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Combined Effects of Termiticides, Volatile Organic Compounds, and Mechanical Stress on Chlorinated Polyvinyl Chloride (CPVC)


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COMBINED EFFECTS OF TERMITICID ES, VOLATILE ORGANIC COMPOUNDS, AND MECHANICAL STRESS ON CHLORI NATED POLYVINYL CHLORIDE (CPVC) By JUSTIN S. SAUNDERS A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2005

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Copyright 2005 by Justin S. Saunders

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This thesis is dedicated to my parent s, Janice Carmelo and Marshall Saunders

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iv ACKNOWLEDGMENTS I would like to thank my family for thei r constant support. I want to thank my friends for the many good times, Colin Hicke y, Dave Melius, and Ryan Welch. I would like to thank Gil Marshall and Tiny Willis for their help with my experiments and great conversations. I would especially like to thank my adviso r, Dr. Phil Koehler, for his mentoring and advancement of my personal self. He has gi ven me the opportunity to present myself before a broad range of audiences, wh ich at the time seemed a chore but only strengthened my knowledge and skills in the area of urban entomology. I would also like to thank Dr. Richard Patterson and Dr. Br ian Cabrera for their accommodations and support with my thesis.

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v TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iv LIST OF TABLES............................................................................................................vii LIST OF FIGURES.........................................................................................................viii ABSTRACT....................................................................................................................... ix CHAPTER 1 LITERATURE REVIEW.............................................................................................1 Subterranean Termite Problems...................................................................................1 Subterranean Termite Biology......................................................................................1 Early Efforts at Termite Control...................................................................................2 Soil Treatments.............................................................................................................3 Modern Soil Termiticides.............................................................................................5 2 COMBINED EFFECTS OF TERMITICIDES AND MECHANICAL STRESS ON CHLORINATED POLYVINYL CHLORIDE (CPVC)........................................7 Introduction................................................................................................................... 7 Materials and Methods.................................................................................................8 Termiticides...........................................................................................................8 Formulation Preparation........................................................................................9 Termiticide dilutions......................................................................................9 Builders sand treatment................................................................................10 Assay Setup.........................................................................................................10 Chemical Analysis for Volati le Organic Compounds (VOCs)...........................12 Data Analysis.......................................................................................................12 Results and Discussion...............................................................................................12 Termiticide Concentrate Assay...........................................................................13 Termiticide Dilutions Assay................................................................................14 Builders Sand Treatment Assay..........................................................................15 Chemical Analysis for Volati le Organic Compounds (VOCs)...........................15 Discussion............................................................................................................16

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vi 3 COMBINED EFFECTS OF TERMITICIDES, CPVC GLUE, AND MECHANICAL STRESS ON CPVC........................................................................32 Introduction.................................................................................................................32 Materials and Methods...............................................................................................32 Termiticides.........................................................................................................32 Assay Setup.........................................................................................................33 Data Analysis.......................................................................................................35 Results and Discussion...............................................................................................35 Dursban Concentrate Assay................................................................................35 Termiticide Dilution Assay.................................................................................36 Water Assay.........................................................................................................36 Discussion............................................................................................................36 4 COMBINED EFFECTS OF VOLA TILE ORGANIC COMPOUNDS AND MECHANICAL STRESS ON CPVC........................................................................39 Introduction.................................................................................................................39 Materials and Methods...............................................................................................39 Chemical Analysis for Volati le Organic Compounds (VOCs)...........................39 Volatile Organic Compounds..............................................................................40 Assay Setup.........................................................................................................40 Data Analysis.......................................................................................................41 Results and Discussion...............................................................................................41 Chemical Analysis for VOCs..............................................................................41 Volatile Organic Compounds Assay...................................................................41 Discussion............................................................................................................42 5 CONCLUSIONS........................................................................................................46 APPENDIX CALCULATIONS FO R BUILDERS SAND TREATMENTS..................49 LIST OF REFERENCES...................................................................................................50 BIOGRAPHICAL SKETCH.............................................................................................53

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vii LIST OF TABLES Table page 2-1 CPVC bending after exposure to Termiticide Concentrate......................................17 2-2 CPVC bending after exposure to Four Times the Label Rate Termiticide Dilution.....................................................................................................................19 2-3 CPVC bending after exposure to Two Times the Label Rate Termiticide Dilutions...................................................................................................................20 2-4 CPVC bending after exposure to Label Rate Termiticide Dilutions........................21 2-5 CPVC bending after exposure to Builders Sand Treated with Three Times the Labeled Volume.......................................................................................................22 2-6 CPVC bending after exposure to Builders Sand Treated with Two Times the Labeled Volume.......................................................................................................23 2-7 CPVC bending after exposure to Builde rs Sand Treated at the Labeled Volume...24 2-8 Results of chemical analysis for Vo latile Organic Compounds using E.P.A. method 8260B..........................................................................................................25 2-9 Results of chemical analysis for th e Major Volatile Organic Compounds in common Termiticides...............................................................................................26 3-1 CPVC bending after exposure to Term iticide, Termiticide Dilutions, and CPVC glue........................................................................................................................... 38 4-2 CPVC bending after exposure to Volatile Organic Compounds..............................45

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i LIST OF FIGURES Figure page 2-1 Assay setup...............................................................................................................28 2-2 Examples of baton failures A) Flex ible baton failures in the foreground, B) Sharp break baton failures on bottom row...............................................................29 2-3 Number of failed batons with termiticide at concentrate held for 8 weeks after set up........................................................................................................................2 9 2-4 Number of failed batons with termiticid e at 4 times the label rate held for 4 weeks after set up.....................................................................................................30 2-5 Number of failed batons with termiticid e at 2 times the label rate held for 4 weeks after set up.....................................................................................................31 2-6 Number of failed batons with termiticide at label rate held for 4 weeks after set up............................................................................................................................. .31

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ix Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science COMBINED EFFECTS OF TERMITICID ES, VOLATILE ORGANIC COMPOUNDS, AND MECHANICAL STRESS ON CHLORI NATED POLYVINYL CHLORIDE (CPVC) By Justin S. Saunders December 2005 Chair: Philip Koehler Major Department: Entomology and Nematology Subterranean termites cause millions of dolla rs in damage annually. The traditional method of preventing termites from causing da mage to a home is a pre-construction soil treatment. This involves an application of te rmiticide to the soil before the slab is poured. Highest application rates are applied to cr itical areas where plumbing and utilities penetrate the slab into the structure. CPVC batons were constructed and fille d with termiticide concentrates, their dilutions or treated builders sand. Term iticides tested were Cyper TC, Demon TC, Dragnet SFR, Dursban TC, Permethrin Pro Termiticide-Turf-Ornamental, Prelude Premise 2, Prevail FT, Speckoz Bifenthrin Termiticide, Speckoz Permethrin TC, Talstar One and Termidor SC. Batons were mechanica lly stressed and bending was measured at various times. Termiticide concentrate failures occurred for Cyper TC, Demon TC, Dragnet SFR, Prelude and Prevail FT within 10 days. Failures

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x occurred for Dursban TC, Permethrin Pro Termiticide-Turf-Ornamental, and Speckoz Permethrin TC between 20-50 days. No failures occurred for Premise 2, Speckoz Bifenthrin Termiticide, Talstar One and Termidor SC. Termiticide dilution, four times the label rate, failures occurred for Prelude Permethrin Pro Termiticide-Turf-Ornamental, and Speckoz Permethrin TC. Termiticide dilution, two times the label rate, failures occurred for Prelude and Permethrin Pro Termiticide-TurfOrnamental. Termiticide dilution, label rate, failures occurred for Permethrin Pro Termiticide-Turf-Ornamental. No failures occurre d for all of the CPVC batons filled with termiticide treated builders sand. To determine the effect of CPVC glue exposure on CPVC batons filled with Dursban TC concentrate and dilutions of Dursban TC, CPVC batons were constructed with a glued joint at the fulc rum point for the mechanical stress. All Dursban TC concentrate batons failed within 10 days. The CPVC batons filled with the Dursban TC dilutions had significant bendi ng from each other and experienced failures in the batons exposed to th e highest CPVC glue levels. Water dilutions of 400 ppm ai were prep ared for the same termiticides. GC/MS analysis revealed 8 major VOCs, 1,2,4 Tric hlorobenzene, 1,2,4 Trimethylbenzene, 1,3,5 Trimethylbenzene, Bromoform, Ethylbenzene, Sec-Butylbenzene, Toluene, and Xylenes and 3 minor VOCs, Benzene, Chloroform, and Styrene. CPVC batons were constructed and filled with the major VOCs. All caused CPVC failure within 4 days. One VOC, 1, 3 5 Trimet hylbenzene, caused failure within minutes and was found in all termiticides that caused CPVC failure.

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1 CHAPTER 1 LITERATURE REVIEW Subterranean Termite Problems In the United States, the termite family Rh innotermitidae consists of four genera of subterranean termites: Coptotermes Heterotermes Reticulitermes and Prorhinotermes Subterranean termites will construct underground tunnels that connect the colony to food and water (Su 1991). Termites use symbionts in th e hindgut to help digest the cellulose in wood to simple sugars that can then be uti lized by the termite. Subterranean termites can damage many species of wood; some of their preferences ar e loblolly pine, slash pine, and sugar maple (Smythe and Carter 1970). In 1934 the estimated losses due to subter ranean termite damage was at least $40 million in the United States (Snyder 1934). In 1966, the damage estimate was raised to $250 million annually (Gentry 1966). Mauldin (1986) estimated that the damage was around $735 million, and Su (1991) estimated it to be at least twice this amount. This just demonstrates that the costs associated with subterranean termite damage have significantly increased. Su (1991) estimate d that 80% of these costs are from subterranean termites with the rest being credited to drywood termites. Subterranean Termite Biology Subterranean termites are considered eu social because they posses many of the social behaviors that make them more succe ssful than a solitary insect. These social behaviors that make them su ccessful insects include overlap of generations, division of labor, and cooperative care for th e young (Hlldobler and Wilson 1990).

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2 The subterranean termite colony consists of three castes: work ers, soldiers, and reproductives. The primary function of the wo rkers is to forage for and consume food sources. Because the soldiers, young, and reprod uctives do not have the ability to feed themselves, the workers will feed them via tr ophollaxis. The soldiers primary function is to defend the colony usually using elongated ma ndibles at the front of their chitinous heads. Soldiers of the genus Coptotermes have a gland above the mandibles called a fontanelle that can produce defe nsive secretions. The reproduc tives in a colony can be of two types: primary reproductives, which ar e the founding king and queen, and secondary reproductives that include any reproductives other than the primary reproductives (Krishna 1969). Early Efforts at Termite Control Hagen (1876) warned of the potential of te rmites to threaten homes and belongings. In 1898, Dr. Karl Heinrich Wolman develope d Wolman salts as a wood preservative (Kreer 1934). Wood treatments were a term ite control option for new construction, but not for existing structures. These treatments were usually toxic compounds, like arsenic oxides, coal-tar creosote oil, or zinc chloride (Randall & Doody 1934a). These compounds were often brushed on to form a barrier, to prev ent infestation. Another option was adding termiticides to term ite galleries in cases of infestation. These termiticides were mainly inorganic poison dusts like arsenical smelter dust, sodium fluosilicate and copper acetoarsenite (Ra ndall & Doody, 1934b). As these dusts were mostly arsenical in nature, they were not safe for extensive use in homes. Due to the relative lack of safe insec ticides, cultural practices were the chief method of early termite control. Such practi ces included the removal of infested wood or wood in contact with the ground. In time, changes in city building codes were

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3 implemented to enforce these practices (Snyde r, 1935). The first one was in Burlington, Iowa in 1923. In 1927, the pacific code bu ilding officials adopted the bureau of entomology and plant quarantine recomme ndations for termite damage prevention. Honolulu did the same thing in 1928. Soil Treatments In the early 20th century, trapping and baiting, sp raying timbers, and injection of poison dusts were all tried and considered to be largely inadequate for termite control (Turner 1941). Fumigation and heat treatments were not feasible either, as there would be no residual control. The only remaining option for chemical control was the barrier method, also known as soil termiticide treatments. Soil treatments were once considered a last result after cultural practices (Randall & Doody, 1934c). Early treatment generally consisted of a broa d application of inorganic poisons like sodium arsenate, ge nerally applied at hi gher active ingredient levels and application rates th an current soil termiticides. In the years before EPA regul ations like FIFRA, there wa s little quality control. For example, Antimite promoted sodium fluor ide, dinitrophenol and sodium arsenate at 10 lbs/30 gal of water, applied by generous drenching (Randall & Doody, 1934c). The American fluoride corporation sold Fluorex V (5% sodium fluosilicate) and Fluorex S (10% magnesium base fluosilicate solution) The E. L. Bruce Company produced Terminix, a mixture of orthodichlorobenzene, toxi c solvents and toxic sa lts. It carried a 5 year guarantee, under the conditi on that wood in the structur e was completely isolated from ground contact. None of these termiticid es were tested by the Termite Investigation Committee.

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4 No concerted effort was made to organi ze or regulate soil termiticide use until 1927 (Brown, 1934). The Termite Investigati on Committee tested borax and magnesium fluosilicate at 5% and 10% (1 gal/10 square f eet). Other solutions tested were sodium chloride, ammonium fluoride, sodium fluoride, sodium fluosilicate, and a kerosene emulsion with 30 ml sodium arsenate per ga llon. Soil fumigation wa s also tested, using carbon bisulfide, carbon tetrachlori de and paradichlorobenzene. DDT (dichloro-diphenyl-trichl oroethane) was used in the 1940s, and proved to be an effective soil poison for at least 10 y ears (Hetrick, 1957). Cyclodienes like aldrin, heptachlor, and dieldrin prove d effective at 1/25 the require d concentration of DDT, and were effective for 7 years. In the long te rm, 0.3% dieldrin proved more persistent than 8% DDT, with a 99% kill of Coptotermes fo rmosanus in 33 year old treated soil in Hawaii (Grace et al., 1993). Cyclodienes have been shown to persis t over 35 years in the continental United States (Kard et al., 1989). The persistence of these organochlorine insecticides generated envir onmental concerns, causing thei r eventual withdrawal from use in the United States in 1988 (Len z et al., 1990; Wood & Pearce, 1991). After 1988, most of the remaining soil termiticides were organophosphates, like Dursban TC (chlorpyrifos). By the early 1990s, pyrethroid termiticides like Dragnet FT (permethrin, FMC) and Demon TC (cypermethrin, Zeneca) appeared. These pyrethroids are highly repe llent to termites (Su et al 1982, 1993, 1995; Su & Scheffrahn, 1990; Smith & Rust, 1990). Beal and Smith (1971) assumed that the efficacy of cyclodienes was due to repellency. This led to the conventional idea that repellency was desirable, and it was seen as a positive quality of the pyrethroid termiticides. In fact, cyclodienes are not repellent.

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5 Termites dont penetrate into soil treated w ith Demon or Dragnet (Su et al., 1993). Dursban is not repellent in itself, but it kills rapidly, causing an accumulation of dead termites. These decomposing termite corp ses repel living termite s (Su et al., 1982). Until recently, it was generally asserted that e ither repellent or non-repellent termiticides would work if the appropriat e concentration were applied thoroughly beneath or around a structure (Su & Scheffrahn, 1990; Forschler, 1994) While this may be true in theory, it is difficult to ensure thorough application in practice. Forschler ( 1994) investigated the ability of Reticulitermes flavipes to find gaps in repellent termiticide soil treatments. Kuriachan and Gold (1997) also investigated gap-finding abilities. In both cases, some termites always survived past 7 days, and gaps were located with varying success. Modern Soil Termiticides Bayer released Premise in 1996. This termiticide ha s imidacloprid as the active ingredient, which is a chlornicotinyl (Abbi nk 1991). This class of chemicals act as neurotoxins, blocking nicotin ic acetylcholine receptors. Unlike the pyrethroids, chlornicotinyls are non-repellent. Kuriachan and Gold (1998) found that termites were unable to locat e 2-7 cm untreated gaps of soil. The termites tunneled into Premise-treated soil and there was 90% mortality at 7 days. With non-repellent termiticides, gaps are less important to protection since termites do not distinguish treated versus non-treated soils. So there is less opportuni ty to exploit gaps. Aventis released Termidor in 1999. This termiticide has fipronil as the active ingredient, which is a phenyl pyrazole (Ibrahim et al., 2003). This class of chemicals acts by interfering with the passa ge of chloride ions through gamma-amino butyric acid

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6 regulated chloride channels, thus disrup ting the central nervous system. Like the chlonicotinyls, the phenylpyrazoles ar e non-repellent (Cole et al., 1993).

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7 CHAPTER 2 COMBINED EFFECTS OF TERMITICIDES AND MECHANICAL STRESS ON CHLORINATED POLYVINYL CHLORIDE (CPVC) Introduction Subterranean termites cause millions of dolla rs in damage annually. The traditional method of preventing termites from causing da mage to a home is a pre-construction soil treatment. This involves an application of te rmiticide to the soil before the slab is poured. Liquid termiticides are either sold as emulsifiable concentrates or suspendable concentrates. Emulsifiable concentrates are a liquid containing the active ingredient, one or more volatile organic compounds (VOCs), and an emulsifier. Examples of these termiticides would be Cyper TC, Demon TC, Dragnet SFR, and Dursban TC. Suspendable concentrates are flowable form ulations formed by suspending finely ground particles in water and/or oil (Mallis 2004, Farm Chemicals Handbook 1997). An example of a suspendable concentrate would be Termidor SC. One major difference between the two formulations is that the emulsifiable concentrates use VOCs to keep the active ingredients dissolved in the solution; wh ereas the suspendable concentrates do not usually use VOCs. The major manufacturer of CPVC pipe has blamed soil termiticides for causing failures in CPVC pipes below structures (N oveon 2003). The following scenario is an example of conditions where such termiticid es may contribute to CPVC failure. In normal practice, termiticides are diluted accordin g to the label instructions and applied to the soil. As a result of improper workmans hip, CPVC water supply lines may be placed

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8 in an incorrect spot after the slab has been poured and the soil has been treated with termiticide. The discovery of this incorrect positioning after the slab has been poured results in a breakout. The builder break s the slab where the CPVC comes up through and re-positions the CPVC to another lo cation, creating stress on the CPVC. At the breakout site the soil needs to be retreated, exposing the CPVC to termiticides a second time. In addition, if an emulsifiable concen trate formulation has been used, the CPVC is being re-exposed to VOCs as well. This co mbination of additional mechanical stress and chemical exposure may weaken the CPVC to the point of causing failure in the water supply line. My objectives were to determine if termiticides and mechanical stress cause significant CPVC bending and failure. I also wanted to determine the identity of VOCs used in commonly used termiticides for new construction. Materials and Methods Termiticides Twelve termiticide concentrates registered for treatment of new construction were used. The twelve termiticides were: Cyper TC (cypermethrin 25.4%; Control Solutions, Inc.; Pasadena, TX), Demon TC (cypermethrin 25.3%; Syngenta, Greensboro, NC), Dragnet SFR (permethrin 36.8%; FMC Corpora tion, Philadelphia, PA), Dursban TC (chlorpyrifos 44.0%; DowAgroSciences, Indianapolis, IN), Permethrin Pro TermiticideTurf-Ornamental (permethri n 36.8%; Micro Flo Compa ny, Memphis, TN), Prelude (permethrin 25.6%; Syngenta, Greensboro, NC), Premise 2 (imidacloprid 21.4%; Bayer, Kansas City, MO), Prevail FT (cypermethrin 24.8%; FMC Corporation, Philadelphia, PA), Speckoz Bifenthrin Termiticide (bifenthrin 7.9%; Speckoz Inc., Alpharetta, GA), Speckoz Permethrin TC (permethrin 36.8%; Speckoz Inc., Alpharetta,

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9 GA), Talstar One (bifenthrin 7.9%; Bayer, Kansas City, MO), and Termidor SC (fipronil 9.1%; BASF, Mount Olive, NJ). All of these termiticides must be diluted according to the label directions before being applied. The label rate s are: 0.05% for Premise 2, 0.06% for Speckoz Bifenthrin Termiticide, Talstar One and Termidor SC, 0.25% for Prevail FT, 0.5% for Cyper TC, Dragnet SFR, Dursban TC, Permethrin Pro Termiticide-TurfOrnamental, and Speckoz Permethrin TC, 1.0% for Demon TC and Prelude Formulation Preparation Termiticide dilutions All termiticides were tested as concentrate in batons. Termiticide concentrates that caused CPVC baton failure within eight weeks were diluted and then reevaluated at four times the label rate. Termiticide dilutions were prepared at four times the label rate by pipetting the concentrate of each termitici de into a volumetric flask and adding deionized water to a final volume of 200 ml. The following quantities of termiticides were used: Cyper TC (15.75 g), Demon TC (31.62 g), Dragnet SFR (10.87 g), Dursban TC (9.09 g), Permethrin Pro (10.87 g), Prelude (31.25 g), Prevail FT (8.06 g), and Speckoz Permethrin TC (10.87 g). The termiticide dilutions in water at four times the label rate that caused CPVC baton failure were diluted to two times the label rate and the label rate and evaluated simultaneously. The following quantities of te rmiticides were used; Permethrin Pro (5.44 g, 2.72 g), Prelude (15.63 g, 7.81 g), and Speckoz Permethrin TC (5.44 g, 2.72 g) were added to water to create the two and one times the label rate termiticide dilutions.

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10 Builders sand treatment The label rate termiticide dilutions were applied at one, two, and three times (7.86, 15.72, 23.58 ml) the labels required volume fo r builders sand (82.85 g, Appendix A). Builders sand (82.85 g) was placed into quart -sized bags prior to termiticide addition. Dilutions of Permethrin Pro, Prelude and Speckoz Permethrin TC were then added to separate bags, and the mixtures of sa nd and termiticide were thoroughly kneaded for five minutes. Assay Setup Chlorinated polyvinyl chlori de pipe (1.27 cm i.d., 1.6 cm o.d., CPVC; Noveon; Cleveland, OH) was cut into 58 cm long ba tons. Caps (1.27 cm i.d.; CPVC; Nimco; Elkhart, IN) were glued onto one end of each baton using a CPVC a dhesive (Oatey, All purpose cement; Cleveland, OH). The appli cation of the CPVC adhesive was standardized and consisted of a single brush stroke around one end of the baton. The cap was then glued in place. To determine whether the volatile organic compounds in termiticides could affect the CPVC batons, 50 ml of termiticide concentrate, the termiticide dilutions, or the treated builders sand (82.85 g) were added to each baton. The open end of the baton was then capped using the same method. A pegboard was created by drilling holes (2.54 cm) into two sheets of 1.27 cm x 1.22 m x 2.44 m pressure treated plywood. Tw o plywood sheets were separated by 19.50 cm .The batons were then placed into the pegboard so that the batons extended ~34.6 cm from the front of the pegboard. To put stress on the batons 1.540 0.027 kg masonry bricks (Lowes, Mooresville, NC; 5.5 cm x 9.0 cm x 19.5 cm) were attached with nylon rope (Lehigh; Mexico; 15.2 m x 0.48 cm) cut into 45.7 cm sections so that the masonry

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11 bricks hung on the long end of the projecting ba ton, 2 cm from end of baton. The length of the rope was 7.62 cm from the bottom of th e baton to the top of masonry brick (Figure 2-1). Termiticide concentrate and dilution experiments were a randomized complete block design with three batons for each trea tment. Controls were de-ionized water (50 ml) in a baton. CPVC bending was determined by measuring the distance between the pegboard and the masonry brick. Failures were considered to be batons breaking or bending so far that the masonry br ick rested against the pegboard. Termiticide concentrate experiments had 12 treatments and a control for a total of 39 batons. Experiments were run for 8 week s. CPVC bending was measured at 1, 2, 3, 4, 6, & 8 weeks. Daily observations we re made to assess failures. Termiticide dilution experiments at 4 times the label rate had 8 treatments and a control for a total of 27 batons. Experime nts were run for 4 weeks. CPVC bending was measured weekly and daily observations were made to assess failures. Termiticide dilutions at 2 and 1 times the label rate had 3 treatments and a control for a total of 12 batons. Experiments were run for 4 weeks. CPVC bending was measured weekly and daily observations were made to assess failures. Experiments with treated builders sand were set up as a randomized complete block design with three batons for each volume of treatment. Controls were builders sand treated with de-ionized water (7.86, 15.72, 23.58 ml) in a baton. For each volume of application there were 3 treatments and a cont rol for a total of 12 ba tons. The experiment had a total of 3 different volumes for a total of 36 batons and was run for 4 weeks. CPVC bending was determined by measuring the distance between the pegboard and the

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12 masonry brick. CPVC bending was measured w eekly and daily observations were made to assess failures. Chemical Analysis for Volati le Organic Compounds (VOCs) All 12 termiticides were diluted to 40 0 ppm AI in deionized water and were analyzed using the E.P.A. method 8260B to determine the presence of VOCs (EPA 1992; Nelson 2003). Samples (5 l) were injected in to the Purge & Trap attached to the gas chromatograph/mass spectrometer (GC/MS). The samples were under helium flow to have the VOCs volatilize off of the samples, and were collected in the Purge & Trap. The collected VOCs were then run through the GC/MS to determine which VOCs were present. Data Analysis The bending data were analyzed using one way analysis of variance and means were separated using Student Newman-Kuels test when P values for the analysis of variance were sign ificant (n = 3, = 0.05; SAS Institute 2001). Results and Discussion Water caused little bending (<2 cm) of CPVC batons and no breakage. In contrast, some termiticides caused si gnificant CPVC bending or break ing. In contrast, some termiticides were observed to either make the baton more flexible or more brittle. As a baton became flexible, CPVC bending increased, eventually reaching a maximum bending distance of ~26 to28 cm, at which distan ce the baton was bent in an arc with the brick touching the pegboard (Figure 2-2a). For batons that became brittle, a sharp break occurred at the supporting area of the pegboa rd (Figure 2-2b). This break caused the brick to drop and rest agains t the pegboard, resulting in a maximum bending distance of ~26 to 28 cm.

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13 Termiticide Concentrate Assay At 1 week, treatments that caused break ing or significant bending were Cyper, Dragnet, Prelude, and Prevail (Table 2-1). Cyper and Demon treatments had one baton failure each. Prelude, and Prevail tr eatments had two baton failures each. The Dragnet treatment had three baton failures. At 2 weeks treatments that caused break ing or significant bending were Cyper, Demon, Dragnet, Prelude, and Prevai l. Cyper and Demon treatments had 1 baton failure each. The Prelude treatment had 2 baton failures. The Prevail treatment had 3 baton failures. At 3 weeks treatments that caused break ing or significant bending were Cyper, Demon, Dragnet, Prelude, and Prevail. Cyper, Demon, and Dursban treatments had 1 baton failure each. The Prel ude treatment had 3 baton failures. At 4 weeks treatments that caused breaki ng or significant be nding were Dursban, Cyper, and Demon. Cyper, and Demon treatments caused significantly more bending than the Dursban treatment. Cyper, Demon, and Dursban treatments had 1 baton failure each. At 6 weeks treatments that caused breaking or significant bending were Permethrin Pro, Cyper, Demon, and Dursban. Permethrin Pro, Cyper, Demon, and Dursban treatments caused significantly greater bending than the Permethrin Pro treatment. The Permethrin Pro treatment had 1 baton failure. The Dursban treatment had 2 baton failures. Cyper and Demon treatments had 3 baton failures each. At 8 weeks treatments that caused breaking or significant bending were Dursban and Permethrin Pro. The Permet hrin Pro treatment caused significantly

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14 greater bending than the Dursban treatment Premise 2, Speckoz Bifenthrin, Talstar One, Termidor, and water treatments ha d no baton failures at 8 weeks. All other treatments had three baton failures each. Termiticide Dilutions Assay The experiments with termiticide dilutions at four times the label rate resulted in fewer treatment failures. At 1 week no treatments had caused significant bending. However, Permethrin Pro, Prelude, and Sp eckoz Permethrin treatments had 2 baton failures each (Table 2-2). At 2 weeks the Prelude treatment had caused significant bending. Permethrin Pro and Speckoz Permethr in treatments had 2 baton failures each. The Prelude treatment had 3 baton failures at 2 weeks. At 3 weeks no further treatments had caused significant bending. Permethrin Pro and Speckoz Permethrin treatments had 2 baton failures each. At 4 weeks no fu rther treatments had caused significant bending. Permethrin Pro and Speckoz Permethr in treatments that had 2 baton failures each. In the experiments with termiticide diluti ons at two times the label rate, only 1 treatment caused all three batons to fail. At 1 week no treatments had caused significant bending (Table 2-3). However, the Prelude tr eatment had 1 baton failure. At 2 weeks no treatments caused significant bending. The Pe rmethrin Pro treatment had 1 baton failure and the Prelude treatment had 2 baton failu res. At 3 weeks no treatments had caused significant bending. The Permethrin Pro treatm ent had 1 baton failure and the Prelude treatment had 2 baton failures. At 4 weeks the Prelude treatment had caused significant bending. The Permethrin Pro treatment had 1 baton failure and the Prelude treatment had 3 baton failures.

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15 The experiments with the label rate termiticide dilution resulted in only 1 treatment with significant bending, and no treatment had all three batons fail. At 1 and 2 weeks no treatments caused significant bending (Table 2-4). No treatments had baton failures at 1 week or 2 weeks. At 3 weeks the Prelude treatment had caused significant bending. In addition, the Prelude treatment had 2 baton failures. At 4 weeks the Prelude treatment had still caused significant bendi ng and still had 2 baton failures. Builders Sand Treatment Assay The builders sand treated at three time s the labeled volume caused significant bending for some of the termiticides. At 1 and 2 weeks the Prelude treatment had caused significant bending (Table 2-5). No tr eatments had baton failure. At 3 weeks no further treatments caused significant bending. No treatments had baton failure. At 4 weeks the Permethrin Pro, Prelude, and Sp eckoz Permethrin treatments had caused significant bending. Permethrin Pro, Prel ude, Speckoz Permethrin, and water treatments had no baton failures at 4 weeks were. The experiments with builders sand treat ed at two and one times the labeled volume had similar results. The experi ments resulted in no treatments bending significantly from the controls, and no trea tments had baton failures at 1, 2, 3, and 4 weeks (Table 2-6 & 2.7). Chemical Analysis for Volatile Organic Compounds (VOCs) The analysis indicated eight VOCs present in the termiticides with quantities above 100 l: 1,2,4 Trichlorobenzene, 1,2,4 Trimet hylbenzene, 1,3,5 Trimethylbenzene, Bromoform, Ethylbenzene, Sec-Butylbenzene, Toluene, and Xylenes (Table 8). Other VOCs that were present but in quantities less than 100 l were: Benzene, Chloroform,

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16 and Styrene. Another table was constructed to show which termiticides had the presence of these high quantity VOCs (Table 2-9). Discussion Termiticide formulations are complex mixtures of active ingredients, solvents, emulsifiers, and other additives. VOCs are found as components of most formulations and are much smaller molecules than the ac tive ingredients, maki ng them capable and likely suspects that can degrade CPVC. Termiticides will have the highest concentra tion of VOCs in their concentrate form. Dilution lowers the VOC concentration, and th is is evident in th e results with the concentrate assay having more failu res than the dilutions assays. The treated builders sand experiments indicated that if the termiticide has something to bind with then the VOCs are le ss of a problem. Similar to the previous experiments, the more VOCs present the more CPVC bending that occurs. VOCs were present in all of the tested termiticides except for Termidor a suspendable concentrate. Termiticides with the same active ingredient often had the same VOCs present in the analyzed samples. However, the quantities found present for each VOC varied from termiticide to termiticide. All of the termiticides concentrates that caused failure of the CPVC batons had some combination of these VOCs. In fact, all of the termiticide concentrates that failed had one VOC in common: 1,3,5-Trimethylbenzene (Table 2-9).

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17Table 2-1 CPVC bending after exposu re to Termiticide Concentrate CPVC Bending (cm SE) Trt 1 wk 2 wks 3 wks 4 wks 6 wks 8 wks Cyper 17.60 4.11a 18.63 3.60a 19.37 3.32a 20.10 2.97a 25.63 0.27ab ----Demon 16.80 4.79ab 19.47 3.37a 23.60 1.38a 25.10 0.61a 25.97 0.28ab ----Dragnet 26.07 0.27a --------------------Dursban 2.17 0.03b 3.17 0.07b 11.33 7.48b 11.83 7.23b 19.07 6.94ab 26.00 0.17b Permethrin 2.27 0.18b 3.77 0.38b 5.90 0.26b 7.10 0.06bc 15.63 5.55bc 26.97 0.29a Pro Prelude 18.87 8.28b 19.03 8.12a 27.43 0.28a ------------Premise 2 1.30 0.26b 1.47 0.20b 1.63 0.18b 1.93 0.09c 2.07 0.12d 2.13 0.19c Means followed by same letter are not si gnificantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001)

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18Table 2-1 cont. CPVC bending after exposure to Termiticide Concentrate CPVC Bending (cm SE) Trt 1 wk 2 wks 3 wks 4 wks 6 wks 8 wks Prevail 19.97 6.39a 26.30 0.21a ----------------Speckoz 0.73 0.18b 1.10 0.20b 1.37 0.19b 1.37 0.19c 1.47 0.22d 1.57 0.24c bifenthrin Speckoz 1.90 0.06b 3.33 0.26b 4.73 0.23b 6.40 0.65bc 9.83 0.98cd 27.50 0.21a permethrin Talstar0.97 0.03b 1.20 0.06b 1.43 0.09b 1.53 0.09c 1.77 0.09d 1.87 0.12c One Termidor 1.03 0.18b 1.37 0.15b 1.57 0.15b 1.63 0.15c 1.83 0.22d 1.93 0.22c Water 0.97 0.07b 1.23 0.13b 1.53 0.13b 1.57 0.12c 1.83 0.03d 1.83 0.03c Means followed by same letter are not significantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001)

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19 Table 2-2 CPVC bending after exposure to Four Times the Label Rate Termiticide Dilution CPVC Bending (cm SE) Trt 1 wk 2 wks 3 wks 4 wks Cyper TC 1.00 0.15a 2.33 0.30b 2.60 0.21b 3.00 0.29b Demon 1.43 0.07a 3.33 0.33b 3.77 0.27b 4.33 0.33b Dragnet 0.02 0.07a 1.10 0.26b 1.13 0.23b 1.13 0.23b Dursban 0.37 0.24a 1.27 0.09b 1.30 0.06b 1.70 0.12b Permethrin Pro 18.33 9.17a 18.53 8.97ab 18.67 8.83ab 18.67 8.83ab Prelude 17.47 8.53a 26.00 0.06a --------------Prevail 1.17 0.09a 2.97 0.03b 3.67 0.07b 5.03 0.19b Speckoz 17.93 8.97a 18.20 8.70ab 18.20 8.70ab 18.37 8.54ab permethrin. Water 0.03 0.03a 0.30 0.25b 0.33 0.23b 0.37 0.22b Means followed by same letter are not signifi cantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001)

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20 Table 2-3 CPVC bending after exposure to Two Times the Label Rate Termiticide Dilutions CPVC Bending (cm SE) Trt 1 wk 2 wks 3 wks 4 wks Permethrin Pro 1.57 0.15a 9.93 8.23a 10.63 7.88a 11.23 7.58b Prelude 10.20 8.15a 19.00 7.90a 19.83 7.07a 26.70 0.31a Speckoz 1.33 0.35a 1.33 0.35a 2.70 0.10a 3.83 0.18b permethrin Water 1.20 0.06a 1.20 0.06a 1.57 0.23a 2.13 0.27b Means followed by same letter are not signifi cantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001)

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21 Table 2-4 CPVC bending after exposure to Label Rate Termiticide Dilutions CPVC Bending (cm SE) Trt 1 wk 2 wks 3 wks 4 wks Permethrin Pro 1.10 0.12a 1.10 0.12a 2.03 0.49b 2.80 0.50b Prelude 1.80 0.38a 5.23 1.99a 21.00 5.70a 22.70 4.01a Speckoz Perm. 1.33 0.15a 1.50 0.31a 2.10 0.53b 3.20 0.60b Water 1.20 0.06a 1.20 0.06a 1.57 0.23b 2.13 0.27b Means followed by same letter are not signifi cantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001)

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22 Table 2-5 CPVC bending after exposure to Builders Sand Treated with Three Times the Labeled Volume Means followed by same letter are not signifi cantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001) CPVC Bending (cm SE) Trt 1wk 2 wks 3 wks 4 wks Permethrin Pro 0.73 0.07ab 0.87 0.18ab 1.47 0.54a 2.47 0.22a Prelude 1.27 0.09a 1.27 0.09a 1.47 0.12a 2.17 0.23a Sperckoz 1.03 0.27ab 1.03 0.27ab 1.73 0.12a 2.10 0.30a permethrin Water 0.47 0.03b 0.47 0.03b 0.83 0.18a 1.07 0.23b

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23 Table 2-6 CPVC bending after exposure to Builders Sand Treated with Two Times the Labeled Volume Means followed by same letter are not signifi cantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001) CPVC Bending (cm SE) Trt 1 wk 2 wks 3 wks 4wks Permethrin Pro 0.63 0.09a 0.93 0.26a 1.33 0.64a 1.70 0.45a Prelude 1.43 0.03a 1.43 0.03a 1.63 0.07a 2.23 0.19a Sperckoz Perm. 0.73 0.47a 0.73 0.47a 0.83 0.56a 1.63 0.64a Water 0.40 0.12a 0.47 0.07a 0.67 0.18a 1.07 0.12a

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24 Table 2-7 CPVC bending after exposure to Bu ilders Sand Treated at the Labeled Volume Means followed by same letter are not signifi cantly different from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001) CPVC Bending (cm SE) Trt 1wk 2wks 3wks 4wks Permethrin Pro 0.23 0.03a 0.33 0.09a 0.47 0.09a 0.90 0.31a Prelude 0.97 0.29a 0.97 0.29a 1.27 0.37a 2.27 0.35a Sperckoz 0.33 0.03a 0.47 0.07a 0.70 0.10a 1.50 0.31a permethrin Water 0.67 0.19a 0.77 0.09a 0.87 0.07a 1.60 0.25a

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25 Table 2-8 Results of chemical analysis fo r Volatile Organic Compounds using E.P.A. method 8260B Detected >100 g/l Detected < 100 g/l Not Detected > 5 g/l 1, 2, 4-Trichlorobenzene Benzene 1,1,1,2-Tetrachloroethane 1, 2, 4-Trimethylbenzene Chlo roform 1,1,1-Trichloroethane 1, 3, 5-Trimethylbenzene Styr ene 1,1,2,2-Tetrachloroethane Bromoform 1,1,2-Trichloroethane Ethybenzne 1,1-Dichloroethane Sec-Butylbenzene 1,1-Dichloroethene Toluene 1,2-Dibromo-3chloropropane Xylenes 1,2-Dibromomethane 1,2-Dichlorobenzene 1,2-Dichloroethane 1,2-Dichloropropane 1,2-Dichloropropene 1,3,5-Trichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 2-Chlorotoluene 4-Chlorotoluene Bromodichloromethane Bromomethane Carbon Tetrachloride Chlorobenzene Chloroethane Chloromethane cis-1,2-Dichloroethene cis-1,3Dichloropropene cis-1,4-Dichloro-2-butene Dibromochloromethane Dibromomethane Dichlorodifluoromethane Hexachlorobutadiene Iodomethane Methylene Chloride Tetrachloroethene trans-1,2-Dichloroethene trans-1,3-Dichloropropene trans-1,4-Dichloro-2-butene Trichloroethene Trichlorofluoromethane Vinyl Chloride

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26Table 2-9 Results of chemical analysis for the Major Vo latile Organic Compounds in common Termiticides 1,2,4-Tri1,2,4-Tri 1,3,5 TriBromoform EthylSecToluene Xylenes chloromethylmethylbenzene butylbenzene benzene benzene benzene Cyper X X X X X Demon X X X X X X X Dragnet X X X X Dursban X X X Permethrin X X Pro Prelude X X X X X X Premise 2 X Prevail X X X X X Speckoz X X bifenthrin

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27Table 2-9. Continued. 1,2,4-Tri1,2,4-Tri 1,3,5 TriBromoform EthylSecToluene Xylenes chloromethylmethylbenzene butylbenzene benzene benzene benzene Speckoz X X X permethrin Talstar One X X X Termidor

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Figure 2-1 Assay setup

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29 A B Figure 2-2. Examples of baton failures A) Fl exible baton failures in the foreground, B) Sharp break baton failures on bottom row Figure 2-3. Number of failed batons with term iticide at concentrate held for 8 weeks after set up

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30 Figure 2-4. Number of failed batons with term iticide at 4 times the label rate held for 4 weeks after set up

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31 Figure 2-5. Number of failed batons with term iticide at 2 times the label rate held for 4 weeks after set up Figure 2-6. Number of failed batons with term iticide at label rate held for 4 weeks after set up

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32 CHAPTER 3 COMBINED EFFECTS OF TERMITICIDES, CPVC GLUE, AND MECHANICAL STRESS ON CPVC Introduction As a result of improper workmanship, CPVC water supply lines may be placed in an incorrect spot after the slab has been poured. The di scovery of this incorrect positioning after the slab has been poured resu lts in a breakout. The builder breaks the slab where the CPVC comes up through and re -positions the CPVC line to another spot, creating stress on the CPVC. This will often re quire an additional application of CPVC glue to form a new joint. This exposes the CPVC to glue a second or even a third time. CPVC glue has volatile orga nic compounds in it, which pa rtially degrade the CPVC, temporarily melting it to create a bond betw een the two CPVC objects being glued. This combination of additional mechanical stress and chemical exposure may weaken the CPVC to the point of causi ng breakage and failure in the water supply line. My objectives for this study were to determine whether some termiticide concentrations in combination with CPVC glue woul d cause failure of CPVC pipe. Materials and Methods Termiticides Dursban TC (chlorpyrifos 44.0%; DowAgroSciences, Indianapolis, IN), a termiticide registered for treatment of new c onstruction, was tested in concentrate form and as a series of dilutions. The la beled rate for application of Dursban TC is a 0.5% emulsion. A 2.0% emulsion of Dursban TC, four times the labe l rate, was created by

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33 pipetting 9.09 g of product into a 200 ml volumetric flask an d then adding de-ionized water to a final volume of 200 ml. Assay Setup Chlorinated polyvinyl chloride ( 1.27 cm i.d., 1.6 cm o.d., CPVC; Noveon; Cleveland, OH) was cut into 26 and 31.5 cm long batons. Caps (1.27 cm i.d.; CPVC; Nimco; Elkhart, IN) were glued onto one e nd of the 26 cm batons using a CPVC glue (Oatey, All purpose cement; Cleveland, OH). Th e application of the CPVC glue was standardized and consisted of a single brush stroke around th e open end of the baton and the cap glued in place. The distal 3 cm of one end of a 31.5 cm baton was then exposed to varying amounts of the CPVC glue and/or CPVC prim er (Oatey, Purple Primer; Cleveland, OH). After the varying exposure to the CPVC glue and/or primer a CPVC coupling (1.27 cm i.d., Genova, Davison, MI) was glued in place at the end of the 3 cm section of the 31.5 cm baton. After the coupling was glued in pla ce, the 26 cm baton was then glued onto the other end of the CPVC coupling creating a 58 cm baton with a coupling in the middle. The reasoning behind exposing th is 3 cm section of the baton to the varying CPVC glue levels was that this is the location where a ll of the weight and stress of the baton are focused. The first CPVC glue variation was glui ng on the CPVC coupli ng with the CPVC glue using the standardized method, exposing only the bottom 3 cm of the 31.5 cm baton to the CPVC glue. The second CPVC glue variation was gluing on the CPVC coupling using the CPVC primer and the standard amount of CPVC glue. The third CPVC glue variation was exposing the 3 cm sections to the CPVC glue by submerging them in a glass beaker filled with the CPVC glue for 10 min. The fourth CPVC glue variation was

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34 exposing the 3 cm sections to the CPVC glue by submerging them in a glass beaker filled with the CPVC glue for 10 min, removed, wiped clean, dried for 1 hour, and then submerged again for 10 min. more. To determine whether the different glue va riations in combination with termiticides could affect the CPVC batons, 50 ml of the Dursban TC concentrate or termiticide dilution was added to each baton. The open e nd of the baton was then capped using the standardized method. A pegboard was created by drilling holes (2.54 cm) into two sheets of 1.27 cm x 1.22 m x 2.44 m pressure treated plywood. Tw o plywood sheets were separated by 19.50 cm .The batons were then placed into the pegboard so that the batons extended ~34.6 cm from the front of the pegboard. To put stress on the batons 1.540 0.027 kg masonry bricks (Lowes, Mooresville, NC; 5.5 cm x 9.0 cm x 19.5 cm) were attached with nylon rope (Lehigh; Mexico; 15.2 m x 0.48 cm) cut into 45.7 cm sections so that the masonry bricks hung on the long end of the projecting ba ton, 2 cm from end of baton. The length of the rope was 7.62 cm from the bottom of the baton to the top of masonry brick. The experiments with the glue variations were set up as a randomized complete block design with three batons for each treatm ent level of CPVC glue exposure. For each level of CPVC glue exposure there were 2 treat ments and a control for a total of 9 batons. The experiment had 4 different levels of CPVC glue exposure for a total of 36 batons and was run for 4 weeks. CPVC bending was determined by measuring the distance between the pegboard and the masonry brick. CPVC bend ing was measured at one, two, three, and four weeks. Daily observations were done to assess failures. Failures were considered to

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35 be batons breaking or bending all the way so that the masonry brick rested against the pegboard. Data Analysis The bending data were analyzed using one way analysis of variance and means were separated using Student Newman-Kuels test when P values for the analysis of variance were sign ificant (n = 3, = 0.05; SAS Institute 2001). Results and Discussion Treatments inserted into CPVC batons c ontinuously contacted the interior of the baton over a period of 4 weeks. The combin ation of water and CPVC glue generally caused little CPVC bending and no breakage of the batons. In contrast, the combination of termiticides and CPVC glue did affect the CPVC causing significant bending of the baton. For each treatment the amount of CP VC bending depended on the amount of glue exposure, the more glue exposure the more CPVC bending of the batons. In cases of breakage, a sharp break occurred at the area of CPVC glue exposure on the batons. This break caused the brick to drop and rest ag ainst the pegboard, resu lting in a maximum bending distance of ~22.73 to 25.90 cm. Dursban Concentrate Assay At 1 week, no treatments had bent significantly from each other (Table 3-1). Treatments that had 1 baton failure were ba tons exposed to the standard CPVC glue application. Treatments that had 2 baton failure s were the batons exposed to the standard CPVC glue application and a CPVC primer. Treatments that had 3 baton failures were batons exposed to the 10 and twenty-m inute submersion in the CPVC glue.

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36 At 2 weeks, no treatments had bent signi ficantly from each other but all treatment batons had failed. Treatments that had 3 bat on failures were the batons exposed to the standard CPVC glue and the batons exposed to the CPVC primer + standard CPVC glue. Termiticide Dilution Assay At 1 week, treatments were significant fr om each other (Table 3-1). The treatments with the batons exposed to the 10 minute subm ersion in the CPVC glue bent significantly from the batons exposed to the standard CP VC glue and CPVC primer + standard CPVC glue application. The treatment glue level th at had significantly more bending than the 10 min submersion were the glue level of the twenty-minute submersion. The only treatment glue levels with baton failures (3) were th e twenty-minute submersion batons. At 2, 3, and 4 weeks the treatment with the batons exposed to the 10 minute submersion bent significantly from the batons exposed to the standard CPVC glue a nd the batons exposed to the CPVC primer + standard CPVC glue. At 2, 3, and 4 weeks no treatments experienced baton failure. Water Assay At 1, 2, 3, and 4 weeks treatments were si gnificant from each other (Table 3-1). The treatments with the batons exposed to the CPVC primer + sta ndard CPVC glue and the batons exposed to the 10 minute submer sion bent significantly from the batons exposed to the standard CPVC glue applica tion. The treatment that had even more CPVC bending that was significant from all other treatments were ba tons exposed to the twenty minute submersion in the CPVC glue. Discussion The combination of the Dursban TC concentrate and the CPVC glue exposures resulted in all batons fail ing, resulting in a maximum CP VC bending distance of 22.73

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37 25.90 cm. The high concentration of VOCs from the termiticide concentrate and CPVC glue caused the CPVC batons to fail With the dilution of the Dursban TC concentrate the VOC concentration in the treatment wa s lowered. The combination of those VOCs and the CPVC glue VOCs was enough to cause significant CPVC bending and failure in the highest exposure to the CPVC glue. The CPVC batons that were exposed to the CPVC glue for the longest amount of time showed the most CPVC bending. As th e amount of time the CPVC was exposed went down the CPVC bending also was lowere d. This trend was evident in all three treatments. The experiments also indicated excessive CPVC glue applications can degrade the CPVC in combination with wate r or termiticides resulting in significant CPVC bending.

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38 Table 3-1 CPVC bending after exposure to Termiticide, Termiticide Dilutions, and CPVC glue. CPVC Bending SE cm TRT Glue 1 wk 2 wks 3 wks 4 wks exposure Dursban standard 9.93 8.03a 25.90 0.26a1 --------concentrate standard + 17.70 7.70a 25.50 0.12a1 --------primer 10 min dunk 24.97 0.44a ------------20 min dunk 22.73 0.23a ------------Dursban standard 1.23 0.20c 1.53 0.15b 1.80 0.21b 2.07 0.23b 4X Label standard + 1.80 0.10c 2.10 0.10b 2.30 0.10b 2.60 0.10b primer 10 min dunk 4.40 0.44b 5.53 0.64a 6.20 0.64a 6.63 0.52a 20 min dunk 22.97 0.09a ------------Water standard 0.40 0.31c 0.43 0.30c 0.60 0.35c 0.73 0.33c standard + 1.07 0.03bc 1.17 0.03c 1.27 0.09c 1.43 0.07c primer 10 min dunk 2.13 0.38b 2.47 0.32b 2.77 0.29b 3.13 0.20b 20 min dunk 4.07 0.63a 4.63 0.52a 4.97 0.46a 5.43 0.47a 1 Means compared using students 2 tail test 2 All other means analyzed acco rding to treatment using Student Newman Kuels test, n = 3, = 0.05 Means with the same letter are not significantly different from each other

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39 CHAPTER 4 COMBINED EFFECTS OF VOLA TILE ORGANIC COMPOUNDS AND MECHANICAL STRESS ON CPVC Introduction Soil termiticides are commonly formulated as emulsifiable concentrates or suspendable concentrates. The main difference between the two formulations is that the emulsifiable concentrates will use volatile organic compounds (VOCs) to keep the active ingredient dissolved in the solution. The use of these VOCs leaves th e potential for them to interact with non-target organisms and obj ects. My objectives we re to determine the effects of each individual VOC on CPVC pipe. Materials and Methods Chemical Analysis for Volati le Organic Compounds (VOCs) All 12 termiticides were diluted to 40 0 ppm AI in deionized water and were analyzed using the E.P.A. method 8260B (EPA 1992; Nelson 2003) to determine the presence of VOCs. Samples (5 l) were inject ed into the Purge & Trap attached to the gas chromatograph/mass spectrometer (GC/MS). The samples were under helium flow to cause the VOCs to volatilize off of the samples for collection in the Purge & Trap. The collected VOCs were then run through the GC/MS to determine which VOCs were present. These quantities were then compared with standards and amended into parts per billion (ppb; g/l).

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40 Volatile Organic Compounds Volatile organic compounds found in quantities above 100 g/l were purchased and used. The eight VOCs were: 1,2,4 Trichlorobenzene (Sigma-Aldrich Reagent Plus 99%), 1,2,4 Trimethylbenzene (Sigma-Aldrich 98%), 1,3,5 Trimethylbenzene (SigmaAldrich 98%), Bromoform (Sigma-Aldrich 99+%), Ethylbenzene (Fischer Scientific certified), Sec-Butylbenzene (Sigma-Aldrich 99+%), Toluene (Fischer Scientific 99.9%), and Xylenes (Fischer Scientific 99.5%). Assay Setup Chlorinated polyvinyl chloride ( 1.27 cm i.d., 1.6 cm o.d., CPVC; Noveon; Cleveland, OH) was cut into 58 cm long ba tons. Caps (1.27 cm i.d.; CPVC; Nimco; Elkhart, IN) were glued onto one end of each baton using a CPVC glue (Oatey, All purpose cement; Cleveland, OH). The applicatio n of the CPVC glue was standardized and consisted of a single brush stroke around the open end of the baton and the cap glued in place. To determine whether the volatile orga nic compounds found in termiticides could affect the CPVC batons, 50 ml of a volatile organic compound was added to each baton. The open end of the baton was then capped using the same method. A pegboard was created by drilling holes (2.54 cm) into two sheets of 1.27 cm x 1.22 m x 2.44 m pressure treated plywood. Tw o plywood sheets were separated by 19.50 cm .The batons were then placed into the pegboard so that the batons extended ~34.6 cm from the front of the pegboard. To put stress on the batons 1.540 0.027 kg masonry bricks (Lowes, Mooresville, NC; 5.5 cm x 9.0 cm x 19.5 cm) were attached with nylon rope (Lehigh; Mexico; 15.2 m x 0.48 cm) cut into 45.7 cm sections so that the masonry

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41 bricks hung on the long end of the projecting ba ton, 2 cm from end of baton. The length of the rope was 7.62 cm from the bottom of th e baton to the top of masonry brick. Volatile organic compound experiments we re a randomized complete block design with 3 batons for each treatment. Controls were de-ionized water (50 ml) in a baton. The experiment had 8 treatments and a control for a total of 27 batons and was run for 1 week. CPVC bending was determined by meas uring the distance between the pegboard and the masonry brick. Failures were considered to be batons breaking or bending all the way so that the masonry brick rested agai nst the pegboard. CPVC bending was measured at 1 week and daily observations were done to assess failures. Data Analysis The data was compared using a one-way analysis of variance, and means were separated using Student Newman-Keuls test when P values were significant (n = 3, = 0.05; SAS Institute, 2001). Results and Discussion Chemical Analysis for VOCs The analysis indicated eight VOCs present in the termiticides with quantities above 100 l: 1,2,4 Trichlorobenzene, 1,2,4 Trimet hylbenzene, 1,3,5 Trimethylbenzene, Bromoform, Ethylbenzene, Sec-Butylbenzene, Toluene, and Xylenes. Other VOCs that were present but in quantities less than 100 l were: Benzene, Chloroform, and Styrene. A second table was constructed to show which of these major VOCs were associated with each termiticide (Table 4-1). Volatile Organic Compounds Assay Treatments inserted into CPVC batons c ontinuously contacted the interior of the baton over a period of 1 week. Water caused little bending with 0.8 to < 1.1 cm of CPVC

PAGE 52

42 bending and no breakage of the baton (Table 42). In contrast the VOCs did affect the CPVC causing significant bending of the ba ton. CPVC bending was observed to be either making the baton more flexible or mo re brittle. As the batons became flexible, CPVC bending increased, eventually reachi ng a maximum bending distance of ~26.90 to 27.63 cm, at which distance the baton was bent in a semicircle with the brick touching the pegboard. For batons that became brittle, ba ton breakage occurred resulting in a sharp break at the supporting area of the pegboard. Th is break caused the brick to drop and rest against the pegboard, resulting in a maximum bending distance of ~26.90 to 27.63 cm. All of the treatments, except for the contro ls, experienced all 3 batons failing by the 4th day. The measurements at 1 week consiste d of only the controls being measured and all treatments had CPVC bending si gnificant from the controls. Discussion The VOCs tested in the experiments were found in high quantitie s in the analyzed samples. The VOCs were tested separately fr om each other to see their individual affects on the CPVC. The concentrations of VOCs used in the experiments were higher than the reported quantities but again they were tested this way to see their individual affects on the CPVC. These VOCs all had detrimental aff ects to the CPVC batons causing failure to all experimental units within four days. VOCs were present in all of the tested termiticides except for Termidor a suspendable concentrate. Termiticides with the same active ingredient often had the same VOCs present in the analyzed samples. However, the quantities found for each VOC varied from termiticide to termiticide.

PAGE 53

43Table 4-1. Results of chemical analysis for Major Volatile Organic Compounds _____________________________________________________________________________________________ Solvent concentration ( g/ liter) in Termiticide Concentrate 1,2,4-Tri1,2,4-Tri 1,3,5 TriBromoform EthylSecToluene Xylenes chloromethylmethylbenzene butylbenzene benzene benzene benzene Cyper 343.21 32.36 0.94 6,982.82 14.52 Demon 3,375.92 335.52 134.52 864.23 853.9 316.59 751.99 Dragnet 36.19 10.28 56.89 0.98 Dursban 565.27 852.03 463.2 Permethrin 2.03 37.48 Pro Prelude 5.63 58.73 48.76 10.51 188.21 356.885 Premise 2 124.86 Prevail 49.94 28.27 1.94 2.71 5.88 Speckoz 0.97 12.74 bifenthrin _________________________________________________________________________________________________

PAGE 54

44 Table 4-1 cont. Results of chemical analysis fo r Major Volatile Organic Compounds _________________________________________________________________________________________________ Solvent concentration ( g/ liter) in Termiticide Concentrate 1,2,4-Tri1,2,4-Tri 1,3,5 TriBromoform EthylSecToluene Xylenes chloromethylmethylbenzene butylbenzene benzene benzene benzene Speckoz 2.01 5.37 38.07 permethrin Talstar One 3.03 3.75 1.09 Termidor _________________________________________________________________________________________________

PAGE 55

45 Table 4-2 CPVC bending after exposu re to Volatile Organic Compounds CPVC Bending (cm SE) Trt 1 wk 1, 2, 4-Trichlorobenzene 26.90 0.15a 1, 2, 4-Trimethylbenzene 27.13 0.49a 1, 3, 5-Trimethylbenzene 27.63 0.22a Bromoform 26.97 0.07a Ethylbenzene 27.13 0.28a Sec-Butylbenzene 26.93 0.09a Toluene 26.97 0.12a Water 0.13 0.07b Xylenes 27.27 0.12a Means followed by same letter are not significantly diff erent from each other. (Student Newman Kuels test, n = 3, = 0.05; SAS Institute 2001)

PAGE 56

46 CHAPTER 5 CONCLUSIONS Subterranean termites cause millions of dolla rs in damage annually. The traditional method of preventing termites from causing da mage to a home is a pre-construction soil treatment. This involves an appl ication of termiticide to the so il before the slab is poured. Termiticide formulations are complex mixtures of active ingredients, solvents, emulsifiers, and other additives. VOCs are found as components of most formulations and are much smaller molecules than the ac tive ingredients, maki ng them capable and likely suspects that can degrade CPVC. Termiticides have the highest concentration of VOCs in their concentrate form. Dilution with water lowers the VOC concentr ation. In my study, I constructed batons and filled them with termiticides and dilutions of termiticides. When the CPVC batons were mechanically stressed, most termiticide concentrates caused the pipe to fail. Dilutions of termiticides to four, two, and one times the label rates caused reduced amounts of failure compared with the concen trated termiticide. Batons filled with termiticide treated builders sand did not br eak even when mechanically stressed. Termiticides were mixed to 400 ppm ai in water. The resultant solutions were analyzed for the presence of VOCs. VOCs were present in all of the tested termiticides except for Termidor a suspendable concentrate. Termiticides with the same active ingredient often had the same VOCs presen t in the analyzed samples. However, the quantities found of each VOC varied from termiticide to termiticide. All of the termiticides concentrates that caused failure of the CPVC batons had some combination

PAGE 57

47 of these VOCs. In fact, all of the termiticide concentrates that failed had one VOC in common: 1,3,5-Trimethylbenzene. Batons with a glue joint located at the fulcrum point were constructed and filled with Dursban TC and water based dilutions. The batons were then mechanically stressed. The termiticide concentrated, mechanical stress, and CPVC glue resulted in all batons failing, reaching a maximum CPVC bending distance of 22.73 25.90 cm. The high concentration of VOCs from the termiticide concentrate and the acetonic VOCs in the CPVC glue caused the CPVC batons to fail. With the dilution of the Dursban TC concentrate, the VOC concentration in the tr eatment was lowered. Similarly, dilutions of terititicides caused si gnificant CPVC bending and failure in the highest exposure to the CPVC glue. CPVC batons were constructed and filled with VOCs rather than termiticides. The VOCs tested in the experiments were found in quantities >100 ug/liter in the analyzed samples. All tested VOCs had caused failure of the CPVC batons within four days. One VOC 1, 3, 5, Trimethylbenzene cause d batons to fail within minutes and was a solvent found in all termiticide concentrat es that caused CPVC baton failure. Termiticides have been blamed for causing CPVC failure in new construction. My studies demonstrate that the VOCs found in mo st of the termiticide formulations cause CPVC batons to fail when they are mechanica lly stressed. Mechanical stress can be in the form of pipe bending or water pressure. The problem of termiticides degrading CPVC and causing failure or rupture may be solved in the following ways: 1) avoid repeated applications of termiticides that contain VOCs particularly ones containing 1, 3, 5, Trimethylbenzene, to areas where breakout s have occurred, 2) avoid exposure of

PAGE 58

48 CPVC pipe to liquid termiticides, especially annular spaces of plastic sleeves around CPVC where it penetrates the slab or tub box enclosures where puddles of termiticide can occur, 3) avoid treating areas where there has been repeated or excessive application of CPVC glue, and 4) avoid treati ng areas where CPVC pipe has been mechanically stressed by bending or excessive water pressure.

PAGE 59

49 APPENDIX CALCULATIONS FOR BUILDERS SAND TREATMENTS Baton Volume = rL = (0.635 cm) (58 cm) = 73.4725 cm Builders Sand Density = 112.76 gm soil = x gm soil = 82.85 gm 100 cm 73.4725 cm 73.4725 cm Amount of termiticide spray solution to treat 73.4725 cm; 4 gal = 15,140 ml 10 ft 141,584.233 cm 15,140 ml = x ml termiticide = 7.86 ml termiticide 141,584.233 cm 73.4725 cm 73.4725 cm

PAGE 60

50 LIST OF REFERENCES Abbink, J. 1991. Zur biochemie von imidacloprid. Pflanzenschutz-Nach richten Bayer 44: 183-194. Beal, R. H. and V. K. Smith. 1971. Relative susceptibilities of Coptotermes formosanus Reticulitermes flavipes and R. virginicus to soil insecticides. J. Econ. Entomol. 64: 472-475. Brown, A. A. 1934. Introduction, pp 21-27. In : Kofoid, C. A. [ed.] Termites and termite control. University of Ca lifornia Press, Berkeley. Cole, L.M., R.A. Nicholson, and J.E. Casida. 1993. Action of phenylpyrazole insecticides at the GABA-gated chloride ch annel. Pestic. Biochemical. Physiol. 46: 47-54. Environmental Protection Agency (EPA). 1992. Test methods for organic chemical analysis of municipal and industr ial wastewater. Washington, D.C. Farm Chemicals Handbook 1997. 83: E30E31., Meister Publishing Company, Willioughby, OH. Ibrahim, S.A., G. Henderson, and H.Fei. 2003. Toxicity, repellency, and horizontal transmission of fipronil in the form osan subterranean termite (Isoptera: Rhinotermitidae). J. Econ. Entomol. 96: 461-467. Forschler, B. T. 1994. Survivorshhip and t unneling activity of Reticulitermes flavipes (Kollar) (Isoptera: Rhinotermitidae) in re sponse to termiticide soil barriers with and without gaps of untreated soil. J. Entomol. Sci. 29: 43-54. Gentry, J. W. 1966. Formosan subterranean termite. A new pest in the continental United States. Agric. Chem. 21: 63-64 Grace, J. K., J. R. Yates, M. Tamashiro, and R. T. Yamamoto. 1993. Persistence of organochlorine insecticides for Formos an subterranean termite (Isoptera: Rhinotermitidae) control in Hawaii. J. Econ. Entomol. 86: 761-766. Hagen, H. A. 1876. The probable danger from white ants. Amer. Naturalist 10(7): 401-410. Hetrick, L. A. 1957. Ten years of testing organic insect icides as soil poisons against the Eastern subterranean termite. J. Econ. Entomol. 50: 316-317.

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51 Hlldobler, B. and E. O. Wilson. 1990. The ants. Harvard University Press, Cambridge, MA. 732. Kard, B. M., J. K. Mauldin, and S. C. Jones. 1989. Evaluation of soil termiticides for control of subterranean termites (Isoptera). Sociobiology 15: 285-297. Kreer, J. G. 1934. Termites. Exterminators Log 2(11): 6-8, 14-15. Krishna, K. 1969. Chapter 1, Introduction. pp. 1-17. In : Krishna, K, and F. M. Weesner [eds.] Biology of termites. Academic Press, New York. Kuriachan, I. and R. E. Gold. 1998. Evaluation of the ability of Reticulitermes flavipes Kollar, a subterranean termite (Isoptera : Rhinotermitidae), to differentiate between termiticide treated a nd untreated soils in a la boratory test. Sociobiology 32: 151-166. Lenz, M., J. A. L. Watson, R. A. Barrett, and S. Runko. 1990. The effectiveness of insecticidal soil barriers ag ainst subterranean termites in Australia. Sociobiology 17: 9-36. Mallis, Arnold. 2004. Handbook of pest control, 8th ed., pp. 1079-1084. Mallis handbook and technical traini ng company, Cleveland ,OH Mauldin, J. K. 1986. Economic impact and control of term ites in the United States, pp. 130-143. In: Vinson, S.B. [ed.], Economic impact and control of social insects. Praeger, New York. Nelson, Peg. 2003. Index to EPA test methods. US EPA New England Region 1 Library. pp 20-32. Noveon 2003. November,2005. Noveon Plumbing Systems. http://www.flowguardgold.com/designIns tallation/chemical Compatibility.asp Randall, M. and T. C. Doody. 1934a. Wood preservatives and protective treatments, pp 385-416. In : Kofoid, C. A. [ed.] Termites and termite control. University of California Press, Berkeley. Randall, M. and T. C. Doody. 1934b. Poison dusts, pp 385-416. In : Kofoid, C. A. [ed.] Termites and termite control. University of California press, Berkeley. Randall, M. and T. C. Doody. 1934c. Ground treatments, pp 385-416. In : Kofoid, C. A. [ed.] Termites and termite control. Univ ersity of California Press, Berkeley. Smith, J. L. and M. K. Rust. 1990. Tunneling response and mo rtality of the Western subterranean termite (Isoptera: Rhinotermitidae) to soil treated with termiticides. J. Econ. Entomol. 84: 181-184.

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52 Smythe, R. V. and F. L. Carter. 1970. Feeding responses to sound wood by Coptotermes formosanus, Reticulitermes fl avipes, and R. virg inicus. (Isoptera: Rhinotermitidae) Ann. Entomol. Soc. Amer. 63: 841-847. Snyder, T. E. 1934. Termite control. Exterminators Log 2(10) : 5-12. Snyder, T. E. 1935. Termite research in the United States. Exterminators Log 3(12): 78. Statistical Analysis Softw are Institute (SAS). 2001. Statistical analysis software computer program, version 8.01. Institute, S. A. S., Cary, NC. Su, N. Y. 1991. Termites of the United States and their control. SP World 17: 12-15 Su, N. Y. and R. H. Scheffrahn. 1990. Comparison of eleven soil termiticides against the Formosan subterranean termite and Ea stern subterranean termite (Isoptera: Rhinotermitidae). J. Econ. Entomol. 83: 1918-1924. Su, N. Y., R. H. Scheffrahn, and P. M. Ban. 1993. Barrier efficacy of pyrethroid and organophosphate formulations against subterranean termites (Isoptera: Rhinotermitidae). J. Econ. Entomol. 86: 772-775. Su, N. Y., M. Tamashiro, J. R. Yates, and M. H. Haverty. 1982. Effect of behavior on the evaluation of insecticides for preven tion or remedial control of the Formosan subterranean termite. J. Econ. Entomol. 75: 188-193. Su, N. Y., G. S. Wheeler, and R. H. Scheffrahn. 1995. Subterranean termite (Isoptera: Rhinotermitidae) penetration into sand treated at various thicknesses with termiticides. J. Econ. Entomol. 88: 1690-1694. Turner, N. 1941. Termites and their contro l. Pests 9(3): 22-27. Windholtz, M., S. Budavari, R. F. Blum etti, E. S. Otterbein [eds.]. 1983. The Merck index: an encyclopedia of chem icals, drugs, and biologicals, 10th ed. Merck & Co., Inc. Rahwa, N.J. Wood, T. G. and M. J. Pearce. 1991. Termites in Africa: the environmental impact ofcontrol measures and damage to crops trees, rangeland and rural buildings. Sociobiology 19: 221-234.

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53 BIOGRAPHICAL SKETCH Justin Saunders was born on December 28, 1977, in Richmond, VA, to Marshall and Janice Saunders. He has a brother and a sister, Graham and Ann Marshall Saunders. He and his family lived in Richmond, VA, for two years. After this time his father took a job in West Palm Beach, FL. Justin a ttended Suncoast High School from 1992-1995. His senior year of high school was finished at Forest Hill High School from 1995-1996. After high school he attended the University of S outh Florida starting in August of 1996. He earned a Bachelor of Science in biology in May of 2002. After graduation he began work in several different veterinary clinics in Ta mpa and Gainesville, FL. He applied several times to the University of Floridas Doctor of Veterinary Medici ne program, but the program did not know what it was missing out on. During the application process to the veterinary program he started work in the Urban Entomology Laboratory where he saw the great potentials for graduates of th e program. After being fed up with the Vet School he gained interest and acceptance in to the masters degree program in urban entomology.


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Title: Combined Effects of Termiticides, Volatile Organic Compounds, and Mechanical Stress on Chlorinated Polyvinyl Chloride (CPVC)
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Title: Combined Effects of Termiticides, Volatile Organic Compounds, and Mechanical Stress on Chlorinated Polyvinyl Chloride (CPVC)
Physical Description: Mixed Material
Copyright Date: 2008

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COMBINED EFFECTS OF TERMITICIDES, VOLATILE ORGANIC COMPOUNDS,
AND MECHANICAL STRESS ON CHLORINATED POLYVINYL CHLORIDE
(CPVC)














By

JUSTIN S. SAUNDERS


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE

UNIVERSITY OF FLORIDA


2005

































Copyright 2005

by

Justin S. Saunders
































This thesis is dedicated to my parents, Janice Carmelo and Marshall Saunders
















ACKNOWLEDGMENTS

I would like to thank my family for their constant support. I want to thank my

friends for the many good times, Colin Hickey, Dave Melius, and Ryan Welch. I would

like to thank Gil Marshall and Tiny Willis for their help with my experiments and great

conversations.

I would especially like to thank my advisor, Dr. Phil Koehler, for his mentoring and

advancement of my personal self. He has given me the opportunity to present myself

before a broad range of audiences, which at the time seemed a chore but only

strengthened my knowledge and skills in the area of urban entomology. I would also like

to thank Dr. Richard Patterson and Dr. Brian Cabrera for their accommodations and

support with my thesis.
















TABLE OF CONTENTS



A C K N O W L E D G M E N T S ................................................................................................. iv

LIST OF TA BLE S ....................................................... .. ........... ............ .. vii

L IST O F FIG U R E S .............. ............................ ............. ........... ... ........ viii

ABSTRACT ........ ........................... ...... .......... .......... ix

CHAPTER

1 LITERATURE REVIEW ............................................................ ............... 1

Subterranean Termite Problem s ...................................................... ...............1
Subterranean T erm ite B iology ........................................................... .....................
E arly E efforts at Term ite C ontrol............................................................................. 2
S o il T re atm en ts ................................................................................3
M odem Soil Term iticides .......................................................... ..............5

2 COMBINED EFFECTS OF TERMITICIDES AND MECHANICAL STRESS
ON CHLORINATED POLYVINYL CHLORIDE (CPVC)............... ..................7

In tro d u ctio n ...................................... .................................. ................ 7
M materials and M methods ................................................................. ....................... 8
T e rm itic id e s .................................................................................8
F orm ulation P reparation ....................................... .......................................9
Term iticide dilutions ................................ ... ......... ................ .9
B builders sand treatm ent........................................................... ............... 10
A ssay S etu p ................... ..... ............................ ...................... .............. .......10
Chemical Analysis for Volatile Organic Compounds (VOCs) ..........................12
D ata A n aly sis ................................................................... ............... 12
R esu lts an d D iscu ssion ..................................................................... .... ..............12
Term iticide C concentrate A ssay .............................................. ............... ... 13
T erm iticide D ilutions A ssay ............................................................ ................ .. 14
Builders Sand Treatment Assay ..................................................15
Chemical Analysis for Volatile Organic Compounds (VOCs) ..........................15
D iscu ssio n ...................................... .............................. ................ 16





v









3 COMBINED EFFECTS OF TERMITICIDES, CPVC GLUE, AND
M ECHAN ICAL STRESS ON CPVC ............................................. .....................32

In tro du ctio n ..................................... ................... ............................ 3 2
M materials and M methods ....................................................................... ..................32
T e rm itic id e s .........................................................................................................3 2
A ssay S etu p ................................................................................................... 3 3
D ata A n a ly sis ................................................................................................. 3 5
R results and D discussion ..................... .. .. .......................... ..... ..... 35
D ursban Concentrate A ssay ........................................ .......................... 35
T erm iticide D ilution A ssay ................................................. ............... ...36
W after A ssay .................................................. ................ 3 6
Discussion ............. ..... ....................................36

4 COMBINED EFFECTS OF VOLATILE ORGANIC COMPOUNDS AND
MECHANICAL STRESS ON CPVC ............................................. ............... 39

In tro du ctio n ...................................... ................................................ 3 9
M materials and M methods ................. ..................................................................... 39
Chemical Analysis for Volatile Organic Compounds (VOCs) ..........................39
V volatile O organic C om pounds ................................... .......................... .. ......... 40
A ssay S etu p ..................................................... ................ 4 0
D ata A n aly sis................................................ ................ 4 1
R results and D discussion .............................................. .... .... ... .... 4 1
Chem ical A analysis for V O C s ........................................ ......................... 41
Volatile Organic Compounds Assay ....................................... ............... 41
D iscu ssion ...................................... .............................. ................ 4 2

5 C O N C L U SIO N S ............................................................................. ................. .. 4 6

APPENDIX CALCULATIONS FOR BUILDERS SAND TREATMENTS ..................49

L IST O F R E F E R E N C E S ........................................................................ .....................50

B IO G R A PH IC A L SK E TCH ..................................................................... ..................53
















LIST OF TABLES


Table page

2-1 CPVC bending after exposure to Termiticide Concentrate............................... 17

2-2 CPVC bending after exposure to Four Times the Label Rate Termiticide
D ilution .......... ... ......... ............................................ ...... .. ..... ... 19

2-3 CPVC bending after exposure to Two Times the Label Rate Termiticide
D ilu tio n s ............ ............ .. ........... .. .................................................2 0

2-4 CPVC bending after exposure to Label Rate Termiticide Dilutions........................21

2-5 CPVC bending after exposure to Builders Sand Treated with Three Times the
L labeled V olum e ................... .... ............................ .. ...... .. ............. 22

2-6 CPVC bending after exposure to Builders Sand Treated with Two Times the
L labeled V olum e ................... .... ............................ .. ...... .. ............. 23

2-7 CPVC bending after exposure to Builders Sand Treated at the Labeled Volume ...24

2-8 Results of chemical analysis for Volatile Organic Compounds using E.P.A.
m ethod 8260B ........................................................................25

2-9 Results of chemical analysis for the Major Volatile Organic Compounds in
com m on Term iticides....... .................................... .. ............. .. ......26

3-1 CPVC bending after exposure to Termiticide, Termiticide Dilutions, and CPVC
glu e ....................................................................................... 3 8

4-2 CPVC bending after exposure to Volatile Organic Compounds............................45
















LIST OF FIGURES


Figure p

2-1 A ssay setup ............................................................................................... ........28

2-2 Examples of baton failures A) Flexible baton failures in the foreground, B)
Sharp break baton failures on bottom row .................................... ............... 29

2-3 Number of failed batons with termiticide at concentrate held for 8 weeks after
set u p ............................................................................... 2 9

2-4 Number of failed batons with termiticide at 4 times the label rate held for 4
w weeks after set up ........................ ......... .. .... ..... ............... 30

2-5 Number of failed batons with termiticide at 2 times the label rate held for 4
w eek s after set u p .............. .............. ........... ...... .............. ................ .. 3 1

2-6 Number of failed batons with termiticide at label rate held for 4 weeks after set
u p .................. ..................................... ........................... 3 1















Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Science

COMBINED EFFECTS OF TERMITICIDES, VOLATILE ORGANIC COMPOUNDS,
AND MECHANICAL STRESS ON CHLORINATED POLYVINYL CHLORIDE
(CPVC)

By

Justin S. Saunders

December 2005

Chair: Philip Koehler
Major Department: Entomology and Nematology

Subterranean termites cause millions of dollars in damage annually. The traditional

method of preventing termites from causing damage to a home is a pre-construction soil

treatment. This involves an application of termiticide to the soil before the slab is poured.

Highest application rates are applied to critical areas where plumbing and utilities

penetrate the slab into the structure.

CPVC batons were constructed and filled with termiticide concentrates, their

dilutions or treated builders sand. Termiticides tested were Cyper TC, Demon TC,

Dragnet SFR, DursbanTM TC, Permethrin Pro Termiticide-Turf-Ornamental, Prelude,

Premise 2, Prevail FT, Speckoz Bifenthrin Termiticide, SpeckozTM Permethrin TC,

Talstar OneTM, and Termidor SC. Batons were mechanically stressed and bending was

measured at various times. Termiticide concentrate failures occurred for Cyper TC,

Demon TC, Dragnet SFR, Prelude, and Prevail FT within 10 days. Failures









occurred for DursbanTM TC, Permethrin Pro Termiticide-Turf-Ornamental, and

SpeckozTM Permethrin TC between 20-50 days. No failures occurred for Premise 2,

Speckoz Bifenthrin Termiticide, Talstar OneTM, and Termidor SC. Termiticide

dilution, four times the label rate, failures occurred for Prelude, Permethrin Pro

Termiticide-Turf-Ornamental, and SpeckozTM Permethrin TC. Termiticide dilution, two

times the label rate, failures occurred for Prelude and Permethrin Pro Termiticide-Turf-

Ornamental. Termiticide dilution, label rate, failures occurred for Permethrin Pro

Termiticide-Turf-Ornamental. No failures occurred for all of the CPVC batons filled with

termiticide treated builders sand.

To determine the effect of CPVC glue exposure on CPVC batons filled with

DursbanTM TC concentrate and dilutions of DursbanTM TC, CPVC batons were

constructed with a glued joint at the fulcrum point for the mechanical stress. All

DursbanTM TC concentrate batons failed within 10 days. The CPVC batons filled with the

Dursban TM TC dilutions had significant bending from each other and experienced

failures in the batons exposed to the highest CPVC glue levels.

Water dilutions of 400 ppm ai were prepared for the same termiticides. GC/MS

analysis revealed 8 major VOCs, 1,2,4 Trichlorobenzene, 1,2,4 Trimethylbenzene, 1,3,5

Trimethylbenzene, Bromoform, Ethylbenzene, Sec-Butylbenzene, Toluene, and Xylenes

and 3 minor VOCs, Benzene, Chloroform, and Styrene.

CPVC batons were constructed and filled with the major VOCs. All caused CPVC

failure within 4 days. One VOC, 1, 3 5 Trimethylbenzene, caused failure within minutes

and was found in all termiticides that caused CPVC failure.














CHAPTER 1
LITERATURE REVIEW

Subterranean Termite Problems

In the United States, the termite family Rhinnotermitidae consists of four genera of

subterranean termites: Coptotermes, Heterotermes, Reticulitermes, and Prorhinotermes.

Subterranean termites will construct underground tunnels that connect the colony to food

and water (Su 1991). Termites use symbionts in the hindgut to help digest the cellulose in

wood to simple sugars that can then be utilized by the termite. Subterranean termites can

damage many species of wood; some of their preferences are loblolly pine, slash pine,

and sugar maple (Smythe and Carter 1970).

In 1934 the estimated losses due to subterranean termite damage was at least $40

million in the United States (Snyder 1934). In 1966, the damage estimate was raised to

$250 million annually (Gentry 1966). Mauldin (1986) estimated that the damage was

around $735 million, and Su (1991) estimated it to be at least twice this amount. This just

demonstrates that the costs associated with subterranean termite damage have

significantly increased. Su (1991) estimated that 80% of these costs are from

subterranean termites with the rest being credited to drywood termites.

Subterranean Termite Biology

Subterranean termites are considered eusocial because they posses many of the

social behaviors that make them more successful than a solitary insect. These social

behaviors that make them successful insects include overlap of generations, division of

labor, and cooperative care for the young (Holldobler and Wilson 1990).









The subterranean termite colony consists of three castes: workers, soldiers, and

reproductive. The primary function of the workers is to forage for and consume food

sources. Because the soldiers, young, and reproductive do not have the ability to feed

themselves, the workers will feed them via trophollaxis. The soldier's primary function is

to defend the colony usually using elongated mandibles at the front of their chitinous

heads. Soldiers of the genus Coptotermes have a gland above the mandibles called a

fontanelle that can produce defensive secretions. The reproductive in a colony can be of

two types: primary reproductive, which are the founding king and queen, and secondary

reproductive that include any reproductive other than the primary reproductive

(Krishna 1969).

Early Efforts at Termite Control

Hagen (1876) warned of the potential of termites to threaten homes and belongings.

In 1898, Dr. Karl Heinrich Wolman developed Wolman salts as a wood preservative

(Kreer 1934). Wood treatments were a termite control option for new construction, but

not for existing structures. These treatments were usually toxic compounds, like arsenic

oxides, coal-tar creosote oil, or zinc chloride (Randall & Doody 1934a). These

compounds were often brushed on to form a barrier, to prevent infestation.

Another option was adding termiticides to termite galleries in cases of infestation.

These termiticides were mainly inorganic poison dusts like arsenical smelter dust, sodium

fluosilicate and copper acetoarsenite (Randall & Doody, 1934b). As these dusts were

mostly arsenical in nature, they were not safe for extensive use in homes.

Due to the relative lack of safe insecticides, cultural practices were the chief

method of early termite control. Such practices included the removal of infested wood or

wood in contact with the ground. In time, changes in city building codes were









implemented to enforce these practices (Snyder, 1935). The first one was in Burlington,

Iowa in 1923. In 1927, the pacific code building officials adopted the bureau of

entomology and plant quarantine recommendations for termite damage prevention.

Honolulu did the same thing in 1928.

Soil Treatments

In the early 20th century, trapping and baiting, spraying timbers, and injection of

poison dusts were all tried and considered to be largely inadequate for termite control

(Turner 1941). Fumigation and heat treatments were not feasible either, as there would

be no residual control. The only remaining option for chemical control was the barrier

method, also known as soil termiticide treatments.

Soil treatments were once considered a last result after cultural practices (Randall

& Doody, 1934c). Early treatment generally consisted of a broad application of

inorganic poisons like sodium arsenate, generally applied at higher active ingredient

levels and application rates than current soil termiticides.

In the years before EPA regulations like FIFRA, there was little quality control.

For example, Antimite promoted sodium fluoride, dinitrophenol and sodium arsenate at

10 lbs/30 gal of water, applied by "generous drenching" (Randall & Doody, 1934c). The

American fluoride corporation sold Fluorex V (5% sodium fluosilicate) and Fluorex S

(10% magnesium base fluosilicate solution). The E. L. Bruce Company produced

Terminix, a mixture of orthodichlorobenzene, toxic solvents and toxic salts. It carried a 5

year guarantee, under the condition that wood in the structure was completely isolated

from ground contact. None of these termiticides were tested by the Termite Investigation

Committee.









No concerted effort was made to organize or regulate soil termiticide use until 1927

(Brown, 1934). The Termite Investigation Committee tested borax and magnesium

fluosilicate at 5% and 10% (1 gal/10 square feet). Other solutions tested were sodium

chloride, ammonium fluoride, sodium fluoride, sodium fluosilicate, and a kerosene

emulsion with 30 ml sodium arsenate per gallon. Soil fumigation was also tested, using

carbon bisulfide, carbon tetrachloride and paradichlorobenzene.

DDT (dichloro-diphenyl-trichloroethane) was used in the 1940s, and proved to be

an effective soil poison for at least 10 years (Hetrick, 1957). Cyclodienes like aldrin,

heptachlor, and dieldrin proved effective at 1/25 the required concentration of DDT, and

were effective for 7 years. In the long term, 0.3% dieldrin proved more persistent than

8% DDT, with a 99% kill of Coptotermes formosanus in 33 year old treated soil in

Hawaii (Grace et al., 1993). Cyclodienes have been shown to persist over 35 years in the

continental United States (Kard et al., 1989). The persistence of these organochlorine

insecticides generated environmental concerns, causing their eventual withdrawal from

use in the United States in 1988 (Lenz et al., 1990; Wood & Pearce, 1991).

After 1988, most of the remaining soil termiticides were organophosphates, like

DursbanTM TC (chlorpyrifos). By the early 1990s, pyrethroid termiticides like Dragnet

FT (permethrin, FMC) and Demon TC (cypermethrin, Zeneca) appeared. These

pyrethroids are highly repellent to termites (Su et al. 1982, 1993, 1995; Su & Scheffrahn,

1990; Smith & Rust, 1990). Beal and Smith (1971) assumed that the efficacy of

cyclodienes was due to repellency. This led to the conventional idea that repellency was

desirable, and it was seen as a positive quality of the pyrethroid termiticides. In fact,

cyclodienes are not repellent.









Termites don't penetrate into soil treated with Demon or Dragnet (Su et al., 1993).

Dursban is not repellent in itself, but it kills rapidly, causing an accumulation of dead

termites. These decomposing termite corpses repel living termites (Su et al., 1982).

Until recently, it was generally asserted that either repellent or non-repellent termiticides

would work if the appropriate concentration were applied thoroughly beneath or around a

structure (Su & Scheffrahn, 1990; Forschler, 1994). While this may be true in theory, it

is difficult to ensure thorough application in practice. Forschler (1994) investigated the

ability of Reticulitermes flavipes to find gaps in repellent termiticide soil treatments.

Kuriachan and Gold (1997) also investigated gap-finding abilities. In both cases, some

termites always survived past 7 days, and gaps were located with varying success.


Modern Soil Termiticides

Bayer released Premise in 1996. This termiticide has imidacloprid as the active

ingredient, which is a chlornicotinyl (Abbink 1991). This class of chemicals act as

neurotoxins, blocking nicotinic acetylcholine receptors.

Unlike the pyrethroids, chlornicotinyls are non-repellent. Kuriachan and Gold

(1998) found that termites were unable to locate 2-7 cm untreated gaps of soil. The

termites tunneled into Premise-treated soil and there was 90% mortality at 7 days. With

non-repellent termiticides, gaps are less important to protection since termites do not

distinguish treated versus non-treated soils. So there is less opportunity to exploit gaps.

Aventis released Termidor@ in 1999. This termiticide has fipronil as the active

ingredient, which is a phenylpyrazole (Ibrahim et al., 2003). This class of chemicals acts

by interfering with the passage of chloride ions through gamma-amino butyric acid






6


regulated chloride channels, thus disrupting the central nervous system. Like the

chlonicotinyls, the phenylpyrazoles are non-repellent (Cole et al., 1993).














CHAPTER 2
COMBINED EFFECTS OF TERMITICIDES AND MECHANICAL STRESS ON
CHLORINATED POLYVINYL CHLORIDE (CPVC)

Introduction

Subterranean termites cause millions of dollars in damage annually. The traditional

method of preventing termites from causing damage to a home is a pre-construction soil

treatment. This involves an application of termiticide to the soil before the slab is poured.

Liquid termiticides are either sold as emulsifiable concentrates or suspendable

concentrates. Emulsifiable concentrates are a liquid containing the active ingredient, one

or more volatile organic compounds (VOCs), and an emulsifier. Examples of these

termiticides would be Cyper TC, Demon TC, Dragnet SFR, and DursbanTM TC.

Suspendable concentrates are flowable formulations formed by suspending finely ground

particles in water and/or oil (Mallis 2004, Farm Chemicals Handbook 1997). An example

of a suspendable concentrate would be Termidor SC. One major difference between the

two formulations is that the emulsifiable concentrates use VOCs to keep the active

ingredients dissolved in the solution; whereas the suspendable concentrates do not

usually use VOCs.

The major manufacturer of CPVC pipe has blamed soil termiticides for causing

failures in CPVC pipes below structures (Noveon 2003). The following scenario is an

example of conditions where such termiticides may contribute to CPVC failure. In

normal practice, termiticides are diluted according to the label instructions and applied to

the soil. As a result of improper workmanship, CPVC water supply lines may be placed









in an incorrect spot after the slab has been poured and the soil has been treated with

termiticide. The discovery of this incorrect positioning after the slab has been poured

results in a "breakout." The builder breaks the slab where the CPVC comes up through

and re-positions the CPVC to another location, creating stress on the CPVC. At the

"breakout" site the soil needs to be retreated, exposing the CPVC to termiticides a second

time. In addition, if an emulsifiable concentrate formulation has been used, the CPVC is

being re-exposed to VOCs as well. This combination of additional mechanical stress and

chemical exposure may weaken the CPVC to the point of causing failure in the water

supply line. My objectives were to determine if termiticides and mechanical stress cause

significant CPVC bending and failure. I also wanted to determine the identity of VOCs

used in commonly used termiticides for new construction.

Materials and Methods

Termiticides

Twelve termiticide concentrates registered for treatment of new construction were

used. The twelve termiticides were: Cyper TC (cypermethrin 25.4%; Control Solutions,

Inc.; Pasadena, TX), Demon TC (cypermethrin 25.3%; Syngenta, Greensboro, NC),

Dragnet SFR (permethrin 36.8%; FMC Corporation, Philadelphia, PA), DursbanTM TC

(chlorpyrifos 44.0%; DowAgroSciences, Indianapolis, IN), Permethrin Pro Termiticide-

Turf-Ornamental (permethrin 36.8%; Micro Flo Company, Memphis, TN), Prelude

(permethrin 25.6%; Syngenta, Greensboro, NC), Premise 2 (imidacloprid 21.4%;

Bayer, Kansas City, MO), Prevail FT (cypermethrin 24.8%; FMC Corporation,

Philadelphia, PA), Speckoz Bifenthrin Termiticide (bifenthrin 7.9%; Speckoz Inc.,

Alpharetta, GA), SpeckozTM Permethrin TC (permethrin 36.8%; Speckoz Inc., Alpharetta,









GA), Talstar OneTM (bifenthrin 7.9%; Bayer, Kansas City, MO), and Termidor SC

(fipronil 9.1%; BASF, Mount Olive, NJ).

All of these termiticides must be diluted according to the label directions before

being applied. The label rates are: 0.05% for Premise 2, 0.06% for Speckoz

Bifenthrin Termiticide, Talstar OneTM, and Termidor SC, 0.25% for Prevail FT, 0.5%

for Cyper TC, Dragnet SFR, DursbanTM TC, Permethrin Pro Termiticide-Turf-

Ornamental, and SpeckozTM Permethrin TC, 1.0% for Demon TC and Prelude.

Formulation Preparation

Termiticide dilutions

All termiticides were tested as concentrate in batons. Termiticide concentrates that

caused CPVC baton failure within eight weeks were diluted and then reevaluated at four

times the label rate. Termiticide dilutions were prepared at four times the label rate by

pipetting the concentrate of each termiticide into a volumetric flask and adding de-

ionized water to a final volume of 200 ml. The following quantities of termiticides were

used: Cyper TC (15.75 g), Demon TC (31.62 g), Dragnet SFR (10.87 g), DursbanTM

TC (9.09 g), Permethrin Pro (10.87 g), Prelude (31.25 g), Prevail FT (8.06 g), and

SpeckozTM Permethrin TC (10.87 g).

The termiticide dilutions in water at four times the label rate that caused CPVC

baton failure were diluted to two times the label rate and the label rate and evaluated

simultaneously. The following quantities of termiticides were used; Permethrin Pro (5.44

g, 2.72 g), Prelude (15.63 g, 7.81 g), and SpeckozTM Permethrin TC (5.44 g, 2.72 g)

were added to water to create the two and one times the label rate termiticide dilutions.









Builders sand treatment

The label rate termiticide dilutions were applied at one, two, and three times (7.86,

15.72, 23.58 ml) the label's required volume for builders sand (82.85 g, Appendix A).

Builders sand (82.85 g) was placed into quart-sized bags prior to termiticide addition.

Dilutions of Permethrin Pro, Prelude, and SpeckozTM Permethrin TC were then added

to separate bags, and the mixtures of sand and termiticide were thoroughly kneaded for

five minutes.

Assay Setup

Chlorinated polyvinyl chloride pipe (1.27 cm i.d., 1.6 cm o.d., CPVC; Noveon;

Cleveland, OH) was cut into 58 cm long batons. Caps (1.27 cm i.d.; CPVC; Nimco;

Elkhart, IN) were glued onto one end of each baton using a CPVC adhesive (Oatey, All

purpose cement; Cleveland, OH). The application of the CPVC adhesive was

standardized and consisted of a single brush stroke around one end of the baton. The cap

was then glued in place.

To determine whether the volatile organic compounds in termiticides could affect

the CPVC batons, 50 ml of termiticide concentrate, the termiticide dilutions, or the

treated builders sand (82.85 g) were added to each baton. The open end of the baton was

then capped using the same method.

A pegboard was created by drilling holes (2.54 cm) into two sheets of 1.27 cm x

1.22 m x 2.44 m pressure treated plywood. Two plywood sheets were separated by 19.50

cm .The batons were then placed into the pegboard so that the batons extended -34.6 cm

from the front of the pegboard. To put stress on the batons 1.540 + 0.027 kg masonry

bricks (Lowes, Mooresville, NC; 5.5 cm x 9.0 cm x 19.5 cm) were attached with nylon

rope (Lehigh; Mexico; 15.2 m x 0.48 cm) cut into 45.7 cm sections so that the masonry









bricks hung on the long end of the projecting baton, 2 cm from end of baton. The length

of the rope was 7.62 cm from the bottom of the baton to the top of masonry brick (Figure

2-1).

Termiticide concentrate and dilution experiments were a randomized complete

block design with three batons for each treatment. Controls were de-ionized water (50

ml) in a baton. CPVC bending was determined by measuring the distance between the

pegboard and the masonry brick. Failures were considered to be batons breaking or

bending so far that the masonry brick rested against the pegboard.

Termiticide concentrate experiments had 12 treatments and a control for a total of

39 batons. Experiments were run for 8 weeks. CPVC bending was measured at 1, 2, 3, 4,

6, & 8 weeks. Daily observations were made to assess failures.

Termiticide dilution experiments at 4 times the label rate had 8 treatments and a

control for a total of 27 batons. Experiments were run for 4 weeks. CPVC bending was

measured weekly and daily observations were made to assess failures.

Termiticide dilutions at 2 and 1 times the label rate had 3 treatments and a control

for a total of 12 batons. Experiments were run for 4 weeks. CPVC bending was

measured weekly and daily observations were made to assess failures.

Experiments with treated builders sand were set up as a randomized complete block

design with three batons for each volume of treatment. Controls were builders sand

treated with de-ionized water (7.86, 15.72, 23.58 ml) in a baton. For each volume of

application there were 3 treatments and a control for a total of 12 batons. The experiment

had a total of 3 different volumes for a total of 36 batons and was run for 4 weeks. CPVC

bending was determined by measuring the distance between the pegboard and the









masonry brick. CPVC bending was measured weekly and daily observations were made

to assess failures.

Chemical Analysis for Volatile Organic Compounds (VOCs)

All 12 termiticides were diluted to 400 ppm AI in deionized water and were

analyzed using the E.P.A. method 8260B to determine the presence of VOCs (EPA 1992;

Nelson 2003). Samples (5 .il) were injected into the Purge & Trap attached to the gas

chromatograph/mass spectrometer (GC/MS). The samples were under helium flow to

have the VOCs volatilize off of the samples, and were collected in the Purge & Trap. The

collected VOCs were then run through the GC/MS to determine which VOCs were

present.

Data Analysis

The bending data were analyzed using one way analysis of variance and means

were separated using Student Newman-Kuels test when P values for the analysis of

variance were significant (n = 3, a = 0.05; SAS Institute 2001).

Results and Discussion

Water caused little bending (<2 cm) of CPVC batons and no breakage. In contrast,

some termiticides caused significant CPVC bending or breaking. In contrast, some

termiticides were observed to either make the baton more flexible or more brittle. As a

baton became flexible, CPVC bending increased, eventually reaching a maximum

bending distance of -26 to28 cm, at which distance the baton was bent in an arc with the

brick touching the pegboard (Figure 2-2a). For batons that became brittle, a sharp break

occurred at the supporting area of the pegboard (Figure 2-2b). This break caused the

brick to drop and rest against the pegboard, resulting in a maximum "bending" distance

of -26 to 28 cm.











Termiticide Concentrate Assay

At 1 week, treatments that caused breaking or significant bending were Cyper,

Dragnet, Prelude, and Prevail (Table 2-1). Cyper and Demon treatments had one

baton failure each. Prelude, and Prevail treatments had two baton failures each. The

Dragnet treatment had three baton failures.

At 2 weeks treatments that caused breaking or significant bending were Cyper,

Demon, Dragnet, Prelude, and Prevail. Cyper and Demon treatments had 1

baton failure each. The Prelude treatment had 2 baton failures. The Prevail treatment

had 3 baton failures.

At 3 weeks treatments that caused breaking or significant bending were Cyper,

Demon, Dragnet, Prelude, and Prevail. Cyper, Demon, and DursbanTM

treatments had 1 baton failure each. The Prelude treatment had 3 baton failures.

At 4 weeks treatments that caused breaking or significant bending were DursbanTM,

Cyper, and Demon. Cyper, and Demon treatments caused significantly more bending

than the DursbanTM treatment. Cyper, Demon, and DursbanTM treatments had 1 baton

failure each.

At 6 weeks treatments that caused breaking or significant bending were

Permethrin Pro, Cyper, Demon, and DursbanTM. Permethrin Pro, Cyper, Demon, and

DursbanTM treatments caused significantly greater bending than the Permethrin Pro

treatment. The Permethrin Pro treatment had 1 baton failure. The DursbanTM treatment

had 2 baton failures. Cyper and Demon treatments had 3 baton failures each.

At 8 weeks treatments that caused breaking or significant bending were

DursbanTM and Permethrin Pro. The Permethrin Pro treatment caused significantly









greater bending than the DursbanTM treatment. Premise 2, Speckoz Bifenthrin, Talstar

OneTM, Termidor, and water treatments had no baton failures at 8 weeks. All other

treatments had three baton failures each.

Termiticide Dilutions Assay

The experiments with termiticide dilutions at four times the label rate resulted in

fewer treatment failures. At 1 week no treatments had caused significant bending.

However, Permethrin Pro, Prelude, and SpeckozTM Permethrin treatments had 2 baton

failures each (Table 2-2). At 2 weeks the Prelude treatment had caused significant

bending. Permethrin Pro and SpeckozTM Permethrin treatments had 2 baton failures each.

The Prelude treatment had 3 baton failures at 2 weeks. At 3 weeks no further treatments

had caused significant bending. Permethrin Pro and SpeckozTM Permethrin treatments

had 2 baton failures each. At 4 weeks no further treatments had caused significant

bending. Permethrin Pro and SpeckozTM Permethrin treatments that had 2 baton failures

each.

In the experiments with termiticide dilutions at two times the label rate, only 1

treatment caused all three batons to fail. At 1 week no treatments had caused significant

bending (Table 2-3). However, the Prelude treatment had 1 baton failure. At 2 weeks no

treatments caused significant bending. The Permethrin Pro treatment had 1 baton failure

and the Prelude treatment had 2 baton failures. At 3 weeks no treatments had caused

significant bending. The Permethrin Pro treatment had 1 baton failure and the Prelude

treatment had 2 baton failures. At 4 weeks the Prelude treatment had caused significant

bending. The Permethrin Pro treatment had 1 baton failure and the Prelude treatment

had 3 baton failures.









The experiments with the label rate termiticide dilution resulted in only 1 treatment

with significant bending, and no treatment had all three batons fail. At 1 and 2 weeks no

treatments caused significant bending (Table 2-4). No treatments had baton failures at 1

week or 2 weeks. At 3 weeks the Prelude treatment had caused significant bending. In

addition, the Prelude treatment had 2 baton failures. At 4 weeks the Prelude treatment

had still caused significant bending and still had 2 baton failures.

Builders Sand Treatment Assay

The builders sand treated at three times the labeled volume caused significant

bending for some of the termiticides. At 1 and 2 weeks the Prelude treatment had

caused significant bending (Table 2-5). No treatments had baton failure. At 3 weeks no

further treatments caused significant bending. No treatments had baton failure. At 4

weeks the Permethrin Pro, Prelude, and SpeckozTM Permethrin treatments had caused

significant bending. Permethrin Pro, Prelude, SpeckozTM Permethrin, and water

treatments had no baton failures at 4 weeks were.

The experiments with builders sand treated at two and one times the labeled

volume had similar results. The experiments resulted in no treatments bending

significantly from the controls, and no treatments had baton failures at 1, 2, 3, and 4

weeks (Table 2-6 & 2.7).

Chemical Analysis for Volatile Organic Compounds (VOCs)

The analysis indicated eight VOCs present in the termiticides with quantities above

100 pl: 1,2,4 Trichlorobenzene, 1,2,4 Trimethylbenzene, 1,3,5 Trimethylbenzene,

Bromoform, Ethylbenzene, Sec-Butylbenzene, Toluene, and Xylenes (Table 8). Other

VOCs that were present but in quantities less than 100 ptl were: Benzene, Chloroform,









and Styrene. Another table was constructed to show which termiticides had the presence

of these high quantity VOCs (Table 2-9).

Discussion

Termiticide formulations are complex mixtures of active ingredients, solvents,

emulsifiers, and other additives. VOCs are found as components of most formulations

and are much smaller molecules than the active ingredients, making them capable and

likely suspects that can degrade CPVC.

Termiticides will have the highest concentration of VOCs in their concentrate form.

Dilution lowers the VOC concentration, and this is evident in the results with the

concentrate assay having more failures than the dilutions assays.

The treated builders sand experiments indicated that if the termiticide has

something to bind with then the VOCs are less of a problem. Similar to the previous

experiments, the more VOCs present the more CPVC bending that occurs.

VOCs were present in all of the tested termiticides except for Termidor a

suspendable concentrate. Termiticides with the same active ingredient often had the same

VOCs present in the analyzed samples. However, the quantities found present for each

VOC varied from termiticide to termiticide. All of the termiticides concentrates that

caused failure of the CPVC batons had some combination of these VOCs. In fact, all of

the termiticide concentrates that failed had one VOC in common: 1,3,5-Trimethylbenzene

(Table 2-9).












Table 2-1 CPVC bending after exposure to Termiticide Concentrate

CPVC Bending (cm + SE)

Trt 1 wk 2 wks 3 wks 4 wks 6 wks 8 wks

Cyper 17.60 4.11a 18.63 3.60a 19.37 3.32a 20.10 2.97a 25.63 0.27ab

Demon 16.80 4.79ab 19.47+ 3.37a 23.60+ 1.38a 25.10+ 0.61a 25.97+ 0.28ab


Dragnet

DursbanTM

Permethrin
Pro

Prelude

Premise2


26.07 + 0.27a

2.17 + 0.03b

2.27 + 0.18b


18.87 + 8.28b

1.30 + 0.26b


3.17 + 0.07b

3.77 + 0.38b


19.03 8.12a

1.47 + 0.20b


11.33 + 7.48b

5.90 + 0.26b


27.43 0.28a

1.63 + 0.18b


11.83 7.23b

7.10 + 0.06bc


19.07 + 6.94ab

15.63 + 5.55bc


1.93 +0.09c 2.07+0.12d
1.93 + 0.09c 2.07 + 0.12d


26.00 + 0.17b

26.97 0.29a





2.13 + 0.19c


Means followed by same letter are not significantly different from each other. (Student Newman Kuels test, n = 3, a = 0.05; SAS Institute 2001)












Table 2-1 cont. CPVC bending after exposure to Termiticide Concentrate

CPVC Bending (cm + SE)

Trt 1 wk 2 wks 3 wks 4 wks


Prevail

Speckoz
bifenthrin

SpeckozTM
permethrin

Talstar-
OneTM

Termidor

Water


19.97 6.39a

0.73 + 0.18b


26.30 + 0.21a

1.10 + 0.20b


1.37 + 0.19b


1.90 + 0.06b 3.33 + 0.26b 4.73 + 0.23b


0.97 0.03b 1.20 0.06b 1.43 + 0.09b


1.03 + 0.18b

0.97 + 0.07b


1.37 + 0.15b

1.23 + 0.13b


1.57 + 0.15b

1.53 + 0.13b


1.37 + 0.19c


6.40 + 0.65bc


1.53 + 0.09c


1.63 + 0.15c

1.57 + 0.12c


1.47 +0.22d


9.83 + 0.98cd


1.77 + 0.09d


1.83 + 0.22d

1.83 + 0.03d


1.57 + 0.24c


27.50 + 0.21a


1.87 + 0.12c


1.93 + 0.22c

1.83 + 0.03c


Means followed by same letter are not significantly different from each other. (Student Newman Kuels test, n = 3, c = 0.05; SAS
Institute 2001)


6 wks


8 wks









Table 2-2 CPVC bending after exposure to Four Times the Label Rate Termiticide
Dilution


Trt

Cyper TC

Demon

Dragnet

DursbanTM

Permethrin Pro

Prelude

Prevail

SpeckozTM
permethrin.

Water


1 wk

1.00 + 0.15a

1.43 + 0.07a

0.02 0.07a

0.37 + 0.24a

18.33 + 9.17a

17.47 8.53a

1.17 + 0.09a

17.93 + 8.97a


0.03 + 0.03a


CPVC Bending (cm SE)

2 wks

2.33 + 0.30b 2.

3.33 + 0.33b 3.

1.10 + 0.26b 1.

1.27 0.09b 1.

18.53 + 8.97ab 1I

26.00 + 0.06a

2.97 + 0.03b 3

18.20 + 8.70ab 18.


0.30 + 0.25b 0


3 wks

60 + 0.21b

77 0.27b

13 + 0.23b

30 + 0.06b

8.67 + 8.83ab



.67 0.07b

.20 + 8.70ab


.33 + 0.23b


4 wks

3.00 + 0.29b

4.33 + 0.33b

1.13 + 0.23b

1.70 + 0.12b

18.67 + 8.83ab



5.03 + 0.19b

18.37 + 8.54ab


0.37 0.22b


Means followed by same letter are not significantly different from each other. (Student
Newman Kuels test, n = 3, c = 0.05; SAS Institute 2001)









Table 2-3 CPVC bending after exposure to Two Times the Label Rate Termiticide
Dilutions


CPVC Bending (cm SE)

Trt 1 wk 2 wks 3 wks 4 wks


Permethrin Pro 1.57 + 0.15a 9.93 8.23a 10.63 + 7.88a 11.23 + 7.58b

Prelude 10.20 + 8.15a 19.00 + 7.90a 19.83 + 7.07a 26.70 + 0.31a

SpeckozTM 1.33 0.35a 1.33 0.35a 2.70 + 0.10a 3.83 0.18b
permethrin

Water 1.20 + 0.06a 1.20 + 0.06a 1.57 + 0.23a 2.13 + 0.27b


Means followed by same letter are not significantly different from each other. (Student
Newman Kuels test, n = 3, c = 0.05; SAS Institute 2001)









Table 2-4 CPVC bending after exposure to Label Rate Termiticide Dilutions


CPVC Bending (cm SE)

Trt 1 wk 2 wks 3 wks 4 wks

Permethrin Pro 1.10 + 0.12a 1.10 + 0.12a 2.03 0.49b 2.80 + 0.50b

Prelude 1.80 + 0.38a 5.23 1.99a 21.00 5.70a 22.70 4.01a

SpeckozTM Perm. 1.33 0.15a 1.50 + 0.31a 2.10 + 0.53b 3.20 + 0.60b

Water 1.20 + 0.06a 1.20 + 0.06a 1.57 + 0.23b 2.13 + 0.27b



Means followed by same letter are not significantly different from each other. (Student
Newman Kuels test, n = 3, c = 0.05; SAS Institute 2001)









Table 2-5 CPVC bending after exposure to Builders Sand Treated with Three Times the
Labeled Volume


CPVC Bending (cm SE)

Trt lwk 2 wks 3 wks 4 wks


Permethrin Pro 0.73 0.07ab 0.87 + 0.18ab 1.47 + 0.54a 2.47 0.22a

Prelude 1.27 + 0.09a 1.27 + 0.09a 1.47 + 0.12a 2.17 + 0.23a

SperckozTM 1.03 0.27ab 1.03 0.27ab 1.73 0.12a 2.10 + 0.30a
permethrin

Water 0.47 0.03b 0.47 0.03b 0.83 + 0.18a 1.07 + 0.23b


Means followed by same letter are not significantly different from each other. (Student
Newman Kuels test, n = 3, c = 0.05; SAS Institute 2001)









Table 2-6 CPVC bending after exposure to Builders Sand Treated with Two Times the
Labeled Volume



CPVC Bending (cm SE)

Trt 1 wk 2 wks 3 wks 4wks


Permethrin Pro 0.63 0.09a 0.93 0.26a 1.33 0.64a 1.70 + 0.45a

Prelude 1.43 + 0.03a 1.43 + 0.03a 1.63 + 0.07a 2.23 + 0.19a

SperckozTM Perm. 0.73 0.47a 0.73 0.47a 0.83 0.56a 1.63 0.64a

Water 0.40 + 0.12a 0.47 + 0.07a 0.67 + 0.18a 1.07 + 0.12a


Means followed by same letter are not significantly different from each other. (Student
Newman Kuels test, n = 3, c = 0.05; SAS Institute 2001)









Table 2-7 CPVC bending after exposure to Builders Sand Treated at the Labeled Volume


CPVC Bending (cm SE)

Trt lwk 2wks 3wks 4wks


Permethrin Pro 0.23 0.03a 0.33 0.09a 0.47 + 0.09a 0.90 + 0.3 la

Prelude 0.97 0.29a 0.97 + 0.29a 1.27 + 0.37a 2.27 + 0.35a

SperckozTM 0.33 0.03a 0.47 0.07a 0.70 + 0.10a 1.50 + 0.31a
permethrin

Water 0.67 + 0.19a 0.77 0.09a 0.87 + 0.07a 1.60 + 0.25a

Means followed by same letter are not significantly different from each other. (Student
Newman Kuels test, n = 3, c = 0.05; SAS Institute 2001)










Table 2-8 Results of chemical analysis for Volatile Organic Compounds using E.P.A.
method 8260B

Detected >100 tg/l Detected < 100 tg/l Not Detected > 5 tg/l


1, 2, 4-Trichlorobenzene
1, 2, 4-Trimethylbenzene
1, 3, 5-Trimethylbenzene
Bromoform
Ethybenzne
Sec-Butylbenzene
Toluene
Xylenes


Benzene
Chloroform
Styrene


1,1,1,2-Tetrachloroethane
1,1,1 -Trichloroethane
1,1,2,2-Tetrachloroethane
1,1,2-Trichloroethane
1,1-Dichloroethane
1,1-Dichloroethene
1,2-Dibromo-3chloropropane
1,2-Dibromomethane
1,2-Dichlorobenzene
1,2-Dichloroethane
1,2-Dichloropropane
1,2-Dichloropropene
1,3,5-Trichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2-Chlorotoluene
4-Chlorotoluene
Bromodichloromethane
Bromomethane
Carbon Tetrachloride
Chlorobenzene
Chloroethane
Chloromethane
cis-1,2-Dichloroethene
cis-l,3Dichloropropene
cis-1,4-Dichloro-2-butene
Dibromochloromethane
Dibromomethane
Dichlorodifluoromethane
Hexachlorobutadiene
lodomethane
Methylene Chloride
Tetrachloroethene
trans-1,2-Dichloroethene
trans-1,3 -Dichloropropene
trans-1,4-Dichloro-2-butene
Trichloroethene
Trichlorofluoromethane
Vinyl Chloride












Table 2-9 Results of chemical analysis for the Major Volatile Organic Compounds in common Termiticides

1,2,4-Tri- 1,2,4-Tri 1,3,5 Tri- Bromoform Ethyl- Sec- Toluene Xylenes
chloro- methyl- methyl- benzene butyl-
benzene benzene benzene benzene


Cyper X X X X X

Demon X X X X X X X

Dragnet X X X X

DursbanTM X X X

Permethrin X X
Pro

Prelude X X X X X X

Premise2 X

Prevail X X X X X

Speckoz X X
bifenthrin













Table 2-9. Continued.


1,2,4-Tri-
chloro-
benzene


1,2,4-Tri
methyl-
benzene


1,3,5 Tri-
methyl-
benzene


Bromoform Ethyl- Sec-
benzene butyl-
benzene


Toluene Xylenes


SpeckozTM X X X
permethrin

Talstar OneTM X X X

Termidor
















































-~


Figure 2-1 Assay setup













































Figure 2-2. Examples of baton failures A) Flexible baton failures in the foreground, B)
Sharp break baton failures on bottom row


Dragnet


Cyper


Speckoz
(Pern.)


Dursban


Premi' -
Specki z

l*I One
8 Termidor
Water


Figure 2-3. Number of failed batons with termiticide at concentrate held for 8 weeks after
set up


weeks

















Prelude



25
SPermethrin Pro
E Speckoz (Pernm
2


1,5





a5 Cyper
Demon
Dragnel
0 0___ a Dursbai
0 1 2 3 4 Prevail
Weeks Water



Figure 2-4. Number of failed batons with termiticide at 4 times the label rate held for 4
weeks after set up















Prelude


Permethrin Pro


S,/ Speckoz IPenim.)
0 1 2 3 4
Weeks



Figure 2-5. Number of failed batons with termiticide at 2 times the label rate held for 4
weeks after set up


Prelude


Perinetlrin Pi u
Speckoz IPn in


O


Weeks


Figure 2-6. Number of failed batons with termiticide at label rate held for 4 weeks after
set up














CHAPTER 3
COMBINED EFFECTS OF TERMITICIDES, CPVC GLUE, AND MECHANICAL
STRESS ON CPVC

Introduction

As a result of improper workmanship, CPVC water supply lines may be placed in

an incorrect spot after the slab has been poured. The discovery of this incorrect

positioning after the slab has been poured results in a "breakout." The builder breaks the

slab where the CPVC comes up through and re-positions the CPVC line to another spot,

creating stress on the CPVC. This will often require an additional application of CPVC

glue to form a new joint. This exposes the CPVC to glue a second or even a third time.

CPVC glue has volatile organic compounds in it, which partially degrade the CPVC,

temporarily melting it to create a bond between the two CPVC objects being glued. This

combination of additional mechanical stress and chemical exposure may weaken the

CPVC to the point of causing breakage and failure in the water supply line. My

objectives for this study were to determine whether some termiticide concentrations in

combination with CPVC glue would cause failure of CPVC pipe.

Materials and Methods

Termiticides

DursbanTM TC (chlorpyrifos 44.0%; DowAgroSciences, Indianapolis, IN), a

termiticide registered for treatment of new construction, was tested in concentrate form

and as a series of dilutions. The labeled rate for application of DursbanTM TC is a 0.5%

emulsion. A 2.0% emulsion of DursbanTM TC, four times the label rate, was created by









pipetting 9.09 g of product into a 200 ml volumetric flask and then adding de-ionized

water to a final volume of 200 ml.

Assay Setup

Chlorinated polyvinyl chloride (1.27 cm i.d., 1.6 cm o.d., CPVC; Noveon;

Cleveland, OH) was cut into 26 and 31.5 cm long batons. Caps (1.27 cm i.d.; CPVC;

Nimco; Elkhart, IN) were glued onto one end of the 26 cm batons using a CPVC glue

(Oatey, All purpose cement; Cleveland, OH). The application of the CPVC glue was

standardized and consisted of a single brush stroke around the open end of the baton and

the cap glued in place.

The distal 3 cm of one end of a 31.5 cm baton was then exposed to varying

amounts of the CPVC glue and/or CPVC primer (Oatey, Purple Primer; Cleveland, OH).

After the varying exposure to the CPVC glue and/or primer a CPVC coupling (1.27 cm

i.d., Genova, Davison, MI) was glued in place at the end of the 3 cm section of the 31.5

cm baton. After the coupling was glued in place, the 26 cm baton was then glued onto the

other end of the CPVC coupling creating a 58 cm baton with a coupling in the middle.

The reasoning behind exposing this 3 cm section of the baton to the varying CPVC glue

levels was that this is the location where all of the weight and stress of the baton are

focused.

The first CPVC glue variation was gluing on the CPVC coupling with the CPVC

glue using the standardized method, exposing only the bottom 3 cm of the 31.5 cm baton

to the CPVC glue. The second CPVC glue variation was gluing on the CPVC coupling

using the CPVC primer and the standard amount of CPVC glue. The third CPVC glue

variation was exposing the 3 cm sections to the CPVC glue by submerging them in a

glass beaker filled with the CPVC glue for 10 min. The fourth CPVC glue variation was









exposing the 3 cm sections to the CPVC glue by submerging them in a glass beaker filled

with the CPVC glue for 10 min, removed, wiped clean, dried for 1 hour, and then

submerged again for 10 min. more.

To determine whether the different glue variations in combination with termiticides

could affect the CPVC batons, 50 ml of the DursbanTM TC concentrate or termiticide

dilution was added to each baton. The open end of the baton was then capped using the

standardized method.

A pegboard was created by drilling holes (2.54 cm) into two sheets of 1.27 cm x

1.22 m x 2.44 m pressure treated plywood. Two plywood sheets were separated by 19.50

cm .The batons were then placed into the pegboard so that the batons extended -34.6 cm

from the front of the pegboard. To put stress on the batons 1.540 + 0.027 kg masonry

bricks (Lowes, Mooresville, NC; 5.5 cm x 9.0 cm x 19.5 cm) were attached with nylon

rope (Lehigh; Mexico; 15.2 m x 0.48 cm) cut into 45.7 cm sections so that the masonry

bricks hung on the long end of the projecting baton, 2 cm from end of baton. The length

of the rope was 7.62 cm from the bottom of the baton to the top of masonry brick.

The experiments with the glue variations were set up as a randomized complete

block design with three batons for each treatment level of CPVC glue exposure. For each

level of CPVC glue exposure there were 2 treatments and a control for a total of 9 batons.

The experiment had 4 different levels of CPVC glue exposure for a total of 36 batons and

was run for 4 weeks. CPVC bending was determined by measuring the distance between

the pegboard and the masonry brick. CPVC bending was measured at one, two, three, and

four weeks. Daily observations were done to assess failures. Failures were considered to









be batons breaking or bending all the way so that the masonry brick rested against the

pegboard.

Data Analysis

The bending data were analyzed using one way analysis of variance and means

were separated using Student Newman-Kuels test when P values for the analysis of

variance were significant (n = 3, a = 0.05; SAS Institute 2001).

Results and Discussion

Treatments inserted into CPVC batons continuously contacted the interior of the

baton over a period of 4 weeks. The combination of water and CPVC glue generally

caused little CPVC bending and no breakage of the batons. In contrast, the combination

of termiticides and CPVC glue did affect the CPVC causing significant bending of the

baton. For each treatment the amount of CPVC bending depended on the amount of glue

exposure, the more glue exposure the more CPVC bending of the batons. In cases of

breakage, a sharp break occurred at the area of CPVC glue exposure on the batons. This

break caused the brick to drop and rest against the pegboard, resulting in a maximum

bending distance of -22.73 to 25.90 cm.

Dursban Concentrate Assay

At 1 week, no treatments had bent significantly from each other (Table 3-1).

Treatments that had 1 baton failure were batons exposed to the standard CPVC glue

application. Treatments that had 2 baton failures were the batons exposed to the standard

CPVC glue application and a CPVC primer. Treatments that had 3 baton failures were

batons exposed to the 10 and twenty-minute submersion in the CPVC glue.









At 2 weeks, no treatments had bent significantly from each other but all treatment

batons had failed. Treatments that had 3 baton failures were the batons exposed to the

standard CPVC glue and the batons exposed to the CPVC primer + standard CPVC glue.

Termiticide Dilution Assay

At 1 week, treatments were significant from each other (Table 3-1). The treatments

with the batons exposed to the 10 minute submersion in the CPVC glue bent significantly

from the batons exposed to the standard CPVC glue and CPVC primer + standard CPVC

glue application. The treatment glue level that had significantly more bending than the 10

min submersion were the glue level of the twenty-minute submersion. The only treatment

glue levels with baton failures (3) were the twenty-minute submersion batons. At 2, 3,

and 4 weeks the treatment with the batons exposed to the 10 minute submersion bent

significantly from the batons exposed to the standard CPVC glue and the batons exposed

to the CPVC primer + standard CPVC glue. At 2, 3, and 4 weeks no treatments

experienced baton failure.

Water Assay

At 1, 2, 3, and 4 weeks treatments were significant from each other (Table 3-1).

The treatments with the batons exposed to the CPVC primer + standard CPVC glue and

the batons exposed to the 10 minute submersion bent significantly from the batons

exposed to the standard CPVC glue application. The treatment that had even more CPVC

bending that was significant from all other treatments were batons exposed to the twenty

minute submersion in the CPVC glue.

Discussion

The combination of the DursbanTM TC concentrate and the CPVC glue exposures

resulted in all batons failing, resulting in a maximum CPVC bending distance of 22.73 -









25.90 cm. The high concentration of VOCs from the termiticide concentrate and CPVC

glue caused the CPVC batons to fail. With the dilution of the DursbanTM TC concentrate

the VOC concentration in the treatment was lowered. The combination of those VOCs

and the CPVC glue VOCs was enough to cause significant CPVC bending and failure in

the highest exposure to the CPVC glue.

The CPVC batons that were exposed to the CPVC glue for the longest amount of

time showed the most CPVC bending. As the amount of time the CPVC was exposed

went down the CPVC bending also was lowered. This trend was evident in all three

treatments. The experiments also indicated excessive CPVC glue applications can

degrade the CPVC in combination with water or termiticides resulting in significant

CPVC bending.










Table 3-1 CPVC bending after exposure to Termiticide, Termiticide Dilutions, and
CPVC glue.


CPVC Bending SE cm

TRT Glue 1 wk 2 wks 3 wks 4 wks
exposure


Dursban
concentrate


Dursban
4X Label










Water


standard

standard +
primer

10 min dunk

20 min dunk


standard

standard +
primer

10 min dunk

20 min dunk


standard

standard +
primer

10 min dunk

20 min dunk


9.93 + 8.03a 25.90 0.26a1 ---

17.70 7.70a 25.50 0.12a -----


24.97 + 0.44a ---

22.73 0.23a -----


1.23 0.20c 1.53 0.15b

1.80+0.10c 2.10+0.10b


4.40 + 0.44b 5.53 + 0.64a

22.97 + 0.09a ---


0.40 + 0.31c 0.43 + 0.30c

1.07 + 0.03bc 1.17 + 0.03c


2.13 + 0.38b 2.47 + 0.32b

4.07 + 0.63a 4.63 + 0.52a


1.80 + 0.21b

2.30 + 0.10b


6.20 0.64a





0.60 + 0.35c

1.27 + 0.09c


2.77 0.29b

4.97 + 0.46a


2.07 + 0.23b

2.60 + 0.10b


6.63 + 0.52a





0.73 + 0.33c

1.43 + 0.07c


3.13 + 0.20b

5.43 + 0.47a


1Means compared using students 2 tail test
2 All other means analyzed according to treatment using Student Newman Kuels test, n =
3, a = 0.05 Means with the same letter are not significantly different from each other














CHAPTER 4
COMBINED EFFECTS OF VOLATILE ORGANIC COMPOUNDS AND
MECHANICAL STRESS ON CPVC

Introduction

Soil termiticides are commonly formulated as emulsifiable concentrates or

suspendable concentrates. The main difference between the two formulations is that the

emulsifiable concentrates will use volatile organic compounds (VOCs) to keep the active

ingredient dissolved in the solution. The use of these VOCs leaves the potential for them

to interact with non-target organisms and objects. My objectives were to determine the

effects of each individual VOC on CPVC pipe.

Materials and Methods

Chemical Analysis for Volatile Organic Compounds (VOCs)

All 12 termiticides were diluted to 400 ppm AI in deionized water and were

analyzed using the E.P.A. method 8260B (EPA 1992; Nelson 2003) to determine the

presence of VOCs. Samples (5 il) were injected into the Purge & Trap attached to the

gas chromatograph/mass spectrometer (GC/MS). The samples were under helium flow to

cause the VOCs to volatilize off of the samples for collection in the Purge & Trap. The

collected VOCs were then run through the GC/MS to determine which VOCs were

present. These quantities were then compared with standards and amended into parts per

billion (ppb; tlg/1).









Volatile Organic Compounds

Volatile organic compounds found in quantities above 100[lg/l were purchased and

used. The eight VOCs were: 1,2,4 Trichlorobenzene (Sigma-Aldrich, Reagent PlusTM >

99%), 1,2,4 Trimethylbenzene (Sigma-Aldrich, 98%), 1,3,5 Trimethylbenzene (Sigma-

Aldrich, 98%), Bromoform (Sigma-Aldrich, 99+%), Ethylbenzene (Fischer

Scientific, certified), Sec-Butylbenzene (Sigma-Aldrich, 99+%), Toluene (Fischer

Scientific, 99.9%), and Xylenes (Fischer Scientific, 99.5%).

Assay Setup

Chlorinated polyvinyl chloride (1.27 cm i.d., 1.6 cm o.d., CPVC; Noveon;

Cleveland, OH) was cut into 58 cm long batons. Caps (1.27 cm i.d.; CPVC; Nimco;

Elkhart, IN) were glued onto one end of each baton using a CPVC glue (Oatey, All

purpose cement; Cleveland, OH). The application of the CPVC glue was standardized

and consisted of a single brush stroke around the open end of the baton and the cap glued

in place.

To determine whether the volatile organic compounds found in termiticides could

affect the CPVC batons, 50 ml of a volatile organic compound was added to each baton.

The open end of the baton was then capped using the same method.

A pegboard was created by drilling holes (2.54 cm) into two sheets of 1.27 cm x

1.22 m x 2.44 m pressure treated plywood. Two plywood sheets were separated by 19.50

cm .The batons were then placed into the pegboard so that the batons extended -34.6 cm

from the front of the pegboard. To put stress on the batons 1.540 + 0.027 kg masonry

bricks (Lowes, Mooresville, NC; 5.5 cm x 9.0 cm x 19.5 cm) were attached with nylon

rope (Lehigh; Mexico; 15.2 m x 0.48 cm) cut into 45.7 cm sections so that the masonry









bricks hung on the long end of the projecting baton, 2 cm from end of baton. The length

of the rope was 7.62 cm from the bottom of the baton to the top of masonry brick.

Volatile organic compound experiments were a randomized complete block design

with 3 batons for each treatment. Controls were de-ionized water (50 ml) in a baton. The

experiment had 8 treatments and a control for a total of 27 batons and was run for 1

week. CPVC bending was determined by measuring the distance between the pegboard

and the masonry brick. Failures were considered to be batons breaking or bending all the

way so that the masonry brick rested against the pegboard. CPVC bending was measured

at 1 week and daily observations were done to assess failures.

Data Analysis

The data was compared using a one-way analysis of variance, and means were

separated using Student Newman-Keuls test when P values were significant (n = 3,a =

0.05; SAS Institute, 2001).

Results and Discussion

Chemical Analysis for VOCs

The analysis indicated eight VOCs present in the termiticides with quantities above

100 [il: 1,2,4 Trichlorobenzene, 1,2,4 Trimethylbenzene, 1,3,5 Trimethylbenzene,

Bromoform, Ethylbenzene, Sec-Butylbenzene, Toluene, and Xylenes. Other VOCs that

were present but in quantities less than 100 [tl were: Benzene, Chloroform, and Styrene.

A second table was constructed to show which of these major VOCs were associated with

each termiticide (Table 4-1).

Volatile Organic Compounds Assay

Treatments inserted into CPVC batons continuously contacted the interior of the

baton over a period of 1 week. Water caused little bending with 0.8 to < 1.1 cm of CPVC









bending and no breakage of the baton (Table 4-2). In contrast the VOCs did affect the

CPVC causing significant bending of the baton. CPVC bending was observed to be

either making the baton more flexible or more brittle. As the batons became flexible,

CPVC bending increased, eventually reaching a maximum bending distance of -26.90 to

27.63 cm, at which distance the baton was bent in a semicircle with the brick touching the

pegboard. For batons that became brittle, baton breakage occurred resulting in a sharp

break at the supporting area of the pegboard. This break caused the brick to drop and rest

against the pegboard, resulting in a maximum bending distance of -26.90 to 27.63 cm.

All of the treatments, except for the controls, experienced all 3 batons failing by the

4th day. The measurements at 1 week consisted of only the controls being measured and

all treatments had CPVC bending significant from the controls.

Discussion

The VOCs tested in the experiments were found in high quantities in the analyzed

samples. The VOCs were tested separately from each other to see their individual affects

on the CPVC. The concentrations of VOCs used in the experiments were higher than the

reported quantities but again they were tested this way to see their individual affects on

the CPVC. These VOCs all had detrimental affects to the CPVC batons causing failure to

all experimental units within four days.

VOCs were present in all of the tested termiticides except for Termidor, a

suspendable concentrate. Termiticides with the same active ingredient often had the same

VOCs present in the analyzed samples. However, the quantities found for each VOC

varied from termiticide to termiticide.












Table 4-1. Results of chemical analysis for Major Volatile Organic Compounds

Solvent concentration ([tg/ liter) in Termiticide Concentrate

1,2,4-Tri- 1,2,4-Tri 1,3,5 Tri- Bromoform Ethyl- Sec- Toluene Xylenes
chloro- methyl- methyl- benzene butyl-
benzene benzene benzene benzene


Cyper

Demon

Dragnet

DursbanTM

Permethrin
Pro

Prelude

Premise2

Prevail

Speckoz
bifenthrin


343.21

3,375.92

36.19

565.27


5.63


58.73


49.94


32.36

335.52

10.28

852.03

2.03


48.76


134.52


0.94

864.23


6,982.82

853.9

56.89

463.2

37.48


10.51


28.27


1.94


316.59


188.21


124.86

2.71

0.97


14.52

751.99

0.98







356.885


5.88


12.74













Table 4-1 cont. Results of chemical analysis for Major Volatile Organic Compounds

Solvent concentration ([tg/ liter) in Termiticide

1,2,4-Tri- 1,2,4-Tri 1,3,5 Tri- Bromoform Ethyl-
chloro- methyl- methyl- benzene
benzene benzene benzene


Concentrate

Sec- Toluene Xylenes
butyl-
benzene


SpeckozTM
permethrin

Talstar OneTM

Termidor


2.01


3.03


5.37


38.07


3.75


1.09









Table 4-2 CPVC bending after exposure to Volatile Organic Compounds




CPVC Bending (cm SE)

Trt 1 wk


1, 2, 4-Trichlorobenzene 26.90 + 0.15a

1, 2, 4-Trimethylbenzene 27.13 0.49a

1, 3, 5-Trimethylbenzene 27.63 0.22a

Bromoform 26.97 0.07a

Ethylbenzene 27.13 0.28a

Sec-Butylbenzene 26.93 0.09a

Toluene 26.97 0.12a

Water 0.13 + 0.07b

Xylenes 27.27 + 0.12a

Means followed by same letter are not significantly different from each other. (Student Newman Kuels test,
n = 3, a = 0.05; SAS Institute 2001)














CHAPTER 5
CONCLUSIONS

Subterranean termites cause millions of dollars in damage annually. The traditional

method of preventing termites from causing damage to a home is a pre-construction soil

treatment. This involves an application of termiticide to the soil before the slab is poured.

Termiticide formulations are complex mixtures of active ingredients, solvents,

emulsifiers, and other additives. VOCs are found as components of most formulations

and are much smaller molecules than the active ingredients, making them capable and

likely suspects that can degrade CPVC.

Termiticides have the highest concentration of VOCs in their concentrate form.

Dilution with water lowers the VOC concentration. In my study, I constructed batons

and filled them with termiticides and dilutions oftermiticides. When the CPVC batons

were mechanically stressed, most termiticide concentrates caused the pipe to fail.

Dilutions of termiticides to four, two, and one times the label rates caused reduced

amounts of failure compared with the concentrated termiticide. Batons filled with

termiticide treated builders sand did not break even when mechanically stressed.

Termiticides were mixed to 400 ppm ai in water. The resultant solutions were

analyzed for the presence of VOCs. VOCs were present in all of the tested termiticides

except for Termidor a suspendable concentrate. Termiticides with the same active

ingredient often had the same VOCs present in the analyzed samples. However, the

quantities found of each VOC varied from termiticide to termiticide. All of the

termiticides concentrates that caused failure of the CPVC batons had some combination









of these VOCs. In fact, all of the termiticide concentrates that failed had one VOC in

common: 1,3,5-Trimethylbenzene.

Batons with a glue joint located at the fulcrum point were constructed and filled

with DursbanTM TC and water based dilutions. The batons were then mechanically

stressed. The termiticide concentrated, mechanical stress, and CPVC glue resulted in all

batons failing, reaching a maximum CPVC bending distance of 22.73 25.90 cm. The

high concentration of VOCs from the termiticide concentrate and the acetonic VOCs in

the CPVC glue caused the CPVC batons to fail. With the dilution of the DursbanTM TC

concentrate, the VOC concentration in the treatment was lowered. Similarly, dilutions of

terititicides caused significant CPVC bending and failure in the highest exposure to the

CPVC glue.

CPVC batons were constructed and filled with VOCs rather than termiticides.

The VOCs tested in the experiments were found in quantities >100 ug/liter in the

analyzed samples. All tested VOCs had caused failure of the CPVC batons within four

days. One VOC 1, 3, 5, Trimethylbenzene caused batons to fail within minutes and was a

solvent found in all termiticide concentrates that caused CPVC baton failure.

Termiticides have been blamed for causing CPVC failure in new construction. My

studies demonstrate that the VOCs found in most of the termiticide formulations cause

CPVC batons to fail when they are mechanically stressed. Mechanical stress can be in

the form of pipe bending or water pressure. The problem of termiticides degrading

CPVC and causing failure or rupture may be solved in the following ways: 1) avoid

repeated applications of termiticides that contain VOCs particularly ones containing 1, 3,

5, Trimethylbenzene, to areas where breakouts have occurred, 2) avoid exposure of






48


CPVC pipe to liquid termiticides, especially annular spaces of plastic sleeves around

CPVC where it penetrates the slab or tub box enclosures where puddles of termiticide can

occur, 3) avoid treating areas where there has been repeated or excessive application of

CPVC glue, and 4) avoid treating areas where CPVC pipe has been mechanically stressed

by bending or excessive water pressure.















APPENDIX
CALCULATIONS FOR BUILDERS SAND TREATMENTS

Baton Volume = fr2L = H(0.635 cm)2 (58 cm) = 73.4725 cm3


Builders Sand Density


112.76 gm soil
100 cm3


x gm soil
73.4725 cm3


82.85 gm
73.4725 cm3


Amount of termiticide spray solution to treat 73.4725 cm3; 4 gal.
10ft


15,140 ml
141,584.233 cm3


15,140 ml
141,584.233 cm3


x ml termiticide = 7.86 ml termiticide
73.4725 cm3 73.4725 cm3
















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BIOGRAPHICAL SKETCH

Justin Saunders was born on December 28, 1977, in Richmond, VA, to Marshall

and Janice Saunders. He has a brother and a sister, Graham and Ann Marshall Saunders.

He and his family lived in Richmond, VA, for two years. After this time his father took a

job in West Palm Beach, FL. Justin attended Suncoast High School from 1992-1995. His

senior year of high school was finished at Forest Hill High School from 1995-1996. After

high school he attended the University of South Florida starting in August of 1996. He

earned a Bachelor of Science in biology in May of 2002. After graduation he began work

in several different veterinary clinics in Tampa and Gainesville, FL. He applied several

times to the University of Florida's Doctor of Veterinary Medicine program, but the

program did not know what it was missing out on. During the application process to

the veterinary program he started work in the Urban Entomology Laboratory where he

saw the great potentials for graduates of the program. After being fed up with the Vet

School he gained interest and acceptance into the master's degree program in urban

entomology.