Group Title: Bulletin - University of Florida. Agricultural Experiment Station ; 290
Title: A study of some trace elements in fertilizer materials
CITATION THUMBNAILS PAGE IMAGE ZOOMABLE
Full Citation
STANDARD VIEW MARC VIEW
Permanent Link: http://ufdc.ufl.edu/UF00026393/00001
 Material Information
Title: A study of some trace elements in fertilizer materials
Series Title: Bulletin University of Florida. Agricultural Experiment Station
Physical Description: 15 p. : ; 23 cm.
Language: English
Creator: Gaddum, L. W ( Leonard William ), b. 1890
Rogers, L. H ( Lewis Henry ), 1910-
Publisher: University of Florida Agricultural Experiment Station
Place of Publication: Gainesville Fla
Publication Date: 1936
 Subjects
Subject: Fertilizers -- Analysis   ( lcsh )
Genre: government publication (state, provincial, terriorial, dependent)   ( marcgt )
bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Bibliography: Bibliography: p. 15.
Statement of Responsibility: by L.W. Gaddum and L.H. Rogers.
General Note: Cover title.
 Record Information
Bibliographic ID: UF00026393
Volume ID: VID00001
Source Institution: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: aleph - 000924368
oclc - 18210172
notis - AEN4986
 Related Items
Other version: Alternate version (PALMM)
PALMM Version

Full Text





HISTORIC NOTE


The publications in this collection do
not reflect current scientific knowledge
or recommendations. These texts
represent the historic publishing
record of the Institute for Food and
Agricultural Sciences and should be
used only to trace the historic work of
the Institute and its staff. Current IFAS
research may be found on the
Electronic Data Information Source
(EDIS)

site maintained by the Florida
Cooperative Extension Service.






Copyright 2005, Board of Trustees, University
of Florida






February, 1936


UNIVERSITY OF FLORIDA
AGRICULTURAL EXPERIMENT STATION
GAINESVILLE, FLORIDA
WILMON NEWEL, Director








A STUDY OF SOME TRACE ELEMENTS

IN FERTILIZER MATERIALS



By

L. W. GADDUM and L. H. ROGERS


TECHNICAL BULLETIN








Bulletins will be sent free to Florida residents upon application to
AGRICULTURAL EXPERIMENT STATION
GAINESVILLE, FLORIDA


Bulletin 290








EXECUTIVE STAFF

John J. Tigert, M.A., LL.D., President of the
University
Wilmon Newell, D.Sc., Director
H. Harold Hume, M.S., Asst. Dir., Research
Harold Mowry, M.S.A., Asst. Dir., Adm.
J. Francis Cooper, M.S.A., Editor
Jefferson Thomas, Assistant Editor
Clyde Beale, A.B.J., Assistant Editor
Ida Keeling Cresap, Librarian
Ruby Newhall, Administrative Manager
K. H. Graham, Business Manager
Rachel McQuarrie, Accountant

MAIN STATION, GAINESVILLE

AGRONOMY
W. E. Stokes, M.S., Agronomist**
W. A. Leukel, Ph.D., Agronomist
G. E. Ritchey, M.S.A., Associate*
Fred H. Hull, Ph.D., Associate
W. A. Carver, Ph.D., Associate
John P. Camp, M.S., Assistant
ANIMAL HUSBANDRY
A. L. Shealy, D.V.M., Animal Husbandman*
R.' B. Becker, Ph.D., Dairy Husbandman
W. M. Neal, Ph.D., Asso. in An. Nutrition
D. A. Sanders, D.V.M., Veterinarian
M. W. Emmel, D.V.M., Asst. Veterinarian
N. R. Mehrhof, M.Agr., Poultry Husbandman
W. W. Henley, B.S.A., Asst. An. Husbandman
Bradford Knapp, Jr., M.S., Asst. An. Hush.
P. T. Dix Arnold, B.S.A., Assistant Dairy
Husbandman
L. L. Rusoff, M.S, Laboratory Assistant
Jeanette Shaw, M.S., Laboratory Technician
CHEMISTRY AND SOILS
R. W. Ruprecht, Ph.D., Chemist**
R. M. Barnette, Ph.D., Chemist
C. E. Bell, Ph.D., Associate
R. B. French, Ph.D., Associate
H. W. Winsor, B.S.A., Assistant
ECONOMICS, AGRICULTURAL
C. V. Noble, Ph.D., Agricultural Economist*
Bruce McKinley, A.B., B.S.A., Associate
Zach Savage, M.S.A., Associate
A. H. Spurlock, M.S.A., Assistant
ECONOMICS, HOME
Ouida Davis Abbott, Ph.D., Specialist**
C. F. Ahmann, Ph.D., Physiologist
ENTOMOLOGY
J. R. Watson, A.M., Entomologist**
A. N. Tissot, Ph.D., Associate
H. E. Bratley, M.S.A., Assistant
HORTICULTURE
A. F. Camp, Ph.D., Horticulturist"5
G. H. Blackmon, M.S.A., Horticulturist and
Associate Head of Department
A. L. Stahl, Ph.D., Associate
F. S. Jamison, Ph.D., Truck Horticulturist
R. J. Wilmot, M.S.A., Specialist, Fumigation
Research
R. D. Dickey, B.S.A., Assistant Horticulturist
PLANT PATHOLOGY
W. B. Tisdale, Ph.D., Plant Pathologist**
George F. Weber, Ph.D., Plant Pathologist
R. K. Voorhees, M.S., Assistant***
Erdman West, M.S., Mycologist
Lillian E. Arnold, M.S., Assistant Botanist
Stacy O. Hawkins, M.A., Assistant Plant
Pathologist
SPECTROGRAPHIC LABORATORY
L. W. Gaddum, Ph.D., Biochemist
L. H. Rogers, M.A., Spectroscopic Analyst


BOARD OF CONTROL
Geo. H. Baldwin, Chairman, Jacksonville
A. H. Blanding, Bartow
A. H. Wagg, West Palm Beach
Oliver J. Semmes, Pensacola
Harry C. Duncan, Tavares
J. T. Diamond, Secretary, Tallahassee

BRANCH STATIONS
NORTH FLORIDA STATION, QUINCY
L. O. Gratz, Ph.D., Plant Pathologist in
Charge
R. R. Kincaid, Ph.D., Asso. Plant Pathologist
J. D. Warner, M.S., Agronomist
Jesse Reeves, Farm Superintendent
CITRUS STATION, LAKE ALFRED
A. F. Camp, Ph.D., Horticulturist in Charge
John H. Jefferies, Superintendent
W. A. Kuntz, A.M., Assoc. Plant Pathologist
B. R. Fudge, Ph.D., Associate Chemist
W. L. Thompson, B.S., Asst. Entomologist
EVERGLADES STATION, BELLE GLADE
A. Daane, Ph.D., Agronomist in Charge
R. N. Lobdell, M.S., Entomologist
F. D. Stevens, B.S., Sugarcane Agronomist
Thomas Bregger, Ph.D., Sugarcane Physiologist
G. R. Townsend, Ph.D., Assistant Plant
Pathologist
J. R. Neller, Ph.D., Biochemist
R. W. Kidder, B.S., Assistant Animal
Husbandman
Ross E. Robertson, B.S., Assistant Chemist
B. S. Clayton, B.S.C.E., Drainage Engineer*
SUB-TROPICAL STATION, HOMESTEAD
H. S. Wolfe, Ph.D., Horticulturist in Charge
W. M. Fifield, M.S., Asst. Horticulturist
Geo. D. Ruehle, Ph.D., Associate Plant
Pathologist
W. CENTRAL FLA. STA., BROOKSVILLE
W. F. Ward, M.S.A.. Asst. An. Husbandman
in Charge*

FIELD STATIONS
Leesburg
M. N. Walker, Ph.D., Plant Pathologist In
Charge
W. B. Shippy, Ph.D,. Asso. Plant Pathologist
K. W. Loucks, M.S., Asst. Plant Pathologist
J. W. Wiljon, Ph.D., Associate Entomologist
Plant City
A. N. Brooks, Ph.D., Plant Pathologist
Cocoa
A. S. Rhoads, Ph.D., Plant Pathologist
Hastings
A. H. Eddins, PF.D., Plant Pathologist
Monticello
G. B. Fairchild, M.S.. Asst. Entomologist***
Bradenton
David G. Kelbert, Asst. Plant Pathologist
C. C. Goff, M.S., Assistant Entomologist
Sanford
E. R. Purvis, Ph.D., Assistant Chemist,
Celery Investigations
Lakeland
E. S. Ellison, Ph.D., Meteorologist*
B. H. Moore, A.B., Asst. Meteorologist*
W. O. Johnson, B.A., Asst. Meteorologist*
R. T. Sherouse, Asst. Meteorologist*
M. L. Blanc, Asst. Meteorologist*
*In cooperation with U.S.D.A.
** Head of Department.
*** On leave.








A STUDY OF SOME TRACE ELEMENTS
IN FERTILIZER MATERIALS

L. W. GADDUM and L. H. ROGERS

INTRODUCTION
In recent years, agricultural science has come to realize the
importance of the trace elements1 in their relation to plant and
animal nutrition. This realization has arisen from observations
of agricultural workers that certain elements (thallium, seleni-
um, arsenic, and others) produced toxic responses in plants when
applied in comparatively small amounts to the soil, while others
(boron, copper, manganese, zinc, and others) stimulated plant
growth. Indeed, the use of some of these elements has, under
certain conditions, become recommended fertilizer practise.
While emphasis has been placed on the favorable responses ob-
tained by the use of boron, copper, manganese and zinc, there
has been no intention to exclude others from the list of import-
ant trace elements. At this station, the studies on the effects
of these elements (1), (7), (3), (5), (2),2 have suggested that
a more complete knowledge of the composition of soils, plants,
animals and fertilizers might be of some help in attacking prob-
lems of plant and animal nutrition.
In certain cases the analysis of soils, plant and animal tissues,
and fertilizers by chemical methods, however, presents some
difficulty. When the element is present in extremely small pro-
portions, the chemical separations usually necessary for the
identification and estimation frequently involve possibilities
either of contamination from the reagents and apparatus em-
ployed or loss of the element during the course of the procedure.
The fact that the separation of calcium, barium and strontium
is not easy (4), (8), (10) is well known to the analytical chem-
ist; in fact, spectroscopic check of the efficiency of separation
is sometimes recommended (10). Moreover, since the procedures
1 In this study the term "trace elements" is used to denote those elements
found in small concentrations in plant and animal tissues. These elements
have been given various designations such as "rarer", "minor" and "less-
common" elements, "secondary plant nutrients" and so forth. As pointed
out by Young (12) none of these designations is satisfactory. Since the
only characteristic common to these elements, and not shared by other
elements, is their importance in small concentrations, their definition should
express this fact.
2 Figures in parentheses (Italic) refer to Literature Cited in the back
of this bulletin.






Florida Agricultural Experiment Station


involved in the microchemical methods are often time-consum-
ing, the cost of labor becomes an important factor.
In recent years, however, the field of spectrography has been
extended to include quantitative work, thus providing agricul-
tural science with a very sensitive method of analysis supple-
mentary to microchemical methods. Accordingly, for a study
of the trace elements in agricultural materials spectrographic
methods seemed to be indicated.
This bulletin deals with the results of a spectrographic study
of certain fertilizer materials and is preliminary to a more com-
plete study of soils, plant tissues and fertilizers.3

EXPERIMENTAL METHODS AND PROCEDURES
The experimental procedure was designed to permit a com-
parison of the materials with respect to proportions of certain
elements present in magnitudes detectable by spectrography on
the original sample. The elements chosen for first study were
those which either are already deemed important because of
their action on plant growth through soil or spray (boron, cop-
per, manganese, zinc, antimony, arsenic, lead) or might later
acquire importance because of their occurrence in plant ashes
analyzed in this laboratory (frequent in the case of barium,
strontium, chromium and titanium; occasionally in the case of
nickel, cobalt, vanadium, silver and tin).
In this work, no effort was made to increase the proportions
of the elements in the samples by precipitation or other chem-
ical methods. By concentration methods, it probably would
have been possible to detect the presence of some elements which
are reported as "not detected"; this procedure, however, might
have given rise to erroneous impressions, since the concentration
procedure does not alter the fact that the element might have
been "undetectable" by the spectrograph on the original sample.
The mere presence of a given element in very minute quantities
is, of course, interesting but some notion of its proportion in
the sample is more important practically. Accordingly, it seemed
best to base this study on proportions of the elements detectable
spectrographically in the original sample.
The sample as received at the laboratory (usually about one
pound of material) was dried at 1100 C.; the dried sample was
then well pulverized and homogenized. A 5- to 10-gram portion
8 The work was financed in part by the Florida Agricultural Research
Institute; Mr. Frank L. Holland, director, assisted in the collection of
samples.






Trace Elements in Fertilizer Materials.


of this material was further pulverized and homogenized. Par-
ticular care was taken to insure homogeneity since non-uniform-
ity of the material would seriously affect the results when small
aliquots (about 20 mg.) are being used for the analysis. The
organic materials were ashed at 4500 C., the temperature being
measured by means of a pyrometer (at this temperature, zinc
is not volatilized (9) but there may be a loss of arsenic and
antimony). This ash was then pulverized and homogenized as
above.
A 20 mg. aliquot of the homogenized material was volatilized
in a 220 volt are using a current of 9 to 10 amperes. Specially
purified graphite was used as electrodes; repeated spectra of
the graphite electrodes were made to insure a control of elec-
trode impurities. In taking the spectrum of the sample, the arc
was maintained until the sample was completely volatilized.
Incomplete volatilization would permit fractionation, involving
a possible retention of the higher boiling elements in the residue.
This might vitiate estimates of the amounts of the elements
present.
A Littrow spectrograph with linear dispersion of about 30
inches between 2250 A. and 5500 A. was used. Two prisms were
used with this instrument-a glass prism for lines of wave length
greater than 3800 A. and a quartz prism for the shorter wave
lengths. To make use of the sensitiveness of the 2138 A. zinc
line, a quartz Cornu type spectrograph with linear dispersion
of about nine inches between 2100 A. and 8000 A. was used for
the zinc determinations.
A mixture of the 23 elements included in the analysis was
used as a wave length standard, by means of which the lines
in the spectra of the samples were identified.
Spectra of mixtures containing varying proportions of the
elements served as standards with which the density of the lines
in the spectra of the samples could be compared. These density
comparisons served as an index to the proportion of the elements
present in the sample.
The data thus obtained are not intended as precision deter-
minations, but are indicative of the "order of magnitude" of the
proportions of the elements present. To avoid misunderstand-
ing as to precision, and also to retain a legitimate basis for com-
parison, the data are presented in "range" form. (For example:
.01-.05 recorded in the table should be read: The proportion of
the element in the sample lies between .01% and .05%.)








TABLE 1.-SOME MINERAL CONSTITUENTS OF FERTILIZER AND SOIL AMENDMENT MATERIALS.
ISample Stron- I Manga- Vana- Titani- I I I I Chromi- B
No. Bar tium Nickel Cobalt nese dium Ium Silver Copper Tin I Zinc Lead um Boron
Liming Materials
Calcium magnesium carbonate--(Fla.).. 502 .005-.01 .05-.1 N.D. N.D. .05-.1 N.D. .005-.01 N.D. .005-.01 N.D. N.D. N.D. .003-.008 .05-.1
Calcium magnesium earbonate-(Tenn.) 503 .01-.05 .05-.1 .005-.01 N.D. .1-.5 N.D. .01-.05 N.D. .01-.05 N.D. TR TR .001-.005 .05-.1
Calcium magnesium hydrate...................... 504 .01-.05 .05-.1 N.D. N.D. .05-.1 N.D. TR N.D. .005-.01 N.D. N.D. N.D. TR .05-.1
Calcium sulfate (gypsum) ........................ (a)** 505 .05-.1 .1-.5 N.D. N.D. .005-.01 TR .03-.08 N.D. .005-.01 N.D. N.D. TR .001-.005 TR
Calcium silicate .......... 506 .05-.1 .1-.5 .008-.03, N.D. .1-.5 TR .01-.05 N.D. .005-.01 N.D. TR .005-.01 .008-.03 .08-.3
Calcium hydrate ...................................... 508 .01-.05 .1-.5 N.D. N.D. .05-.1 TR TR N.D. .003-.008 N.D. N.D. N.D. .003-.008 .01-.05
Calcium carbonate (Florida limestone).. 509 .01-.05 .1-.5 N.D. N.D. .05-.1 .005-.01 TR N.D. .003-.008 N.D. N.D. N.D. .003-.008 .01-.05
Dolomitic limestone ............ .......... 895 .01-.05 .01-.05 N.D. N.D. .05-.1 N.D. .01-.05 N.D. 1.005-.01 N.D. .01-.05 N.D. TR .01-.05
Hardwood ashes* ....................................... (b) 536 1%+ 1%+- .01-.05 .001-.005 1%+ TR .1-.5 N.D. .1-.5 .01-.05 ? .05-.1 .005-.01 .1-.5
Phosphatic Materials
Dicalcium phosphate .............................. 1027 .05-.1 .05-.1 N.D. N.D. .1-.5 .008-.03 N.D. TR .05-.1 N.D. .1-.5 TR .005-.01 .01-.05
Superphosphate ......................................... 521B .05-.1 .1-.5 TR N.D. .1-.5 .01-.05 .005-.01 TR .05-.1 N.D. .1-.5 N.D. .008-.03 TR
Triple superphosphate .............................. 522 .01-.05 .1-.5 .01-.05 .001-.005 .1-.5 .01-.05 .01-.05 .001-005 .1-.5 .005-.01 TR .005-.01 .01-.05 .05-.1
Soft phosphate ................................ .... (a) 523 .05-.1 .1-.5 .008-.03 TR .05-.1 .008-.03 .01-.05 TR .01-.05 N.D. ? .003-.008 .008-.03 .05-.1
Colloidal phosphate .................................... 524 .1-.5 1%+ .01-.05 .001005 .1-.5 .01-.05 .1-.5 .001-005 .01-.05 TR ? .01-.05 .05-.1 .1-.5
Ammo-phos 16-20-0 ........................... 893 .01-.05 .05-.1 .05-.1 TR .05-.1 .01-.05 .005-.01 N.D. .05-1 N.D. .005-.01 .03-08 .005-01 .1-.5
Ammo-phos 11-48-0 ._................................ 894 .05-.1 .1-.5 .008-.03 TR .08-.3 .1-.5 .005-.01 N.D. .01-.05 N.D. .05-.1 .03-.08 .01-.05 .1-.5
Ground pebble float .................................... 500 .05-.1 .1-.5 .01-.05 N.D. .1-.5 .008-.03 .05-.1 .05-.01 .01-.05 N.D. 7 .01-.05 .008-.03 .1-.5
Bone meal (raw)* ......................7 .05-.1 .08-.3 N.D. N.D. .03-.08 N.D. .00803 N.D. .008-03 N.D. .03-.08 .0-.01 001-.005 .03-.08
Bone meal (steamed) ........ ....... (b) 538A .03-.08 .03-.08 N.D. N.D. .008.03 N.D. .008-.03 N.D. .008-03 TR .005-.01 .0-.08 TR TR
Bone meal (steamed)* ...................... 886 .05-.1 .05-.1 N.D. N.D. .008-.03 N.D. N.D. N.D. .008-.03 N.D. .008-.03 .0.008 008 TR N.D.
Potash Sources
Sulfate of potash.............................................. 511 .005-.01 .1-. N.D. N.D. .005-.01 N.D. ND. N.D .01.05 ND. N.D. N.D. N.D. N.D.
Nitrate of Soda No. 1 and potash........................ 515 .05-.1 .01-.05 N.D. N.D. N.D. N.D. N.D. N.D. .001-.005 N.D. N.D. N.D. TR .1-.5
Carbonate of potash....................... ..... 525 .05-.1 .1-.5 .005-.01 .001-.005 1% N.D. .005-.01 N.D. .1-.5 N.D. N.D. .0 008 .05-.1
German nitrate of potash.............. ............ 526 TR .1-.5 N.D. N.D. TR N.D. N.D. N.D. TR N.D. N.D. N.D. TR N.D.
Hydrated carbonate of potash....................... 882 TR N.D. N.D. N.D. ? N.D. N.D. N.D. TR .05-.1 N.D. N.D. N.D. N.D.
Kainit......................... ........................................ 517 .005-.01 1%+ N.D. N.D. .005-.01 N.D. .01-.05 N.D. .001-.005 N.D. N.D. N.D. TR T
Kainit 20% ....................................... ..... .... 518 .01-.05 1%+ N.D. N.D. .01-.05 TR .05-.1 N.D. .001-.005 N.D. N.D. N.D. .001-.005 .05-.1
Inorganic Nitrogen Sources
Nitrate of soda No. 2 ............................. 513 T .01-.05 N.D. N.D. .005-.01 N.D. ND. N.D. .001-.005 N.D. N.D. N.D. N.D. N.D.
Nitrate of soda No. 1 ............................ 516 .01-.05 .01-.05 N.D. N.D. N.D. N.D. N.D. N.D. .001-.005 N.D. N.D. N.D. TR .05-.1
Sulfate of ammonia from source 1........ (a) 514 TR N.D. N.D. N.D. .005-.01 N.D. N.D. N.D. .05-.1 TR .01-.05 TR N.D. N.D.
Sulfate of ammonia from source 2..-... 877 TR N.D. N.D. N.D. N.D. N.D. N.D. N.D. .005-.01 N.D. TR N.D. TR N.D.
Sulfate of ammonia from source 3....... 884 .005-01 N.D. N.D. N.D. .005-.01 N.D. N.D. N.D. .01-.05 N.D. .05-1 .008-.03 TR N.D.
Sulfate of ammonia from source 4 ....... 885 .005-.01 N.D. N.D. N.D. N.D. N.D. N.D. N.D. .001-.005 N.D. TR TR TR N.D.
Cal-nitro 16% ........... ............... 887 01-05 .1 001-.005 N.D. .1-.5 TR .01-.05 N.D. .005-.01 .05-.1 .01-.05 .01-.05 .001-.005 T
Ammo-phos 16-20-0 ....................... (b) 893 .01-.05 .05-.1 .05-.1 TR .05-.1 .01-.05 .005-.01 N.D. .05-.1 N.D. .005-.01 .0-.08 .005-.01 .1-.
Ammo-phos 11-48-0 .................................... 894 .05-.1 .1-.5 .008-.03 TR .08-.3 .1-.5 .005-.01 N.D. .01-.05 N.D. .05-.1 .03-.08 .01-.05 .1-.5










TABLE 1.-SOME MINERAL CONSTITUENTS OF FERTILIZER AND SOIL AMENDMENT MATERIALS.-Continued.

Sample| I Stron- i C Manga- Vana- Titani- I | I Z IChromi-
SNo. Barium I tium Nickel I Cobalt nese I dium um Silver I Copper Tin | Zinc I Lead um I Boron


Insoluble Organic Nitrogen Sources
Ground tobacco stems (foreign)*........................ 531
Ground tobacco (foreign)*........ .... .. 532
Tobacco stems*............................................. 889
Cottonseed meal* ................................. ....... 534
Castor pomace*....................................................... 540
Fish scrap (foreign)*........................................... 527
Fish scrap*................ .... ................ ....... 891
Dried blood* .................................. ... 53
High grade tankage (blood and bone)*.............. 530
South American bird guano*........................... 533
Goat manure*..... ............................ 1023
Milorganite* ......................................... ... 1024


.01-.05
.01-.05
.03-.08
.001-.0051
.003-.008
.008-.03
.005-.01
.001-.005
.01-.05
.01-.05
.05-.1
.01-.05


.05-.1
.05-.1
.03-.08
TR
.001-.005
.01-.05
.03-.08
.005-.01
.01-.05
.03-.08
.05-.1
.008-.03


.001-.005
.001-.005
TR
TR
.001-.005
TR
N.D.
TR
N.D.
N.D.
TR
.01-.05


.05-.1 TR .05-.1
.05-.1 TR .05-.1
.08-.3 .008-.03 .01-.05
.003-.008 N.D. N.D.
.003-.008 N.D. .001-.005
.01-.05 TR .005-.01
.01-.05 TR TR
.001-.005 N.D. TR
.01-.05 N.D. .005-.01
.03-.08 N.D. .008-.03
.08-.3 008-.03 .3-.8
.05-.1 .001-005 .1-.5


N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
TR
TR
N.D.
N.D.
N.D.
.01-.05


.01-.05
.01-.05
.01-.05
.008-.03
.008-.03
.008-.03
.01-.05
.001-.005
.01-.05
.01-.05
.01-.05
.01-.05


N.D.
N.D.
N.D.
TR
N.D.
N.D.
.03-.08
TR
N.D.
N.D.
N.D.
.01-.05


1 .001-.005
? .008-.03
? .008-.03
.001-.005 TR
.008-.03 TR
TR N.D.
.005-.01 .03-.08
.005-.01 .005-..01
.01-.05 TR


.25%+ .05-.1


Soluble Organic Nitrogen Sources
Cyanamide............................................. 520 05- I .1-. ND. N.D. .05-.1 TR .005-.01 N.D. .01-.05 N.D. T N.D. .003-.008 .05-.1
Urea.................................. ... 528 N.D. N.D. N.D. N.D. N.D. N.D. "N.D. N.D. .005-.01 N.D. N.D. N.D. N.D. N.D.
Calures............. ..... ............................ 529 TR .01-.05 .00 1 N.D5- .01 -.01 N.D. N.D. N.D. .01-05 N.D. N.D. .05-.1 N.D. N.D.


Miscellaneous Soil Amendment Materials
Kieserite .................. ......... ............ ............. o501
Sulfur flour ........................................ ..... ... 519
Flowers of sulfur................................................ 881
Manganese sulfate 65%..................................... 512
Manganese sulfate.................... ............ ...... 896
M anganese ore................ .................................. 888
Iron sulfate .............................. ............... I 497
Zinc sulfate (ZnSO4.5H20) (Zinc flake)............ 498
Zinc sulfate (ZnSO4.1H20) (Granular zinc)......! 499
Zinc sulfate (ZnSO4.7H20) (crystal).................. 879
Copper sulfate................... .................. ... 510
Cadmium sulfate................................................... 878
Barium sulfate ................................................. 880
Nickel sulfate (crystal)............................... ... .. 883
Cobalt sulfate ... ........................ 897


TR
.005-.01
.005-.01
1%+
.005-.01
1%-" +
TR
N.D.
N.D.
TR
TR
TR
P
N.D.
N.D.


N.D.
N.D.
N.D.
.05-.1
.01-.05
.1-.5
N.D.
N.D.
N.D.
N.D.
TR
N.D.
1%+
N.D.
N.D.


N.D.
N.D.
N.D.
.05-.1
.01-.05
.1-.5
N.D.
N.D.
N.D.
TR
.01-.05
.01-.05
N.D.
P
.1-.5


N.D.
N.D.
N.D.
.005-.01
.001-.005
.01-.05
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
P


TR
.005-.01
N.D.
P
P
P
.01-.05
.05-.1
.01-.05
.005-.01
TR
.01-.05
N.D.
.01-.05
.01-.05


N.D.
N.D.
N.D.
TR
N.D.
.01-.05
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
TR
N.D.


.01-.05
N.D.
N.D.
.01-.05
N.D.
.01-.05
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.


N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
.01-.05
N.D.
N.D.
N.D.
N.D.


.05-.1
.008-.03
.001-.005
.1-.5
.01-.05
.1-.5
.05-.1
.01-.05
.05-.1
.01-.05
P
.005-.01
.01-.05
.05-.1
.1-.5


N.D.
N.D.
N.D.
TR
TR
TR
N.D.
N.D.
N.D.
N.D.
N.D.
.005-.01
N.D.
N.D.
N.D.


.01-.05 N.D.
TR N.D.
N.D. N.D.
.08-.3 .008-.03
.08-.3 N.D.
1%+ N.D.
? N.D.
P .008-.03
P .03-.08
P .08-.3
1%+ .05-.1
1%+ .1-.5
TR N.D.
.03-.08 N.D.
.005-.01 TR


.001-.005
.001-.005
.001-.005
TR
TR
TR
TR
TR
TR
TR
.008-.03
.25%+


.05-.1
.05-.1
.05-.1
TR
TR
TR
TR
TR
N.D.
.01-.05
.1-.5
.25-%+


The figures in the table denote "percentage" and are on the dry basis. (See text, page 5 for discussion of ranges.)
"P" denotes "present but not estimated"; "N.D." denotes "not detected"; "TR" denotes "trace" (see text, page 8); "?" denotes "possible trace but not positive identifi-
cation"; "+" following a percentage value signifies that "the value given is a minimum" (see text. page 8).
The data for these samples are expressed on the dry basis, although the analyses were made on the dry ash.
** For explanation of (a) and (b) sub-grouping see text, page 11.


.003-.008 N.D.
N.D. .01-.05
TR N.D.
TR .1-.5
TR .1-.5
.005-.01 .01-.05
N.D. .01-.05
N.D. N.D.
N.D. N.D.
N.D. N.D.
N.D. N.D.
TR N.D.
TR .01-.05
N.D. TR
N.D. N.D.


,


,


,


,


,


,


,


,


,


,


, ,


,


.


I


I


I


I


I


I


I


.


,


S


,






Florida Agricultural Experiment Station


For most of the elements involved, determinations of much
greater precision could have been attained by the use of "internal
standard" methods. In view of the great variability of the
materials, however, and the consequent large sampling error
involved, greater precision in the analysis would have been not
only superfluous but probably misleading.

PRESENTATION OF DATA

Among the samples the following groups are represented:
phosphatic materials; potash sources; inorganic nitrogen sources;
organic nitrogen sources, insoluble and soluble; liming and other
soil amendment materials. The experimental data, tabulated in
accord with the above classification, are presented in Table 1.
All data presented in the table are based on multiple deter-
minations. Where close checks were obtained from duplicate
determinations, these results were considered sufficient; where
any ambiguity existed, however, four and sometimes more de-
terminations were used.
The approximate sensitivity of the method is:- for silver,
cobalt, chromium, copper, magnesium, and nickel: between
0.0001% and 0.001%; for aluminum, barium, calcium, iron,
manganese, lead, tin, strontium, titanium, vanadium, and zinc4:
between 0.001% and 0.01%; for boron, bismuth, cadmium, an-
timony, and silicon: between 0.01% and 0.1%; for arsenic:
between 0.1% and 1% (6).
In view of the varying sensitivities listed above, the term
"trace" used in the table has a varying significance. In all cases,
the term "trace" corresponds to the lower limit of sensitivity
for the element involved. Thus a "trace" of chromium would
signify about 0.0001%, whereas a trace of boron would signify
about 0.01%.
The notation "1%+" signifies merely that the element was
present in a proportion of 1% or more. The quantitative stand-
ards were not made to include percentages greater than 1%
and consequently no comparisons could be made for proportions
greater than that amount.
The sample of goat manure (No. 1023) contained a large
amount of rock and sand; obviously considerable variability may
be expected in such samples.

4Ryde and Jenkins (6) assign a sensitivity between 0.01% and 0.1%
to zinc; in this study the zinc line 2138 A. was used to increase the sensi-
tivity to that given here.






Trace Elements in Fertilizer Materials


Calcium, magnesium and silicon were found, of course, in all
samples in varying quantities. The proportions present were
not estimated, however, as the study was limited to trace ele-
ments.
Iron was found in all samples in widely varying proportions;
nearly every sample contained aluminum, but great dispersion
existed in the proportions found.
Cadmium was detected in only four samples other than the
cadmium sulfate. In the three zinc sulfate samples it was
present in the proportion of "1 percent or more"; in the Mil-
organite it was present in a proportion between .08% and .3%.
Bismuth was detected in only one sample; in the Milorganite
it occurred in a proportion between .03% and .08%.
Arsenic was detected in only one sample; in the ammonium
sulfate sample No. 877 it was present in a proportion between
.1% and .5%. In connection with arsenic, however, it should
be recalled that the sensitivity of the method for arsenic is not
great. Moreover, as pointed out above, arsenic if present might
be lost during the ashing process.
Antimony was detected in none of the samples analyzed. Like
arsenic, however, antimony if present might be lost during the
ashing process.
DISCUSSION

From a consideration of the natural sources of the materials
studied, with all the possibilities of handling contaminations
involved, one might reasonably expect to find a wide variety of
trace elements. Reports of analyses of plant and animal tissues
have shown the presence of many of these elements in these
materials; ores, rocks and other mineral materials are, of course,
of widely varying composition with respect to the trace elements.
It is superfluous to cite the extensive literature on this subject,
as good bibliographies have been published elsewhere (11), (12).
It is pertinent, however, to point out that the proportions in
which, and the frequency with which, the trace elements occur
in plants, animals and soils differ widely.
The literature indicates, and it has been found in this labora-
tory, that some elements (copper, manganese, chromium, barium,
strontium, etc.) occur in plant tissues with a regularity which
suggests a possible physiologic significance. On the other hand,
some elements (tin, silver, etc.) have been found sporadically





Florida Agricultural Experiment Station


in plant tissues; these occurrences may possibly be accidental
rather than physiologically significant.
For the purposes of this study, the elements may be classified
into several groups: first, those which occur universally in plant
tissues and are easily detected by ordinary chemical methods
(sodium, potassium, calcium, iron, etc.); second, those which
occur in plant tissues with some regularity and in proportions
which lie in the field of microchemistry and direct spectrographic
observation (copper, boron, barium, etc.); third, those which
may occur more or less frequently (frequency of occurrence un-
known, in general) in rather smaller proportions which lie in
the field covered by spectrography with auxiliary chemical con-
centration. Since the first group does not include the trace
elements and since little seems to be known of the consistency
of occurrence of members of the third group, this study was
limited to certain members of the second group.
The data show a wide dissemination of certain elements in
the second group in the materials analyzed, particularly copper,
manganese, boron, chromium, barium, and strontium. The fre-
quent presence of these elements in fertilizer materials is par-
ticularly interesting, since spectrographic analyses of a variety
of plant ashes revealed the frequent occurrence of copper, man-
ganese, boron, chromium, barium, strontium, titanium and zinc.
Nickel, cobalt, vanadium, silver, tin and lead, which were occa-
sionally detected in the fertilizer materials, sometimes occurred
in the plant ashes whose analyses are mentioned above. Bismuth,
arsenic and antimony were found only rarely in the fertilizer
materials; neither have they been found extensively in plant
ashes.
Among the soil amendment materials are several which are
worthy of mention-the zinc samples, the manganese samples
and the copper sulfate. It is interesting in connection with
their use as amendments or spray materials to note the great
amount of certain impurities contained, particularly cadmium
in the zinc samples, zinc in the copper sulfate, and zinc in one
of the manganese samples. In all these cases, the impurities
mentioned were present in proportions of 1% or greater, al-
though considerable variation in the proportion of impurities
has been noted in different lots of the same material.
A variation in the proportion of each element in samples of
different lots of the same material from the same source is to






Trace Elements in Fertilizer Materials


be expected, especially in fertilizer materials, because of the
lack of control (with respect to the trace elements) in the prepa-
ration of the material.5 Wide variations in the proportions of
trace elements present in different lots of a given fertilizer
material have been found in this laboratory. During the course
of the work, a report of analyses of similar materials has ap-
peared (12), and on comparing the data given in Table 1 with
this report, considerable differences are found. Since it does
not seem possible to account for these differences by experi-
mental error in either Young's method or the method used in
this study, it may be assumed that they are due to variations
in the different lots of materials.
In addition to this variation from lot to lot of a given material
there occurs also considerable variability among the members
of certain of the groups shown in Table 1. Some of the groups
are fairly homogeneous as regards their content of certain ele-
ments; in other cases, considerable dispersion exists within the
groups as regards the proportions of certain elements present.
In the former case some preliminary comparisons may be made
among the groups; in the latter case it is difficult to formulate
any generalizations. Thus, in the case of the boron content of
the inorganic nitrogen sources, the average for the entire group
lies in the range .03% to .08%. Yet five out of the nine samples
contained no detectable boron.
On examination of the data in Table 1, however, it became
obvious that some of the non-homogeneous groups could be di-
vided into two homogeneous sub-groups. Thus, among the in-
organic nitrogen sources, cal-nitro and the two ammo-phos sam-
ples form a homogeneous sub-group distinctly different from the
remainder of the group in its proportions of trace elements. It
is worthy of note in this connection that this division into sub-
groups usually reflects a difference in natural sources or a differ-
ence in treatment in the manufacture of the materials in question.
If the data in Table 1 are examined in the light of the sepa-
ration into the sub-groups (marked a and b in Table 1), some
generalizations seem permissible.

5 In this connection it should be noted that a value obtained from a
composite of samples taken at different times is no index to the variability
of the samples constituting the composite. Such index can be obtained
only by analysis of the separate samples and consideration of their devia-
tions from the mean value obtained above.






Florida Agricultural Experiment Station


To facilitate a comparison of the various classes of materials
with respect to their content of trace elements, a system of
numbers is used to denote the range in which the approximate
mean value of a given class lies. In some instances, certain
materials in a group were markedly above (or below) the bulk
of the group in their content of certain elements; in some of
these cases (denoted in Table 2 by an asterisk) the mean value
was determined for the bulk of the group. In other cases, the
data were too non-homogeneous to permit the determination of
any reasonable mean value; in Table 2 this fact is indicated by
a blank space.
Since the soluble organic nitrogen sources and miscellaneous
soil amendment materials did not lend themselves readily to
tabulation, these groups are omitted from the table.
In Table 2 is presented a comparison of the various classes
of materials analyzed.
It is apparent that wide differences exist among the groups
as regards the variety of trace elements found consistently in
the members of the group. Only two of the elements (barium
and copper) were detected consistently in all the groups listed
in Table 2.
In addition to the two elements mentioned above, the phos-
phatic group (a) and the hardwood ashes contained manganese,
chromium, strontium, nickel, cobalt, vanadium, titanium, lead
and boron. Silver and zinc also were found in the phosphatic
group (a) and tin in the hardwood ashes.
The insoluble organic nitrogen sources also contained a great
variety of trace elements; cobalt, silver and tin being the only
elements in the list which were not found with appreciable regu-
larity in these materials.
The liming materials (a) and the potash sources were low in
nickel, cobalt, silver, tin, zinc and lead; in addition, the potash
group showed no regular content of vanadium.
Of the elements listed, barium, manganese, copper, zinc, lead
and chromium were detected with appreciable regularity in the
inorganic nitrogen group (a).
It is interesting to compare also the various groups with ref-
erence to the relative proportions of the trace elements detected.
The data in Table 2 show that the hardwood ashes and the phos-
phatic group (a) contained high proportions for more of the
elements listed than did the other groups shown in Table 2. For






TABLE 2.-RANGE NUMBERSj FOR FERTILIZER MATERIAL GROUPS.


Material Groups



Liming Materials (a)................... ....................

Liming M materials (b)..........................................................

Phosphatic Materials (a).......................................

Phosphatic M materials (b).................... .............. ........


a 5

5$ M .. U GO

10 13 0* 0 13 5*

1 17 10 6_ 17 5

12 14* 10* 1* 14 10

12 12 0 0 10 0


Potash Sources ........................ .............. ................... 8*1 t 0* 0* 5*1 0*

Inorganic Nitrogen Sources (a)............................................ 7* 0 0 t 0

Inorganic Nitrogen Sources (b)............................................ 11 14 9 1 3* t

Insoluble Organic Nitrogen Sources.................................. 10 11 I1* 0"* 11 t


$ The range numbers denote the range whose mean value is given below (see text, page 12).


Range Number Approximate Mean Value of Range
(in percentages)
0 ...............................................................Not Detected"
1 ...................... .................................... .0001
2 ................................................................ .0003
3 .................................. ... .... ..... .0005
4 ...................... ............................................. .0008
5 ................................................... ........ .001
6 ......................... .. .... .................... .. .003
7 ............................................................... .005
8 ................................................................. .008


Range Number Approximate Mean Value of Range
(in percentages)
9 .... ..... ...... ......................................... .01
10 ..............................................................03
11 .............................................................. .05
12 .................................................... .08
13 ................................................................. .1
14 ........................................................... .3
15 .......................................5
16 ...........................'...... .............. .8
17 ............ ............................................."1% or more"


This range number indicates a qualified mean value obtained by omitting one or more exceptional values.
tA blank space in the table denotes that the data were too non-homogeneous to permit the assignment of a range
number (see text, page 12).


0d 0
s I I
O 0 4, Qo 0


t 0 8 0 0* O* 6
14 0 14 10 t 12 8

9* 1* 11* 0* t 9* 10

9* 0 9 0* 10 10 1*

t 0 ti 0* 0 0 1*

0 0 7* 0* t t 1*

9 0 10 O0* 10 11

t 0* 10 0* 5* t 1*






Florida Agricultural Experiment Station


almost every element in the list, either the hardwood ashes or
the phosphatic group (a) contained the highest proportion.
On the other hand, the inorganic nitrogen group (a) and the
potash sources ranked low in the proportions of trace elements
found. As shown in Table 2, those elements detected with
consistency in these groups were nearly always found in com-
paratively small proportions.

SUMMARY
Spectrographic analyses of 64 fertilizer materials for 18 trace
elements are reported. Considerable variability from lot to lot
of a given material has been noted during the work. Barium,
strontium, copper, manganese, chromium and boron were de-
tected very extensively in the materials. Bismuth, arsenic, an-
timony, cadmium, tin and silver were detected in only a few
samples. Titanium, nickel, cobalt, vanadium, lead and zinc were
occasionally detected in the materials.
From the data, the following general conclusions are drawn:
1. The phosphatic materials (a), the hardwood ashes and the
insoluble organic nitrogen sources contained the greatest
variety of the trace elements studied.
2. The potash sources and the inorganic nitrogen sources (a)
contained the least variety of the trace elements listed.
3. The hardwood ashes and the phosphatic materials (a) con-
tained in general higher proportions of more of the trace
elements than did the other classes of materials.
4. The potash sources and the inorganic nitrogen materials
(a) contained in general smaller proportions of the trace
elements than did the other groups of materials.







Trace Elements in Fertilizer Materials


LITERATURE CITED

1. ALLISON, R. V., O. C. BRYAN, and J. H. HUNTER. The Stimulation of
Plant Response on the Raw Peat Soils of the Florida Everglades
Through the Use of Copper Sulphate and Other Chemicals. Fla.
Agr. Exp. Sta. Bul. 190. 1927.

2. BARNETTE, R. M., J. P. CAMP, and J. D. WARNER. A Study of "Chloro-
sis" in Corn Plants and Other Field Crop Plants. Fla. Agr. Exp.
Sta. Ann. Rept., 1934, p. 49.
3. BECKER, R. B. Deficiencies in Feeds Used in Cattle Rations. Fla.
Agr. Exp. Sta. Ann. Rept., 1932, p. 52.
4. BRAIDECH, M. M., and F. H. EMERY. Spectrographic Determination of
Minor Chemical Constituents in Various Water Supplies in the
United States. Jour. Am. Water Works Assn., 27:557-580 (especially
576). 1935.

5. MOWRY, HAROLD. Propagation, Planting and Fertilizing Tests with
Tung Oil Trees. Fla. Agr. Exp. Sta. Ann. Rept., 1933, p. 91.

6. RYDE, J. W. and H. G. JENKINS. Sensitive Arc Lines of Fifty Elements.
London. Adam Hilger, Ltd. 1930.
7. SKINNER, J. J. and R. W. RUPRECHT. Fertilizer Experiments with
Truck Crops. Fla. Agr. Exp. Sta. Bul. 218. 1930.
8. TANANAEFF, N. A. Zur Frage des Nachweis von Barium, Strontium,
und Calcium in Ihren Gemischen. Zts. fiir Analytische Chemie 100,
391 (1935).
9. THOMPSON, P. K. Recovery of Small Amounts of Zinc from Biologic
Material Ashed by the Incineration Process. Jour. Ind. Hyg. 7:358-
70. 1925.
10. TREADWELL, F. P. and W. T. HALL. Analytical Chemistry, Vol. II,
p. 495. John Wiley & Sons, Inc. 1911.
11. WILLIS, L. G. Bibliography of References to the Literature on the
Minor Elements. Chilean Nitrate Educational Bureau, Inc. 1935.
12. YOUNG, R. S. Certain Rarer Elements in Soils and Fertilizers, and
Their Role in Plant Growth. Cornell University Agr. Exp. Sta.,
Memoir 174. 1935.




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