Protective Clothing Studies in the Field - ACS Publications - American

Since earlier field studies in El Salvador had suggested sig- nificant worker protection against pesticide exposure by wearing fluoroaliphatic treated...
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13 Protective Clothing Studies in the Field

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An Alternative to Reentry JOHN E. DAVIES, H. F. ENOS, A. BARQUET, C. MORGADE, L. J. PETERS, and J. X. DANAUSKAS University of Miami School of Medicine, Department of Epidemiology and Public Health, Miami, FL 33136 V. H. FREED Oregon State University, Department of Agricultural Chemistry, Corvallis, OR 97331

Handling and application of pesticides in other than closed systems, results in exposure of the worker (1, 2, 3). Attendant with exposure, is the possibility of an intoxication resulting in morbidity or mortality. A number of studies beginning shortly after 1945, addressed the route of exposure experienced by pesticide workers, particularly with organic pesticides (2-6). While both dermal and respiratory routes are possible it has been found that the principal route of exposure is dermal with the respiratory route generally many fold less. Dermal exposure cannot be equated with intoxication since the amount of chemical absorbed varies with the chemical, the carrier, and the proportion of the body surface exposed (7). However, prudence would indicate that appropriate protection against this exposure is highly desirable. Accordingly, attention has been given in many of the studies on worker exposure to the role of clothing that might afford such protection (8, 9, 3). Although normal work clothing can provide some protection, assuming it covers a major portion of the body, several workers have found that the clothing may itself become contaminated and afford a continuing exposure (8_, 10, 11). Rubberized or plastic clothing gives significantly more protection than usual textiles and has been used extensively for protective clothing (12, 5) However, even in this case, some permeation may occur (12). Rubberized or plastic clothing though substantially better in reducing dermal exposure, may in hot climates, be quite uncomfortable. As a consequence, workers object to wearing such clothing, thus suffering a higher dermal exposure. Recently light weight disposable plastic suits reported to be much more comfortable, have been developed (5). The work to be reported on here involves an approach of treating normal clothing in order to achieve a level of protection through repellency. It was reasoned that resin treated textile might be repellent to sprays, hence reducing dermal exposure. At the same time, it was hope that the woven textile might retain 0097-6156/82/0182-0169$05.00/0 © 1982 American Chemical Society

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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enough a i r exchange c h a r a c t e r i s t i c s to be comfortable to wear i n hot weather and p a r t i c u l a r l y i n s u b t r o p i c a l and t r o p i c a l regions, where both temperature and humidity may be high. Laboratory t r i a l s were undertaken to assess the c a p a b i l i t y of d i f f e r e n t text i l e s and weaves to a f f o r d p r o t e c t i o n and to determine whether some improvement i n t h i s p r o t e c t i o n , was p o s s i b l e through t r e a t ment with appropriate r e s i n . The i n i t i a l l a b o r a t o r y s t u d i e s were s u f f i c i e n t l y encouraging, that the M i n i s t r i e s of Health and A g r i c u l t u r e i n E l Salvador sponsored a f i e l d t r i a l using cotton p i c k ers as the s u b j e c t s . F i e l d s t u d i e s gave very promising r e s u l t s i n d i c a t i n g that even c l e a n c l o t h i n g a f f o r d e d p r o t e c t i o n to these workers and that the t r e a t e d c l o t h i n g gave a very high degree of repellency. Since e a r l i e r f i e l d s t u d i e s i n E l Salvador had suggested s i g n i f i c a n t worker p r o t e c t i o n against p e s t i c i d e exposure by wearing f l u o r o a l i p h a t i c t r e a t e d c l o t h i n g , s t u d i e s of r e p e l l e n c y and penet r a b i l i t y of d i f f e r e n t f a b r i c s and Scotchgard were measured i n the l a b o r a t o r y . A d d i t i o n a l l y , f i e l d s t u d i e s of p e s t i c i d e p e n e t r a b i l i t y were measured i n e t h i o n exposed workers i n two orange groves in Central F l o r i d a . M a t e r i a l s and Methods Laboratory Studies. The o b j e c t i v e of t h i s p o r t i o n of the s t u dy was to a s c e r t a i n the r e p e l l e n c y or p e n e t r a b i l i t y of t e x t i l e s untreated, and those t r e a t e d w i t h f l u o r o a l i p h a t i c r e s i n s . The c l o t h f o r the most p a r t was that commonly used f o r c l o t h i n g , p a r t i c u l a r l y "work" c l o t h e s . Both c o t t o n and a blend of p o l y e s t e r cotton (65/35) c l o t h of v a r i o u s weights and weaves were used. The 100% c o t t o n c l o t h s were denim, a coarse black c o t t o n c l o t h from Pakistan, and s i n g l e k n i t l i g h t weight c l o t h . The p o l y e s t e r cotton blend c l o t h used, was a l i g h t weight gingham and a denim. Though s e v e r a l treatments t o enhance r e p e l l e n c y of c l o t h were evaluated, primary a t t e n t i o n was given to treatment with f l u o r o a l i p h a t i c r e s i n s . These were a p p l i e d from an a e r o s o l can, spraying the c l o t h u n t i l wet as per d i r e c t i o n s and then allowing the solvent to dry o f f before u s i n g . Patches of approximately 10 by 20 cm were cut from the c l o t h to use f o r study. Repellency T e s t s . To determine the r e p e l l e n c y of treated c l o t h , equal s i z e patches of t r e a t e d and untreated c l o t h were suspended i n a l a b o r a t o r y hood and given e q u a l l y timed sprays of e m u l s i f i e d chemical. This treatment was r e p r o d u c i b l e to plus or minus 10% using the time a p p l i c a t i o n at a given pressure. A f t e r the spray deposit had d r i e d , c l o t h was extracted with solvent and a f t e r a d j u s t i n g the volume, the chemical deposit on the c l o t h determined e i t h e r by g a s - l i q u i d chromatography or spect r o p h o t o m e t r y methods. The r e p e l l e n c y of the t r e a t e d c l o t h was c a l c u l a t e d as the percent of the deposit found on the untreated cloth.

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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Tests of P e n e t r a b i l i t y . Treated and untreated c l o t h as descr i b e d under Repellency, were used f o r these t e s t s . I n t h i s case however, the t e s t patch was backed by an a l p h a - c e l l u l o s e pad (26_> ~L> _13) · The c l o t h w i t h i t s a l p h a - c e l l u l o s e pad was e i t h e r suspended i n the hood, or placed at a 30 working angle and sprayed w i t h the a p p r o p r i a t e chemical, i n a timed spray a p p l i c a t i o n or t r e a t e d w i t h d r o p l e t s a p p l i e d by a micro s y r i n g e . A f t e r the c l o t h had d r i e d , the c e l l u l o s e patch was removed and e x t r a c t e d w i t h s o l v e n t f o r d e t e r m i n a t i o n of the chemical. R e s u l t s were c a l c u l a t e d , as percent of chemical p e n e t r a t i n g the t r e a t e d c l o t h compared to the amount p e n e t r a t i n g the untreated c l o t h . Chemicals Used. Chemicals used i n t h i s study were t e c h n i c a l grade products or b e t t e r , d i s s o l v e d i n xylene w i t h 5% e m u l s i f y i n g agent. The chemicals used i n c l u d e d an o i l s o l u b l e red dye, Dinoseb (2-sec-butyl-4,6 d i n i t r o p h e n o l ) , pentachlorophenol (PCP), I s o p r o p y l N-(3-chlorophenyl) carbamate (CIPC or Chlorpropham), I s o - o c t y l 2,4,5- t r i c h l o r o p h e n o x y a c e t a t e (2,4,5-T), c h l o r p y r i f o s (0, 0 - d i e t h y l 0 - ( 3 , 4 , 6 - t r i c h l o r o 2 - p y r i d y l ) - phosphorothioate), and Ronnel (O-dimethyl 0-2, 4 , 5 - t r i c h l o r o p h e n y l ) phosphorothioate) f o r a p p l i c a t i o n as a spray. The e m u l s i f i a b l e concentrate was d i l u t e d i n water comparable t o 50 g a l l o n s of spray to c o n t a i n the f o l l o w i n g amounts r e s p e c t i v e l y : 2 l b s . f o r c h l o r o p r y i f o s ; 4 l b s . f o r 2,4,5-T; 3 l b s . CIPC and 2 l b s . f o r PCP. Methods of E x t r a c t i o n and Analyses. C h l o r o p y r i f o s , Ronnel, chlorpropham and 2,4,5-T were e x t r a c t e d from the c l o t h or the c e l l u l o s e pad w i t h hexane. Pentachlorophenol r e s i d u e s were ext r a c t e d w i t h benzene. Pentachlorophenol was methylated w i t h diazomethane p r i o r to d e t e r m i n a t i o n by gas chromatography w h i l e the other compounds were determined d i r g c t l y . Dinoseb, on the other hand was e x t r a c t e d w i t h chloroform and p a r t i t i o n e d i n t o 2% Na2 Co3 s o l u t i o n . The y e l l o w e x t r a c t was analyzed c o l o r i m e t r i c a l l y u s i n g the method of P o t t e r (14). Determination by g a s - l i q u i d chromatography u t i l i z e d the gaschromatograph w i t h Ni63 e l e c t r o n capture d e t e c t o r . Column packi n g c o n s i s t e d of carbo-wax, 20m on 100-120 mesh chromosorb WHP. The gas f l o w r a t e was 20 ml per minute. Operating c o n d i t i o n s f o r the gas l i q u i d a n a l y s e s , f o r the d i f f e r e n t compounds was as follows : Table I Operating Conditions f o r GLC Analyses of D i f f e r e n t Compounds Compound 1. 2,4,5-T i s o o c t y l e s t e r 2. pentachlorophenol 3. chlorpropham 4. dursban

Temperature 180° C 140° C 130° C 145° C

Column Dimensions lh lh lh 3

ft' ft 45 ft

1

1

1

1/8 1/8 1/8 1/8

inch inch inch inch

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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Studies

Exposure assessment u s i n g alpha c e l l u l o s e pads and DEP u r i n e e x c r e t i o n were made on 8 workers a p p l y i n g e t h i o n on a d a i l y b a s i s i n two c i t r u s groves i n Orange County, F l o r i d a . The study format was d i v i d e d i n t o three phases: Phase 1 - During t h i s p e r i o d the s u b j e c t s were asked to wear t h e i r normal working c l o t h e s . Alpha c e l l u l o s e patches were attached to the i n t e r i o r and e x t e r i o r on opposing s i d e s of the s h i r t . Timed u r i n e v o i d s were c o l l e c t e d i n the f i e l d . Phase 2 - The same s u b j e c t s were to repeat the f i r s t phase format i n a d d i t i o n were requested to wear OSHA/NIOSH approved r e s p i r a t o r s f o r p e s t i c i d e a p p l i c a t i o n during the mixing p e r i o d s . Phase 3 - The s u b j e c t s were issued 100% c o t t o n denim c o v e r a l l s of uniform design and weight. These s u b j e c t s were d i v i d e d i n t o two groups, one wearing Scotchgard t r e a t e d uniforms and one wearing non-treated c o v e r a l l s . During t h i s study phase, r e s p i r a ­ t o r s were not worn. As i n the f i r s t and second phase, pads and u r i n e s were c o l l e c t e d d a i l y . In the l a b o r a t o r y the a l p h a - c e l l u l o s e pads were r e c e i v e d i n l a b e l l e d 60 ml hexane washed j a r s c o n t a i n i n g 10 cc of methylene c h l o r i d e . The o u t s i d e or e x t e r i o r patches were i d e n t i f i e d by the l e t t e r 0 a f t e r the pad number and the i n s i d e or i n t e r i o r pad by an I . These pads were s t o r e d at -4° u n t i l they were analyzed. In order to compensate f o r v a r y i n g work loads s p e c i f i c to each i n d i v i d u a l , 2 t h i o n concentrations were expressed as ug e t h i o n per 25 cm per hour of exposure. In order to m a i n t a i n a constant e r r o r f a c t o r i n s i d e and out­ s i d e pad p a i r s were analyzed on the same day. Blank analyses were run on each l o t of s o l v e n t and pads to i n s u r e there were no i n t e r f e r i n g peaks. Each blank was concentrated from 50 ml to 1 ml p r i o r to i n j e c t i o n , thus i n s u r i n g that the f i e l d samples which needed c o n c e n t r a t i n g would be f r e e of i n t e r f e r i n g peaks i n the e t h i o n p o s i t i o n . No such peaks were found i n any of the b l a n k s . e

Instrument and column c o n d i t i o n s . A Tracor #222 gas chromatograph equipped w i t h a flame photometric d e t e c t o r (FPD) opera­ t i n g i n the phosphorus mode (526 mu) f i l t e r was used. The opera­ t i n g c o n d i t i o n s of the flame photometric gas chromatographic ana­ l y s e s were as f o l l o w s : Column 6" χ 1/4 g l a s s , carbowax 4% OV-210 on Gas Chrom Q 100/ 120 mesh 190° C, n i t r o g e n f l o w r a t e of 32 cc/min. d e t e c t o r tem­ perature 200° C, i n l e t 230° hydrogen 60 ml/min, a i r 60 ml/min a t t e n t u a t o r 103 χ 8, recorder speed 1/4 inch/min. An i n j e c t i o n of 0.535 of e t h i o n produced a peak of 115 mm. Detector S e n s i t i v i t y (ng) = 0.08 L i m i t s of d e t e c t a b i l i t y ug/25 cm = 01016 *Detector s e n s i t i v i t y was based on 15% s c a l e d e f l e c t i o n . Timed u r i n e v o i d i n g s were c o l l e c t e d and analyzed by the Shaf i k and Peoples modified method (15). D i f f e r e n c e s i n u r i n e were standardized to c r e a t i n i n e l e v e l s on the b a s i s of the recommenda2

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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t i o n s of Metzger et a l . (12) . The Rapid-Stat K i t was used f o r the q u a n t i t a t i o n u s i n g the c o l o r i m e t r i c determination of c r e a t i n i n e i n u r i n e (16). During the t h i r d week the 100% c o t t o n denim c o v e r a l l s provided by the p r o j e c t were washed commercially s i x times to remove s i z i n g .

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Results 1. Laboratory S t u d i e s . - The i n i t i a l experiments to d e t e r mine the r e p e l l e n c y of t r e a t e d and untreated c l o t h i n v o l v e d the use of an e m u l s i f i a b l e concentrate of o i l s o l u b l e red dye i n xyl e n e . A timed a p p l i c a t i o n of an emulsion was made to the c l o t h and f o l l o w i n g d r y i n g , the amount of dye deposited was determined by e x t r a c t i o n and d e t e r m i n a t i o n i n a spectrophotometer. Portions of the patches of c l o t h were sprayed a second time, to determine whether or not there would be a b u i l d up of chemical. The r e s u l t s are presented i n Table I I . Table I I Comparison of D e p o s i t i o n of O i l S o l u b l e Dye Emuls i o n of Treated and Untreated C l o t h 2 mg/cm Deposited on C l o t h A f t e r Both: One Cloth Denim 100% Cotton Coarse White 100% Cotton Coarse B l a c k 100% Cotton S i n g l e K n i t 100% Cotton 50/50 P o l y e s t e r / C o t t o n , Gingham 50/50 P o l y e s t e r / C o t t o n , Denim

T

a

Spray U°

Two •pa

Sprays U°

0.11 0.28 0.25 0.36

0.44 0.52 0.64 0.51

0.29 0.40 0.57 0.87

0.86 0.76 0.80 1.17

0.14

0.19

0.22

0.42

0.20

0.45

0.43

0.77

T^ = t r e a t e d w i t h Scotchgard U = untreated I t d i d i n d i c a t e t h a t the f l u o r o a l i p h a t i c r e s i n treatment imparted c o n s i d e r a b l e r e p e l l e n c y to a l l of the c l o t h s w i t h the p o s s i b l e e x c e p t i o n of the c o t t o n p o l y e s t e r gingham. I t would be presumed t h a t i f the t r e a t e d c l o t h r e p e l l e d sprays, as suggested by the f o r e g o i n g d a t a , c l o t h i n g t r e a t e d s i m i l a r l y would a f f o r d p r o t e c t i o n to the worker exposed to chemicals. A wide a r r a y of chemical types are used as p e s t i c i d e s so t h a t i t i s e n t i r e l y conceivable t h a t w h i l e the t r e a t e d c l o t h may be r e p e l l e n t to one chemical, another may be deposited and penetrate w i t h f a c i l i t y . S e v e r a l types of m a t e r i a l s r e p r e s e n t i n g d i f f e r e n t

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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compositions and weaves, t o a s c e r t a i n whether d i f f e r e n t chemic a l s had v a r y i n g a b i l i t i e s t o d e p o s i t and penetrate were t e s t e d . The r e s u l t s of t h i s study i s presented i n Table I I I . Table I I I Percentage Repellency Imparted by Scotchgard To D i f f e r e n t Chemicals

Treatment

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Concentration of Chemical C l o t h Type and Treatment Given to C l o t h

Chemical Emulsion

Mea^ (ug/cm )

65/35 p o l y e s t e r / c o t t o n Scotchgard treated Dinoseb 0.81 65/35 p o l y e s t e r / c o t t o n untreated Dinoseb 2.63 65/35 p o l y e s t e r / c o t t o n Scotchgard treated C h l o r p y r i f o s 3.28 65/35 p o l y e s t e r / c o t t o n untreated C h l o r p y r i f o s 8.82 65/35 p o l y e s t e r / c o t t o n Scotchgard Chlorpro treated pham 112.5 65/35 p o l y e s t e r / Chlorpro c o t t o n untreated pham 118.2 100% c o t t o n Scotchgard Chlorpro treated pham 113.6 100% c o t t o n Chlorpro untreated pham 135.5 65/35 p o l y e s t e r / c o t t o n Scotchgard treated PCP 60.9 65/35 p o l y e s t e r / c o t t o n untreated PCP 111.7 100% c o t t o n Scotchgard t r e a t e d PCP 87.8 100% c o t t o n untreated PCP 154.8

% Repellency A f f o r d e d by Scotchgard

69.3

62.8

4.74

1.45

45.5

43.3

I t w i l l be noted t h a t w h i l e the treatment imparted r e p e l l e n c y to Dinoseb, c h l o r p y r i f o s and pentachlorophenol, i t was r e l a t i v e l y i n e f f e c t i v e i n the case of chlorpropham. However there i s no i n d i c a t i o n from these data whether t h i s means a chemical l i k e chlorpropham, may penetrate the c l o t h , or whether what was being determined was merely a s u r f a c e d e p o s i t .

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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In Table IV, data are presented where the p e n e t r a t i o n of chemicals through t r e a t e d and untreated c l o t h was determined. In t h i s case, the emulsion was a p p l i e d as a spray t o t r e a t e d and unt r e a t e d c l o t h backed by an a l p h a - c e l l u l o s e pad. A f t e r d r y i n g , the pad was taken, extracted w i t h the appropriate s o l v e n t , and the amount of chemical p e n e t r a t i n g the c l o t h t o the pad, d e t e r mined .

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Table IV P e n e t r a t i o n of Chemicals Through Scotchgard C l o t h to A l p h a - C e l l u l o s e Pads

and Untreated

Surface Deposit of Chemical C l o t h Type and Treatment 65/35 p o l y e s t e r / c o t t o n (T) 65/35 p o l y e s t e r / c o t t o n (U) 100% c o t t o n (T) 100% c o t t o n (U) 65/35 p o l y e s t e r / c o t t o n (T) 65/35 p o l y e s t e r / c o t t o n (U)

Chemical Emulsion

2 ug/cm ug/cm 2

Penetration to A-cellulosg Pad (ug/cm )

Chloropyrifos

57.83

0.88

Chloropyrifos PCP PCP

49.63 53.34 51.95

1.2 0.01 0.54

PCP

45.35

0.0008

PCP

39.91

10.9

T=treated w i t h Scotchgard U=untreated

C l e a r l y the amount of chemical p e n e t r a t i n g the c l o t h t o the pad, i s f a r s m a l l e r than the surface d e p o s i t , d e s p i t e the d i r e c t spraying of the c l o t h . This would suggest that c l e a n , r e l a t i v e l y heavy weight c l o t h i n g i n and of i t s e l f , serves as a p a r t i a l b a r r i e r to the chemicals. In order t o i n s u r e a heavy surface deposit w i t h ample opportun i t y t o penetrate t o the a l p h a - c e l l u l o s e pad, patches of c l o t h were f i x e d a t 30° angle backed w i t h the a l p h a - c e l l u l o s e pad and then the chemical emulsion a p p l i e d dropwise w i t h the microsyr i n g e . The d r o p l e t was allowed to dry and only then was the pad removed f o r analyses. T h i s , i t was f e l t might s t i m u l a t e the exposure that could occur i f c l o t h i n g r e c e i v e d a s p i l l and were not removed immediately. Table V summarizes the r e s u l t s obtained.

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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Table V

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P e n e t r a t i o n of Chemically Treated and Untreated C e l l u l o s e Pads

C l o t h Type and Treatment 100%

Chemical Emulsion

2,4,5-T i s o o c t y l ester 100% cotton (U) 2,4,5-T i s o o c t y l ester 65/35 p o l y e s t e r / 2,4,5-T i s o o c t y l cotton (T) ester 65/35 p o l y e s t e r / 2,4,5-T i s o o c t y l cotton (U) ester 100% cotton (T) PCP 100% c o t t o n (U) PCP 65/35 p o l y e s t e r / c o t t o n (T) PCP 65/35 p o l y e s t e r / cotton (U) PCP 100% cotton (T) Chlorpropham 100% cotton (U) Chlorpropham 65/35 p o l y e s t e r / c o t t o n (T) Chlorpropham 65/35 p o l y e s t e r / cotton (U) Chlorpropham

Concentrat i o n of chemical on c l o t h (ug/cm ) 2

C l o t h to Alpha-

P e n e t r a t i o n to a-cellulose (ug/cm2)

cotton (T)

489.6

0.015

507.4

0.118

473.4

0.016

203.8 9.7 5.96

218.1 N.D. 0.002

7.76

0.002

3.73 43.85 43.66

0.968 0.068 0.204

50.67

0.219

42.88

2.31

(T) = t r e a t e d with Scotchgard (U) = untreated N.D. - Not d e t e c t a b l e

In the r e p e l l e n c y t e s t (Table I I I ) , chlorpropham showed a much higher d e p o s i t i o n on the t r e a t e d c l o t h than the other chemicals t e s t e d . However, i n t h i s p a r t i c u l a r t e s t of p e n e t r a t i o n while i t i s higher than other chemicals the percent p e n e t r a t i n g , i n comparison with the s u r f a c e deposit, i s s m a l l . The treatments seemed to be e f f e c t i v e f o r both PCP and 2,4,5-T i s o o c t y l e s t e r . As a f i n a l e v a l u a t i o n , i t was f e l t necessary to assess the e f f i c a c y of the c l o t h i n preventing dermal a b s o r p t i o n . In t h i s i n s t a n c e , small pieces of c l o t h were sewn i n t o a sleeve that would j u s t f i t over the t a i l of a r a t . Treated and untreated sleeves were f i t t e d to animals and a time spray a p p l i c a t i o n of

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

13.

DA VIES E T A L .

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Clothing

in the

111

Field

appropriate emulsion a p p l i e d . The animals were then h e l d i n metabolism cages f o r 48 hours, during which time the u r i n e was c o l l e c t e d . The u r i n e e x t r a c t e d and analyzed f o r the appropriate chemical or i t s m e t a b o l i t e , to determine the amount adsorbed. In t h i s t e s t , i t was p o s s i b l e only to compare between treatments i . e . , t r e a t e d versus untreated. Table VI presents the data f o r three d i f f e r e n t chemicals.

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Table VI Chemical P e n e t r a t i o n Through C l o t h E x c r e t i o n F o l l o w i n g Dermal Absorption

C l o t h Type and Treatment

a

65/35 P o l y e s t e r / Cotton (T) 65/35 P o l y e s t e r / Cotton (U) 65/35 P o l y e s t e r / Cotton (T) 65/35 P o l y e s t e r / Cotton (U) 65/35 P o l y e s t e r / Cotton (T) 65/35 P o l y e s t e r / Cotton (U) a

Chemical Emulsion

T o t a l Amount (Mg/rat/48 hrs.)

PCP

0.28

PCP

1.11

2,4,5-T i s o o c t y l e s t e r

1.53

2,4,5-T i s o o c t y l e s t e r

4.65 1.02

Ronnel*

28.8

Ronnel* R

( T ) = Treated w i t h S c o t c h g a r d (U) == Untreated {V) uncreated *Analyzed as 2 , 4 , 5 - t r i c h l o r o p h e n o l ,

the major m e t a b o l i t e .

Quite l a r g e d i f f e r e n c e s i n the amount of the chemical excreted by animals i n t r e a t e d t a i l covers as compared to untreated covers i s noted. Even a l l o w i n g f o r some v a r i a t i o n i n spray d e p o s i t i o n , the d i f f e r e n c e s of 3 to 28 f o l d , probably i n d i c a t e s s i g n i f i c a n t p r o t e c t i o n i n the case of the t r e a t e d c l o t h . Field

Studies

The i n d i v i d u a l personal c l o t h i n g worn by the 8 mixers are shown i n Table V I I . We measured the o c c u p a t i o n a l exposure of the 8 mixers to e t h i o n during the three phases of the study. Their p e s t i c i d e exposure w i t h the d i f f e r e n t c l o t h i n g m o d a l i t i e s was determined on the b a s i s of (1) the d a i l y percentage p e n e t r a t i o n of e t h i o n

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

178

PESTICIDE

RESIDUES

AND

EXPOSURE

TABLE V I I

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"Own"

C l o t h i n g C h a r a c t e r i s t i c s of P e s t i c i d e C i t r u s Grove M i x e r s , Orange County, F l o r i d a , 1978

Subject Number 1.

2.

3.

4.

5.

6.

7.

8.

Type of C l o t h i n g Worn S y n t h e t i c , short sleeve s h i r t s ( t h i n ) f r e q u e n t l y open. Work pants c o t t o n and/ or s y n t h e t i c Cotton S h i r t s , sweat s h i r t s and "T" s h i r t s o c c a s i o n a l l y . Work pants. Low shoes. P r i m a r i l y a t h i n s y n t h e t i c s h i r t and trousers. Occasionally synthetic/cotton s h i r t s . Rubber boots. Combinations: "T" s h i r t s and short sleeve s h i r t s . V a r i e t y of work pants, l i g h t weight. V a r i e t y of short sleeve s h i r t s , T" s h i r t s and sweat s h i r t s . Work pants v a r i e d from c o t t o n t w i l l to cotton synthetic. A v a r i e d assortment of s h i r t s , sweat s h i r t s (long and short sleeved) and a t h l e t i c j e r s e y s . Trousers v a r i e d i n c l u d i n g shorts and sandals. Wore heavy army f a t i g u e c o v e r a l l s of a heavier t w i l l f i n i s h than the U n i v e r s i t y of Miami p r o t e c t i v e c l o t h i n g . These m i l i t a r y green f a t i g u e were from a s u r plus s t o r e (had no l a b e l l i n g to d e t e r mine type and weight of f a b r i c - l o n g sleeve). Same as #7 M

Plimmer; Pesticide Residues and Exposure ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

13.

DAViES E T A L .

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Clothing

in the Field

179

i n each worker (15), and (2) the d a i l y c r e a t i n i n e c o r r e c t e d u r i n ary e x c r e t i o n of DEP i n each worker (16, 12). There were m u l t i p l e observations f o r each worker. Results from any wet patch or patches which had been dropped were excluded i n the compilat i o n of the data. In essence, each subject acted as h i s own control. For s t a t i s t i c a l e v a l u a t i o n of the d i f f e r e n t c l o t h i n g modalit i e s , "the unweighted means a n a l y s i s of v a r i a n c e f o r repeated measures was used. The average percent p e n e t r a t i o n of e t h i o n i n each of the pest i c i d e workers during phases 1 and 2 combined and phase 3 (untreated and treated c l o t h i n g ) are shown i n Table V I I I * The mean percent p e n e t r a t i o n of e t h i o n from phases 1 and 2 combined was 27.6 compared to 4 (untreated) and 3.6 (treated) i n phase 3 when p r o t e c t i v e c l o t h i n g was worn. The p r o t e c t i v e p o t e n t i a l of these c l o t h i n g m o d a l i t i e s was a l s o tested by u r i n a r y alkylphosphate excretions (15). The mean DEP concentrations during the s e v e r a l d i f f e r e n t c l o t h i n g modalit i e s worn by the two groups are shown i n Table IX. Average c o r r e c t e d DEP concentrations f o r the mixers was 1.05 ug/ml when wearing t h e i r own c l o t h i n g ; 0.89 ug/ml during phase 2 when they worn t h e i r own c l o t h i n g and a r e s p i r a t o r , and 0.68 ug/ml and 0.69 ug/ml i n phase 3 when these same workers wore new 100% c o t t o n denim c o v e r a l l s , SCOTCHGARD t r e a t e d and u n t r e a t e d .

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11

DISCUSSION A s i g n i f i c a n t degree of p r o t e c t i o n was apparent when the p e n e t r a b i l i t y of c l o t h i n g was assessed on the b a s i s of percentage p e n e t r a t i o n . The d i f f e r e n c e s between percentage e t h i o n penetrat i o n and workers wearing t h e i r own c l o t h i n g when compared to the p e n e t r a t i o n observed with the new c l o t h i n g (treated or untreated) was s i g n i f i c a n t a t the p