from Ricoh Corporation, Sparks, NV. Color
prints were produced by an Epson Stylus Color 800 printer.
Results and Discussion
This discussion section of the vat site studies was
broken into two major sections, confirmed (personally
investigated) and reported (investigated by state-contracted
consultants). In order to facilitate future investigations of
the confirmed vat sites, the locations were overlayed by GIS
on road maps (Figures 3-1 and 3-2). A summary of confirmed
vat sites with the soil map units and taxonomic class revealed
that seven out of nine sites were located on Ultisols (Table
3-4). The only two vat sites not on an Ultisol were located
at the Payne's Prairie State Preserve South Rim location and


138
Figure 3-48. Topographical map of the Tosohatchee vat site


Ill
Figure 3-30. Soil survey map of the Tuscawillow vat site.
Map unit designations: 7B Kanapaha sand, 8B Millhopper
sand, 14 Pomona sand, 18 Wauchula-Orban land complex, 21
Newnan sand, 23 Mulat sand, 29B Lochloosa fine sand, 31B
Blichton sand, and 56 Wauberg sand.


254
2.'
6 FT
1.4
S FT
1.5
10 FT
Sampled 0.5 ft.
() Sampled 0.5 and 2.0 ft.
Sampled 0.5 and 4.0 ft.
EZlArsenic in mg/kg
Figure B-5. Woodward-Clyde Consultants' arsenic survey map
of Dudley Farm cattle dipping vat site. Arsenic detected
in soil samples deeper than 122 cm below surface.


28
and Allred-Rochow scales, it is clear that As is considered to
be positively charged with respect to C, 0 and S. However,
the problem becomes muddled in the case of H. Further
confusion can arise if the electronegativities are assigned
using one of the two remaining systems. For the sake of
consistency and simplicity, the values given by Pauling will
be used throughout the remainder of this dissertation in
assigning oxidation states. This necessitates that As be
regarded as electropositive in relation to C, O, S and H. As
such, the only oxidation states assigned to As will be +5, +3
or 0.
Reduction-Oxidation..Equilibria of Arsenic
The oxidation state of aqueous As is highly dependent on
the pH of the system as illustrated in Figure 2-3.18 Typical
mineral soils or sediments can have pH values in the range 5
to 9 with an Eh values of -300 (water-logged) to +900 (well-
aerated) millivolts (mV). Some of the reduction potentials of
As compounds are given in Table 2-5.18 It is interesting to
note that only the reduction of elemental As to arsine has a
negative E; this means that reduced conditions would be
required in a sterile, pure, aqueous system to produce this
gas.


Northing
233
0 o
O
o
o
o
o
o
o
o
o
o
o
o
5 O
O
o
o
o
o
o
o
o

o
o
o
10 O
O
o
o
o
o
o
o
,0,,-*fP
o
o
15 O
O
o
o
o
o
o
o

o

o
o
20 O
O
o
o
o
o
o
o



o
o
25 O
O
o
o
o
o
o
o



o
o
30 O
O
o
o
o
o
o
o
o

o
o
o
35 O
O
o
o
o
o
o
o



o
o
40 O
O
o
o
o
o
o
o
o

o
o
o
45 O
O
o
o
o
o
o
o
o

o
o
o
50 O
O
o
o
o
o
o
o
o
o
o
o
o
55 O
O
o
o

o

o

o

o
o
60 O
O
o
o
o

o

o

o

o
65 O
O
o


o
o
o

o

o

70 O
O
o
o
o

o
o
o

o

o
75 O

o


o

o

o

o

80
o

o

o
o

o

o

o
85 O

o

o


o

o

o

90
o

o

o
o

o

o

o
95 O

o

o


o

o

o

100
o

o

o
o

o

o

o
105 O

o

o


o

o

o
o
110 O
o
o
o

o
o



o

o
115 O
o
o
o
o


o
o
o

o
o
120 O
o
o
o
o
o
o



o
o
o
125 O
o
o
o
o


o
o
o

o
o
130 O
o
o
o
o
o
o
o


o
o
o
135 O
o
o
o
o
o
o
o
o
o
o
o
o
140 O
o
o
o
o
o
o
o

o
o
o
o
145 O
o
o
o
o
o
o
o
o
o
o
o
o
150 O
o
o
o
o
o
o
o

o
o
o
o
155 O
o
o
o
o
o
o
o
o
o
o
o
o
160 O
o
o
o
o
o
o
o

o
o
o
o
165 O
o
o
o
o
o
o
o
o
o
o
o
o
175 O
o
o
o
o
o
o
o

o
o
o
o
0
5
10
15
20
30
35
40
45
50
55
60
65
Easting
O Elevation only
Elevation and Sampled
Figure A-2. Sampling map for 10205 S.W. Williston Road vat
site. All distances are in meters.


223
the quick field test for arsenic. The latter was based on the
Merck Arsenic Quant Test for Water. Its usage in the field
would allow for faster delineation of plume parameters by
cutting down on lab "turn-around time required to show the
presence of the contaminant. It should be noted that the
field test was actually more sensitive than the laboratory
analysis of the soils. There are several possible
explanations for the elevated concentrations. First, the
weight of the soil used in the field test was estimated by the
field operator and could have been more than the expected
amount. Secondly, the scale used for field results was
initially devised for water, not soil. Thirdly, the presence
of volatile As compounds in the soil has been confirmed, and
transport back to the laboratory, with the necessary lag time
before digestion, may have resulted in the loss of some As.
A fourth possibility is that the digestion procedure used in
the laboratory, which is defined as Total Recoverable Metals
by the U.S.E.P.A., in no way can be construed to mean total
metals present in the soil. However, even with all of these
problems, the field test for arsenic should be considered as
a valid, semi-quantitative measure of the contamination and
can be used to shorten the amount of field work required to
delineate a contaminant As plume in soil.
Plume shape in the soil depended not only on soil
properties, such as amounts of silt, sand, clay and organic
matter as well as hydrologic properties of the site, but


115
Figure 3-33. O.S.G.S. topographical map of the Marion
County vat site.


Effects of physicochemical soil properties on retention
of As were investigated. Particle-size analysis suggested
that soils with higher clay contents retained more arsenic.
Contaminated soils with higher iron and aluminum content also
exhibited higher As concentrations. Ground-penetrating radar
was utilized at a Payne's Prairie vat site to locate the
argillic horizon. Locating of the As plumes was effected by
analysis of hand-augured soil borings. A Fusarium fungal
culture was isolated from near this Payne's Prairie site that
was capable of volatilizing As.
Soil gas collections near the surface overlying the zone
of highest As concentration at two sites were shown to be
essentially free of arsenic, though subsurface soil gas
collections at two vat sites revealed gaseous As.
Mobilization studies were conducted on contaminated soil
columns eluted with various anions under variable oxic
conditions. Other studies involved surfactant extractions. A
cationic surfactant, cetyl trimethyl ammonium bromide, was
compared to a zwitterionic surfactant, 3-[(3-cholamidopropyl)-
dimethylammonia]-1-propane sulfonate. Efficiencies of both
extractants were below that of an anionic surfactant, sodium
dodecyl sulfate, after arsenic has been complexed with a
cationic macrocycle, [16-pyrimidium crown-4]+4.
xviii


202
method of chelate/surfactant washing has been used to extract
As, Cd, Cr, Cu, Pb, Ni, and Zn anions from composite soil
prepared in the laboratory. A recovery of 93% was found using
a chelating agent, ethylene diaminetetraacetic acid (EDTA),
with an anionic phosphatic surfactant at a pH of 8 to 12.100
While this pH range was necessary to fully deprotonate EDTA,
it makes this system impractical for in situ flushing of
Florida soils where the pH is typically 5.5 to 6.5.
The perfect chelator for in situ remediation would have
to: 1) complex the As oxyanions, 2) maintain pH in the normal
range for the soil, 3) be capable of 100% extraction from a
variety of soil types and 4) be non-toxic initially as well as
in its degradation products. A potential chelator, [16-
pyrimidinium crown-4]4+ was chosen (Figure 6-ld). This
macrocycle has a "hole" of 1.3 A, which is far too small to
encircle nitrate, or the even larger arsenical anion. This
chelating agent has been shown to enfold the nitrate anion in
a manner analogous to a hand covering a ball.101 The pH of
this chelating agent in deionized water is 6.8. It also has
the potential for biodegradability, since it is synthesized
from thiamine hydrochloride (Vitamin Bj) With the macrocycle
having a positive charge of four and with the maximum negative
charge of arsenate being negative three, a positively charged
complex should be formed. Hence, it was hypothesized that the
complex would be extractable from soil using an anionic
surfactant.


203
Materials and Methods
Chemicals used were of analytical quality and used as
received from the supplier. Sodium dodecylsulfate (SDS),
thiamine hydrochloride (Vitamin Bl) methanol, and zinc
acetate were obtained from Fisher Scientific Co.
Hexadecyltrimethylammonium bromide (HdtaBr) was supplied by
Sigma Chemical Co. The zwitterionic surfactant, 3 [(3
cholamidopropyl)-dimethyl ammonia]-1-propane sulfonate
(CHAPS), was obtained from Pierce, Inc.
The highly positively-charged macrocycle, [16-
pyrimidinium crown 4]4+, was synthesized based on a
procedure described by Cramer et al.101 Zinc acetate (4.39 g)
was dissolved in 25 mL deionized, distilled water in a 125 mL
Erlenmeyer flask. Thiamine hydrochloride (13.49 g) was added
and the flask hand-shaken until dissolution was complete. The
flask then was loosely capped and placed in a shaking water
bath set initially at 23C. The temperature was raised to
60C and held for ~12 hours. The light yellow supernatant was
vacuum-filtered through Whatman #42 filter paper, and the
white crystals were rinsed three times with 10 mL of methanol.
All supernatant collections were pooled and subsequent slow
evaporation of the supernatant resulted in the formation of
more white crystals. Final yield was 72%.
In all experiments, a known weight of soil that was
contaminated with As from cattle-dipping vat waste was placed


56
Table 3-3. Spectral interference by aluminum in the analysis
of arsenic at wavelength 193.6 nm using a graphite furnace
atomic absorption spectrometer with deuterium background
correction.
Aluminum Concentration
Apparent Arsenic
(mg/L)
Concentration (,ug/L)
10
2.59
25
13.7
50
39.5
100
84.1
250
189.
500
349.


171
switched to an arsenate solution (4.873 g Na2HAs04'7H20) per
1.0 L distilled, deionized water). Effluent fractions were
collected at five-minute intervals using an Isco Retriever 500
Fraction Collector (Isco Inc., Lincoln, NE). All fractions
had weights recorded and 0.5 mL aliquot removed for chloride
analysis. A one milliliter aliquot also was removed for As
analysis by graphite furnace atomic absorption spectrometry
after microwave digestion with nitric acid.
Chloride analysis of the effluent aliquots was performed
for all column studies.88 The procedure involved transferring
0.5 mL aliquot from the column effluent to a 35 mL culture
tube. This aliquot was dried at 60C in an oven. Upon
cooling, twenty milliliters of 0.1 N HN03 were added to
dissolve the residue in the tube. Chloride standards were
made by drying 0.1 g NaCl in an oven at 150C for one hour,
and then allowing it to cool in a desiccator for 0.5 hours.
A stock solution of 1000 mg/mL NaCl,aql was made by dissolving
the dried sodium chloride in 100 mL distilled, deionized
water. Serial dilutions gave chloride standards of 50, 100
and 150 yUg/mL. Twenty milliliters of standard or sample were
used for chloride analysis after the ionic strength was
adjusted by addition of 0.4 mL KN03 ionic strength adjuster
solution (Fisher Scientific, Orlando, FL). A magnetic stir
bar aided in mixing. Chloride concentration was measured
using a chloride ion-specific electrode in conjunction with a
double junction reference electrode. Since all of these


Table 3-12
Selected metal concentrations in soil 0.9 meters north of U.F. vat
Horizon
Arsenic
Iron
Aluminum
Manganese
(mg As/kg soil)
(mg Fe/kg soil)
(mg Al/kg soil)
(mg Mn/kg soil)
A
26.9
261.
711.
3.0
El
7.7
173 .
505.
2.0
E2
2.7
116.
255.
1.0
Bt
33.8
412.
1037.
1.0
Btg
24.3
320.
1197.
1.0


49
(three miles) to the nearest vat; hence, it can be assumed
that vats are no farther than 3.2 kilometers apart;
e) the number of vats per Florida county were recorded, often
with the original owner's name;
f) tax rolls should also reveal the original owner of the
cattle, since the taxman was invariably present at major
dipping operations; and
g) holding areas such as auction houses and railway heads
invariably had vats nearby.
All of these assumptions can be utilized to find cattle
dipping vat sites. Clearly, the easiest way to locate a vat
is still through anecdotes from the people involved in using
them.
Materials and Methods
Those vats that were located during the course of this
study usually came from anecdotal accounts, primarily by the
Payne's Prairie park staff (Butch Hunt, Jack Gillem, Jim
Weimer, and Howard Adams). Other sources included previous vat
surveys by Woodward-Clyde, Inc., and sources located on the
University of Florida campus.19
All vat sites near the University of Florida were
visually confirmed and the surrounding soil was sampled for As
contamination, if the site was accessible. Only one confirmed
vat site for this study was not in Alachua County. This site


190
Mechanically Pumped Column Study
An attempt to take an intact soil core for a column study
was made by pushing a glass tube into the soil. Due to the
blunt ends of the tube; however, some compaction was
inevitable. The soil column was connected to a pump and
saturated with 50 mM potassium chloride from bottom of the
column. The flow then was reversed and the column leached
with a solution of sodium arsenate (4.86 g/L). Concentration
of the arsenic was based on historical recipes for manufacture
of the cattle dipping vat solution, which called for 1.92 mg
As03 per mL of solution. The fractions were collected and
analyzed for arsenic and chloride (Figure 5-10) Pore volume
of the column was determined from the chloride data to be
15.99 mL. The saturated water content was determined for
intact soil cores taken at the same time and place as the soil
column. These data were used to calculate the gravimetric
water content (0.0092 mL water/g soil) by the difference in
weight of the saturated soil and dried soil divided by the
weight of the dry soil. Since the height (3 cm) and internal
diameter (5.4 cm) of the soil core were known, then the bulk
density of the soil could be determined by dividing the weight
of the dry soil by its volume (Table 5-1) Porosity was found
by multiplying soil bulk density by the gravimetric water
content and dividing by the density of water (Table 5-1) .
Flow rate of the pump was set by using a typical flux for


University of Florida Foundation
vat 97
Jackson's Gap vat 102
Payne' s Prairie South Rim vat 105
Payne's Prairie U.S. 441 vat 105
Tuscawillow vat 110
Marion County vat 110
Reported Vat Sites 113
Blackwater River State Forest vat .... 116
Cecil Webb vat 116
Jay Livestock Market vat 122
Lake Arbuckle vat 126
Lake Kissimmee vat 129
Myakka River vat 129
Okaloosa-Walton Community College
vat 133
Tosohatchee vat 137
St. Marks Wildlife Refuge vat 137
Walker Ranch vat 141
Conclusions 145
4 BIOLOGICAL VOLATILIZATION OF ARSENIC 149
Introduction 149
Materials and Methods 150
Results and Discussion 154
Conclusions 159
5 COLUMN STUDIES ON THE MOBILITY OF ARSENIC . 161
Introduction 161
Materials and Methods 163
Results and Discussion 174
Differential Pressure Column Studies . 174
Mechanically Pumped Column Study .... 190
Conclusions 195
6 SURFACTANT EXTRACTION OF ARSENIC FROM SOIL . 198
Introduction 198
Materials and Methods 203
Results and Discussion 206
Conclusions 218
7 CONCLUSION 220
APPENDICES
A RAW DATA FOR CONFIRMED VAT SITES 228
B RAW DATA FOR REPORTED VAT SITES 249
V


4
added. Slaked lime is made by calcining calcium carbonate
from limestone, marble or seashells to form an anhydrous
calcium oxide (quicklime) that can be subsequently reacted
with water. After addition of the slaked lime, the vat
solution was to stand for several hours. Then, for each 378
liters in the vat, 2.7 kilograms of copperas was to be added.
Copperas, ferrous sulfate (FeS04.7H 0) is a strong reducing
agent. After ten to twelve hours, "the arsenic unites with
the copperas (iron) and will have fallen to the bottom of the
vat as an insoluble, harmless precipitate or sediment."5
Since ferrous sulfate is quickly converted to the ferric form
under basic conditions and arsenite [As (III)] is reduced to
arsenate [As (V)], the precipitate would most likely be
FeAsO,, barring complexation with other metals and anions in
the vat solution.
An interesting side note is that, at a 1992 U.S.E.P.A.
workshop, the Bechtel Corporation and Artech Systems Inc.
presented the "Cashman Process" in which acid leach of
arsenical flue dust was treated with iron and gypsum
(CaS04.2H0) to form ferric arsenate. A long-term stability
test over a period of several months was performed on a 3
meter thick pile of residues, by collecting the run-off. An
estimate of 4 to 8 million years was given for all the As to
leach out of such piles.6 In this case, as in the cattle
dipping precipitation/burial method, underlying assumptions
were made concerning 1) low carbon input, 2) persistence of a


REFERENCE LIST 267
BIOGRAPHICAL SKETCH 277
vi


145
The arsenic should be slightly retained in this horizon;
however, due to the poor drainage, the As plume would be
expected to be quite mobile. Indeed, the As survey map,
provided by the Woodward-Clyde consultants, revealed very
little arsenic in close proximity to the vat. The range was
<0.7 to 2.3 mg As/kg soil.
Conclusions
Locating of the vats described in this dissertation was
done largely through anecdotal evidence. Without the
knowledge of Butch Hunt, Payne's Prairie Security Officer, and
Jack Gillem, Payne's Prairie Park Manager, many of these vats
would not have been located. Vats were also found by reports
submitted by several environmental consulting firms to various
state agencies.19,68
The various soil series that were found at these vats
provided several bits of information. Among these items are:
1) As tends to associate with aluminum and iron
oxides/hydroxides found in soil clay layers and 2) if the
hydraulic conductivity of the clay is low, the downward
transport of As is restricted, although high clay content
alone does not necessarily stop vertical movement of the As
(i.e., the Dudley Farm site). It was also observed that the
topography of an argillic horizon influenced the shape of the
As contamination plume (i.e., the Bison Pen and Williston Road


175
under aerobic and unsaturated conditions (Table 5-1). The
effects of leaching with aqueous solutions of KC1 or KN03
resulted in little displacement of As from the soil (Figure 5-
4) under high oxic conditions. It is interesting to note that
the chloride anion appeared to be capable of displacing more
arsenate than the nitrate anion. One possible hypothesis that
explains this behavior invokes the supposition of low oxic
micro-sites within the soil column that promote the reduction
of arsenate to the more mobile arsenite ion by microorganisms
under chloride elution; whereas, the presence of nitrate could
inhibit this phenomenon. In fact, a testament to biological
viability of this soil came from the observation of fungal
mycelia that grew out of the holes drilled in the side of the
column. Further evidence for this hypothesis was obtained
when the column was placed under N2(g, in the second study.
Upon leaching with phosphate buffer, the amount of As eluted
increased substantially (Figure 5-5). There was certainly an
anionic displacement mechanism, particularly in light of the
homologous chemistry exhibited between phosphate and arsenate.
Batch extractions on soils that have been air-dried, sieved,
and/or stored at room temperature, all exhibit significant
displacement of arsenate by phosphate.47'86 One investigation
using batch extractions concluded that 1 N NH4C1 and 0.5 M
NH4NO3 removed less than 0.1 ^g As/g soil, while 0.5 M KH,P04
could extract arsenic in the percent recovery range 10.2 to
37.2, depending on the soil type.47
A second investigation


222
There were ninety-four vats located in Alachua County,
Florida. This dissertation documents the location of
approximately ten percent of the total vats in this county.
The conditions of these vats ranged from virtually intact to
almost total excavation, with only loose rubble left to mark
the vat location.
The second objective of this dissertation is closely
related to the first. The second goal was to assess the
physical and chemical properties that affect arsenic at these
sites. The amount of As contamination found in the soil at
these vat sites depended on the area's hydrology and on the
soil's ability to retain the arsenic. It was found that, in
general, As was accumulated in soil with high clay or organic
matter content. An uncoated Quartzipsamment soil retained
little As, and the location of arsenic at the sites with
these soils remained a mystery. Argillic horizons, on the
other hand, could retain As in the top several centimeters of
the horizon at some sites. At these sites, the topography of
the argillic horizon determined the shape of the contaminant
plume. At other sites, where the hydrology differed, As was
found to have moved vertically as well as horizontally.
To facilitate the mapping of these plumes, three
essential basics were proposed for the field protocol. First
was prior knowledge of field conditions by study of soil
survey and topographical maps; second was on-site inspection
to confirm soil and water conditions; and lastly, the use of


151
The Bison Pen vat site had soil samples taken for
chemical and biological experiments using a ten-centimeter
bucket auger at a depth of 132 centimeters and at a distance
of 12.2 meters south from the vat, where the arsenic
contamination reached a maximum of 110 mg As/kg soil. All
samples were placed in plastic bags, transported to the
laboratory and stored at 4C until further use. No samples
were stored for more than three months to insure biotic
viability.
A surface soil gas flux trap was constructed using a
15x30x30 cm box constructed of 0.63-cm thick plexiglass. The
box was covered with aluminum foil and rested on a 10-cm
aluminum collar driven into the soil.79 Gas collection at 49.6
L hr-1 was facilitated by a 2.5 amp air pump attached to a
rotometer. The gas collection box was placed over an
undisturbed area in close proximity to the soil that had the
maximum As concentration for the two sites that were tested.
For the Payne's Prairie Bison Pen vat site, the gas flux trap
was located 12 meters south of the center of the vat. For the
Dudley Farm location, the plexiglass box was situated 2.1
meters east of the center of the vat. Volatile As gases were
collected for six weeks and nine weeks at the Payne's Prairie
and Dudley Farm sites, respectively. The gaseous As species
were trapped using a Supelco ORBA-32 tube that contained 0.65
g activated charcoal.


275
93. Bromfield, S.M., "Reduction of Ferric Compounds by Soil
Bacteria, Journal of General Microbiology, 1954, 11,
1-6.
94. Jacobs, L.W., J.K. Syers, and D.R. Keeney, Arsenic
Sorption by Soils, Soil Science Society of America
Journal, 1970, 34, 750-754.
95. Rhue, R.D., W.G. Harris, R.B. Brown, and R.C. Littell,
"A Soil-Based Phosphorous Retention Index for Animal
Waste Disposal on Sandy Soil, Final Project Report,
U.S.E.P.A. Grant #9004984910, U.S. Environmental
Protection Agency, Washington, D.C., 1994, 41.
96. Kuhlmeier, P.D., Partitioning of Arsenic Species in
Fine-Grained Soils, Air and Waste Management
Association, 1997, 47, 481-490.
97. Jury, W.A., W.R. Gardner, and W.H. Gardner, Soil
Physics, 5th Edition, John Wiley & Sons, Inc., New
York, NY, 1991, 226-227.
98. Clarke, A.N. and D.J. Wilson Soil Surfactant
Flushing/Washing, In: Hazardous Wastesite Soil
Remediation, Theory and Application of Innovative
Technologies, Wilson, D.J. and Clarke, A.N. (Eds),
Marcel Dekker, Inc., 1994, 493-550.
99. Vigon, B.W. and A.J. Rubin Practical considerations in
the surfactant-aided mobilization of contaminants in
aquifers, Journal of Water pollution Control
Federation, 1989, 61, 7, 1233-1240.
100. Esposito, P., J. Hessling, B.B. Locke, M. Taylor and M.
Szabo, "Results of Evaluations of Contaminated Soil
Treatment Methods in conjunction with CERCLA BDAT
program", Proceedings of the Air Pollution and Control
Association, 1998, 88-6B.5.
101. Cramer, R.E., V. Fermin, E. Kuwabasa, R. Kirkup, and M.
Selman, "Synthesis and Structure of the Chloride and
Nitrate Inclusion Complexes of [16-pyrimidium crown-
4]4+, Journal of the American Chemical Society, 1991,
113, 7033-7034.
102. Jafvert, C.T. and J.K. Heath, "Sediment-and Saturated-
Soil-Associated Reactions involving an Anionic
Surfactant (Dodecylsulfate). 1. Precipitation and
Micelle Formation", Environmental Science and
Technology, 1991, 25 (6), 1031-1038.


269
23. Pearce, F., "Arsenic in Tapwater Linked to Skin
Cancer", New Scientist, 1993, 5.
24. Yamauchi, H. and B.A. Fowler, "Toxicity and Metabolism
of Inorganic and Methylated Arsenicals", In: Arsenic
in the Environment, Part II: Human Health and Ecosystem
Effects, Nriagu, J.O. (Ed), John Wiley and Sons Ltd.,
New York, 1994, 35-53.
25. Yamanaka, K., H. Ohba, A. Hasegawa,R. Sawamura and
S. Okada, "Mutagenicity of dimethylated metabolites of
inorganic arsenics", Chemical Pharmicology Bulletin,
1989, 37, 2753-2756.
26. Irgolic, K.J., "Determination of Organometallic
Compounds in Environmental Samples with Element-
Specific Detectors" In: Trace Metal Analysis and
Speciation, Krull, I.S. (Ed), 1991, 47, 21-48.
27. Freeze, R.A. and J.A. Cherry, "Groundwater", Prentice-
Hall, Inc., New Jersey, 1979, Chapter 9, 388-413.
28. U.S.E.P.A., "Chemical-specific parameters for toxicity
characteristic contaminants", Document 600/s, 3-91/004,
1992.
29. Tadesse, B., J.D. Donaldson, and S. Grimes,
"Contaminated and Polluted Land: A General Review of
Decontamination Management and Control", Journal of
Chemical Technology and Biotechnology, 1994, 60, 227-
240.
30. Edmundson, R.S., In: "Dictionary of Organometallic
Compounds: As Arsenic", Macintyre, J.E. (ed.),
Chapman and Hall University Press, Cambridge, Great
Britain, 1995, 1, 195.
31. Cotton, F.A. and G. Wilkinson, Advanced Inorganic
Chemistry", John Wiley and Sons, New York, New York,
1980,440-442.
32. Pauling, L., The Nature of the Chemical Bond, Cornell
University Press, Ithaca, New York, 1960, 88.
33. Huheey, J.E., Inorganic Chemistry Principles of
Structure and Reactivity", Harper and Row Publishers,
New York, New York, 1978, 142-172.
34. Essington, M.E., "Solubility of Barium Arsenate", Soil
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1570.


166
used to purge both the solution entering the column and the
vial used to collect column effluent (Figure 5-2). Suctions
were adjusted at column inlet and outlet to obtain the desired
flow rates.
The third column consisted of the Bt material taken from
the Bison Pen vat site at a depth of 152-165 cm and 12.5 m
south of the vat. Total recoverable As was 55.1 mg/kg. This
column was flushed under aerobic, unsaturated conditions. It
was similar in most respects to the first column except that
the column itself was constructed from polyvinyl chloride
(PVC) with holes drilled in the side. Glass frits were used
at each end of the column so that input and effluent solutions
could be maintained under the desired suctions. Soil was
packed into the column and the water content was adjusted
prior to placing the end caps on the column.
The fourth column consisted of the A horizon material
taken from the Agualf at the Williston Road vat site. The
soil was taken from the 15 to 30 cm depth at a distance of
about 67 m south-southwest of the vat. It had a total
recoverable As concentration of 51.2 mg/kg. Because of the
high organic matter content, water flow was extremely slow
through this material. In order to maintain a reasonable flow
rate, solution was ponded on this soil to provide a positive
pressure head for water flow. All solutions were exposed to
ambient air and no attempt was made to maintain anaerobic


CHAPTER 1
INTRODUCTION
Purpose and Statement of Problem
The primary area of interest in this study was focused
upon arsenic (As)- contaminated soils in Florida that resulted
from the extensive long-known use of cattle dipping for the
purpose of tick eradication. The investigation was divided
into four objectives. First was evaluation of the extent of
As contamination at selected cattle dipping vat sites. A
second objective was the assessment of physical and chemical
properties that affect retention and mobility of As at these
sites. Third was an attempt to fit the movement of As in soil
to a one-dimensional transport model that included a
retardation factor. A final objective involved the
examination of biotic as well as chemical extraction methods
that affect the release of As from soil.
Cattle Dipping Vats
In Florida, as in many other southern states, one source
of soil contamination by As can be ascribed to the extensive
use of cattle dipping vats to eradicate ticks. Vats became
the preferred method of eradication by virtue of the
1


125
Figure 3-39. Soil survey map of the Jay Livestock market
vat site. Map unit designations:
5 Bonifay loamy sand, 9,10 Dothan fine sandy loam,
25 Lucy loamy sand, 31,32 Orangeburg sandy loam,
43 Tifton sandy loam, and 47 Troup-Orangeburg-Cowarts
complex.
-J


192
water in a Florida soil as 20 cm3/cm2' hour. Since the
internal diameter of the column was 2.5 cm, the flow rate was
found to be 3.27 cm3/minute. This meant that the pore
velocity could be calculated as flow rate divided by porosity,
or 23.4 cm/min.
Basically, column flow rates and the concentrations of As
solution were set up to mimic the dumping of an oxidized
cattle dipping vat solution onto a typical Florida soil
adjacent to the dipping vat.
Adsorption isotherms were constructed from experimental
data using the Payne's Prairie Bison Pen A horizon" soil (0-15
cm depth) and either sodium phosphate or sodium arsenate
solutions (Figure 5-11) The plot of log10S versus log10Cps
yielded linear relationships for both arsenate (linear
regression coefficient R2 = 0.995) and phosphate (R2 =
0.9997). This linear relationship between log10S and log10Cps
is typical of a Freundlich isotherm, and can be expressed by
the equation S=KdCpsn, where S is analyte sorbed onto the soil
(ug/g) Kd is the distribution coefficient, CpS is equilibrium
concentration of the analyte in the soil pore solution
(ug/mL), and n affects curve shape and is referred to as a
Freundlich constant.95
By taking the log of the Freundlich expression, the
equation is converted into the linear form y = mx + b, where
the slope of the line represents the Freundlich constant (n)



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44
Cement Solidification. This is an in situ or in-tank
method of storage and immobilization. It is accomplished by
mixing Portland cement with the contaminated soil.
Disadvantages include incompatibility with large amounts of
dissolved sulphate salt or metallic anions such as arsenate,
along with difficulty in hardening over a short time if the
soil has a high amount of organic matter, silt or clay. Long
term effects of this method have not been adeguately studied.
Vitrification. This is an in situ or in-tank method that
is used to immobilize and store contaminants by fusing them
into a glass-like substance. The main disadvantage is the
high energy requirement, particularly with soils of high water
content.
Chemical remediation techniques
Precipitation. This technique can be done as an in situ,
prepared-bed or in-tank method. The premise is separation,
possible volume reduction and/or immobilization by the
formation of insoluble precipitates. This method was
recommended by the Florida State Board of Health, Veterinary
Division, for the As dipping-vat program. The arsenic was to
be precipitated as a ferric salt in basic conditions, and then
buried. Unfortunately, subsequent microbial action reduces
the iron and frees the As species for migration. The main
drawback to this method is a lack of testing on long-term
stability of the precipitates.


162
another so that the biotic viability of the soil was lessened
or destroyed.
As stated previously, the mobility of As is dependent on
its species and oxidation state. Both of these factors can be
changed by either abiotic or biotic process. Bacterial
oxidation and/or reduction of arsenic has been demonstrated by
other researchers.85 Oxidation state of the hydrous metal
oxides may also influence the mobility of As. It has been
stated that the desorption of As can be highly dependent on
the reduction of Fe3+ to Fe2+.21
This investigation focused on the desorption of As from
soil under various oxic conditions and solution flow rates.
Extremely slow flow rates were accomplished by placing the
aqueous solutions in the vertical columns under a low suction
gradient. These systems have been referred to as differential
pressure columns utilizing an average flow velocity.87
Various potassium solutions with differing anions (chloride,
nitrate, and phosphate) were sequentially eluted through these
columns in the hopes of elucidating their effects on biotic
and abiotic desorption mechanisms. A column study at higher
flow rates was undertaken to demonstrate the applicability of
using a one-dimensional transport model in determining the
retardation factor for arsenate in a typical Florida cattle
dipping vat soil. This column investigation involved having
the aqueous solutions mechanically pumped at a steady rate
under high pressure.


78
Pottsburg sand.53 Between 60 and 70 meters, the soil was described
in the soil survey report as a Monteocha loamy sand.53 The
transects then extended into an area mapped as Wauberg sand. The
soil actually found at this site did not match the taxonomy given
for the map units. Inclusions of similar soil were identified.
The soil mapped as Pottsburg sand was taxonomically an Aguod and
the soil mapped as Wauberg sand was an Aqualf. The transects for
the Aqualf had to be performed along lanes cut by machete, since
this was where the dense thicket began (Figure 3-13). The particle
size distribution for the Aquod and Aqualf soils as well as organic
matter content, pH and As concentrations are given in Table 3-7.
The surface, spodic and argillic horizons of all three soils were
plotted in a three-dimensional grid (Figure 3-14A). What is not
clearly shown in this area plot is how the Pottsburg and Monteocha
soil map units overlap. In this transitional phase, the two spodic
horizons do not intersect each other as one would surmise from the
plot. The spodic horizon of the Aquod actually overlaid the Bh
horizon of the soil mapped as Monteocha sand, and was separated
from it by an E horizon located between the organic horizons. In
fact, the Monteocha soil was never clearly identified as a separate
soil in the field, although it is delineated on the soil survey
map. The As contaminant plume's shape was influenced not only by
the soil horizons composition, but also by the contours of these
soil horizons. This is similar to the situation found at the
Payne's Prairie Bison Pen Vat site. The maximum concentration


252
z'-' &"3 or-i 0"-J. . o'-5
0"->C-5
Sampled 0.5 ft.
() Sampled 0.5 and 2.0 ft.
[a]Sampled 0.5 and 4.0 ft.
ESArsenic in mg/kg
Figure B-3. Woodward-Clyde Consultants' arsenic survey map
of Dudley Farm cattle dipping vat site. Arsenic detected
in soil samples at 0-30 cm below surface.


48
research project in 1992, the liability for remediation costs
rested solely with the owner of the property. With estimates
of such costs ranging from $130,000 to $800,000 per site (not
including cost of annual operation and maintenance),4 private
property owners were not willing to admit even having a vat,
much less allow an investigation of the site. One of the
first criteria for site selection thus became the need for
vats to be located on state property. Other factors included
proximity to the University of Florida in Gainesville,
accessibility to the vat and to the surrounding land and, if
possible, availability of anecdotal accounts of the location
and the history of use for the vat site. The latter criterion
is, in fact, the key to locating many of these vats. It must
be remembered that cattlemen who utilized these vats when they
were in their thirties would now be in their sixties. They
thus constitute a location resource that is steadily
disappearing. Some other assumptions and facts also can aid
in locating vats; for instance:
a) a water source was needed (each vat held =5700 liters);
b) vats needed to be drained; therefore, the location would be
at higher elevation in relation to surrounding terrain,
although in some cases only by a matter of centimeters;
c) the Florida sun is an extreme condition that could be
alleviated if the vat were located under tree cover;
d) no cow was expected to travel more than 1.6 kilometers


188
trend was the high oxic Bt" column study, wherein the slowest
rate occurred during the period when it was being leached with
potassium nitrate. It was noted that the Bt" column also had
the highest amount of aluminum in its effluent under leaching
by chloride or nitrate solutions (Figure 5-7) In all cases,
it was noted that the time frame where the leachate was
highest in iron and/or aluminum coincided with a drop in the
flow rate. Both facets could indicate a change in soil
structure within the differential pressure columns. The
ponded, saturated column study was no exception to this
pattern. During the leaching of A" horizon soil with
potassium chloride or potassium nitrate, the flow rate
averaged 0.623 mL/hour. Under phosphate buffer elution, the
leachate's iron concentration reached a maximum of 2,770 /g/L
while aluminum reached 36,530 //g/L and, forty-eight hours
later, the As reached its maximum concentration of 293.3 g/L
(Figure 5-8 and 5-9) Overall, a total of 882 //g As (61.5%)
was released. Concurrent with the increase in ionic leaching
under phosphate elution of the soil, the flow rate dropped to
0.158 mL/hour with a standard deviation of 0.179 mL/hour. It
remained inconclusive whether the decrease in flow rate was
due to: 1) collapse of the soil pore structure or 2) clogging
of the glass frit at the bottom of the columns either by
colloidal movement and coagulation or by precipitation
reactions occurring within the frit itself.


Table A-2. continued
Easting Northing
25 100
30 100
35 100
40 100
15 105
20 105
25 105
30 105
35 105
40 105
45 105
20 110
25 110
30 110
35 110
40 110
45 110
25 115
30 115
35 115
40 115
45 115
25 120
30 120
35 120
40 120
45 120
25 125
30 125
40 130
45 125
Surface
Elevation
(meters)
0.073
0.454
0.430
0.402
0.073
0.067
0.037
0.448
0.436
0.366
0.390
0.064
0.018
0.411
0.393
0.341
0.390
0.034
0.430
0.363
0.347
0.396
0.000
0.424
0.338
0.347
0.390
0.018
0.472
0.287
0.378
Surface or
Spodic Horizon's Arsenic Concentration (mq/kq)
Horizon
Depth Field Results Laboratory Analysis
(meters)
Surface or Spodic Horizon
(mg/kg) Aluminum (mg/kg) Manganese (mg/kg)
-0.127
-0.127
-0.102
-0.127
-0.165
-0.102
-0.102
-0.114
-0.254
-0.127
-0.076
-0.102
-0.127
-0.203
-0.076
6.25
6.25
37.5
1.25
10
0
1.25
12.5
5.37
0.42
3.11
2.28
2.69
5.31
1810
1370
1780
1540
730
780
1740
1940
390
1430
3900
1430
1040
620
970
4300
4400
3700
4700
4100
2200
3500
3700
1700
3600
5900
4400
1400
2000
2700
244


Table 3-5. Selected characteristics of soil 10 meters south of the Bison Pen vat.
Soil
Taxonomic
Class
Depth
(cm)
Horizon
Dominant
Munsell
Color
Particle Size
Distribution (%)
Organic
Matter (%)
PH
Arsenic
(mg As/
kg soil)
Silt
Sand
Clay
Udult
0-30
Ap
10YR 4/1
4.3
95.0
0.7
0.8
5.7

30-91
El
10YR 7/1
3.3
95.8
0.9
0.6
5.8

91-122
E2
10YR 7/2
4.0
95.3
0.7
0.4
5.4
0.8
122-
E3
10YR 6/4
3.4
95.8
0.8
0.3
5.6
21.5
152
152-
Bt
10YR 5/3
2.3
84.4
13.3
0.2
5.3
72.2
178
178-
Btg
10YR 4/2
1.4
78.4
20.2
0.1
5.3
1.8
On
O'


120
Figure 3-35. Soil survey map of the Blackwater River
State Forest vat site. Map unit designations:
5 Bonifay loamy sand, 9,10 Dothan fine sandy loam,
25 Lucy loamy sand, 31,32 Orangeburg sandy loam,
43 Tifton sandy loam, and 47 Troup-Orangeburg-Cowarts
complex.


278
contamination resulting from the usage of cattle dipping vats
in Florida.


Percent Arsenic Recovered
215
Chelate/Soil Weight Ratio (g/g)
Figure 6-6. Effect of chelate to soil weight ratio on the
extraction of arsenic from Payne's Prairie Bison Pen "Bt"
soil samples using 30 mM sodium dodecylsulfate.


108
Figure 3-28. Soil survey map of the Payne's Prairie
U.S. 441 vat site. Map unit designations: 16 Surrency
sand, 17 Wauchula sand, 19 Monteocha loamy sand, 29c
Lochloosa sand, 31c Blichton sand, 49 Lochloosa fine
sand, 50 Sparr fine sand and 52 Ledwith muck.


15
Table 1-1. continued
Time
Description
Reference
recognized by Bureau of Animal
Industries for official work under Dept.
of Agriculture regulations.
14
1957
On April 23, southern cattle tick
(Boophilus annulatus microplus) was
found on 4 ranches in southern
Okeechobee county and 1 ranch in
county. More than 100 ranches in 10
counties were placed under quarantine,
even though the ticks were found to be
non-infectious. Counties affected
included Palm Beach, Hendry, Broward,
St. Lucie, Glades, Highlands, Martin,
Taylor, Dade and Okeechobee. An
eradication program was undertaken by
the Florida Livestock Board and the
Agricultural Research Service.
15
1958
A limited outbreak of R. micronlus
apparently was successfully eradicated.
1
1960
The last reported outbreak of Booohilus
microplus re-infestation occurred in
Florida. No ticks of this variety have
been found since 1961.
1


Table A-l
continued
Easting
9.14
9.14
9.14
9.14
9.14
13.71
13.71
13.71
13.71
13.71
13.71
13.71
13.71
13.71
13.71
13.71
13.71
18.28
18.28
18.28
18.28
18.28
18.28
18.28
18.28
18.28
18.28
18.28
18.28
22.85
22.85
Northing
24.36
18.26
12.61
6.1
0
67.06
60.96
54.86
48.76
42.66
36.56
30.46
24.36
18.26
12.61
6.1
0
67.06
60.96
54.86
48.76
4266
36.56
30.46
24.36
18.26
12.61
6.1
0
67.06
60.96
Surface
Elevation
Argillic
Depth
Arsenic
Aluminum
(meters)
(meters)
(mg/kg)
(mg/kg)
1.631
-1.154
7.13
178.7
0.933
-0.973
0.677
-0.950
0.421
-0.871
0.101
-0.769
2.542
-1.411
2.268
-1.411
97.81
1008.8
2.057
-1.372
110.24
446.2
1.932
-1.411
12.19
1008.8
1.932
-1.295
25.77
786.6
1.695
-1.333
1.11
1088.5
1.439
-1.295
1.186
-1.101
2.89
604.4
0.945
-0.946
<0.7
922.5
0.686
-0.907
<0.7
332.1
0.424
-0.907
<0.7
398.8
0.070
-0.635
2.576
-1.384
19.56
770
1.948
-1.430
29.59
535.2
2.045
-1.197
8.28
7298
1.841
-1.384
<0.7
450.8
1.783
-1.523
<0.7
409.9
1.536
-1.174
<0.7
337.6
1.350
-1.081
<0.7
385.5
1.109
-1.104
<0.7
445.8
0.872
-1.174
0.604
-1.244
0.320
-1.174
0.055
-1.057
2.460
-1.407
2.195
-1.430
17.86
691.9


60
Figure 3-2. Map of roads and vats west of Gainesville, FL


B-4. Woodward-Clyde Consultants' arsenic survey map of
Dudley Farm cattle dipping vat site. Arsenic
detected in soil samples 91-122 cm below
surface 253
B-5. Woodward-Clyde Consultants' arsenic survey map of
Dudley Farm cattle dipping vat site. Arsenic
detected in soil samples deeper than 122 cm
below surface 254
B-6. Woodward-Clyde Consultants' arsenic survey map of
Jackson's Gap cattle dipping vat site . 255
B-7. Woodward-Clyde Consultants' arsenic survey map of
Jay Livestock Market cattle dipping vat site.
Arsenic detected in soil samples 0-30 cm
below surface 256
B-8. Woodward-Clyde Consultants' arsenic survey map of
Jay Livestock Market cattle dipping vat site.
Arsenic detected in soil samples 61-76 cm
below surface 257
B-9. Woodward-Clyde Consultants' arsenic survey map of
Lake Arbuckle cattle dipping vat site . 258
B-10. Woodward-Clyde Consultants' arsenic survey map of
Lake Kissimmee cattle dipping vat site . 259
B-ll. Woodward-Clyde Consultants' arsenic survey map of
Myakka River State Preserve cattle dipping
vat site 260
B-12. Woodward-Clyde Consultants' arsenic survey map of
Okaloosa-Walton Community College cattle
dipping vat. Arsenic detected in soil
samples 0-61 cm below surface 261
B13. Woodward-Clyde Consultants' arsenic survey map of
Okaloosa-Walton Community College cattle
dipping vat. Arsenic detected in soil
samples 152-183 cm below surface 262
B-14. Woodward-Clyde Consultants' arsenic survey map of
Okaloosa-Walton Community College cattle
dipping vat. Arsenic detected in soil
samples 274-305 cm below surface 263
B-15. Woodward-Clyde Consultants' arsenic survey map of
Tosohatchee cattle dipping vat site .... 264
xv


0174
<0.7
70
0170
1.14
87.5
0170
0152
0138
0145
1.41
97.8
19.6
0145 0138
0142
0151
0133
0147
CO. 7 <0.7
33.0
110.
29.6
17.9
0130
0130
135
<0.7
22.1
8.28
96
14 6
132
135
<0.7
<0.7
12.2
<0.7
0122
0114
0117
0124
<0.7
7.13
25.8
<0.7
0114
0112
0109
0109
<0.7
<0.7
1.11
0.76
112
100
0103
104
<0.7
<0.7
<0.7 <0.7
0163
4.29
O 92
2.89
0 91
<0.7
O 86
<0.7
Figure 3-6. Argillic horizon depth and associated As
concentrations at the Payne's Prairie Bison Pen vat.
Depth (cm)
Arsenic (ug/g)
(corrected for Al)


173
based on a procedure described by M. Zhou, which entailed a
90 91
modification of the Murphy-Riley colorimetric test. In
general, ten grams of soil were allowed to equilibrate
overnight with 2.0 mL of 50 mM KCL|aq) that contained from 0 to
2000 mg/L of arsenate or phosphate. The soil plus solution
was stored in acid-washed glass scintillation vials in an
incubator maintained at 25C. The following day, the samples
were transferred to plastic centrifuge tubes that had Whatman
#1 filter paper covering six holes drilled in the bottom. A
plastic collection vessel was attached by cellophane tape to
the bottom of the centrifuge tube. After centrifuging at 1500
RPM for five minutes, the soil solution was filtered through
a 0.45 12m membrane filter, by syringe. A 100 mL aliquot was
transferred to a clean, acid-washed glass centrifuge tube and
dried at 70C. After drying, 20 mL of 0.1 M HN03 were added
to dissolve the residue. A half milliliter aliquot of this
solution then was transferred to another acid-washed 35 mL
glass centrifuge tube. Ten mL of Murphy-Riley ascorbic
acid/molybdate reagent was added. The tubes were allowed to
sit at ambient temperature and the color was considered to be
fully developed after two hours. Absorbance of the blur
solution was measured at a wavelength of 880 nmm using a
Spectronic 20 ultraviolet-visible light spectrometer (Bausch
and Lomb, Rochester, NY) The total amount of P or As
absorbed was calculated by: 5= l'Cos CPS~>Where S is the
10
amount of analyte adsorbed (Mg/g soil), Cos is the original


124
Figure 3-38. Topographical map of the Jay Livestock
Market vat site.


109
Figure 3-29. .S.G.S. topographical map of the
Payne's Prairie U.S. 441 vat site.


54
Table 3-1. Operational parameters for metal analysis by flame
or hydride generation.
Perkin-Elmer 2380 Atomic Absorption Spectrometer
Element
Slit Width
Wavelength
Standard Range
(nm)
(nm)
(mg/L)
Arsenic
0.7
193.6
0.002-0.02
Aluminum
0.7
309.3
5-100
Iron
0.2
248.3
0.3-10
Manganese
0.2
279.5
0.1-10


6-3. Extraction of arsenic from Payne's Prairie Bison Pen
vat soil using CHAPS, 3-[(3-cholamidopropyl)-
dimethylammonia]-1-propanesulfonate
(a zwitterionic surfactant) 208
6-4. Extraction of arsenic from Payne's Prairie Bison
Pen vat soil using sodium dodecylsulfate
(an anionic surfactant) with [16-pyrimidinium
crown-4 ]4+ 209
6-5. Comparison of extraction efficiency for the Bt"
horizon of Payne's Prairie vat soil using
sodium dodecylsulfate (NaSDS) with and
without the chelating agent [16-pyrimidinium
crown-4]4+ 213
6-6. Effect of chelate to soil weight ratio on the
extraction of arsenic from Payne's Prairie
Bison Pen Bt horizon soil samples using
30 mM sodium dodecylsulfate 215
6-7. Effect of chelate to soil weight ratio on the
extraction of arsenic from Payne's Prairie
Bison Pen vat E soil samples using
30 mM sodium dodecylsulfate 216
6-8. Timed trial study of chelate/SDS extraction
of arsenic from Payne's Prairie Bison Pen
vat site soil samples 217
A-l. Sampling map for Payne's Prairie Bison Pen
vat site 229
A-2. Sampling map for 10205 S.W. Williston Road
vat site 233
A-3. Sampling map for Dudley Farm vat site 246
B-l. Woodward-Clyde Consultants' arsenic survey map of
Blackwater State Forest cattle dipping
vat site 250
B-2. Woodward-Clyde Consultants' arsenic survey map of
Cecil Webb cattle dipping vat site .... 251
B-3. Woodward-Clyde Consultants' arsenic survey map of
Dudley Farm cattle dipping vat site.
Arsenic detected in soil samples 0-30 cm
below surface 252
xiv


210
with distilled water but not when an excess of counterion was
added" as in this study. In the case of HdtABr extraction for
these contaminated soils (Figure 6-2), one of the counterions
to the cationic surfactant would be the oxyanions of As. In
fact, demarcation of the CMC becomes not so much a single
concentration, but rather a range as the concentration of
counterions increases.104 This implies that, as the soluble
ion concentration increases, any effects that are reliant upon
micelle formation will not be apparent for some surfactants.
The formation of a critical micelle concentration range will
depend not only on the counterions involved, but on the nature
of the surfactant as well. The greater slope shown for
HdtABr, in comparison to the other two surfactant systems, may
be due to such interactions.
This behavior pattern of surfactants is further
exemplified by the series of extractions done on the Bt
horizon soil samples from the Payne's Prairie Bison Vat Site.
The three surfactant systems showed a shift in the slope of
the extraction curve around the critical micelle concentration
when Bt horizon soils were extracted (Figures 6-2, 6-3 and 6-
4). For the E horizon soil samples, the extraction
efficiencies ranged from 35.3% (cationic surfactant) to 43.4%
(zwitterionic surfactant), and finally to 82.7% (chelator and
anionic surfactant) at the initial test ratio of 1 part soil
to ~60 parts solution after the CMC was exceeded. For the Bt
horizon soil samples, which contained a higher clay content,


Table 3-7. Selected characteristics of soils sampled at Williston Road vat site. These soils
were located within the Pottsburg sand and Wauberg sand map units in the Alachua county soil
survey and represent inclusions of similar soils.
Soil
Taxonomic
Class
Depth
(cm)
Horizon
Dominant
Munsell
Color
Particle Size
Distribution (%)
Organic
Matter (%)
PH
Arsenic
(mg As/
kg soil)
Silt
Sand
Clay
Aquod
0-15
Ap
10YR 5/1
0.6
98.0
1.4
0.75
4.8

15-79
E
10YR 6/1
0.7
97.6
1.7
0.18
5.2
1.24
79-113
Bhl
10YR 2.5/2
3.5
94.2
2.3
1.01
5.4
11.8
113-135
Bh2
10YR 3/2
2.9
95.6
1.5
0.84
6.0
12.9
135-147
Bt
10YR 4/2
8.3
84.4
7.3
0.49
6.4
12.4
147-
Btg
10YR 4/1
1.7
82.2
16.1
0.24
7.2

AquaIf
0-30
A1
10YR 2.5/1
8.0
87.8
4.2
3.38
5.9
51.2
30-46
A2
10YR 2.5/2
2.7
95.6
1.7
1.02
6.2
75.1
46-114
Bw
10YR 3/3
3.3
95.6
1.1
0.45
6.4
60.1
114-
Bt
10YR 4/2
2.8
75.0
22.2
0.37
6.4
99.6
a Soil sample was taken 12 meters northeast of vat.
6 Soil sample was taken 68 meters northeast of vat.
oo
o


140
Figure 3-50. Topographical
Refuge vat site.
map
of the St
Marks Wildlife


227
Bl, it was not a commercially available product. Second, the
ratio of surfactant/chelate to soil weight was not the most
favorable. Third, the biodegradability of the macrocycle is
still largely unknown. This latter area is one that needs
further research before commercial feasibility can be
determined.
Other areas that need further study include: 1) locating
and assessing the remaining vat sites (>80 in Alachua County
alone); 2) evaluation of the risk to humans and livestock; and
3) resolution of the guestion of liability should a problem
be found. The task of locating vats alone is immense. This
is particularly true considering the following facts: 1) that
Florida had 3400; 2) that fourteen other states have the same
problem and 3) that other countries, such as Australia and
South Africa, were known to use cattle dipping vats as well.
Overall, resolution of the problems arising from arsenic
contamination via cattle dipping vat waste will not be laid to
rest easily.


224
biological activities, whether by micro- or macro-organisms,
could also influence the transport and movement of As.
A third objective was to elucidate the factors that may
influence As release from a contaminated soil. This study was
done predominantly using column studies. It was found in all
aqueous and oxic conditions that the application of phosphate
anion was more effective at displacing As than either nitrate
or chloride. For eluviated or argillic horizon soil columns,
iron was released prior to or during the elution of arsenic.
This implied that As anion was associated to some extent with
iron compounds. Only in soil columns containing an argillic
horizon or a relatively high organic matter soil was aluminum
observed to be eluted in noticeable amounts. In general, more
As was released under low oxic conditions than under high oxic
conditions for any given soil.
In an attempt to compare binding properties of a surface
soil for arsenate compared to phosphate, log-log isotherms
were constructed. At the concentrations studied, it was
observed that generally less arsenate was sorbed than
phosphate for any given concentration, although it should be
noted that, at the highest concentration of 2000 //g/mL, there
was no significant difference. The implication is that
arsenate binds less tightly to soil (lower amount sorbed) than
phosphate. Since it has already been demonstrated that
phosphate can displace arsenate from soil, this was not wholly
unexpected.


Table 5-1. Selected soil column characteristics.
Soil
Horizon
Depth
(cm)
Soil
Dry
Weight
(g)
Oxic
Level
Moisture
(g H20/g
dry soil)
Inlet
Height
(cm)
Outlet
Height
(cm)
Bulk
Density
(g/cm3)
Porosity11
(cm3/cm3T)
Bison Pen
Millhopper
sand
E
45-60
31.35
High
0.133
37.0
30.5
1.69
0.362
E
45-60
32.63
Low
0.134
26.3
18.2
1.76
0.336
Bt
152-
165
31.25
High
0.150
27.0
15.0
1.62
0.389
Williston
Road
Aqualf
soil
A
15-30
Low
6.0
25.5
Bison Pen
Millhopper
sand
A
0-5
37.31
Low
0.092
1.52
0.141
1) Assumed particle density for these soils = 2.65 g/cm:


270
35. Cherry, J.A., A.U. Shaikh, D.E. Tallman, and R.V.
Nicholson, "Arsenic Species as an Indicator of Redox
Conditions in Groundwater", Journal of Hydrology, 1979,
43, 373.
36. Bohn, H.L., "Arsenic Eh-Ph Diagram and Comparisons to
the Soil Chemistry of Phosphorus", Soil Science, 1976,
121, 125-127.
37. Irgolic, K.J., "Arsenic Chapter 11", In: Hazardous
Metals in the Environment, Stoeppler, M. (ed.), 1992,
12, 287-350.
38. Thomson, W.T., In: Agricultural Chemicals Book I.
Insecticides, Thomson Publications, Fresno, Calif.,
1986, 1, 87-88.
39. Thomson, W.T., In: Agricultural Chemicals Book II.
Herbicides, Thomson Publications, Fresno, Calif., 1986,
2, 185-190.
40. Thomson, W.T., In: Agricultural Chemicals Book IV.
Fungicides, Thomson Publications, Fresno, Calif., 1986,
27-28.
41. Calvert, C.C., "Arsenicals in Animal Feed and Wastes",
In: Arsenical Pesticides, Woolson, E.A. (ed.), ACS Sym
posium Series 7, American Chemical Society, Washington,
D.C., 1975, Chap. 5, 70-80.
42. Hiltbold, A.E., "Behavior of Organoarsenicals in Plants
and Soils", In: Arsenical Pesticides, Woolson, E.A.
(ed.), ACS Symposium Series 7, American Chemical
Society, Washington, D.C., 1975, Chap. 4, 53-69.
43. Goldberg, S. and R.A. Glaubig, "Anion Sorption on a
Calcareous, Montmorillonitic Soil Arsenic", Soil
Science Society of America Journal, 1988, 52, 1297-
1300.
44. Van Zwieten, L. and A.M. Grieve, "Arsenic and DDT
Contaminated Cattle Tick Dipsites a Review of
Remediation Technologies", Wollongbar Agricultural
Institute, Wollongbar NSW, Australia, 1995, 1-102.
45. Masscheleyn, P.H., R.D. Delaune, and W.H. Patrick,
"Effect of Redox Potential and pH on Arsenic Speciation
and Solubility in a Contaminated Soil",
Environmental Science and Technology, 1991, 25, 1414-
1419.


98
Figure 3-22. U.S.G.S. topographical map of the U.F.
Foundation excavated vat site.


Table A-2. -
Easting Northing
40 35
40 40
45 40
50 40
55 40
40 45
45 45
50 45
55 45
40 50
45 50
50 50
55 50
15 55
20 55
25 55
30 55
35 55
40 55
45 55
50 55
55 55
15 60
20 60
25 60
30 60
35 60
40 60
45 60
50 60
55 60
continued
Surface
Elevation
(meters)
1.698
1.448
1.237
1.472
1.576
1.158
1.198
1.362
1.426
1.027
1.152
1.170
1.210
0.972
0.994
0.951
0.927
0.988
0.988
1.109
1.128
0.981
0.792
0.683
0.823
0.671
0.628
0.863
0.930
0.835
0.774
Surface or
Spodic
Horizon
Depth
(meters)
Horizon's Arsenic Concentration (mq/kq)
Field Results Laboratory Analysis
-0.902 6.25
-1.067 1.25
-0.991 6.25
-1.194 2.5
-1.067 2.5
0
1.2
0.74
1.38
-0.483 1.25 0
-0.432 1.25 0
-0.495 0.625 0.69
-0.254 0 0
Surface or Spodic Horizon
Iron (mg/kg)
Aluminum (mg/kg) Manganese (mg/kg)
2330
17700 3
290
3500 2
990
4300 1
980
6400 1
520
3000 3
2800
8100 8
520
1400 5
1030
2800 3
220
600 2
1790
to
3700 5 -C*.


17
As shown in Table 2-1, although certain areas for As
usage are declining, there remains an overall increase in
demand for As. With this increase in usage comes an increase
in the possibility of environmental contamination. Arsenic is
an element that is toxic at high levels and is considered
carcinogenic at low levels.23,24 The toxicity of As is highly
dependent on its chemical formulation. Table 2-2 illustrates
the toxicological variation among selected arsenical compounds
as well as biological half-lives of the various species.24
Since toxicity data are specific to individual organisms, the
animal tested is listed along with the numerical value. It
should be noted that the 50% lethal doses are median values.
One conclusion that can be drawn from Table 2-2 is that there
are no large differences in the toxicology of inorganic
arsenicals. However, methylated As compounds are far less
toxic than inorganic compounds. It has been hypothesized that
the methylation of inorganic arsenic by organisms is a
detoxification mechanism.20 In contrast, studies on the
toxicologic effects of dimethylarsinic acid (DMA) reveal
damage to DNA and indicate mutagenicity.25
Toxicologists and nutritional experts are well aware that
detrimental as well as beneficial effects are caused not by
the "element" itself but by specific compounds incorporating
the element. As illustrated in Table 2-2, As can be
classified both as highly toxic, when in the inorganic form,


206
Results and Discussion
The surfactant extraction experiments were broken into
two stages consisting of a) comparison of concentration versus
extraction efficiency for the three surfactant systems and b)
optimizing the concentration and shaking time of the best
system to maximize extraction efficiency. Initially, effect
of the surfactant concentration on As extraction efficiency
was investigated. Remediation of soil, whether by flushing or
washing procedures, requires knowledge of not only the overall
effectiveness of the extracting solution, but effect of the
critical micelle concentration (CMC) as well. For two out of
three surfactant systems, sand found in the E horizon allowed
for a sharp demarcation at the CMC characteristic for that
particular surfactant (Figures 6-2, 6-3 and 6-4). The
student's t-test yielded a significance of 0.047 for CHAPS
extraction and 0.096 for Crown/SDS extraction between the two
concentrations bordering the CMC. This indicates that there
was a significant difference in the extraction efficiency
which was attributed to the formation of micelles. However,
for the HdtABr extraction, the student's t-test had a markedly
lower significance factor of 0.267. The CMC for HdtABr in
distilled water is reported to be 0.89 mM.96 However, in the
same report, the authors stated that values of the CMCs,
which were only precise for detergents diluted


a?
i iec^
8
UNIVERSITY OF FLORIDA
3 1262 08554 7205


148
In general, the site sampling protocol should include: 1)
prior study of soil survey and topographical maps, 2) on-site
inspection to confirm soil and water conditions, and 3) usage
of the quick field test for arsenic. In this way, evaluation
of the arsenic contamination at cattle dipping vat sites may
be conducted in a more cost- and time-efficient manner.


Table 5-2. Flow rate variations after sequential elution of differential pressure columns.
Eluant
High Oxic
"E" Column
Flow Rate
(mL/hr)
Low Oxic
E" Column
Flow Rate
(mL/hr)
High Oxic
"Bt" Column
Flow Rate
(mL/hr)
Ponded,
Saturated "A"
Column Flow
Rate
(mL/hr)
KC1
0.197 0.095
0.071 0.031
0.052 0.031
0.671 0.084
KN03
0.111 0.075
0.006 0.003
0.006 0.003
0.575 0.047
KH2POfl/K2HPO(
0.083 0.058
0.009 0.006
0.009 0.006
0.158 0.179
a) plus or minus the standard deviation


260
Q&T Ti
i
Sampled 0.5 ft.
(8) Sampled 0.5 and 2.0 ft.
El Arsenic in mg/kg
Zi Temporary Monitoring Well
:
i2ig
iqol
9l-N3d-an
Si-N3d-an
-Cp3-
9l-M3d-*a, i-N3d-ai
iWl
i-N3d-an
l a>
vi-N3d-an
I7T1
u-s3d-an
(TD
0i-N3d-an
'0>
3-Nja-an
'0>
-N3d-an
0>
9-N3o-an
'0>
-N3d-n
4 0>
c-N3d-an
4'0>
2-N3d-dn
I tz
3 I 3
\t-N3d-an
[7D
6-N3d-an
'0>
?-N3d-an
i-N3d-an
Figure B-ll. Woodward-Clyde Consultants' arsenic survey map
of Myakka River State Preserve cattle dipping vat site.


continued
Table A-3. -
Easting
0.00
49.21
16.41
49.21
16.41
32.81
0.00
49.21
16.41
32.81
0.00
49.21
32.81
16.41
0.00
Northing
164.04
180.45
180.45
196.85
196.85
213.25
213.25
229.66
229.66
246.06
246.06
262.47
262.47
262.47
262.47
Arsenic (mg/kg)
0.4
0.2
0
0.4
0.2
0.5
0
0.6
0
0.1
0.1
0.7
1.9
0.4
0
N>
oo


113
the vat. The vat had been constructed using material
apparently garnered from a nearby railway bed. It was filled
with soil and only the tops of two sides could be seen. The
owner of the property gave anecdotal evidence that the vat had
been constructed by black cowboys who worked for one of his
ancestors. The soil survey map (Figure 3-32) depicted this
soil as a Blichton sand and hand-augured soil samples
supported this listing. Soil samples taken 1 m east of the
vat and at a depth of 64 cm contained at least 37.5 mg As/kg
soil. Four meters to the east of the vat only the upper 15
centimeters of soil contained this much As and, at a depth of
50 cm, the As concentration had fallen to 18.7 mg As/kg soil
according to the As field test. A well was located 60
meters away from the vat and reportedly drawing water from 22
meters deep. No As was detected in the water from this well by
the arsenic field test. The topographical map (Figure 3-33)
shows that the vat is located on the slope of a hill. The
zone of As contamination was apparently moving downhill and
parallel to the well.
Reported Vat Sites
A summary of the vat sites reported by state-contracted
consultants4, along with each vat location's county, possible
soil map units and their taxonomic families are given in Table
3-13. Raw data for these sites are given on site maps in
Appendix B.


52
Particle size distribution of the soil samples was
determined using sodium metaphosphate solution to suspend the
clay. An aliquot of the suspension was taken at a prescribed
depth, dried and determined by weighed to measure the amount
of clay. Sand was separated from silt by wet sieving, dried
and determined by weighing. Percent silt in the soil was
determined by difference [100(% sand + % clay)].67
Soils were digested for metal analysis using U.S.E.P.A.
method #3050 or #3051. The former is a HN02/HC1/H202 digestion
on a hot plate, while the latter is a HN03 digestion using
pressurized teflon bombs and a microwave oven as a heating
source. Both methods yield results termed "Total Recoverable
metals, although method #3050 yields slightly higher results
than method #3051.68,69 All reagents were analytical grade and
obtained from Fisher Scientific Supply Co. (Orlando, FL). The
digestion instrumentation for method # 3051 was a CEM MDS-2000
microwave unit.
The digestates were analyzed for aluminum (Al), iron
(Fe) manganese (Mn) and arsenic (As) by one of four methods.
Al, Fe and Mn were either determined by inductively coupled
argon plasma spectrometry (ICAP) or by flame atomic absorption
spectrophotometry. The As was determined by either a cold
vapor hydride method according to instructions supplied by the
Perkin-Elmer Corporation or by graphite furnace as in
U.S.E.P.A. method #SW846-7060.70 The instrumentation used for


50
was located in adjacent Marion County with the owner amenable
to a cursory examination of the vat, which had been filled
with soil. A total of nine vats were investigated at least to
the extent of 1) obtaining latitude and longitude using
global positioning satellite technology, 2) placement on
topographical and soil survey maps and 3) if permitted by the
landowner, selected soil sampling and analysis for As
contamination. Ten other vat sites were investigated by the
Woodward-Clyde consulting firm and the results were reported
to the Florida Department of Environmental Protection.4
The global positioning survey was accomplished using a
Magellan Model GPS 2000 unit (Magellan Systems Corp., San
Diego, CA) Topographical maps were supplied by the U.S.
Geological Survey, Denver, CO. Soil map units, taxonomic
classes, and soil survey maps were obtained from the U.S.D.A.
Natural Resource Conservation Service.53-62 Vat locations were
superimposed on a road map using latitudes and longitudes by
the program ArcView GIS version 3.0".63
Soil samples were selected on the basis of topography
and tested on-site for As. The on-site As soil test was a
modification of water analysis procedure for the EM Quant
Arsenic Test Kit" (EM Science, Gibbstown, NJ) The test was
rapid, though more gualitative than quantitative. The kit came
with zinc dust, 30% HC1 and 100 indicator strips as well as a
graduated color chart to estimate the concentration of As.


182
lower As release by phosphate from this same column was
probably due to there being a finite amount of arsenic
present, with the greater initial release of As lowering the
amount that could be subsequently released by phosphate later.
Overall, the low oxic column released a total of 41.8 g
arsenic (5.9% of the total As available) in comparison to the
high oxic column's release of 14.7 ng arsenic (2.2% of the
total As available).
The third column to be set up was under aerobic and
unsaturated conditions using Bt horizon (152-165 cm depth)
material from the same site as the previous columns. The
total amount of As in this soil horizon was approximately
fifty times greater than for the E" horizon, although the
iron content was lower while aluminum was higher than in the
general soil. However, it should be noted that the "E horizon
came from directly above the argillic horizon and contained
many red concretions which would have elevated the iron
concentration. There was little As leached from the column
when 50 mM potassium chloride or potassium nitrate solutions
were used (Figure 5-6). Once again, the introduction of the
phosphate anion caused a massive release of arsenic and iron
from the soil. Total As eluted from this column was 1320 iuq,
which was 76.8% of the As in the soil. It was interesting
that release of iron occurred with potassium chloride elution
even though little As was eluted with it. Another facet of
interest was that the elution of iron after phosphate


199
surfactant system, cost of the surfactants, and chelating
agents (if used) and the biodegradability of the reagents,
particularly for in situ remediation efforts. A further
consideration for in situ remediation is delivery of the
surfactant mixture to the contaminant. If the soil has a
high clay content or has low permeability due to other
factors, then the ex situ soil washing procedure may be more
efficient than an in situ soil flushing method. Soil flushing
may also be made impractical by virtue of the surfactant's
biodegradability. If the solutions are not at all inhibitory,
then the soil flushing reagents may serve as a nutrient source
for microorganisms that produce polysaccharides, which could
plug soil pores so that the contaminant cannot be reached
and/or recovered."
The scope of this dissertation does not cover all aspects
of soil flushing or washing to remediate soil contaminated
with As. In fact, the emphasis in this section has been
placed solely on the extraction of As from contaminated soil
by surfactants. For contrast, a cationic surfactant called
hexadecyltrimethylammonium bromide (HdtABr) and a zwitterionic
surfactant named 3-[3-cholamidopropyl)-dimethylammonia]-1-
propane sulfonate (CHAPS) were used to extract As from soil
(Figures 6-la and b). Since As in soil is predominantly a
negatively charged species, the cationic surfactant should
bind to it easily through ionic interactions. If the
concentration of the surfactant is above the critical micelle


27
Table 2-4. Different systems describing electronegativities
(E.N.) of selected elements.3
Element
Pauling
Sanderson
Allred-
Rochow
Mi 1liken-Jaffea
E.N.
E.N.
E.N.
E.N.
Orbital
or
Hybrid
As
2.18
2.53
2.20
1.59
sp
2.58
SP3
C
2.55
2.47
2.50
1.75
P
2.48
sp3
2.75
sp2
3.29
sp
0
3.44
3.46
3.50
3.04
p
4.63
20%s
4.93
sp3
5.54
SP3
s
2.58
2.66
2.44
2.28
p
3.21
SP3
H
2.20
2.31
2.20
2.21
s
a) Electronegativities adjusted to Pauling's scale for
comparison purposes.


38
titrating with iodine until the starch indicator changed
color.50 Knowing the amount of arsenite in the dip was
extremely important in light of the fact that it is more toxic
to cattle than arsenate.
Conversely, the concentration of arsenite may be
increased, rather than decreased, in the dipping vats by
evaporation or by biotic reduction of arsenate. The influence
of bacterial reduction of arsenate in cattle dipping fluids
was described in 1915 as a development that occurred after the
rapid growth of oxidizing bacteria, but only if dipping was
done in sufficient amounts and over short intervals. It was
conjectured that the bath became so rich in nutrients that it
finally formed a favorable medium for the growth of reducing
organisms, which could flourish and counteract the action of
oxidizing microorganisms. It was hypothesized that the
oxidizing organisms worked slowly, but steadily; whereas the
reducing organisms worked sporadically, briefly, and only
during sufficiently rich nutrient conditions.49 Although
there seems to be no literature reporting the isolation of
such a reducing bacterium from cattle dipping fluids, an
anaerobic (also microaerophilic) bacteria has been isolated
from a freshwater marsh sediment that is capable of using As
(V) as an electron acceptor and lactate as the electron
donor.51 This particular strain showed a time lag before
growth was evident that was dependent on the amount of 0;,
present. Oxygen at 1, 3 and 5% induced a lag time of 40


46
drawback is the need to remediate large volumes of
contaminated liquid resulting from the bioleaching process.
Volati]ination. This remediation method occurs naturally
in situ. It may also be carried out in a prepared bed or in
tank. Volatilization of As can be mediated by bacteria,
algae, actinomycetes or fungi or by a mixture of organisms.
This technique exhibits all of the drawbacks exemplified by
the bioleaching process, except that the large volume of
contaminated liquid is replaced by a large volume of highly
toxic gas.
Bioaccumulation and Biosorption. This technique involves
the sorption of As onto microbial biomass or direct
accumulation of As within soil microorganisms. The
remediation may occur in situ, in-tank or in prepared beds.
Drawbacks include soil composition, pH, nutrient requirements,
microbial competition, and bioavailability of the contaminant.
Additional problems arise in regards to biosorption stability
and subsequent separation of bioaccumulated As.


43
system at one or both electrodes. Charged contaminants in
such a system cause water movement to the oppositely charged
electrode. The moving water also carries non-charged
contaminants, usually to the cathode. Drawbacks include a
strong dependence on soil composition and moisture content as
well as limits on the amount of electric charge and the length
of time required to complete the process.
Particle Size Separation. With this method, size
separation is carried out by gravity via an in-tank method.
It requires that the contaminants, such as arsenic, are
associated with the finest soil particles. Drawbacks include
the complexity of the operation and problems with subsequently
treating the fine particles.
Rotary Kiln. This is an in-tank process that is
successful in volume reduction and detoxification.
Disadvantages are that it produces fly ash, a highly
particulate emission that can be as toxic, or more so, than
the original material. It also is limited to small particles
and thus usually needs to have prior size reduction done on
the contaminated material.
Pvrolvsis. This is an in-tank process that is utilized
for volume reduction and detoxification of contaminated soil
that cannot undergo regular incineration in a rotary kiln.
The principal disadvantage is that it can only handle small
quantities at a time.


226
conclusive. One possible explanation is that the post-reactor
soil columns had failed to maintain biotic viability. It was
also found that low oxic conditions for the Fusarium liquid
medium tended to produce more gaseous As than high oxic
conditions. The appearance of a floating fungal mat under low
oxic conditions was postulated as the reason for the lower
conversion of gaseous As to other non-volatile species.
Although volatilization is one method of removing As from
soil, it must be considered a rather hazardous means of
remediation, considering the toxicity of the compounds
generated. A safer method of removing As from soil is by
direct chemical extraction. Several surfactant studies were
initiated to determine the feasibility of removing As from
soil by this procedure.
It was found that 100% of the arsenic in argillic or
eluviated soil horizon samples could be removed by an anionic
surfactant, sodium dodecylsulfate, after complexation of the
arsenic with highly-charged macrocycle cation, [16-
pyrimidinium crown-4]4+. Far less effective were the cationic
surfactant, hexadecyltrimethylammonium bromide, and the
zwitterionic surfactant, 3-[(3-cholamidopropy1)-
dimethylammonia]-l- propane sulfate. It should be noted that
there are potential problems with using the
surfactant/chelator system for remediating soils. The first
potential problem was the cost effectiveness of this method.
Although the macrocycle chelator was synthesized from vitamin


Log P or As Sorbed (ug/g soil)
193
Figure 5-11. Phosphate and arsenate log-log isotherms
for Payne's Prairie Bison Pen vat "A" soil (0-5 cm depth).


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
DISTRIBUTION, MOVEMENT, AND EXTRACTION
OF ARSENIC
IN SELECTED FLORIDA SOILS
By
John E. Thomas
May 1998
Chairperson: R. Dean Rhue
Major Department: Soil and Water Science
Arsenic (As), as a soil contaminant in Florida, can often
be traced to the extensive use of cattle dipping vats to
eradicate ticks. These vats held 5700 liters of arsenical
solution, which was to be disposed of on-site yearly. With
over 3400 sites in Florida, this represented a pervasive
anthropogenic introduction of a potentially toxic contaminant.
Of these 3400 vats, ninety-four were located in Alachua
County, Florida. Out of nine sites studied, the maximum soil
As concentrations at three selected sites ranged from 100 to
767 mg/kg. The differences in As concentrations at these
sites were attributed to a number of factors including
variations in soil, hydrology, and vat history.
xvii


174
concentration (g/mL) of analyte, and Cps is analyte
concentration (g/mL) in the pore solution after twenty-four
hours of equilibration with the soil.
Results and Discussion
Differential Pressure Column Studies
The differential pressure column studies were all
performed using soil that had been contaminated with As and
then weathered for more than thirty years since the last
application of cattle dipping vat solution. Leaching of the
columns was accomplished by sequential applications with
potassium salt solutions of chloride, nitrate, and phosphate.
All three anions are commonly found in commercial fertilizers
in varying amounts. The effect of these anions, as well as
the effect of Eh and pH, on As adsorption and/or desorption
for soils have been the subject of several
studies. '''' The previous investigations were batch
adsorption and/or desorption experiments however, and did not
involve column leaching. Another common feature was the lack
of care to insure biotic viability. Often the soil had been
previously air-dried and stored at room temperature. In the
column studies presented in this section, the soil was handled
so that microbial activity would remain relatively
uninhibited.
The first differential pressure column study involved
the E horizon (45-60 cm depth) from the Bison Pen vat site


CHAPTER 4
BIOLOGICAL VOLATILIZATION OF ARSENIC
Introduction
The transport of As in soils contaminated by the dumping
of waste from cattle dipping vats is highly dependent not only
on the structure and composition of the soil, but also on the
species of As present. One of the determinants of As form is
biological. The biotic influence can be manifested as
reduction, oxidation, or transformation of As. It has been
hypothesized that these actions have evolved as attempts to
negate the toxicity of As. Arsenic may be transformed to a
more mobile ionic species, such as the reduction of arsenate
to arsenite, to facilitate its removal from the immediate
environment. Conversely, oxidation may also be considered a
protective mechanism since arsenate is less toxic than
arsenite. Transformation of As into a less hazardous compound
such as arsenobetaine can occur, as well as the conversion of
As into gaseous arsine.20
One redistribution mechanism is by volatilization.
According to Sandberg and Allen77, as much as 35% of the As
species in soil may be eventually volatilized as arsine,
dimethylarsine, and trimethylarsine. Production of volatile
149


Uft rTJ
si
264
TSR-SEN-2 TSa-aEN-2 73?-a£h-4
oil t] ai
*S?-PEN-5 TSP-3N-5 T3R_=rN-7 TSP-PEN-
dtl di Qd] £]
:=_arN_g 5n-=N-lC TSP-?vM-n -3P-3EN-12
Si g3d zti Gti
j]
5-=cn--. -sa-=;n-:5
(D dS)
'3=-3iS-
sS
'S=-3EN-' 'SS-=n-'2
0 %m
Figure B-15. Woodward-Clyde Consultants' arsenic survey map
of Tosohatchee cattle dipping vat site.