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PB96-196712
NT1S
Information \» our buskwu.
COMPARISON OF METHODS TO DETERMINE
DISLODGEABLE RESIDUE TRANSFER FROM FLOORS
SOUTHWEST RESEARCH INST., SAN ANTONIO, TX
AUG 96
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I ill1 IH
PB96-196712
Information is our businsu.
COMPARISON OF METHODS TO DETERMINE
DISLODGEABLE RESIDUE TRANSFER FROM FLOORS
SOUTHWEST RESEARCH INST., SAN ANTONIO, TX
AUG 96
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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EPA/600/R-96/089
August 1996
COMPARISON OF METHODS TO
DETERMINE DISLODGEABLE
RESIDUE TRANSFER FROM FLOORS
FINAL REPORT
by
David E. Camann, H. Jac Harding. Paul W. Geno, and Susan R. Agrawal
Southwest Research Institute
San Antonio, Texas 78228-0510
Contract Number 68-DO-0007
Work Assignment No. 33
Battelle Subcontract No. 34501 (2173)-2135
SwRJ Project 01-5164
Robert G. Lewis
National Exposure Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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TECHNICAL REPORT DATA
1. REPORT NO.
4. TITLE AND ^'BTITLE
Comparison of Methods to Determine Dislodgeable Residue Transfer from
Floors
FB36-136712
5.REPORT DATE
6.PERFORMING ORGANIZATION CODE
1. AUTHOR IST
David E. Canaan. HJ. Hardinr. ?• W. Geno, and S. R. Agrawal
8.PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Southwest Research Institute
San Antonio, TX 78228-0510
10.PROGRAM ELEMENT NO.
bine 28/CC7E1A/E3156
11. CONTRACT/GRANT NO.
68-DO-0007
12. SPONSORING AGENCY NAME AND ADDRESS
13.TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Three methods were evaluated for measurement of freshly-applied pesticide residues on carpeted and vinyl floors.
Tests were conducted to determine the relative performance of the three methods for removal of dislodgeable residues and
to compare them with human skin. The Dow drag sled and the Southwest Research Institute poryurethane foam (PUF)
roller performed better than the California cloth roller. Moistening the sampling media increased the transfer by the drag
sled and the PUF roller, but substantially increased measurement variability. An isopropanol handwipe method efficiently
removed dried pesticide residues from the hands of volunteers (104% of chlorpyrifos, 92% of pyrethrin I)
Both the drag sled ard the PUF roller were found to be acceptable dislodgeable residue methods on the basis of
these studies. The transfer efficiency of the drag sled consistently exceeded the transfer efficiency of the PUF roller, which
consistently exceeded the transfer efficiency of human hand presses. This relationship was observed for a variety of
pesticides, loadings, application methods, and surfaces. The pliable poryurethane foam sampling surface of the PUF roller
with its rolling action is likely to better simulate human skin in its transfer via contact with surfaces than is the denim cloth
of the Dow sled with its drag action. Either mechanical method can be used to estimate dermal transfer of pesticide
residues from recently treated floors. Round-robin testing of the drag sled and PUF roller by potential registrants under
strict QA/QC guidance from EPA is recommended.
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Disclaimer
The information in this document has been funded by the United States Environmental Protection Agency under
(Contract Number 68-DO-0007) to Battelle and Subcontract No. 34501(2173)-2135 to Southwest Research
Institute. It has been subjected to the Agency's peer and administrative review, and it has been approved for
publication as an EPA document Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
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Foreword
The National Exposure Research Laboratory, Research Triangle Park, North Carolina, conducts
intramural and extramural research in the chemical, physical, and biological sciences. This research is intended
to characterize and quantify environmental pollutant levels and the resulting exposures of humans and
ecosystems; to develop and validate models to predict changes in pollutant levels; to determine source-receptor
relationships affecting ambient air quality ard pollutant exposures; and to solve scientific problems relating to
EPA's mission through long-term investigations in the areas of environmental measurement methods, quality
assurance, biomarkers, spatial statistics, exposure assessment, and modeling. The Laboratory provides support
to Program and Regional Offices and state and local groups in the form of technical advice, methods research and
development, quality assurance, field monitoring, instrument development, and modeling for quantitative risk
assessment and regulation. The Laboratory also cc 'sets, organizes, manages, and distributes data on
environmental quality, human and ecosystem exposures, and trends for the Program and Regional offices, the
Office of Research and Development, the scientific community, and the public.
Human exposure to pesticides after application in the home is an area of concern to EPA because of
the toxicity of these chemicals. Dermal exposure through direct skin contact with treated surfaces may be
important, especially for toddlers, but is poorly understood, because sampling m^.ods have not been validated.
The work described in mis report evaluates and validates mechanical methods for determining the amount of
pesticide residue on floors which transfers to the hands through direct contact
Gary J. Foley
Director
National Exposure Research Laboratory
Research Triangle Park, NC 27711
ui
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Abstract
Comparisons were made of transfer of formulated pesticide residues from treated carpets and vinyl
flooring by three dislodgeable residue methods and by human skin. The Dow drag sled and the Southwest
Research Institute polyurethane foam (PUF) roller performed better than the California cloth roller.
Moistening die sampling media increased the transfer by the drag sled and the PUF roller, but substantially
increased measurement variability. An isopropanol handwipe method efficiently removed dried pesticide
residues from the hands of volunteers (104% of chlorpyrifos, 92% of pyrethrin I).
Both the drag sled and the PUF roller were found to be acceptable dislodgeable residue methods
on the basis of these studies. The transfer efficiency of the drag sled consistently exceeded the transfer
efficiency of the PUF roller, which consistently exceeded the transfer efficiency of human hand presses This
relationship was observed for a variety of pesticides, loadings, application methods, and surfaces. The pliable
polyurethane foam sampling surface of the PUF roller with its rolling action is likely to better simulate human
skin in its transfer via contact with surfaces than is the denim cloth of the Dow sled with its drag action.
Either mechanical method can be used to estimate dermal transfer of pesticide residues from recently treated
floors. Round-robin testing of the drag sled and PUF roller by potential registrants under strict QA/QC
guidance from EPA is recommended. The work reported herein was performed by Southwest Research
Institute under U.S. Environmental'Protection Agency Contract No. 68-DO-0007 to Battelle Memorial
Institute.
IV
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Contents
Abstract iii
List of Figures vii
List of Tables viii
Section 1. Introduction 1
Section 2. Conclusions 3
Section 3. Recommendations 4
Section 4. Materials and Methods 5
4.1 Facility Preparation 5
4.2 Dislodgeable Residue Methods 5
4.3 Hand Press and Wipe Methods 8
4.4 Pesticide Application 8
4.5 Sampling Designs for Experiments on Floors 10
4.6 Sampling Design for Experiment 4 11
4.7 Protocols and Informed Consent 11
4.8 Sample Analysis 12
4.9 Data Adjustment 12
Section 5. Results and Discussion 13
5.1 Conduct of Experiments 13
5.2 Data Quality 13
5.3 Transfers from Carpet by Methods as Described by Their Developers 14
5.4 Modification of PUF Roller Sampler 15
5.5 Effect of Moistened Contact Media on Transfers from Carpet Experiment 3 17
5.6 Field Performance of the Transfer Sampling Methods Using Dry and Moistened .
ContactMedia 18
5.7 Effects of PUF Roller Sampling Variables on Chlorpyrifos Transfer from Carpet 18
5.8 Effects of Drag Sled Sampling Variables on Chlorpyrifos Transfer from Carpet 19
5.9 Effect of Temperature on Transfer of Pesticide Residues from Carpet 20
5.10 Reduction in Transfer of Pesticide Residues from Carpet with Time after Application ... 21
5.11 Effect of Carpet Cleaning on Transfer of Chlorpyrifos Residues 21
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Contents (Cont'd)
5.12 Efficiency of Removal of Chloipyrifos and Pyrethrin I Residues from Human Skin by
the Isopropanol Handwipe Method 21
5.13 Comparison of Transfers of Pesticide Residues from Flooring by the Drag Sled, PUF
Roller, and Human Hand Presses 23
5.14 Comparison of Percent Mean Transfers of Pesticide Residues from Flooring by
Mechanical and Hand Press Methods 25
References .. 26
APPENDICES
A. Protocol for the Determination of Wipe Removal Efficiency of Chlorpyrifos and Pyrethrins
Formulated Mixture Residues from Hands (Experiment 4)
B. Protocol for the Comparison of Transfers by the Drag Sled, PUF Roller, and Human Hand
Press of Chlorpyrifos and Piperonyl Butoxide Formulated Mixture Residues from Sheet Vinyl
Flooring (Experiment 7)
VI
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Figures
Page
1 California cloth roller 6
2 Dow drag sled 6
3 PUF roller sampling instrument (1992 model) 7
4 Sampling layout for Experiment 7 9
5 Details of cylinder/frame assembly of modified PUF roller sampler 17
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Tables
1 Characteristics of Dislodgeable Residue Methods as Described by Developer and Used for
Experiments 1 and 2 27
2 Characteristics of Dislodgeable Residue and Hand Press Methods as Used for Experiment 7 28
3 Pesticide Applications to Flooring for Experiments .. 29
4 Sampling Design of Experiments 1 and 2 30
5 Sampling Design of Experiment 3 31
6 Sampling Design of Experiment 5A: Effect of Number of Passes of PUT Roller Sampler on
Chlorpyrifos Dislodgeable Residue Transfer 32
7 Sampling Design of Experiment 5B: Effect of Sampling Pressure and Speed of PUF Roller
Sampler on Chlorpyrifos Dislodgeable Residue Transfer 33
8 Sampling Design of Experiment 5C: Effect of Carpet Length Traversed by PUF Roller Sampler
on ChJorpyrifos Dislodgeable Residue Transfer 34
9 Sampling Design of Experiment 5D: Effect of Sampling Pressure and Speed of Drag Sled
on Chlorpyrifos Dislodgeble Residue Transfer 35
10 Sampling Design of Experiment 5E: Effect of Carpet Length Traversed by Drag Sled on
Chlorpyrifos Dislodgeable Residue Transfer 36
11 Sampling Design of Experiment 6: Comparison of Chlorpyrifos and Pyremrins Residue
Transfers from Carpet by Drag Sled Sampler, PUF Roller Sampler, and Hand Press by Three
Human Subjects 37
12 Sampling Design of Experiment 7: Comparison of Chlorpyrifos and Piperonyl Butoxide
Residue Transfers from Sheet Vinyl Flooring by Drag Sled Sampler, PUF Roller Sampler, and
Hand Press by Three Human Subjects 38
13 Sampling Design of Experiment 8A: Effect of Temperature on Transfer of Aged Residues 39
14 Sampling Design of Experiment 8B: Effect of Temperature on Transfer of Fresh Residues 40
15 Sampling Design of Experiment 4: Determination of Handwipe Removal Efficiency 41
16 Sampling Periods and Environmental Measurements Made During Transfer Sampling 42
17 Isopropanol Handwipe Laboratory Blanks and Field Blanks (ug/sample) 43
18 Field Spike Recoveries (%) from Alpha-cellulose Coupons 45
19 Field Spike Recoveries (%) from Denim Drag Cloths 46
20 Field Spike Recoveries (%) fromDry PUF Rings 47
21 Field Spike Recoveries (%) from Isopropanol-moistened SOF-WICK& Gauze Handwipes 48
22 Spike Recoveries (%) from Aluminum Foil Squares 49
23 Comparison of Transfers of Chlorpyrifos Residues from Plush Nylon Carpet in Experiment 1
by Cloth Roller, Drag Sled, and PUF Roller 50
24 Comparison of Transfers of Chlorpyrifos Residues from Level-loop Polypropylene Carpet
in Experiment 2 by Cloth Roller, Drag Sled, and PUF Roller 51
25 Comparison of Transfers of Chlorpyrifos Residues from Plush Nylon Carpet in Experiment 3
by the Drag Sled and PUF Roller Using Dry and Moistened Contact Media 52
26 Observations from Field Use of Dislodgeable Residue Methods 53
27 Experiment 5A: Effect of Number of Passes of PUF Roller Sampler on Transfer of Fresh
Chlorpyrifos Residue from Plush Carpet 54
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Tables (Cont'd)
Page
28 Experiment 5B: Effect of Pressure and Speed of PUF Roller Sampler on Transfer of Fresh
ChJorpyrifos Residue from Plush Carpet 55
29 Experiment 5C: Effect of Carpet Length Traversed by PUF Roller Sampler on Transfer of
Fresh Chlorpyrifos Residue from Plush Carpet 56
30 Experiment 5D: Effect of Pressure and Speed of Drag Sled Sampler on Transfer of Fresh
Chlorpyrifos Residue from Plush Carpet 57
31 Experiment 5E: Effect of Carpet Length Traversed by Drag Sled Sampler on Transfer of
Fresh Chlorpyrifos Residue from Plush Carpet 58
32 Effect of Temperature on Transfer of Aged CLlorpyrifos Residues from Plush Carpet by the
Drag Sled and PUF Roller in Experiment 8A 59
33 Effect of Temperature on Transfer of Aged Piperonyl Butoxide Residues from Plush Carpet by
the Drag Sled and PUF Roller in Experiment 8A 60
34 Effect of Temperature on Transfer of Aged Pyrethrin I Residues from Plush Carpet by the
Drag Sled and PUF Roller in Experiment 8A 61
35 Effect of Temperature on Transfer of Fresh ChJorpyrifos Residues from Plush Carpet by the
Drag Sled and PUF Roller in Experiment 8B 62
36 Effect of Temperature on Transfer of Fresh Piperonyl Butoxide Residues from Plush Carpet by
the Drag Sled and PUF Roller in Experiment 8B 63
37 Effect of Temperature on Transfer of Fresh Pyrethrin I Residues from Plush Carpet by the
Drag Sled and PUF Roller in Experiment 8B 64
38 Reduction in Chlorpyrifos Transfer from Plush Carpet Using the Drag Sled and PUF Roller
with Time after Application '. 65
39 Reduction in Piperonyl Eutoxide Transfer from Plush Carpet Using the Drag Sled and PUF
Roller with Time after Application 66
40 Reduction in Pyrethrin I Transfer from Plush Carpet Using the Drag Sled and PUF Roller
with Time after Application 67
41 Reduction in Chlorpyrifos Transfer from Used Plush Nylon Carpet After Commercial
Cleaning by Water Extraction 68
42 Elutior. Efficiency from Aluminum Foil Squares and Extraction Efficiency from Isopropanol-
moistened Gauze Wipes for Chlorpyrifos and Pyrethrin 1 in Experiment 4 69
43 Wipe Removal Efficiency of ChJorpyrifos Residue from the Human Hand by the Isopropanol
Handwipe Method in Experiment 4C 70
44 Wipe Removal Efficiency of Pyrethrin I Residue from the Human Hand by the Isopropanol
Handwipe Method in Experiment 4C 71
45 Comparison of Transfers of Chlorpyrifos Residues from Plush Carpet in Experiment 6A by
Drag Sled, PUF Roller, and Human Hand Press 72
46 Comparison of Transfers of Piperonyl Butoxide Residues from Plush Carpet in Experiment 6A
by Drag Sled, PUF Roller, and Human Hand Press 73
47 Comparison of Transfers of Pyremrin I Residues from Plush Carpet in Experiment 6A by
Drag Sled, PUF Roller, and Human Hand Press 74
48 Comparison of Transfers of Chlorpyrifos Residues from Plush Carpet in Experiment 6B by
Drag Sled, PUF Roller, and Human Hand Press 75
IX
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Tables (Cont'd)
Page
49 Comparison of Transfers of Methoprene Residues from Plush Caipet in Experiment 6B by
Drag Sled, PUF Roller, and Human Hand Press 76
50 Comparison of Transfers of Piperonyl Butoxide Residues from Plush Carpet in Experiment 6B
by Drag Sled, PUF Roller, and Human Hand Press 77
51 Comparison of Transfers of Pyrethrin I Residues from Plush Carpet in Experiment 6B by
Drag Sled, PUF Roller, and Human Hand Press 78
52 Comparison of Transfers of Chlorpyrifos Residues from Sheet Vinvl Flooring in Experiment 7
by Drag Sled, PUF Roller, and Human Hand Press 79
53 Comparison of Transfers of Piperonyl Butoxide Residues from Sheet Vinyl Flooring in
Experiment 7 by Drag Sled, PUF Roller, and Human Hand Press 80
54 Comparison of Transfers of Pyrethrin 1 Residues from Sheet Vinyl Flooring in Experiment 7
by Drag Sled, PUF Roller, and Human Hand Press 81
55 Comparison of Transfer of Fresh Dried Formulated Pesticide Residues from Flooring by
Drag Sled, PUF Roller, and Human Hand Presses 82
56 Percent Mean Transfer of Fresh Chlorpyrifos Residues by Flooring and Transfer Method 83
57 Percent Mean Transfer of Fresh Dried Residues by Flooring, Active Ingredient, an Transfer
Method 84
58 Stability of the Ratio of Transfers by Drag Sled and PUF Roller to Transfers by the Human
Hand Press 85
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Section 1
Introduction
Dermal transfer through contact with residues of pesticides applied to floors and subsequent skin
absorption or ingestion through hand-to-mouth activity are routes of human exposure which need better
evaluation, especially for young children. The Dow drag sled (Vaccaro and Cranston, 1990), the California cloth
roller (Ross et al., 1991), and the Southwest Research Institute (SwRI) polyurethane foam (PUF) roller
(Hsu et al, 1990) (Patent No. 5,243,865) are dislodgeable residue sampling methods which have recently been
developed to estimate the transfer of a chemical from a contaminated surface to the skin. This work assignment
compared these methods to provide some of the data to determine which provides the most accurate, reproducible,
economical, and facile performance. Precision and bias relative to human skin pick-up were also investigated.
The goal was to obtain data from which standardized methods can be established for use by registrants and
researchers.
The first phase of this work assignment compared both the rate (ng/cm2 of carpet contacted) and the
variability of transfer from carpet after broadcast spray application of a chlorpyrifos formulation by each of these
methods as currently employed by the developer. Three experiments were performed:
Exp. 1. Transfer comparison of the three methods using dry sampling media on new plush cut-pile nylon
carpet.
Exp. 2. Transfer comparison of the three methods using dry sampling media on new level-loop
polypropylene carpet
Exp. 3. Transfer comparison of the better two methods using both dry and moist sampling media on
new plush cut-pile nylon carpet
In the second phase of the work assignment, transfers determined by human skin contact were compared
to transfers obtained by the better-performing mechanical methods (Le., the drag sled and the PUF roller).
Experiments 4 through 8 were performed:
Exp. 4. Determination of 'be wipe removal efficiency by an isopropanol handwipe method of two
pesticides (chlorpyrifos and pyrethrins) mat have been applied to the skin of the hands.
Exp. 5. Experiments 5A through 5E investigated the effects of sampling variables on the amount and
variability of dislodgeable residue transfer of formulated chlorpyrifos from plush carpet when
i
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using the drag sled and PUF roller. The sampling variables which were evaluated included
traverse distance, number of repeat passes over the same section of carpet, speed, and transfer
pressure.
Exp. 6. Comparison of the transfers of formulated chlorpyrifos, pyrethrins, piperonyl butoxide, and
methoprene residues from plush nylon carpet obtained by the drag sled, the PUF roller, and
human hand presses.
Exp. 7. Comparison of the transfers of formulated chlorpyrifos, pyrethrins, and piperonyl butoxide
residues from sheet vinyl flooring obtained by the drag sled, the PUF roller, and human hand
presses.
Exp. 8. Evaluation of the effect of air/carpet temperature on the transfer of fresh and aged residues of
formulated chlorpyrifos, pyrethrins, and piperonyl butoxide residues by the drag sled and the
PUF roller from plush nylon carpet
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Section!
Conclusions
1. Transfers as currently performed by the developer were largest for the California cloth roller, intermediate
for die drag sled, and smallest for the PUF roller when using dry sampling media on two types of carpet.
2. The California cloth roller is less practical and more variable than the drag sled or PUF roller methods.
3. Transfers with moist media are larger, but substantially more variable, than transfers with dry media, for
both the PUF roller and the drag sled.
4. An isopropanol hand wipe method efficiently removed dry pesticide residues from the bands of two
volunteer subjects within the first minute after their transfer from aluminum foil to the Lwd. Wipe
removal efficiency was determined by mass balance after accounting for extraction and elution efficiency.
The mean wipe removal efficiencies were 104% (s=l 1%, n=12) for formulated chlorpyhfos, and 92%
(s=28%, n= 12) for pyrethrin I (formulation fortified with analytical standard).
5. Both the drag sled and the PUF roller transferred an amount of formulated chlorpyrifos residue from plush
carpet which was generally proportional to the length of carpet traversed. An essentially constant amount
of chlorpyrifos appeared to transfer to the PUF roller on each of the first 20 passes over a 1 m strip of
plush carpet.
6. Increasing the pressure applied to chlorpyrifos-treated plush carpet through the sampling medium had
little effect on chlorpyrifos transfer by the drag sled, but produced a nearly proportional increase in
transfer by the PUF roller.
7. As the carpet temperature increases, the drag sled and PUF roller bod) transfer slightly larger amounts
of fresh and aged residues from plush carpet
8. The transfer efficiency of formulated pesticide residues from treated carpet? and vinyl flooring was
consistently highest for the drag sled, intermediate for the PUF roller, and lowest for human skin.
9. The flooring material and application method and/or formulation had major effects on transfer, bat the
specific active ingredient had virtually no effect
10. The observed mean ± standard deviation of die multiplier cf hand press transfers obtained by die
mechanical methods was 7.4 ± 2.8 for die drag sled and 3.3 ±2.1 for die PUF roller. Eimer mechanical
method can be used to estimate dermal transfer of pesticide residues from recently treated floors.
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Section 3
Recommendations
1. Both die drag sled and die PUF roller were found to be acceptable dislodgeable residue methods on the
basis of this study.
2. Round-robin testing of die drag sled and PUF roller is recommended under strict QA/QC guidance from
EPA.
3. Dermal transfer of pesticide residues can be estimated from transfer by the drag sled or PUF roller.
Ratios which appear to apply to measurements on recently treated floors were obtained in this study.
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Section 4
Materials and Methods
4.1 Facility Preparation
All experiments were performed on the SwRI campus. All except Experiment 4 were performed in an
empty room (9 ft x 15 ft) in a 42 ft x 10 ft 3-room trailer, and in half of the adjacent empty room for
Experiments 1 and 2. Virgin flooring was installed prior to some experiments: a DuPont* StainmasterCM 100%
nylon continuous filament textured plush cut-pile carpet and padding prior to Experiment 1, a Shaw Mark®
Provider 26 polypropylene tufted textured level-loop carpet and padding prior to Experiment 2, an Evans and
Black® ScotchgariP* 100% nylon Saxony plush cut-pile carpet and padding prior to Experiment 3, and
Armstrong Explorer SolarianNo. 66510 sheet vinyl installed on V* in. wood underlayment prior to Experiment 7.
The plush cut-pile nylon carpet used for Experiment 3 was reused for succeeding experiments. It was cleaned
using a commercial water extraction system prior to the conduct of Experiments 5 A, SB, SCI, SC2, SE1, SE2,
5D, 6A, 6B, and 8B. Each cleaning consisted of application of a spot cleaner to remove marks, extraction using
a chemical carpet cleaner, rinsing with clean water, and drying for 48 hours with rapid air ventilation. Experiment
4 was performed in three extraction laboratories.
4.2 Dislodgeable Residue Methods
In Experiments 1, 2, and 3, die dislodgeable residue methods were performed as employed by their
developers. Relevant characteristics of these dislodgeable residue methods are summarized and contrasted in
Table 1.
The California cloth roller was constructed and the method performed as described by Ross et al. (1991).
A soap-washed and precleaned dry 17 in. x 17 in. cloth of percale bed sheet was placed on the carpet and covered
with a sheet of plastic. A 2 ft long by 4 in. diameter sewer pipe, filled with 25 pounds of steel shot ballast and
wrapped in a sheet of high density PUF, was rolled forward and backward over the plastic/cloth/carpet sandwich
ten times (Figure 1). After the 20 passes, the percale cloth was picked up and analyzed
The drag sled method was performed using the initial configuration described by Vaccaro and Cranston
(1990). Briefly, a precleaned dry 4 in. x 4 in. denim weave cloth supplied by B. Shurdut, Dow Chemical
Company, was attached beneath foil under a 3 in. x 3 in. plywood block and an 8-Ib weight mounted (Figure 2).
The sled was dragged once over a 3 iax 4 ft carpet strip at 6-8 cm/s. After me single pass, me denim cloth was
removed for analysis.
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Foam Cover
(S1 em Lx 1cm thick)
Weighted PCV Cylinder
(63cmx13cmdia.)
Handle
(13cmx2.5cmdla.)
Percale Bedsheet
(43 cm x 43 cm)
Plastic Beg
Figure 1. California cloth roller.
•*— Waight
Wood«n Block
Cotton Donim
Collection Media
Figure 2. Dow drag sled
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The original PUF roller sampler (Hsu et al., 1990) was used for Experiments 1 and 2. A precleaned dry
PUF ring (3 in. length. 3.5 in. OD, 1.62 in. ID) was secured on the 8 in length x 2 in. OD cylindrical 7.2 Ib
stainless steel roller. The new (October 1992) model of the PUF roller sampler was constructed and used for
Experiment 3 and later experiments. A precleaned dry PUF ring was secured on the 3 in length x 1.75 in OD
cylindrical 0.37 kg aluminum roller (F;gure 3). The PUF roller was rolled once over a 3 in x 1.0 m carpet strip
at 10 on s once in both directions. After the two passes, the PUF ring was sbt and removed from the roller for
analysis.
Stainless Steel
Weight
I
Snap-On
PUF Ring
Figure 3. PUF roller sampling instrument (1992 model).
In Experiment 3, PUF rings and denim cloth were used which had been moistened with deionized water.
A precleaned PUF ring was uniformly moistened with 5.0 ± 0.1 g of water in the laboratory by spraying the rug
surface with an atomizer, compressing with a squeeze tool to obtain uniform water distribution, weighing and
sealing in a steel canister until use. The sampling surface of the denim cloth was moistened with 0.5 ± 0.1 g of
water from the atomizer and weighed just prior to mounting under the drag sled When moistened at these levels,
the PUF ring and denim cloth were observed to produce equivalent moisture trails at method pressure on a glass
surface.
Later experiments involved only the drag sled and the PUF roller dislodgeable residue methods. To allow
more direct cross-comparisons of these methods with each other and the human band press, a single pass over
a floor traverse distance of 1.0 m was used a? a standard floor sampling technique for both methods. Relevant
characteristics of the methods as employed in Experiment 7 are presented in Table 2.
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4J Hand Press and Wipe Methods
In Experiments 6B and 7, a set often presses of the treated flooring was made w.tb each hand by three
subjects on three days in a reproducible manner. Prior to each daily pair of hand presses, eacli subject thoroughly
washed his hands with soap and water. The subject was cautioned to avoid touching any surfaces during the hand
press and wipe sequence. The subject then placed a disposable nitrile glove over the non-test hand. The second
hand was gloved to prevent contamination while performing the press and wipe procedure on the first hand and
to prevent the isopropanol from drying out the skin of the second hand prior to the hand press (avoiding an
abnormal skin condition mat could affect hand press transfer efficiency). A rar .'stock template was placed over
the designated area for floor sampling to expose a 3 in. (7.6 cm) x 25 in. (63.5 cm) treated strip. Whale kneeling
on a cardboard mat, each subject performed a series of ten presses of the palm of the test hand to adjacent
sections of flooring exposed by the template a' a pressure of ca. 1.0 psi for 1 sec each with fingers held off of the
surface. An isopropanol nandwipe of the hand was performed as described by Camann et al. (1995) in a clean
area in another building After washing both hands with soap and water, the glove was removed from the second
test hand and a clean glove placed over the second non-test hand. The press and wipe procedures described above
were then repeated using the second hand.
The nandwipe utilized two Sof-Wick* 4 in. x 4 in. 6-ply dressing sponges which had been pre-cleaned
prior to use. Each sponge was laced with 10 mL of Optima grade isopropanol. The subject was asked to perform
a genera] wipe of each hand with the first sponge. The second sponge was used to wipe around and between each
digit Both sponges were then placed in a single container and an additional 50 mL of isopropanol was added.
The subject performed all direct handling of the sponges from preparation to placement in the sample container.
although handling via forceps was also permitted Immediately following each handwipe procedure, the subject
thoroughly washed his hands to remove any remaining pesticides residues.
4.4 Pesticide Application
Application of the formulated pesticide to test flooring was conducted by a licensed pest control applicator
according to label instructions for flea control treatment The active ingredients of the formulations applied for
each experiment are listed in Table 3. Each application was accomplished in 2-3 min.
Chlorpyrifos was broadcast applied in the early experiments. The formulated product, Dursban* L.O.
(EPA Registration No. 464-571) which contains 41.5% chlorpyrifos (O.O-diemyl O-[3,5,6-trichJoro-2-
pyridyljphosphorothioate), was applied approximately 40 cm above the carpet as a 0.50% aqueous spray (40
mL/3.785 L water) at a rate of 1 gal 1600 fr with a hand-held fan broadcast nozzle attached to an air pressurized
tank.
For Experiments 6 and 7, which involved human hand presses of the treated flooring, a pesticide
formulated mixture was applied according to label instructions to control a light infestation of fleas. A
chlonpyrifospvrethnns'piperonyl butoxide formulated mixture was broadcast applied for Experiments 6A, 8B,
and 7. The formulated emulsifiable concentrate products. Dursban* L.O. (EPA Registration No. 62719-55),
which contains 41.5% chlorpyrifos (O.O-diethyl O-[3,5,6-tnchloro-2-pyridyl]phosphorothioate), and Kicker*
(EPA Registration No. 4816-707AA), which contains 6.0% pyrethrins and 60.0% technical piperonyl butoxide
were tank mixed at 2/3 fl. oz. (20 mL) Dursban* L.O. and 0.5 fL oz. (15 mL) Kicker* per gallon of water to yield
025% chkxpyrifos, 0.025% pyrethrins, and 025% piperonyl butoxide in the aqueous spray. The mixture was
applied approximately 40 cm above the floor at a rate of 1 gallon of diluted mixture per 1600 square feet with
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9
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a hand-held fan broadcast nozzle attached to an air pressurized tank. For Experiment 6B. Vet-Kern* Siphocrol*
premise spray (EPA Registration No. 2724-338-11785). which contains 0.015% metboprene. 0.20% pyrethrins.
and 1.0-: technical piperonyl butoxide, was applied from the aerosol can using a sweeping motion to supplement
the residues left on the carpet after Experiment 6A.
The trailer was ventilated for 2 hr immediately after application. All windows were opened and window
air conditioning units were operated in fresh return air mode. During the first 30 min and last 15 min of the
ventilation period, both doors were opened and a box fan was operated outside the test room doorway to allow
mai-tTTum cross ventilation. For experiments performed in warm weather, air conditioner units were returned to
the usual recirculated air mode just prior to sampling and remained on throughout the sampling period of the
experiment.
4J Sampling Designs for Experiments on Floors
The designs to determine comparative method transfers in the floor sampling experiments employed many
common design and QA'QC elements. Adjacent samples using each compared dislodgeable residue and hand
transfer metiiod and a deposition coupon were collected sequentially1 within a rectangular block of treated carpet
or vinyl Six replicate blocks were sampled in most experiments, although fewer were employed when there was
insufficient available treated surface. The block design of the sample layout for Experiment 7 is illustrated in
Figure 4.
Deposition coupons, consisting of absorbent alpha-cellulose pads (4 in. x 4 in.) backed with aluminum
foil were placed on the carpet (or teflon sheets on vinyl flooring) prior to the pesticide application and picked up
before the adjacent dislodgeable residue/hand samples from the block were collected Residues measured on the
coupon (or coupon set) gave an estimate of the surface loading of residue remaining on adjacent carpeting/vinyl
during sampling in the block.
Field blanks of each method were obtained by sampling prior to the application to assess contamination
potential during sampling and handling. Deposition coupon(s) were placed at the designated locations in each
sampling block shortly before the application commenced. Field samples were collected in the first block upon
label allowed re-entry, Le., when the carpet was dry (which was operationally defined as 2 hours after application.
but checked by hand contact). The dislodgeable residue samples of a block were collected from specific
randomized locations in the block after the deposition coupons) were picked up. All samples were collected in
one block before proceeding to the next block. Spikes of the precleaned dislodgeable residue media and of a
deposition coupon were made both before and after the set of replicate block samples were collected; these field
spikes were used to assess and potentially adjust for losses during transport, storage, and extraction.
The design used for Experiment 1 on new plush cut-pile carpet and for Experiment 2 on new level-loop
polypropylene carpet is presented in Table 4. The design used to compare transfers with dry and moistened media
is presented in Table 5. The designs used to evaluate the effects on transfer of PUF roller sanyiing variables in
Experiments 5A, SB, and 5C and of drag sled sampling variables in Experiments SD and 5E are given in
Tables 6-10. Tables 11 and 12 present the designs employed in Experiments 6 and 7 to compare transfers of
applied pesticides from phish carpet and from sheet vinyl obtained by the drag sled, PUF roller, and human hand
presses. The designs used in Experiments 8A and 8B to investigate the effect of temperature on transfers of aged
and fresh pesticide residues by the drag sled and PUF roller are presented in Tables 13 and 14.
10
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4.6 Sampling Design for Experiment 4
4,6,1 Task 4A: Determination of Aluminum Foil Elusion Efficiency
In order to (Jasmine the efficiency of removal of chJorpyrifos and natural pyrethrins from aluminum foil
squares, seven foils were spiked with 250 uL of me diluted formulated mixture. AD additional seven foils were
spiked with 25 uL of tbe formulated mixture. The factor often difference in spike levels was to determine if
aluminum foil elution efficiency is independent of tbe amount of pesticide spiked. Two additional foils • -rre
extracted without spiking to serve as control blanks. In order to verify the level of the pesticides in the spike
solution, two 300 ml. portions of 1:1 emerhexane were each spiked with 250 uL and with 25 uL of the diluted
formulated mixture.
4,6.2 Task 4B: Determination of Handwipe Extraction Efficiency
The efficiency of the extraction method for removal of the target pesticides from the handwipes was
evaluated by spiking seven moistened, precleaned handwipes with 250 uL of the diluted formulated mixture. An
additional seven wipes were spiked with 25 uL of the diluted formulated mixture. The factor often difference
in spike lex-els was to determine if the handwipe extraction efficiency is independent of the amount of pesticide
spiked. Two handwipes were extracted without spiking and served as control blanks, and two aliquots of
isopropanol were each spiked with 250 uL and with 25 uL of the diluted formulated mixture.
4.6.3 Task 4C: Determination ofHanthvipe Removal Efficiency
Handwipe removal efficiency experiments were performed using two human subject volunteers on each
of three days. On each day prior to sampling, the subjects hands were inspected for rashes, abrasions or cuts in
the skin. When any such sores existed, me experiment was postponed until the hand healed. On Days 1,2, and
3, five aluminum foil squares were spiked with 50 uL of the diluted formulated mixture as described above, one
aluminum foil square was spiked with 25 uL of the diluted formulated product, and one foil square served as a
control blank. Hand presses were performed on four of the 50 uL spiked foil squares, corresponding to each hand
of each "f the two subjects. A disposable nitrile glove was placed over the non-test hand for the press and wipe
of die test hand. The order in which me two hands were sampled was alternated on the three days. The double
isopropan'l handwipe procedure described above was initiated immediately (widiin 1 min) following each hand
press. On each day. one additional handwipe (Le., isopropanol-moistened pair of Sof-Wick* sponges) was spiked
directly widi 50 uL of me diluted formulated mixture, one handwipe was spiked with 25 uL of me diluted
formulated mixture and one handwipe served as a control blank. In order to verify the level of tbe pesticides in
the spike solution, one 300 mL portion of 1:1 emerhexane each was spiked with 50 uL and with 25 uL of the
diluted formulated mixture and one portion served as an extraction blank. A summary of samples for the three
described tasks is given in Table 15.
4.7 Protocols and Informed Consent
A protocol was wnrur to describe each planned experiment in detail and was submitted to me project
officer prior to concf a of the experiment Estimates were made and documented in each protocol of the expected
dermal exposure of the volunteer human subjects who participated in Experiments 4, 6. and 7. Prior to the
conduct of each of these experiments, their protocols and consent forms were approved by the Institutional
Review Board of the University of Texas Health Science Center at San Antonio, and informed consent of each
volunteer subject was obtained. The protocols for Experiments 4 and 7 are given in Appendices A and B,
respectively.
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4.8 Sample Analysis
Dislodgeable residue samples were SoxhJet-extracted with 6% ethyl etber^4% bexane; extraction
coTTEnenced within 24 hours after sampling. The pair of deposition coupons from a block were usually combined
and nnsed with 6-c ether-bexane as a single sanple. Isopropanol-saturated handwipes were shake extracted with
1:1 dietnyl etberbexane (Camann et aL, 1995).
Extracts from Experiments 1,2,3, and 5 were analyzed for chlorpyrifos by GC/ECD on two dissimilar
columns and quanbtated from the DB-5 column results. Extracts from Experiments 4,6,7, and 8 were analyzed
for chlorpyrifos, metboprene, piperonyl butoxide and or pyrethrin I on a Fisons MD-800 GC/MS operating in
selected ion monitoring mode.
4.9 Data Adjustment
Crude results (jig sample) from each 6dd sample were adjusted for contamination by subtracting the field
blank result as appropriate. Extraction efficiency was evaluated by maintaining a control chart of the field spike
recoveries for each matrix. Since field spike recoveries were generally close to 100°/o (see Results), the reported
data have not been adjusted for extraction inefficiency', except as specifically noted This result was divided by
the sampled carpet area (see Tables 1 and 2) to determine the measured transfer rate (ng cm2 of carpet comacted)
for dislodgeable residue samples and the measured surface loading (ng-'cm2) for coupon samples.
12
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Section 5
Results and Discussion
5.1 Conduct of Experiments
The experiments were conducted over a 13-month period from August 1992 through August 1993. The
sampling dates and times are given in Table 16. The temperature and relative humidity of the trailer room air
were monitored during each sampling period beginning with Experiment 5; mean levels are reported in Table 16.
The mean carpet temperature during each transfer sampling period of Experiments 7 and 8 is also presented in
Table 16.
5.2 Data Quality
5.2.1 Field Blanks
Field blanks were obtained with the cloth roller, drag sled, and PUF roller before pe&ucide applications.
The low amounts obtained on these field blanks in comparison with measurements after application established
that transfers from the floor were elevated substantially by each application.
The pesticide amounts recovered on each of the hand press/isopropanol handwipe field blank samples in
Experiments 4,6,and 7 are presented in Table 17, along with the isopropanol gauze laboratory blank results. A
field blank consisted of a hand press by a subject onto me test surface or a superimposed clean surface in the
same room where the hand press samples were subsequently collected, followed by die double isopropanol wipe
of me band after the subjects walked to a clean area in another building. The field blank hand press consisted
of a single press/rub of clean aluminum foil in Experiment 40, a single press through a cardstock template onto
48 on2 of a commercially-cleaned reused plush carpet in Experiment 6A, and ten adjacent hand presses onto a
clean cardstock strip placed over me test flooring in Experiments 6B and 7. Chlorpyrifos was recovered in 41
of the 42 hand press field blanks, in amounts ranging from 0.10 to 0.88 ug/sample. Piperonyl butoxide was
detected in 2 of 34 hand press field blanks, but at levels (0.06 fig and 0.03 ug) similar to those in solvent blanks.
Pyretfarin I and methoprene were not detected in the band press field blanks. Neither cWorpyrifbs nor p>Tethrin
I were detected in the three isopropanol gauze lab blanks analyzed in Experiment 4C, which were the only lab
blanks performed.
The source of the chlorp;Tifos contamination seen in the hand press field blanks is unclear. Chlorpyrifos
is used extensively in the southern United States for indoor and outdoor insect control. The Chlorpyrifos levels
were similar on both hands of ail subjects on each day that hand press field blanks were obtained The mean
chtorpyrifosblankk*TfccoIk«edonDay2of
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oc the osier days. The subjects always performed their presses of the same hand in the sequence A. B. and C.
Subject A had elevated chJorpyrifos levels in the first (right) hand press blank he performed on Day 2 of
Expenmem 4C. on Day OA of Experiment 6A. and on Day 2 of Experiment 7. Through monthly chlorpyrifos
dip treatments of his dogs, and by petting then: before work. Subject A is likely 10 have had some chJorpyrifos
residue on his hands each morning. However, be washed his hands with soap and water several times before the
day's field blank sampling commenced Subject A carried the bar of Ivory £ soap to the sink where the subjects
used it to wash their hands before and after eacb hand press. It is possible mat chJorpyrifos residues were
transferred to, and torn, the faucet handle or the soap bar during hand washing by the sampling team or subjects.
Another possibility is mat these hand blanks reflect ambient chJorpyrifos residues which were previously
transferred to the sJcin. Chlorpyrifos in fats and oils which are deeply embedded in the skin may not be removed
by washing with soap and water. However, the more efficient double isopropanol handwipe procedure may
remove the fats and oils containing the chJorpyrifos, to yield the residues seen in the hand press field blanks.
5.2.2 FieldSpikes
Series of field spikes were obtained across the eight experiments fur alphr -cellulose deposition coupons.
denim drag cloths. PUT rings, isopropanol-moistened Sof-Wick* gauze handwipcs. ?nd aluminum foil squares.
The field spike recoveries of chlorpyrifos, methoprene. piperony] butoxide, and pyTviiirin I for each of these series
are presented by matrix in Tables 18 through 22.
Chlorpyrifos recoveries from alpha-cellulose coupons, drag cloths, PUF rings, and aluminum foil were
essentially quantitative, with mean field spike recoveries near 100%. ChJorpyrifos recovery from isopropanol-
moistened gauze was slightly lower, averaging 86%. Mean recoveries of methoprene. piperonyl butoxide. and
pyrethnn I from these media were generally within one standard deviation of 100%. although recoveries of
piperonyl butoxide from alpha-cellulose and of merhopreae from isopropanol-moistened gauze were lower.
The field sample results for most individual experiments have Dot been adjusted for field spike recovery*.
as originally planned Adjustment was not needed because the mean field spike recoveries were so close to 100%.
Due to the variability of spike recoveries and the presence of outliers in the spike recovery* series, it was felt mat
adjustment for field spike recovery on a per experiment basis would have increased me variability of the fi;ld
sample results without improving dieir accuracy.
5 J Transfers from Carpet by Methods as Described by Tbdr Developers
The first two experiments compared the transfers of freshly dry chlorpyrifos residues from carpet by the
cloth roller, the drag sled, and the PUF roller. Each transfer sampling method was performed as described in
Table 1. Le., as conducted by its developers: Ross et al. (1991), Vaccaro and Cranston (1990). and Hsu et a).
(1990). This was done to permit intercomparison of transfers among prior studies which employed one of these
methods to support registration of pesticides used in the home. It should be noted however, that these sampling
methods differed in characteristics which are likely to affect transfer, such as 20 passes of a roller over a cloth
laid on the carpet vs. 2 passes of the PUF roller and 1 pass of die drag sled over a carpet strip.
The transfer method comparisons were coixlucted on two rxjpdar types of new-carpet a nylon plush
pile carpet in Experiment 1 and a polypropylene level-loop carpet in Experiment 2. Results of the transfer
mettod comparisons are presented in Table 23 for the nylon phtsh carpet and in Table 24 for die polypropylene
level-loop carpet
14
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The professional applicator, who performed these applications as well as those for later experiments, was
observed to glance over his shoulder frequently to avoid stepping on the deposition coupons, as instructed, as he
stepped backward while performing the broadcast application. In addition, it appeared that the applicator
sometimes inadvertently applied a double dose of the formulation to the boundary areas between adjacent
segments along his application pathway. The variation in deposition coupon amounts and their surface loading
estimates sometimes reflected this deposition variability, as for example in Experiment 1. However, in other
experiments the deposition coupons may fail to reflect the non-uniformity in the amount applied due to the chance
effect of its occurrence relative to the coupon placement The applicator was never asked to change these
practices which contributed to deposition variability on the test flooring.
The variability in formulation deposition produced an inherent variability in the transfer measurements
from the test carpets and sheet vinyl. Transfer measurement variability was also affected by the size of the area
sampled, due to the averaging effect of sampling a larger area. Thus, measurement using a deposition coupon
of a small area was susceptible to greater variation man the mechanical transfer measurements, which
encompassed much larger areas of carpet For example, the coefficient of variation of the deposition coupon
measurements was substantially larger than for the mechanical measurements in Experiment 1 (see Table 23).
However, transfer measurement va: lability is reduced by increasing the sampled surface area only to the extent
mat the deposition variation was randomly distributed over the treated test flooring. Application practices limited
the excess deposition to specific overlap locations whose area could exceed the contacted surface area of a
transfer measurement The amount of variation in transfer measurements obtained by a specific method could
itself vary substantially from one experiment to another, due solely to whether excess deposition occurred in one
or more of the flooring areas pre-designated for collection of the replicate transfer samples. Thus, in this study,
inferences based on transfer measurement variability must be drawn with caution. Such inferences may only be
warranted when the observed pattern of variation persisted across several experiments.
When performed as described by the method developers, transfer, per cm2 of contacted carpet were
highest for the cloth roller, intermediate for the drag sled, and lowest for the PUF roller, both froji plush nylon
carpet in Experiment 1 and from level-loop polypropylene caipet in Experiment 2. As shown by the coefficient
of variation, all three mechanica] surface transfer methods gave more repeatable performance on the plush nylon
carpet than on the level-loop polypropylene car )wt. However, mis observation may be an artifact caused by non-
uniform application of the chlorpyrifos formulation, as discussed above.
The cloth roller displayed more variation in the transfer of chlorpyrifos residue from the plush nylon
carpet than did the drag sled or the PUF roller. However, the coefficients of variation of the rates, in ng/cm2, of
transfer of chlorpyrifos from level-loop polypropylene caipet by the three methods were quite similar in
Experiment 2.
Transfers obtained with the cloth roller were larger for rolls oriented with and against the lay of the plush
nylon carpet fibers (x± a = 780 ± 140 ng/cm2, n=4) man for rolls across the lay of the fibers (430 ± 10 ng/cm2,
n=2) in Experimert 1. In Contrast, transfers with the drag sled and the PUF roller were not observed to vary with
the orientation of the drag/roll relative to the lay of the carpet fibers in these or later experiments. The additional
transfer variation observed with the cloth roller in Experiment I can largely be attributed to mis directional
sampling effect.
5.4 Modification of PUF Roller Sampler
In 1988 SwRI developed a foam roller instrument to simulate pesticide exposure to infants. It was
demonstrated mat the foam pressed by the roller with a contact rolling motion across an aluminum foil surface
15
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has similar characteristics to the human hand in terms of trans% of dried pesticide analytical standard residues
(Hsu et aL, 1990). EPA evaluated the PUF roller sampler and other methods for monitoring the potential
exposure of young children to pesticides in the residential environment in a nine-home pilot studv (Lewis et ah,
1994). EPA also suggested mat a pesticide manufacturer use the instrument to measure dislodgeable residue
from turf. The pesticide manufacturer expressed difficult)' in using the SwRI instrument, and the EPA evaluation
recommended hardware improvements for easier field use. Consequently, SwRI modified the instrument to
address the concerns and make h easier to use.
5.4.1 Original Design
The original roller sampler consisted of a ring of polyurethane foam (PUF) surrounding a 32 kg stainless
steel cylinder. The ring was brought from the laboratory in a glass jar, removed and placed on the cylinder at
die sampling site. The cylinder was then bolted to a roller assembly which allowed the user to roll the PUF across
the floor. The roller assembly had wheels and was designed to transfer acy pressure from the user through the
handle to die wheels instead of the PUF ring. Thus, the cylinder remained in correct with the floor at a constant
pressure. To acquire samples, the roller assembly was pulled along the floor for a specified distance at a specified
speed When the sampling was complete, the PUF rings were removed and placed in jars for transport to a lab
for extraction and analysis.
Comments from users of die instrument indicated some problems. One common concern expressed was
that the instrument was cifficuli to transport to the field due to ^ulkiness, and it was difficult to assemble at die
field site! A ring stand was required for assembly, and bolts had to be removed widi a wrench each time a new
PUF ring was used Another user complaint was dat there was potential for contamination of the rings when they
were removed from the cylinder.
The most important criterion for die new design was diat die redesigned instrument should be simple to
assemble in die field preferably with no extra pieces of equipment A means of rapidly mounting the PUF ring
on the roller and removing the PUF ring after sampling while preventing contamination was also important.
Other criteria for the redesign included maintaining the concept of die wheels and handle being connected
allowing the wheels to take any excess force exerted on me handle, while the PUF ring maintains a constant force
on die surface.
5-4.2 Design Modifications
The first major design change was to replace the large stainless steel cylinder with a smaller aluminum
cylinder and a separate weight block. The cylinder is the same width as me foam ring, preventing the foam from
being contaminated when it is slid on or off the cylinder. This is particularly impoitaut if the instrument is used
outdoors where die potential for cylinder contamination would be greater. The weight of die original stainless
steel cylinder created die desired pressure through the foam onto the surface. Wim a smaller aluminum cylinder,
» separate weight was necessary to create die required pressure. The weights were fashioned of stainless steel
blocks and mounted on arms supporting die ahnninr'. cylinder (see Figure 3). By having separate weight blocks,
the pressure exerted on die surface could be varied (see Experiment 5B).
Another feature mat was modified was the method of attaching me cylinder to the instrument. The
original design used hex nuts which are cumbersome and lime consuming to remove and replace. The new
design utilizes spring clips and grooves which hold nV cylinder in place when it is being rolled across a surface,
but allow the user to "soap" the cylinder in and out of the instrument. The support bars to which the cylinder
attaches have grooves on die underside to hold die cylinder. The support bars can be angled backwards to allow
die cylinder to be replaced easily. ~, ais is shown in Figure 5.
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Figure 5. Details of cylinder/frame assembly of modified PUF roller
sampler.
The original PUF roller sampler was redesigned to allow for easier uie on indoor surfaces as well as for
outdoor use. We decided to enlarge the wheels to provide easiei rolling across uneven surfaces often experienced
outdoors. If a rock or other obstacle gets in front of the wheels, the larger diameter and higher axle allow the
instrument to roll over the obstacle with little resistance.
To ^u^tate transport to a fteld site, the handle was febricated to be detacha^ The handle was made
in two pieces which screw together, and the lower handle piece screws into a fitting on the axle. The handle
pieces are 54 and 59 cm long. When disassembled, the length of the base is 32 cm. In addition, since the long
stainless steel cylinder was replaced by a shorter ahnninum cylinder, the overall width of the instrument could
be reduced to 23 cm. (The original model has a base of 72 cm x 37 cm, which includes the non-removable
handle.)
5J Effect of Mofsteied Cratoct Media «• TrusfersfronCvpet: Experiment 3
Moistening the medium m contact with a treated carpet should provkfe an indication of die transfer which
occurs when a child crawls on a carpet with hands which s/he has recently mourned. The effect on transfers of
chlorpyhfos residues from a new plush nylon carpet of pie-moistening the contact surfaces of the denim drag
doth and the PUF roller cover were investigated in Experiment 3.
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The results of tins experiment are presenteu in Table 25. After moistening the contact surface with a
water aerosol spray, the mean transfer rate increased moderately (ca. 60%) with the drag sled, but markedly (8-
fold) with the PUF roller. The greater proportional increase using the moistened PUF roller appears to reflect
the 10-fold larger moisture content of the moistened PUF ring (5 g) than the moistened drag cloth (0.5 g), rather
than their similar moisture transfers onto a glass surface. As indicated by the coe.7icient of variation, the
measurement variability of both methods increased substantially when moist contact media were used. The
increased measurement variation with moistened media may be a serious impediment to the use of moistened
media in field studies, since many more replicates would be required to detect a difference in transfer rates. The
increased variability was a factor in our decision to perform all subsequent floor transfer experiments using dry
contact media.
5.6 Field Performance of the Transfer Sampling Methods Using Dry and Moistened Contact Media
The strengths and weaknesses of each o. die three dislrdgeable residue methods which were observed
while conducting these experiments are summarized in Table 26. Though it is simple in design and configured
from readily available materials, the California cloth roller method consistently showed some inherent
weaknesses. It was difficult and cumbersome to or* .-ate due to the heavy weight of the roller and the fact that
operation required the user to be on his
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presumably due to non-uniform deposition". The additional amount transferred to the PUF roller with each
additional pass remained approximately 10 ug/pass, from the first pass through tfc: twentieth pass. At the
applied chlorpyrifos loading (23 ug/cnr'X each sampled carpet strip contained about 18 mg of chlorpyrifos. This
reservoir of chlorpyrifos in the nylon plush carpet was sufficient to yield a relatively constant additional transfer
of about 10 ug with each pass of the PUF roller sampler.
5.7.2 Effects on Transfer of Contact Pressure and Speed of PUF Roller: Experiment SB
The contact pressure of die PUF ring with the treated carpet was varied by removing the weight blocks
(2,400 Pa) and by adding additional weights (18,000 Pa). The results of Experiment SB are summarized in Table
2o. The transferred chlorpyrifos amount increased from 8.0 ± 1.4 ug at 2,400 Pa, to 26.8 ± 5.2 ug at 7,300 Pa,
and to 46.6 ± 17.8 fig at 18,000 Pa. The increase in PUF roller transfer amount was proportional to the contact
pressure.
Replicate runs at a more rapid sampling speed of 30 cm/s were also performed, while using the standard
7,300 Pa pressure. PUF roller transfer was suglith/ less (21.4 ± 5.8 ug) at 30 cm/s than at 10 cm/s (26 8 ±
52 ug).
5.7.3 Effect on Transfer of Length of Carpet Strip Traversed by PUF Holler: Experiment 5C
The carpet strip traversed by the PUF roller to collect a sample was lengthened from 9 cm (stationary for
3 s) to 25 cm, 1.0 m, 3.0 m, and 10.C m to evaluate its effect on transfer. After subtracting the mean stationary
transfer of 1.27 ug, *he mean transfer amount increased from 2.1 ug over 25 cm to 11.4 ug over 1.0 m, 57 ug
over 3.0 m, and 79 ug over 10.0 m. The amount of transfer to the PUF ring increased quire uniformly with
distance traversed over the first 3 m of treated plush nylon carpet, but increased slowly as more carpet was
traversed.
5.8 Effects of Drag Sled Sampling Variables on Chlorpyrifos Transfer from Carpet
The effects of varying the contact pressure, traverse speed, and traverse distance of the drag sled en the
transfer of fresh dry chlorpyrifos residues from nylon plush carpet to the dragged cloth were investigated in
Experiments 5D an J 5E.
5.8.1 Effects on Transfer of Contact Pnssure and Speed of Drag Sled: Experiment 5D
Increasing the contact pressure exerted by me drag sled on a treated nylon plush carpet had very little
effect on the transfer of chlorpyrifos residue tome cloth: from 36 ± 13 ug at 2,100 Pa, to 56 ± 28 ug at 4,500 Pa,
and to 43 ± 10 ug at 15,600 Pa (Table 30). Increasing the traverse speed of the drag sled at 4,500 Pa appears
to reduce the amount rfchlorpyriibs transferred, from 56 ± 28 ug at 7 cm/s to 31 ±21 ug at 20 cm/s (Table 30).
5.S.2 Effect on Transfer afLength of Carpet Ftrip Traversed by Drag Sled: Experiment 5E
Wnen placed stationary on the carpet for 3 s (as is often done before sampling commences) a mean of
0.63 ug of chlorpvrifos transferred to me cloth beneath die drag sled (Table 31). This is about half me mean of
127 ugtransferrW to the PIJF ring berjcamthr stationary PUF roto The mean transfer amount to the
drag cloth increased from 42 ug over the first 17 cm traversed, to 0.86 ug over 92 cm, 124 ug over 2.9 m, and
302 ug over 9.8m. Although it was low on the 92 cm traverse, the amount of transfer from the treated plush
carpet increased relatively uniformly with distances up to 10 m traversed by me drag sled
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5.9 Effect of Temperature on Transfer of Pesticide Residues from Carpet
Experiments 5 A through SE were intentionally perfonned over a 9°C range of indoor air temperatures
to permit an estrate of the effect of air temperature on transfer of fresh cbJorpyrifos residue from plush carpet
by the PIT roller and the drag sled However, application variability and possible effects of uncontrolled
variables between the experiments confounded the apparent effect of air temperature. Consequently, additional
experiments were designed and conducted to investigate the specific effect of temperature on transfers by the PUF
roller and by the drag sled of both aged residues (applied 3 1 to 37 days earlier, Experiment 8A) and fresh residues
(Experiment SB) of chlorpyrifos, piperonyl butoxide, and pyrethrin I from nylon plush carpet.
5.9.1 Effect of Temperature on Transfer ofA&d Residues: Experiment 8A
The plush carpet had been treated with chlorpyrifos, piperonyl butoxide, and pyrethins 37 days prior to
Experirc^nt 8A (for Experiment 6A) and again with piperonyl butoxide and pyremrins 31 days before
Experiment 8A (for Experiment 6B). Experiment 8A involved triplicate transfer sampling of the carpet with both
the drag sled and the PUF roller, first at cool carpet and indoor air temperatures, followed by repeat sampling at
moderate and hot temperatures (see Table 13). The mean indoor air temperature increased from 1 7 =C to 2? =C
to 34 :C, while the mean carpet temperature increased less rapidly from 22 °C to 27CC to 31 °C during the three
sampling blocks. Transfer results are discussed in relation to the carpet temperature, which we consider the more
relevant temperature measurement The results are presented in Tables 32 (cbJorpyrifos), 33 (piperonyl
butoxide), and 34 (pyremrin I). Substantial transfer measurement variability obscures clear trends. Mean
transfers of aged chlorpyrifbs residues increased by approximately a factor of 2 as the carpet temperature was
raised from 22 SC to 3 1 CC: from 0.46 ug to 1 .05 ug with the drag sled and from 0.43 ug to 0.78 ug with the PUF
roller. Transfers with the drag sled also increased by about a factor of 2 for aged piperonyl butoxide and a factor
of 1.5 for aged pyremrin I with this rise in carpet temperature. However, transfers with the PUF roller of aged
piperonyl butoxiue and pyremrin I were basically unchanged with mis rise in carpet temperature. Air samples
taken during the cool and hot sampling periods showed that the indoor air concentrations of chlorpyrifos and
piperonyl butoxide more than doubled with this temperature rise.
5. 9.2 Effect of Temperature on Transfer of Fresh Residues: Experiment 8B
After a formulated mixture of chlorpyrifos, piperonyl butoxide, and pyremrins had dried on the plush
carpet, triplicate transfer samples were again collected with the drag sled and the PUF roller at cool, moderate,
and hot indoor temperatures (see Tab'e 14). The mean carpet temperatures were 23 °C, 27 °C, and 30 c C during
the three sampling periods. Coupon-adjusted transfers of chlorpyrifos increased from the cool to the hot carpet
temperature by 21% (from 1 1.2 ug at 23 eC to 13.6 ug at 30CC) with the drag sled and by 35% (from 5. 1 ug to
6.9 ug) with the PUF roller (Table 35). The corresponding increases in coupon-adjusted transfers of piperonyl
butoxide were 47% (from 15.0 ug to 22. 1 ug) with the drag sled and 37% with the PUF roller (Table 36). The
increase in pyremrin I transfers was slightly larger 61% with the drag sled and 54% with the PUF roller
(Table 37). The larger transfers obtained in the fresh residue experiment may be responsible for the mote
consistent transfer increase with rising carpet temperature observed for fresh residues than for aged residues.
5.1 0 Reduction in Transfer of Pesticide Residues from Carpet with Time after Application
Transfer samples of residues remaining on the plush carpet were usually collected in duplicate with the
drag sled and tiiePUF roller just prior to cleaning the carpet for the next experiment One objective was to obtain
an estimate of the reduction in transfer of the residue with time after application. This was achieved by
comparing die mean transfer amounts «>n die day of application and on the subsequent day before cleaning. All
20
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of the data relevant to reduction in chlorpyhfos transfer with time after application is presented in Table 38. In
the seldom-used trailer, chlorpyrifos transfers from the plush carpet with die drag sled were reduced by an order
of magnitude within a rionth after application and by two orders of magnitude after three months. Chlorpyrifos
transfers from the same carpet with the PUF roller declined more gradually with time after application, but still
approached two orders of magnitude after three months. The simultaneous reduction in transfers of piperonyl
butoxide (Table 39) and pyrethhn I (Table 40) from the same plush carpet was similar to the reduction in
chlorpyrifos transfer within the first month after application.
5.11 Effect of Carpet Cleaning on Transfer of Chlornyrifos Residues
The plush nylon carpet used in Experiment 3 was commercially cleaned by water extraction before each
of eight subsequent chlorpyrifos applications. The pair of duplicate chlorpyrifos transfer samples collected by
the same method just before cleaning and again just before the application (usually 48 to 72 hrs after cleaning
to allow the carpet to dry) can be used to assess the effectiveness of the "*rpet cleaning in reducing chlorpyrifos
residues on the carpet surface. The mean chlorpyrifos transfers before an- after cleaning are shown in Table 41.
The first three cleanings produced substantial reductions (4- to 15-fold) in chlorpyrifos transfer from the carpet.
However, the fifth, seventh, and eighth cleanings did not reduce surface chlorpyrifos transfer from the carpet at
all. It is unclear whether residue build-up in the trailer or incomplete drying after cleaning contributed to the
apparent ineffectiveness of the later cleanings.
5.12 Efficiency of Removal of Chlorpyrifos «nd Pyrethris I Residues from Human Skin by the
Isopropanol Handwipe Method
5.12.1 Determination of Wipe Removal Efficiency
The merits and limitations of a mass balance approach to determination of removal efficiency for hand
washes and wipes have recently been discussed by Fenske et al. (1994). Initial experiments were performed to
determine the efficiency of the procedure for die removal of pesticides from human hands. Natural pyrethrins
and chlorpyrifos were selected for dus portion of die study since mey are common pesticides used in die home.
Natural pyrethrins is a mixture of six compounds. The most abundant, pyrethrin I, was selected to be quantitated
for diis experiment. The removal efficiency (RE) for a particular pesticide is calculated by:
RE =
where M^ is die mass of pesticide found on me wipe, M^, is mass of die pesticide applied to die foil, Mfoil
is mass of pesticide remaining on me foil, ECTt is die mean extraction efficiency of die pesticide from die wipe
material and Eel is die efficiency of eluting die pesticide from die aluminum foil square.
Ecl for chlorpyrifos and pyreduins from die aluminum foil squares was determined by spiking seven foil
squares, eacbwidi two levels of die pesticides using die procedure described above. The foils were then extracted
and die amounts of die two compounds recovered were calculated The recovery for each foil was calculated by
drvkh^ die recovered amount by d» spiked amount, which was determined by tiiree replicates of direct analysis
of die spiking solution dissolved in 10% ether in hexane. The means and standard deviations for Ee, for each
analyte at each level were dien calculated These results are grvfn in die upper half of Table 42. Mean Ee, for
chlorpyrifos were 105 ± 18% and 100 ± 7% for 1.86 ug and 23.9 ug spiked respectively. Pyrethrin I recoveries
were 103 ± 26% and 100 ± 11% for 17.5 ug and 246 ug spiked For bodi chlorpyrifos and pyrethrin L, die
recovery decreases from replicate 1 to replicate 7. This is most likely attributed to calibration drift of die GC/MS.
To partially compensate for diis drift, standards were analyzed at die beginning and end of die sequence and the
21
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response factor was taken as the average of the response factors for the two standards. Within the experimental
error, both anaJytes were quantitatively recovered from the aluminum foil.
Eg,,- was determined for chlorpyrifos and pyrethrin I by spiking seven replicates each with two different
amounts of the formulated mixture. The wipes were then extracted and me amount of chlorpyrifos and pyrethrin
I extracted was determined by GC/MS. The lower half of Table 42 shows E^, for each wipe replicate, and the
mean and standard deviation for each anaryte spike level Pyremrin I was extracted with mean recoveries of 97
± 14% and 101 ± 9% for spiking levels of 16.1 and 319 ug. Chlorpyrifos was extracted with recoveries of 88
± 6% and 100 ± 4% for spike levels of 1.93 and 25.2 ug. Within experimental error, pyremrin I was
quantitatively extracted from the wipe material at both high and low levels. Chlorpyrifos recovery was
quantitative at the higher spike level However, it is apparent that the extraction procedure was not as successful
in removing the chlorpyrifos when applied at a level near 2 ug.
At each stage of the wipe process, blanks were analyzed No target pesticides were found at a level above
the detection limit in extraction solvent, blank foil squares or blank dressing sponges when these materials were
extracted and analyzed by GC/MS. In addition to these matrix blanks, handwipe control blank? were performed
on two days during the hand-press experiments. In this experiment, the subjects hands were pressed onto clean
aluminum foil squares men wiped using the handwipe procedure. These results are shown in Table 17. No
pyremrin I was found in the control blanks above the detection limit However, chlorpyrifos at levels ranging
from 0.10 to 0.38 ug were found in each of the eight control blanks. At this time, the source of the chlorpyrifos
in the controls is unclear. Chlorpyrifos is used extensively in the southern United States for indoor and outdoor
insect control. One possibility is that the chlorpyrifos was introduced onto the subjects hands by touching a
contaminated object, such as the faucet or the soap bar during hand washing prior to the experiment A more
likely explanation is that these blank values represent ambient levels of chlorpyrifos. The chlorpyrifos may not
be removed with soap and water since it is deeply imbedded in the fats and oils in the skin. However, these fats
and oils containing the chlorpyrifos are removed from the hands using the 2-propanol wipe.
Once Eel, E^,, and blank levels for each portion of the experiment were understood, the RE for
chlorpyrifos and pyremrin I were experimentally determined using the procedure described above. Results for
the RE of chlorpyrifos are given in Table 43. The amount of chlorpyrifos spiked on the foil was determined from
the mean of six analytical results, obtained from three analyses each of two solutions prepared by dilution of the
spiking solution in 1:1 diethyl etherhexane. The amount of chlorpyrifos left on the foil was determined by
extraction of the foil square and has been corrected for Ee, and blank results. The amount of chlorpyrifos placed
on the hand was calculated as the difference between the amount spiked on the foil and the amount remaining on
the foil. The amount removed by handwipe was the analytical result obtained from the handwipe corrected for
blank and ECTt results. The percent removed was the amount of chlorpyrifos placed on the hand divided by the
amount removed by the handwipe. The RE ranged from 85 to 119% over the course of the three days of the
experiment. The mean RE for chlorpyrifos was found to be 104 ± 11% for the twelve measurements. RE results
for pyrethrin I are given in Table 44. A wider variation in the removal efficiency was observed with results
ranging from 56 to 144%. The mean RE for the twelve measurements was 92 ± 28%.
5.12.2 Discussion
Hand washes have been employed to monitor hand exposure to pesticides, but they require the handling
cf large vohmre of sorvert and are also diffioihw 1994). Hand wash studies
using chlorpyrifos showed recoveries of 30% with ethanol and 43% with 10% 2-propanol in water after
immediate exposure to dried formulation (F jnske et al 1994). Our results for wipe removal efficiency using 2-
propanol are significantly higher. We attribute the high removal efficiency of our technique to a combination of
22
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the solvation of the pesticides by the undiluted 2-propanol and the mechanical removal by the wiping action.
Once the wipe has been performed, the dressing sponges are kept moist with 2-propanol. This prevents strong
bonding of the polar pesticides to the cellulose material and enhances extraction efficiency.
At this time, removal efficiencies following an extended period of time after exposure (i.e., 30 min) have
not been performed However, based upon control blank results presented in Table 17, it is anticipated that the
described controlled double wipe procedure may efficiently extract pesticides deeply embedded in the skin.
The efficiency of dermal penetration of a particular pesticide depends upon the type and concentration
of the pesticide, the solvent and surfactant used and the physical form of the formulation. Concerns have been
raised that a 2-propanol wipe uiay enhance the penetration of certain pesticides through the skin. Experiments
should be performed to investigate possible penetration effects and to compare the removal efficiency of a wipe
using 100% 2-propanol with wipes using other solvents such as mild aqueous surfactants or diluted alcohol
solutions. We would anticipate, however, mat these alternative solvents would not be as efficient in removing
pesticides that have been incorporated into the fats and oils in the skin.
5.13 Comparison of Transfers of Pesticide Residues from Flooring by the Drag Sled, PUF Roller, and
Human Hand Presses
A major objective of mis project was to compare mechanical dislodgeable residue methods to presses by
the human hand with respect to transfer of formulated pesticide residues from treated flooring. The data to make
these transfer comparisons of the drag sled and PUF roller with human hand presses was developed by
performing Experiments 6 and 7.
5.13.1 Comparison of Transfers fro* Plush Carpet: Experiment 6A
Transfers from treated plush carpet by the drag sled, the PUF roller, and a single press of a human hand
in Experiment 6A are given for chlorpyrifos residues in Table 45, for piperonyl butoxide residues in Table 46,
and for pyrethrin I residues in Table 47. It was difficult to detect the amount transferred to the subjects' hand by
a single press through the template onto 48 on2 of the treated carpet. The hand transfer of chlorpyrifos was
usually less man the mean hand wipe background of 0.26 ug on Experiment 6A field blanks. Similarly, the hand
transfer of piperonyl butoxide seldom exceeded the detection limits of the hand press sample and the hand wipe
field blank. Pyrethrin I was not detected in any single hand press samples. It would have been desirable to
determine hand transfer based on a single press, as attempted in mis experiment, in order to avoid the possibly
non-additive accumulation of residue transfer with additional presses onto adjacent carpet sections. However,
feck of transfer detection with a single hand press rendered mis approach infeasible. Instead, Experiment 6B was
planned and conducted to obtain the needed transfer comparison of the drag sled and PUF roller to the hand press.
However, Experiment 6A did demonstrate that a single pass of the drag sled gave a 3- to 4-fold greater transfer
of all three formulated pesticides from the treated plush carpet than did a single pass of the PUF roller.
5.13.2 Comparison of Transfers from Plush Carpet: Experiment 6B
For Experiment 66, a formulation ctf methoprene, piperonyl butoxide, and natural pyrethrins was applied
by aerosol spray can to the same plush carpet used in Experiment 6A on the fourth day after its completion,
without recleaning the carpet The same sampling design was used, except that each hand palm was pressed onto
ten adjoining areas of the treated carpet through an elongated template. The transfer comparisons from
Experiment 6B are given for cUcrpyrifos, methoprene, piperonyl butoxide, and pyrethrin I in Tables 48 through
51, respectively. The transfer rate of each pesticide from the plush carpet was largest for the drag sled,
23
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intermediate for die PUF roller, and smallest for the human hand press. For example, the average transfer rates
in ng/cm2 were 9.2 (drag sled), 2.9 (PUF roller), and 1.3 (hand press) for chlorpyrifos, and 128 (drag sled), 58
(PUF roller), and 17 (hand press) for piperonyl butoxide. Transfer rates appeared more variable for the hand
press man for the drag sled or PUF roller.
5.13.3 Comparison of Transfers from Sheet Vinyl: Experiment 7
The same experimental design was also used to compare pesticide residue transfers from sheet vinyl. The
transfer comparisons from Experiment 7 are given for chlorpyrifos, piperonyl butoxide, and pyrethrin I in Tables
52 through 54, respectively. Similar to the transfers from carpet, the transfer rate of each pesticide from the sheet
vinyl was largest for the drag sled, intermediate for the PDF roller, and smallest for the human hand press. For
example, the average transfer rates in ng/cm2 were 1890 (drag sled), 780 (PUF roller), and 255 (hand press) for
t hlorpyrifos, and 192 (drag sled), 116 (PUF rollerX and 39 (hand press) for pyrethrin I.
5.13.4 Summary of Transfer Comparisons
The means and standard deviations of the transfer rates obtained in Experiments 6A, 6B, and 7 are
presented in Table 55. This table illustrates that the transfer rate was consistently largest for the drag sled,
intermediate for the PUF roller, and smallest for the human hand press, for all types of flooring and pesticides
examined.
5.14 Comparison of Percent Mean Transfers of Pesticide Residues from Flooring by Mechanical and
Hand Press Methods
5.14.1 Percent Mean Transfers of Chlorpyrifos
Chlorpyrifos transfers from flooring were measured in most of the sampling experiments. The mean
transfer of the applied chlorpyrifos residue, defined as the ratio of the mean transfer rate (ng/cm2) to the mean
surface loading (ng/cm2) is given by experiment and transfer method in Table 56. The percent mean transfer of
chlorpyrifos is much greater from sheet vinyl than from carpet Inspection suggests that the percent of
chlorpyrifos transferred from new carpet (Experiments 1-3) may be larger than the percent transferred from used
carpet (Experiments 5A-5E, 6A, and 8BX since mis pattern was observed both with the drag sled and the PUF
roller.
5.14.2 Comparison of Percent Mean Pesticide Residue Transfers in Experiments 6 and 7
The percent mean transfers of the pesticides applied to carpet and sheet vinyl in Experiments 6 and 7 are
presented in Table 57. A given method (drag sled, PUF roller, or hand press) transferred virtually the same
percentage of applied residue of all the formulation': active ingredients from the treated flooring in a given
experiment The percent transferred from sheet vinyl after broadcast application (Experiment 7) was nearly an
order of magnitude larger man me percent transferred from plush carpet after aerosol can application (Experiment
6BX and two or more orders of magnitude larger man the percent transferred from plush carpet after broadcast
application (Experiment 6A). There was more than an order of magnitude greater transfer of dried residues from
plush carpet after application of an aerosol can formulation (Experiment 6B) than after broadcast application of
a water-based formulation (Experiment 6A). These major effects of flooring and application method (or
formulation) on percentage transfer were found by all three methods.
24
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5.14.3 Stability of the Ratio of Mechanical and Hand Press Transfers
Table 57 indicates that the transfer efficiency is about three times higfor for the drag sled than for the PUF
roller, and about three times higher for the PUF roller than for the hand press, for every active ingredient, flooring.
and application method investigated To obtain a more precise estimate of this relationship, the ratio of the
mechanical method transfer mean (n=2) to the simultaneous hand press transfer mean (n=6) was calculated for
the 1 7 specific sets of pesticide within day within experiment for which hand transfers were measurable. The
transfer rates and ratios are presented in Table 58. Both the drag sled/hand press ratio and the PUF roller/hand
press ratio are quite stable over the broad range of transfer rates obtained in these 1 7 sets. The mean ± standard
deviation of these ratios were 7.4 ± 2.8 for drag sled/hand press and 3.3 ± 2.1 for PUF roller/hand press.
These observations indicate that the PUF roller and the drag sled can bom be used to estimate transfers
of formulated pesticide residues from flooring to a human hand by press contact. Crude estimates of the transfer
to human skin of residues of pesticides recently applied to a floor surface can be calculated from drag sled or PUF
roller measurements of the surface, by dividing by the appropriate mean transfer ratio given in Table 58.
25
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References
Camann, D.E., Geno, P.W., Harding, HJ., Clothier, J.M., and Giardino, NJ. (1995). Evaluation of
environmental exposure assessment methods for the NCI/EPA farm occupation exposure study (NEOFOS). EPA
Contract Number 68D10150, Southwest Research Institute Project 01-5278-100, San Antonio, TX.
Fenske, R A and Lu, C. (1994). Determination of handwash removal efficiency: incomplete removal of the
pesticide chlorpyrifos from skin by standard handwash techniques. Am. Ind. Hyg. Assoc. J. 55:425-432.
Hsu, J.P., Camann, D.E, Scbattenberg, H J., Wheeler, H.G., Villalobos, K., Kyle, M., Quarderer. S., and Lewis,
R.G. (1Q90). New dermal exposure sampling technique. In: Proc. Measurement of Toxic and Related Air
Pollutants, VIP-17, Air and Waste Management Association, Pittsburgh, PA, 489-497.
Lewis, R.G., Fortmaim, R.C, and Camann, D.E. (1994). Evaluation of methods for monitoring the exposure of
small children to pesticides in the residential environment Arch. Environ. Contain. Toxicol. 26:37-46.
Ross, J., Fong, H.R., Tbongsinthusak, T., Margetich, S., and Krieger, R. (1991). Measuring potential dermal
transfer of surface pesticide residue generated from indoor logger use: using the CDFA roller method
Vaccaro, JJL and Cranston, RJ. (1990). Evaluation of dislodgeable residues and absorbed doses of chlorpyrifos
following indoor broadcast applications of chlorpyrifo>based emulsifiable concentrate. Internal Report, Dow
Chemical, Midland, MI.
26
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Table I. Chancterirtica of Dialndgf able Rendue Method* m Described by Developer and Used for l-xperimcnts I ami 2
Property
California Cloth Roller
Dow Drag Sled
SwRIPUF Roller
Sampling medium (material)
Surface ofaampling medium
Contact motion
Percale bednheel (50% cotton. 50%
pnlyerter)
Square (42.9 cm)2
Roll
Face (IrMUntaneouacontact area pressed 440 cm2 - 42.9 cm * 10.2 cm
through aampling medium)
Mam exerting preaaure through
aampling medium
PreMure exerted through
aampling medium
Sampled carpet area
Number of paaaeti over aimpled
carpet area
Sampling speed over carpet
14.4kg
2400 Pa - (14.4 kgX9.8 m/»2V
((0.61 m)(O.IOm)|
0.184m2-(0.429m)2
20
0.23 mis
Denim weave cloth
(predominantly cotton)
Square (10.2 cm)2
Drag
58 cm2 = (7.6 cm)2
3.4ft kg
5,900 Pa " (3.4A kgM9.
(0.076 m)2
0.093 m2- 0.076 m« 1.22m
I
0.07 m/«
Polyurelhane foam riiiR T.ilyclhcr,
0.029 g/cm')
Curved exterior oftinp, (t)D = 8.9 cm.
length" 7.6 cm)
Roll
38.6 cm2 • 7.6 cm M S.I cm
3.25 kg;'3.10 kgh
8300 Pa;* 8,000 Pah = (3.10 kg)
(9.8 m/82)/I(0.076 mMO.05 m)|
0.076 m2 • 0.076 m * 1.0 m
2
0.10 m/a
a Original PUF roller mmpler
b 1992 model ofPUF roller aampler
-------
Table 2. Characteristics of Dislodgeahte Residue and Hand Press Methods as Used for Kxncrimcnl 7
Drag Sled
PUF Roller
(October 1992 Model)
Human Hand Press
K>
00
Sampling medium
Surface of sampling medium
Contact motion
Face (instantaneous pressed contact
area through sampling medium)
Mass exerting pressure through
sampling medium
Pressure exerted through sampling
medium
Sampled carpet area
Number of pasaes over sampled
carpet area
Sampling apeed over carpet
Denim weave cloth (predominantly
cotton)
Square (10.2 cm)7
Drag
7.6 cm * 7.6 cm » 58 cm1
3.46kg
5,900 Pa • (3.46 kgX9.8 mVy
(0.076 m)2
7.6 cm « 1.0 m • 0.076 m2
I
0.07 tn/s
Polyurclhane foam (PDF) ring
(0.029 g/cm\ polycthcr)
Curved exterior of ring(OD * 8.9 cm.
length « 7.6 cm)
Roll
7.6 cm « 5.1 cm » 38.6 cm*
3.10kg
8,000 Pa * (3.10 kg) (9.8 m/s2)/
(0.076 m) (0.05 m))
7.6 cm M 1.0 m « 0.076 m7
I
0.10 m/s
Skin on palm of hand
Palm (ca. 8 cm * 8 cm)
Ten presses (for I s)
7.6cm x 7.6 cm "58 cm2
NA
6,900Pa«I.Opsi
10" 7.6cm « 6.3 cm « 0.048 m2
I
NA
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N>
Table 3. Pesticide Applications to Flooring for Expcrmcnts
Treatment
Experiment Date
1 8-4-92
2 8-10-92
3 11-24-92
5A 3-2-93
SB 3-9-93
SCI 3-16-93
5C2 3 25-93
SEI 4-20-91
5E2 4-27-93
5D 5-19-93
6A 6-16-93
6B 6-22-93
8B 7-29-93
7 8-10-93
Flooring
Material
Plush carpet (new)
Level-loop carpet (new)
Plush carpet (new)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Plush carpet (used)
Sheet vinyl (new)
Applied
Formulation
Dursban L.O.
Dursban L.O.
Dursban L.O.
Dursban L.O.
Dursban L.O.
Dursban L.O.
Dursban L.O.
Dursban L.O.
Dursoan L.O.
Dursban L.O.
Dursban L.O.
Kicker
Siphotrolc
Dursban L.O.
Kicker
Dursban L.O.
Kicker
Active
Ingredients
Chlorpyrifos (0.5%)^
Chlorpyrifos (0.5%)
Chlorpyrifos (0.5%)
Chlorpyrift. i(0.5%)
Chlorpyrifos (0.5%)
Chlorpyrifos (C.5%)
Chlorpyrifos (0.5%)
Chlorpyrifos (0.5%)
Chlorpyrifos (0.5%)
Chlorpyrifos (0.5%)
Ciilorpyrifos (0.25%)
Piperonyl butoxide (0.25%)
Pyrethrin 1 (0.025%)
Methoprene(O.OI5%)
Piperonyl butoxide (1 .0%)
Pyrethrin 1 (0.2%)
Chlorpyrifos (0.25%)
Piperonyl butoxide (0.25%)
Pyrethrin 1 (0.025%)
Chlorpyrifos (0.25%)
Piperonyl butoxide (0.25%)
Pyrethrin . {0.025%)
Deposition Rntc"
(x±s)
ug/cm2
13.5*8.2
10.6 ±1.2
19.8 ±3.3
23.4 ±1.1
26.6 ±1.3
12.8 ±0.8
23.5 ±4.2
24.0-1 I.I
31.3 ±0.04
31. 2 ±5.6
5.4 ± 0.9
5.3 ±1.0
0.85 ±0.1 5
O.I l± 0.01
5.4 ±0.6
1.8 ±0.3
5.6 ±1.6
4.5 ±1.4
0.08 ± 0.20
8.3 ± 0.5
7.3 ±1.2
1.4 ±0.01
a From deposition coupons collected on day of application
b Composition in aqueous spray
c Aerosol spray can
-------
Tab* 4 Sampling Design of Experiments 1 and 2
Number of Replicates, by Method
Sample Category
FieW Tiisak (ore-apphcaDoc)
Dursban LO application
Field samples (begin 2 hours post
application)
F^ld spikes (at son and end of field
Too] Samples
c -Cellulose
Deposition Coupon
1
6
2
9
Clc±
Roller
1
6
2
9
Drag
Sled
1
6
2
9
PUF
Roller
1
6
2
9
Total
Samples
4
24
8
36
30
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Table 5. Sampling Design of Experiment 3
Number of Replicate;, by Method
Drag Sled
Sample Category
Field blank (pre-application)
DufEban LO application
Replicate field samples (begin
2 hours post application)
Field spikes (at start and end
of fr Id sampling)
Total Samples
a -Cellulose
Cfposrbun Coupon
1"
5«
2*
8*
Dry
Clc*
1
4
2
7
Moist
Cloth
1
5
2
8
PUF
Dry
PUF
1
4
2
7
Roller
Moist
PUF
1
5
2
8
Total
Samples
5
23
10
38
a Two a
-------
Tabk 6. Sampling Design of Experiment 5A: Effect of Number of Passes of PUF Roller Sappier* on
Chlorpyiifos Disiodgeabk Residue Tranter
Sniping Variables
Number of Samples by Type
fedoorAir Roller
•
Cool 1
(-20-Q
2
4
8
20
Field Spikes
•. . . Bi v I bczoic GAipct rlrmfid
PUFRuDer
|T1JI
3
3
3
3
3
2
*
25
Deposit
Cmnn
V4P«i|V\l
r
i
i
i
{ f
i
i
i ,
ie
0
4
ion
us ' Tool
>
29
a Nonnil preuare (7300 Pa) and spaed (0.1 mVs) ovc/ 1 m leafdi of carpet
c FOOT ooeUulosc ""ip«»« laid out in ooadtruts of block ate fm>bir>f^ as mf cunpk for cxn^tion **"^
analysis
d Two background lewd samples taken using PUF roOet and two background levels taken with the drag
sled
32
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Tabk 7. Sampling Design of Expenmrat 5B: Zffect of Sampling Pressure and Speed of PUF
Roller Sampler* on Chlorpyrifos Dislodgeable Residue Transfer
Sampling Variables
Nanber of Sampler by Type
Indoor
Air
ickxp-
Warm
(-3TC)
Fkld Spa
neia Blai
PUF
t^CSSQFC
2.400 Pa
(No weights)
(0.35 psi)
Normal
(Child weight)
7.300 Pa
(1.05 psi)
18.000 Pa
(Adult weight)
(2.6 psi)
Normal
7.300 Pa
«s
I*™-1* *^"*
Roller
Speed
°i™u'"
0.1 -j/s
0.1 m/s
0.1 m/s
Fast
(-0.3 m/s)
pet doped
!t]ir*fUM
PUF
V>Mf1^_ f\_,
KOUCf ^JC
Frrliritrf ^
3
3
'
.
3
2
2
2
^•Sw .
18
M^^*4^1«^H
position
Mipcns Total
' 1
t
i
31
I J
lc
0
0
4 22
a Single pass over 1 m length of carpet
b Segment room into north, central, and south blocks
c Four a-cellulose coupons laid oat in quadrants of Mock are combined as one simple
33
-------
Table 8. Sampling Design of Experiment 5C: Effect of Carpet Length Traversed by PUF Roller Sampler*
on Chlorpyriios Lislodgeable Rtddue Transfer
Sampling Variables
Temp.
Moderate
(-25«C)
Field Spikes
FieM Blanks
Traverse
Length
0.0 m
(surkmary-3 s)
025m
(1 revolution of
compressed PUF ring)
1.0m
3m
10m
1 before application
Day 1
Number of Samples by Type
Day 2
Roller Depos. Roller Depos.
RepLb Coupons RepLk Coupons Total
2 f
2
2 { 2
2
1
I
2 1
1 2 f
2
*y 2 < f
2
1
I
e 2 0
1
•
1
20 20
IS 3 IS 2
35
a Single pass at normal pressure (7300 Pa) and speed (0.1 m/s)
b Segment room into north and south blocks
c Four a-cellulose coupons per block
34
-------
Table 9. Sampling Design of Experiment 5D: Effect nf Sampling Pressure and Speed of Drag
Sled* on Chlorpyrifos Dislodgeble Residue Transfer
Indoor
Air
Tsmp.
Warm
(25-30°Q
Sampling Variables
Number of Samples by Type
Drag Sled
Pressure
Light weight
2,100 Pa
Normal
4.500 Pa
(Child weight)
(0.87 psi)
Adult weight
15.600 Pa
O2 psi)
Normal
4.500 Pa
Speed
0.07 m/s
0.07 m/s
0.07 m/s
Fast
(0.2 m/s)
Drag
Ci»«l
AKU
Replicatesb
3
3
3
3
Deposition
Coupons Total
f 1
'
1C
Field Spikes
r- 1^ m i
field Blanks
before carpet clfjfifd
2
*»
^^^^H
22
0
0
26
a Single pass, over 1 m length of carpet
b Segment room into nor h, central, and tooth blocks
c Four a-cellulose coupons laid out in quadrants of block are combined as one sample
d Two background levei samples taken using PDF roller and .wo background levels taken with
the drag sled
35
-------
Tabk 10. Sampling Design of Experiment 5E: Effect of Cupel Length Traversed by Drag Sled* on
Cfalorpyiifos Dislodgeabte Residue Transfer
Sampling Variables
Indoor
Air
Temp.
Traverse
Length
Number of Samples by Type
Day 1
Drag
Sled Depos.
RepLb Coupons
Day 2
Drag
Sled
RepLb
Depos.
Coupons
Total
Cool 0.0 m
r20-25°Q (stationary-3«)
0.25m
1.0m
3m
10m
Field Spikes
Field Blanks
before carpet cleaned
before application
2
2
2
1
2
-2-
15
f 1
0
0
2
2
2
1
2
2
IS
f 1
I J
0
0
0
35
a Single pass at normal pressure (4.500 Pa) and speed (0.07 m/s)
b Segment room into north and south blocks
c Four a-cellulose coupons per block
36
-------
Table 1 1 . Sampling Design of P-Xperiment 6: Comparison of Chlornyrifns and Pyrclhrins Residue Transfer* from Carpet by Drag Sled Sampler, PUF Roller Sampler,
and 1 land Press by Three 1 luman Subjects
Number of Samples by Type
Day Sample Category
OA Field blank*
OR Field Manks
I-AM Pesticide application
I-AM Field matrix spikes
I-PM OR samples1' •
2-PM DR samples*
3-PM DR sampled
3-PM Field matrix spike
Total DR Samples
Total Field Blanks
Total Field Matrix Spikes
Total Samples
Deposition
Coupon
0
0
1*
2§
2§
2§
I1
6
0
_2_
8
Drag Sled
2
0
1
2
2
2
1
6
2
_2_
10
Hand Press
Subject A Subject R Subject C
PUF
Roller L R L R L R Total
2 II II II
Oil II II
1 1 1
211 II II
211 II II
211 II II
1 1 1
66 66
24 4 4
_2. .2- _2_ _0_
10 12 12 10
10
6
5
12
12
12
5
36
16
IQ_
62
a The two a-celtulose coupons in a block are combined and extracted together as a single sample
b The samples collected from different treated carpel areas within each block are two deposition coupons, one drag sled, one PUF roller and one press/wipe by each
subject of the same hand
-------
Table 12. Sampling Design of ttxperimcnt 7: Comparison of Chlorpyrifo.i and Pipcrnnyl Rulnxiile Residue Transfer* fhnn Sheet Vinyl Flooring by Drag Sled Sampler.
PUF Roller Sampler, and Hand Press by Three Human Suhjccls
Number of Samples by Type
Pay Sample Category
Hand Press
Deposition
Coupon
Subject A
Subject B
Drag Sled
PUF Roller
Subject C
Total
oo
2
3-AM
3-AM
3-PM
4-PM
5PM
S-PM
Field blanks
FieM blank*
Pesticide application
Field matrix tpflcet
DR sampled
DR samples'1
Field matrix ipflce
0
0
2*
2'
21
J1.
0
2
I
2
2
2
I
0
2
I
2
2
2
I
I I
I I
I
I I
I I
I I
I
I I
I I
I
I I
I I
I I
6
10
5
12
12
12
5
Total DR Samples
Total FieU Blanks
Total Field Matrix Spike!
Total Sample!
6
0
JL
8
6
2
_2_
10
6
2
_2_
10
6
4
_2._
12
6
4
_2_
12
6
4
_Q_
10
36
16
JO.
62
a The two Teflon coupons in • block are combined and extracted together as a single sample
b The sample! collected from difTerenl treated vinyl areas within each block are two deposition coupons, one drag sled, one PUF roller and one press/wipe by each subject
of the same hand
-------
Table 13. -Campling Design of Experiment 8A: Effect of Temperature on Transfer of Aged Residues
Category
Field Matrix Spike
Diskxigeable Residue SampV?*
DR Samples*
DR Samples*
Field Matrix Spike
Total Field Samples
Total Field Matrix Spikes
Total Samples
Condition (Time)
Start (AM)
Cool(-20°C)
(late AM)
Moderate (25-27'Q
(Early PM)
Hot (30-35 "C)
(LatePM)
Finish
Number of Samples by Type
Drag Sled PUT Roller Air Sample
1 ' 1
3 3 1 (16h)
3 3
3 3 1 (4h)
_L J_ _
992
-2_ _2_ _0_
11 11 2
Total
2
7
6
7
_2_
20
4
24
a Measure temperature of air (6 in. above carpel) and carpet at beginning and end of each sample set
39
-------
Table 14. Sampling Design of Experiment SB: Effect of Temperature on Transfer of Fresh Residues'
r
Sample Category
Field Blanks
Pesticide Application'
Fkld Matrix Spike
DR Samples'
DR Samples'
Field Manx Spike
Total Field Samples
Total Field Blanks
Total Field Matrix Spikes
Total Samples
a Chlorpynfos (025%). pyrethrii
b The rwo a
-------
Table i 5. Sampling Desigr. of Experiment 4: Determinaboo of Handwipe Removal Efficiency
Number of Replicates, by Spike Amount
Task-Da>
4A - Aluminum
4B - Handwipe
Sample Type
Foil Eiution Efficiency
Aluminum foil squares
Extraction solvent spikes
Extraction Efficiency
Isopropanol handwipes
Extraction solvent spikes
250 uL
Formulated
Mixture
7
2
7
2
25 uL
Formulated
Mixture
7
2
7
2
Blank
2
2
2
2
Total
Samples
16
6
16
6
4C - Handwipe Removal Efficiency
AC - Da\ !
4C
4C - Dav3
Tout Samples
Aluminum foil squares
Hand presses - subject A: LH
subject B: L/R
Isopropanol handwipes
Extraction solvent spikes
Aluminum foil squares
Hand presses - subject A: L'R
subject B: L'R
Isopropanol handwipes
Extraction solvent spikes
Aluminum foil squares
Hand presses - subject A: L'R
subject B: L'R
Isopropano! handwipes
Extraction solvent spikes
4*1
2
4*1
2
4*1
JL
I
i
30
4+1
I
4*1
25
11
5
II
-i.
109
41
-------
Tib* l-i
crpl^sg Penoos iai Egvimnmrsa1. Measurerarou Mode During Transfer
Rooo: Air
1
1
2
3
4C
4C
4C
5A
5B
I 5C
5C
5E
5E
5D
6A
6A
6A
6B
6B
6B
8A
8B
7
7
'
• Colkcudi
fe Sling ptycfc
c Ambient (o
d Sbccivmyl
Dr.
1
2
3
1
2
1
^
1
2
3
1
2
3
3
4
5
PCEDUIU
ronirtcf»
iBdoorto
S*.
D.IC
8-4-92
8-10-92
11-24-92
3-3-93
3-17-93
3-24-93
3-2-93
3-9-93
3-16-93
3-25-93
4-20-93
4-27-93
5-19-93
6-16-93
6-17-93
6-18-93
6-22-93
6-23-93
6-24-93
7-23-93
7-29-93
8-10-93
f-11-93
T 12-93
to AMX>
vc HOOT
I « _. _|MMM AM
1 j ouove oa
n«w4innftc
mplinf Period
Time
1042-1229
1048-1238
1047-1231
10*5-1055
1130-113'
1125-1142
1102-1255
1305-1401
1105-1158
1220-1303
1125-1220
1048-1145
1105-1222
1316-1410
1413-1452
1325-1502
1330-1416
1328-1411
1550-1639
Coo! 10*4-1 1C)
Mod: 1316-1335
Hoc 1614-1634
Cool: 1125-1153
Mod: 1329-1355
Hot 1607-1634
1541-1620
1324-1403
1323-1402
m
Mean
Temp*. 'C
301
31*
20s
18
27
23
24
22
22
27
22
23
23
22
22
22
17
27
34
21
30
34
22
E
Men.
ReUuve Meu Carpel
Humidityb. *C Temp. 'C
61C
58C
29e
54
40
62
66
61
65
50
58
54
53
56
61
60
22
71 27
76 31
55 23
52 27
51 30
52 24*
49 23d
49 24c
V«W*/ •
flooring »«m>«'««""»
42
-------
Table 17.
Isopropanol Handwipe Laboratory Blanks and Field Blanks* Gig/sample)
Exp-Day-Subj/Hand Chlorpyrifos
Mstboprene
Piperonyl
Butoxide
Pyrethrinl
Lah Blanks- Twmmnanol Sof-Wickflt) Cau7f
4C-1
4C-2
4C-3
FiVlH RlanVc-
4C-2-AR
4C-2-BR
4C-2-AL
4C-2-BL
4C-3-AL
4C-3-BL
4C-3-AR
4C-3-BR
Field Blauks-
6A-OA-AR
6A-OA-BR
6A-OA-CR
6A-OA-AL
6A-OA-BL
6A-OA-CL
6A-OB-AR
6A-OB-BR
6A-OB-CR
6A-OB-AL
6A-OB-BL
6A-OB-CL
Field Blanks-
6B-0-AR
6B-0-BR
6B-0-CR
6B-0-AL
6B-0-BL
6B-0-CL
6B-4-AL
6B-4-BL
6B-4-CL
6B-4-AR
6B-4-BR
6B-4-CR
7-1-AL
7-1-CL
7-1-AR
7-1-CR
<0.01
<0.01
<0.01
O.05
<0.05
0.05
Sinele H""^ Press onto Aluminum Fofl/Isopro panel Handwroe
OJ8
0.12
023
0.14
0.10
020
0.11
0.13
____
«»«.
O.05
O.05
0.05
0.05
O.05
0.05
O.05
O.05
Sincle Hand Press onto Cleaned Caroet f48 cm VIsonroDanol Handwioe
0.60
026
0.45
024
025
0.19
0.15
0.16
0.14
022
026
0.15
<0.05
O.05
<0.05
<0.05
<0.05
O.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
0.06b
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
O.05
<0.05
O.05
O.05
O.05
O.05
O.05
O.05
0.05
O.05
O.05
O.05
0.05
O.05
Ten Hand Presses onto Cl*an QajQjstock M80 cm Wsoprown0! Han
-------
Continued
ChJorpyriJbs
Methoprene
Piperonyl
Biaoxide
Pywhrinl
Field Rbt~Vc- Tec Haod Presses onw Clean Cardstock (480 an^iTsooroo
7-2-AR
7-2-BR
7-2-CR
7-2-AL
7-2-BL
7-2-CL
0.86
025
027
031
024
<0.40
O.40
<0.40
O.40
<0.40
<0.04
'd>
O.45
<0.45
0.45
<0.45
<0.4S
<0.45
<0.90
O.90
<0.90
<0.90
<0.90
O.90
AD 6etd blink hand presses WOT performed abovr (oo. in Exp. 6A) tbe surface in the same room where band press
samples were colkcud on other days
Presen: in soK-ent blank »«»mp«r le\ el
1ST = QuantiutioD obscured by inurfereace
44
-------
Tib>; i 6. Field Spike Recoveries (%) from Alpha-cellulose Coupons
Exi*-=-«
Rtnge of spike amounts.
ME
1-1
1-2
2-1
2-2
3-:
3-2
5A
5B
5C1
5C2
5D
5E1
5E2
6A
6B-2
6B-3
8B-1
SB-2
No. samples, n
Mean.*
Suldev.t
Coef. of vahabon
Pipcronyl
CbJorp\Tifos Methoprene Butoxide Pyrethrin 1
(527-3000) (163-18.9) (856-1430) (33.5-114)
88
71
93
98
106
110
103
95
56*
86
108
118
94
98 67 122
108 160
93 137
92 69 102
103 78 109
16(15)* 235
949(97.5)* 100.5 71.3 »26.0
15.1 (\\.4f 10.6 5.9 23.2
0.159(0.117)* 0.106 0.082 0.184
a Exclude* apparent outlier
45
-------
Table 19. Field Spike
ExperimenT
Range of spike
•mounts, ng
1-1
1-2
2-1
2-2
3-1
3-2
5D-I
5D-2
SEI-:
5EI-2
5E2-1
5E2-2
6A-2
6A-3
6B-2
6B-3
7-5
8A-I
8A-2
8B-1
8B-2
No. samples, n
Mean. &
Std dev.. s
Coef. of variation
Recoveries (%) from Denim Drag Cloths
Cbloipyrifos Metboprene
(0.24-500) (0.04-0.17)
115
88
113
2081
98
101
86
88
133
116
I(K
91
90
97
III %
116 120
82
154* 153*
203* 132*
89
93
21(18)* 4(2)*
113.1(100.6)* 125.2(108.0)*
35.3(13.9)* 23.8(17.0)*
0.312(0.138) 0.190(0.157)*
Piperonyl
Butoxide Pyrcthrin 1
(5.1-88) (0.31-0.68)
73 87
76 118
145
NDbj
115 105
75 92
76 121
5 7(6)*
83.0 95.4(111.3)*
17.9 46.4(21.3)*
0216 0.486(0.192)*
a Excludes apparent outliers)
b ND - Noi detected
46
-------
Table 20. Field Spike
Experiment
Range of spike amounts,
Hg
1-1
1-2
2-1
2-2
3-1
3-2
5A-1
5A-2
5B-1
5B-2
5CJ-1
5C1-2
5C2-1
5C2-2
6A-2
6A-3
6B-2
6B-3
7-3
7-5
8A-1
8A-2
8B-1
8B-2
No. samples, n
Mean.*
Std. dev., s
Coef. of variation
Recoveries (°/i) from Dry PUF Rings
Piperonyl
Chlorpyrifos Methoprene Butoxide
(0.24-500) (0.04-0.17) (5.1-8.8)
108
34«
117
144
107
108
.90
103
138
104
101
103
77
84
86 72
89 73
107 105
93 96
98 118
100 105
118 128
120 118
97 85
97 84
24 (23)« 4 6
101.0(103.9)* 111.8 89.5
21.1 (15.9? 14.1 18.3
0209(0.153)* 0.126 0205
Pyrethrinl
(0.31-0.68)
99
91
160
133
104
143
107
101
8
117.2
24.8
0212
a Excludes apparent outlier
47
-------
Table 21. Field
Experiment
Range of spike
amounts, ug
4B-L1
4B-L2
4B-L3
4B-L4
4B-L5
4B-L6
4B-L7
4B-H1
4B-H2
4B-H3
4B-H4
4B-H5
4B-H6
4B-H7
6A-2-1
6A-2-2
. 6A-3-1
6A-3-2
6B-2-1
6B-2-2
6B-3-1
6B-3-2
7-3-1
7-3-2
7-5-1
7-5-2
No. samples, n
Mean, x
Std. dev., s
Coef. of variation
Spike Recoveries (%) from Is opropanol-inoistened
Chlorpyrifos Methoprene
(0.95-25.2) 0.17
95
86
96
79
84
91
84
105
97
106
96
101
97
95
69
75
79
59
54 58
58 68
70 87
69 85
95
101
86
96
26 4
85.5 74.5
14.9 13.9
0.175 0.187
SOF-W1CK« Gauze
Piperonyl
Butoxidi
(4.5-7.4)
70
72
78
56
141
150
167
126
8
107.5
43.1
0.401
Hand wipes
PyrethrinI
(0.31-319)
97
109
111
81
83
110
86
113
103
112
97
100
90
93
122
117
98
53
84
85
99
100
291*
155
228*
171
26(24)"
114.9(102.9)*
49.1 (23.7)1
0.427 (0.23 1)1
a Excludes apparent outliers
48
-------
Table 22. Spike Recoveries (%) from Aluminum Foil Squares'
Experiment 4A Replicate
Cblofpyrifos
Pyielhrinl
Low Spike Amounr
4A-L1
4A-L2
4A-L3
4A-L4
4A-L5
4A-L6
4A-L7
n
K
s
1.86ng
137
119
90
108
99
92
90
7
105
18
17-5
153
122
94
101
88
80
84
7
103
26
High Spike Amount1"
4A-H1
4A-H2
4A-H3
4A-H4
4A-H5
4A-H6
4A-H7
D
*
S
23.9
107
110
100
91
95
92
104
7
100
7
246. (ig
116
112
106
89
95
87
95
7
100
11
a Spiked formulated mixture allowed to diy on foil before
b Spiked amount determined from the mean of the analysis of
three replicates each of two solvent spikes
49
-------
Table 2.1. Comptriran of Transfers of Chlorpyrifos Residues from Plush Nylon Carpel in l-xperimcnt 1
Deposition
Sampled
Block Direction1*
1
II
III
IV
V
VI
No.
AAV
AAV
X
X
AAV
AAV
samples, n
Coupon
Amount
Hg
2.960
660
750
1,560
1,390
990
Mean, X
Std. dev., a
Coef. of variation
•
b
Surface •
Loading
ng/cnv
28,800
6,400
7.300
15,200
1.1,500
9.600
6
13,470
8,240
0.61
Cloth Roller
Transfer
Amount
MB
1,110
1.430
780
820
1.450
1,760
Transfer
Rale
ng/cm2
605
775
424
443
786
958
6
665
211
0.32
by Clolh Roller,
Drag Sled
Transfer
Amount
Mg
1X2
138
165
149
218
161
Transfer
Rale
ng/cm2
196
148
177
160
234
173
6
181.3
30.5
0.17
Drag Sled, and PUF Roller'
PUF Roller
Transfer Transfer
Amount Rale
ug ng/cm2
106 140
79 104
81 106
96 126
70 92
131 172
6
123.2
29.4
0.24
Sampled carpel area, number of passes, and pressure as defined in Table 1
Direction relative to lay of carpet pile: A - against, W r with, X - across
-------
Table 24. Comparison of Transfers of Chlorpyrifos Residues from Level-loop Polypropylene C'nrpet in Experiment 2 by ("loth Roller, Drag Sled, and PUF
Roller*
Deposition Cloth Roller Drag Sled PUF Roller
Sampled
Direction*1
Block
1
II
III
IV
V
VI
No. samples,
Mean,*
Sid. dev., s
A/W
A/W
X
X
A/W
A/W
n
Coupon
Amount
"8
1,220
970
1,000
950
1.210
1,180
Coef. of variation
Surface Transfer Transfer Transfer
Loading Amount Rate Amount
ng/cm* MR ng/cm2 MB
11,800 750
9,400 410
11,700 880
11.500 530
9.800 280
9,200 340
6
10,570
1,230
0.12
408 113
224 114
476 138
290 202
154 285
183 127
6
289
129
0.45
Transfer
Rate
ng/cm2
122
123
148
217
306
137
6
175.5
73.0
0.42
Transfer Transfer
Amount Rate
Mg ng/cm2
150 197
90 118
134 176
80 105
83 109
201 264
6
161.5
63.0
0.39
a Sampled carpet area, number of passes, and pressure as defined in Table 1
b Direction relative to lay of carpel pile: A - against, W - with. X - across
-------
N>
Table 23. Comparison of Transfers of Chlorpyrifos Residues from Plush Nylon Carpel in Experiment 3 by the Drag Sled nnd PUP Roller Using Dry find Moistened
Contact Media*
Dry Contact Medium (Standard) Moistened Contact Medium
Sampled
Block Direction1*
1 A/W
II X
III X
IV A/W
V A/W
No. samples, n
Mean, *
Std. dev., s
Coef. of variation
Deposition
Coupon Surface
Amount Loading
Mg ng/cn/
4.490 21,800
4,810 23,400
4.370 21.200
3.260 15,800
3.460' 16.800
5
19.800
3.300
0.17
Drag Sled
Transfer
Amount
Mg
c
45
80
58
116
Transfer
Rate
ng/cm2
_ __
48
86
63
125
4
80.4
33.3
0.41
PUF Roller
Transfer Transfer
Amount Rate
MB ng/cm2
«_ -
34 45
47 62
39 51
37 49
4
51.6
7.3
0.14
Drag Sled
Transfer Transfer
Amount Rate
Mg ng/cm2
152 164
53 57
90 96
261 281
54 59
5
131
94
0.72
PUF Roller
Transfer Transfer
Amount Rate
Mg ng/cm2
47 62
434 572
505d 580"
397 522
281 370
5
421
218
0.52
a Sampled carpet area, number of passes, and pressure as defined in Table 1
b Direction relative to lay of carpet pile: A -against, W- with. X- across
c No data since no sample planned
d Carpet area sampled was 870 cm2
-------
Table 26. Observations from Field Use of Dislodgeable Residue Methods
Strengths
Weaknesses
Cloth Roller
• Simple in design
• Inexpensive to build from available materials
Drag Sled
• Simple in design
• Inexpensive to build from available materials
• Simple to use
PL F Roller
• Consistent use across operators due to few
variables
• Relatively simple to use
• Foam roller contact is more like skin contact
• Sampling cloth tends to bind and shift from
original position
• Plastic bag cover may adhere to PUF sleeve on
roller from stark
• Difficult to operate due to mass of roller
• Operator must contact treated surface
• Susceptible to added pressure from operator
• Transfer affected by roll orientation relative to lay
of carpet fibers
• Drag contact unlike most skin contact with carpet
• Drag contact is potentially directional relative to
lay of carpet fibers
• Expensive to build or purchase
53
-------
Table 27.
Number
of
Passes4
1
2
4
8
20
Experiment 5 A: Effect of Number of Passes' of PUF Roller Sampler on Transfer of Fresh Chlorpyrifos
Residue from Plush Carpet
Replicate
Sampler
Direcrionb
A
W
X
A
W
X
A
W
X
A
W
X
A
W
X
Crude
5.7
18.6
9.1
46.6
11.4
24.5
26.4
66.4 ,
56.7
52.9
86.5
94.8
128
114
276
Transfer Amount, ug Coefficient
of
Adjusted Mean Std. Dev. Variation
4.4 9.9 6.6 0.67
17.3
7.9
45 J 26.2 17.8 0.68
10.1
23.2
25.1 48.5 20.9 0.43
65.1
55.4
51.6 76.8 22 2 0.29
85.2
93.5
127 172 90 0.52
113
275
Mean Transfer
Rate
ug/pass
9.9
13.1
12.1
9.6
8.6
a Repeat passes over 1.0 m strip of treated carpet
b Direction relative to lay of carpet pile: A - against, W--with. X-across
c Adjusted transfer = crude transfer - mean stationary (3 s) transfer (determined in Exp. 5C) = crude transfer •
1.27ug
54
-------
Table 2e. Expcmnem 5B. Effect of Pressure and Speed of PUF Roller Sample; oo Transfer of Fresh
Chlorp>Tifos Residue from Plush Carper*
PUF Roller
Appbed
Pressure Speed
Pa ms
2.400 0.1
(0.35 psi)
"uoo o.i
(1. 05 psi)
18,000 0.1
(2.6 psi 1
7JOG 0.3
(1.05psi>
Replicate
Sample7
Direction11
A
W
X
A
W
X
A
W
X
A
W
X
Transfer Amount, ug
Amount Mean Sid. Dev.
8.9 8.0 1.4
6.4
8.8
32.6 26.8 5.2
25.5
22.4
65.4 46.6 17.8
29.9
44.6
23.6 21.4 5.8
25.8
14.9
Coefficient
of
Variation
0.18
0.19
0.38
0.27
a Single pass over 1 m length of carpet
b Direction relative to lay of carpet pile: A - against. W - with. X - across
55
-------
Taris Ty Experiment 5C: Effect of Carpet Length Traversed by PUF Roller Sampler* oo Tnnsfer of Fresh
Cb'orpynfos Residue from PJusb Carpel
PIT Rolier
Tra-.erx
Lerg±
Repjcaie
Da>-
Direcnonb
Transfer Amount, fig
Crude Adjusted* Mean Sid Dev.
Coefficient Mean Transfer
of Rjue
Vananon
00m
(saaonzrv
for 3$)
0.25 m
1.0m
30m
10.0m
1-W
1-X
2-W
2-X
1-A
1-W
2-A
2-W
1-A
1-W
2-A
2-W
1-A
1-W
2-A
2-W
1-W
2-W
0.89
1.10
2.03
1.05
2J8
4.18
2.08
4.91
18.3
9.8
d
~9.9
48.6
56.9
596
68.8
103.3
57.0
1.11
2.92
0.81
3.64
17.0
8.5
~8.6
47.3
55.6
58.3
67.5
102.0
557
2.1
11.4
57.2
79
1.4
4.9
8.3
33
0.65
0.43
0.14
0.41
8.4
11.4
19.0
7.9
a Single pass at normal pressure (7.300 Pa) and speed (0.1 m s)
b Half experiment performed on each of ruodays. Direction relanve to lay of carpet pile: A -against. W-
wiih. X - across
c Adjusted transfer = crude transfer-mean sia:K>oar> (3 s) transfer (determined for 0.0 ml = crude transfer -
1.27 Mg
d Lost dunng extraction
-------
Table 30. Experiment 5D: Effect of Pressure and Speed of Drag Sled Sampler on Transfer of Fresh
Chlorpyrifos Residue from Plush Carper1
Drag Sied
Applied
Pressure
Pa
2,100
4,500
15,600
4,500
Replicate
Speed Sampler
m/s Direction1*
O-O"7 A
W
X
0.07 A
W
X
0.07 A
W
X
0.2 A
W
X
Transfer Amount, ug/m
Amount Mean Std Dev.
22
46
41
86
32
49
45
33
52
24
54
14
36.3 12.7
55.7 27.6
43.3 9.6
30.7 20.8
Coefficient
of
Variation
0.35
0.50
0.22
0.68
a Single pass over I m length of carpet
b Direction relative to lay of carpet pile: A - against, W - with, X - across
57
-------
Tahis 3: ExpeniTKn: 5E. Effect of Carpc: Length Traversed by Drag Sled Sampler* on Transfer of Fresh
Chiorpynfcs Residue from Plush Carpel
Drag Sied
Traverse
Lesnh
0.0 rr.
(saaosary
for 3 sj
0.1" in
092 m
2.92 m
9?6m
Replicate
Da>-
Direcnonb Crude
1-W
1-X
2-W
2-X
NA
1-W
2-A
2-W
1-A
I-W
2-A
2-W
1-A
1-W
2-A
2-W
1-W
2-W
i Sir.gJe pas* « normal
0.88
0.53
0.22
0.90
5.1
4.1
4.7
5.4
8.1
6.9
10.S
n.o
52
216
110
120
266
340
pressure (4.500
Transfer Amount, ug
Adjusted0 Mean
4.5 4.2
3.5
4.1
4.8
7.5 8.6
6.3
10.2
104
52 124
215
109
119
265 302
339
Pa) and speed (0.0? m s)
Coefficient Mear Transfer
of • Kate
Std. Dev. Variation n.e'pass
0.6 0.13 24.8
2.0 0.24 9.4
68 0.55 42.4
52 0.17 31.0
b Half expenmen: performed oo each of r* o da> s Direction relative to lay of carpet pile: A - against, W - with.
X - across
Adjusted transfer = crude transfer - mean stationary (3 s) transfer (determined for 0.0 m)c crude transfer •
0.63 ug
58
-------
Tabis 32. Effect of Temperance on Transfer of Aged Chlorpyrifos Residues from Plush Carpet by the Drag
Sled and PUF Roller in Experiment 8A*
Tertp. Mean Temperature, "C Room Air
Condition Coocemn&on Sampled
(Biocki Air Carpet ug''m3 Directionb
Coo: 1? 22 4.3 A
W
X
1
s
Moderate 27 27 A
W
X
*
s
Ho: 34 31 9.5 A
W
X
X
s
Transfer Amount, ug
Drag Sled
OJ7
0.50
0.50
0.46
0.08
1.09
0.85
0.98
0.97
0.12
0.98
1.22
0.95
1.05
0.14
PUF Roller
0.49
0.29
0.50
0.43
0.12
0.74
0.10
0.74
0.53
0.37
1.04
0.53
0.76
0.78
0.25
a Single pass over I m strip of carpet as described in Table 2
b Direction relate e 10 lay of carpet pile. A - against. W - with, X - across
59
-------
Table 33. Effect of Temperature on Transfer of Aged Piperonyl Butoxide Residues from Plush Carpet by the
Drag Sled and PLJF Roller in Experiment 8A§
Temp. Mean Temperature, °C • Room Air
Condition Concentration Sampled
(Block) Air Carpet ugto3 Direction1*
Cool 17 22 0.17 A
W
X
*
s
Moderate 27 27 A
W
X
X
s
Ho: 34 31 0.40 A
W
X
X
s
Transfer Amount,
ug
Drag Sled PUF Roller
2.5
1.7
3.3
2.5
0.8
5.9
8.0
3.9
5.9
2.0
6.5
5.5
2.4
4.8
2.1
3.4
2.9
2.8
3.0
0.3
4.8
0.8
2.6
2.7
2.0
5.0
2.1
3.5
3.6
1.4
a Single pass over 1 m strip of carpet as described in Table 2
b Direction relative to lay of carpet pile: A - *^ Jnst, W - with, X - across
60
-------
Table 34. Effect of Temperature on Transfer of Aged Pyrethrin I Residues from Plush Carpel by the Drag Sled
and PUF Roller in Experiment 8A*
Temp. Mean Temperature, °C Room Air
Condition Concentration Sampled
(Block) Air Carpet ng/m3 Direction6
Cool 17 22 O.05 A
W
X
k
s
Moderate 27 27 A
W
X
*
s
Hot 34 31 <0.3 A
W
X
*
s
Transfer Amount,
Mg
Drag Sled PUF Roller
0.17
0.44
0.22
0.28
0.14
0.49
0.59
0.29
0.46
0.16
0.56
0.31
0.36
0.41
0.13
0.30
0.42
0.33
0.35
0.06
0.64
0.05
0.17
0.41
0.33
0.44
0.24
0.26
0.31
0.11
a Single pass over 1 m strip of carpet as described in Table 2
b Direction relative to lay of carpet pile: A - against, W - with, X - across
61
-------
Table 35. F.flccl of Temperature on Transfer of 1 rcsh Chlorpyrifos Residues from Plush Cnrpcl by the Drnji Sled nml PUT Roller
Mean
Temperature, "C
Temp. Room Air
Condition Concentration
lilock Air Carpel ug/m'
Cool 21 23 6.3
NE
NW
Mean, ft
Sid. dcv.. s
Moderate 30 27
CE
cw
Mean, ft
Std. dcv.. R
Hot 34 30 27.8
SE
SW
Mean,*
Sid. dev., s
Deposition
Coupon Rclnlivc
Amount Coupon
Mg Meonc
720
1.400
1.060 0.92
480
1.530
1.410
1.470 1.27
80
830
1.030
930 0.81
MO
Snmplcd
Direction*1
A
W
X
A
W
X
A
W
X
Drop Sled Transfer, ug
Coupon
Amount Adjustment'1
8.1
R.9
13.9
10.3 11.2
3.1
11.7
30.9
13.5
18.7 14.7
10.6
9.8
6.6
16.6
tl.O 13.6
5.1
in lixpcrimcnt Klf
PUP Roller Transfer, |ip
Amount
5.7
2.6
5.7
4.7
1.8
4.5
6.9
9.3
6.9
2.4
6.3
4.8
5.5
5.5
0.8
Coupon
Adjustment'*
5.1
5.4
6.9
a Single pass over 1 m strip of carpet as described in Table 2
b Direction relative to lay of carpet pile: A - against, W - with, X - across
c ft/(£ft/n)
d Transfer mean/relative coupon mean
i
-------
o\
Table 36. Effect of Temperature on Transfer of Fresh Piperonyl
Temp. Mean Temperature. "C Room Air
Condition Concentration
Block Air Carpel jig/mj
Cool 21 2.1 0.10
NE
NW
Mean, X
Sid. dev.. »
Moderate 30 27
CE
CW
Mean, »
Sid. dev., a
Hot 34 30 0.44
SE
SW
Mean, X
Sid. dev., t
a Single pass over 1 m strip of carpet as described in Table 2
b Direction relative to lay of carpet pile: A - against, W - with,
c */(£*/n)
d Transfer mean/relative coupon mean
Rutoxidc Residues from Plush Carpet by the Drng Sled and PUF Roller in Experiment 8lf
Deposition Drag Sled Transfer, Mg PUF Roller Transfer, ng
Coupon Relative
Amount Coupon
ug Mcanc
570
1,200
890 0.95
440
1,190
1.180
1.180 1.27
10
640
800
720 0.78
120
X- across
Sampled
Direction1*
A
W
X
A
W
X
A
W
X
Coupon
Amount Adjustment*1
110
12.2
19.7
14.3 15.0
4.7
17.8
41.0
22.5
27.1 21.3
12.3
15.5
10.9
25.2
17.2 22.1
7.3
Amount
7.8
3.8
7.5
6.4
2.2
5.2
8.0
10.6
7.9
2.7
8.2
6.4
6.9
7.1
0.9
Coupon
Adjustment''
6.7
6.2
9.2
-------
Tahle 37. Effect of Temperature on Transfer of Fresh Pyrelhrin
Temp. Mean Temperature. "C Room Air
Condition Concentration
Block Air Carpet ug'm'
Cool 21 23 0.18
NE
NW
Mean.*
Std. dev., a
Moderate 30 27
CE
CW
Mean, *
Std. dev., a
Hot 34 30 0.09
SE
SW
Mean. »
Sid. dev., a
• Single pass over 1 m strip of carpel as described in Table 1
b Direction relative to lay of cupel pile: A - against, W - with.
c V(£»/n)
d Transfer mean/relative coupon mean
1 Residues from Plush Cornet by the Drag Sled and PDF Roller in Experiment 8 If
Pi-position Drag Sled Transfer, ug . PUF Roller Transfer. |ig
Coupon Relative
Amount Coupon
ug Mcnnc
78
191
134 0.96
80
167
157
162 1.15
8
III
140
125 0.89
20
X- across
Sampled
Direction*1
A
W
X
A
W
X
A
W
X
Coupon
Amount Adjustment*1
1.50
1.49
2.02
1.67 1.75
0.30
1.80
4.75
2.68
3.08 2.67
1.51
2.69
1.39
3.46
2.51 2.82
1.05
Amount
0.74
0.40
0.83
0.66
0.23
0.58
1.00
1.08
0.89
0.27
1.18
0.74
0.90
0.94
0.23
Coupon
Adjustment*1
0.69
0.77
1.06
-------
Table 3S. Reduction in Chlorp>Tifos Transfer from Flush Carper* Using the Drag Sled and PUF Roller with Time
after Application
Drag Sled Transfer PUF Roller Transfer
Date of Days After Mean Relative
Experiment Application Application |ig Transfer
3 11-24-92
5A 3-2-93
5B 3-9-93
SCI 3-16-93
5C2 3-25-93
5E1 4-20-93
5E2 4-27-93
5D 5-19-93
6A 6-16-93
a Single pass over 1 re strip of carpet
b Two passes over 1 rn strip of carpet
c Aeroto! can application of metbopie
0
93
0
3
0
3
0
6
0
15
0
3
0
17
0
23
0
1
2
6
6*
7
8
31
37
43
ne/py
75
0.27
7.5
4.5
10.9
0.62
55.7
1.02
7.1
2.2
3.5
1.7
6.8
9.2
5.0
0.46
0.63
lEiLnnvptperonyl buloxide
1.00
0.004
1.00
0.60
1.00
0.06
1. 00
0.018
1.00
0.30
0.49
0.24
0.96
1.28
0.69
0.06
0.09
formulation
Mean
Mg
39"
0.56b
27.5b
7.0b
268
4.2
14.0
3.0
9.9
2.6
2.12
0.97
1.09
1.03
2.24
2.31
2.66
0.53
0.43
0.52
Relative
Transfer
1.00
0.014
1.00
0.25
1.00
0.16
1.00
0.22
1.00
0.26
1.00
0.46
0.52
0.49
1.06
1.09
1.26
0.25
0.20
0.24
65
-------
Table 39. Reduction in Piperonyl Butoxide Transfer from Plush Carpet Using the Drag Sled and PUF Roller with
Time after Application
Drag Sled Transfer
PUF Roller Transfer
Experiment
Date of
Application
Days After
Application
Mean
Mg
Relative
Transfer
Mean
Mg
Relative
Transfer
6A
6B
6-16-93
6-22-93
0
1
2
6
0
1
2
25
31
37
8.1
3.0
4.9
2.4
131
IDS
55.6
2.5
2.4
1.00
0.38
0.61
0.30
1.00
0.80
0.42
0.019
0.018
2.3
1.2
1.4
1.1
54
34
44
4.3
3.0
2.3
1.00
0.53
0.61
0.48
1.00
0.63
0.81
0.08
0.06
0.04
66
-------
Table 40. Redu.non in Pyrethrin 1 Transfer from Plush Carpet Using the Drag Sled and PUF Roller with Time after
Applicanon
Date of Days After
Experiment Application Application
6A 6-16-93 0
1
2
6
6B 6-22-93 0
1
2
25
31
37
Dreg Sled
Mean
fg
1.39
0.43
0.54
0.45
40.9
38.0
12
0.28
0.17
Transfer
Relative
Transfer
1.00
0.31
0.39
0.32
1.00
0.93
0.18
0.007
0.004
PUF
Roller Transfer
Mean Relative
\ig Transfer
0.26
0.15
0.12
0.18
13.8
9.9
12.8
0.29
0.35
0.17
1.00
0.59
0.46
0.67
1.00
0.72
0.92
0.021
0.025
0.013
67
-------
Table 4!. Reduction in Chlorpvrifos Transfer* from Used Plush Nylon Orpet After Commercial Cleaning
by Water Extraction
Mean Transfer (ug) by Method
Date Carpet
Cieanedb
2-25-93
3-5-93
3-12-93
3-22-93
4-9-93
4-23-93
5-14-93
6-11-93
Experiment
Performed
After Cleaning
5A
5B
SCI
5C2
5E1
5E2
5D
6A
Drag
Before
Cleaning
0.3e
0.7
4.6
0.6
1.0
Sled
After
Cleaning
0.05*
0.8
1.0
1.5
\2
PUF Roller
Before
Cleaning
0.6"
7.0"
4.2
3.5
0.7
After
Cleaning
O.Id
0.4"
1.0
1.6
O.S
a Sirgie pass over 1 m strip of carpel
b Cleaning consisted of application of a spot cleaner to remove marks, extraction using a chemical carpet
cleaner, nnsing with clean water, and drying for 48 hours with rapid air ventillation
c Pass over 4 ft stnp
d Two passes over I m stnp
68
-------
Tabic 42. Elunon Efficiency from Aluminum Foil Squares and Extraction Efficiency
moistened Gauze Wipes for Chloqjyrifos and Pyrethrin 1 in Experiment 4
Spiked
Experiment AnaJyte
Spike
Level
4A: EJution Efficiency from Aluminum Foil
CbJorpyrifos
i
PyietiuiD I
4B Extracnon Efficiency from
Chlorpyrifos
Pyrethrin 1
Low
High
Low
High
Spiked
Amount*
"g
Squares*1
1.86
23.9
17.5
246.
No. of
Replicates
0
7
7
7
7
Isopropanol-moistened Sof-Wick* Gauze
Lou
High
Low
High
1.93
25.2
16.1
319.
7
7
7
7
Mean
105.1
99.9
103.2
99.9
Hand wipes
87.8
99.7
96.9
101.1
from Isopropanol-
Recovery.
Std.
Dev.
17.7
12
26.1
11.3
6.2
4.5
13.6
8.8
Coefficient
of Variation
0.168
0.072
0.253
0.113
0.071
0.045
0.140
0.087
a Spiked amount * as determined from the mean of the analysis of three replicates each of rwo solvent spikes
b Spiked formulated mixture was allowed to cry on foil before extraction
69
-------
j tr j -.-
V.':;>•* Rrrrjrva! Efficiency of Chtorpynfc-s Residue from tbe Hu.-nar Hand b> tbe Isopropano!
Metbod tn Experiment *C
Amount
Spiked
onto Fo:!-
Ufi or Foil
•ftr Hand Press*
Tiinsferred
u> Hand
Ranched b\
Removal
EfTicienc>
3-3-93 AL
BL
AR
BR
3-!--93 AR
BR
AL
BL
3-:4-93 AL
BL
AR
BR
So replicates, n
Removal efficiency mear*
Removal efficiency sid dt
Coefficier.t of vacation
4.32
4.32
4.32
4.32
4.20
4.20
4.20
4.20
4.26
4.26
4.26
4.26
0.63
0.78
0.25
OJ6
O.S4
0.9?
0.24
0.5g
0.56
0.90
0!5
O.'?0
3.69
3.54
4.07
4.06
3.36
3.23
3.V6
3.62
3.70
3.36
4.11
3.56
3.14
3.17
4.19
4.11
3.53
3.59
4.69
3.52
4.24
3.29
4.6!
397
85.2
89.4
103.0
101.3
105.1
111.1
118.5
97.2
114.5
98.0
116.9
111.7 '
12
104.3
10.7
0102
a Wipe performed within one minuie ater hand pms imo dried residue on aluminum foil
b Sp^ed amount was determined from tbe mean of toe anaJ>-sis of three replicates each of two solvent spikes
c Corrected for mean elution efficiencv of 105 l*« = Mfoi. '1.051
d Corrected for mean handwipe field blank of 0 18 »ig and for mean isopropanol SOF-WICK& gauze
extraction efficiency of 87.8% dunng Experiment 4 = (M^— - 0.18 ug)t).878
70
-------
Tfble 44. Wipe* Removal Efficiency of Pyrethrin I Residue from the Human Hand by the Isopropanol
Handwipe Method in Experiment 4C
Amount, ug
Date
Subject Spiked
Hand onto Foilb
Left on Foil
after Hand Press0
Transferred
to Hand
Removed by
Handwipe
Removal
Efficiency
3-3-93
3-17-93
3-24-93
AL
BL
AR
BR
AR
BR
AL
BL
AL
BL
AR
BR
40.5
40.5
40.5
40.5
51.1
51.1
51.1
51.1
44.8
44.g
44.8
44.8
No. replicates, n
Removal efficiency mean
Removal efficiency std. dev.
Coefficient of variation
6.4
7.6
4.1
2.9
13.1
14.8
3.4
7.4
8.6
10.4
2.5
11.5
34.1
32.8
36.4
37.5
38.0
36.3
47.7
43.8
36.2
34.4
42.2
33.3
19.0
20.7
24.6
25.7
29.2
36.8
43.8
38.0
46.2
40.0
43.1
48.1
55.6
63.0
67.6
68.4
76.7
101.2
91.9
86.8
127.7
116.1
102.0
144.4
12
91.8
27.6
0.300
a Wipe performed within one minute after hand press into dried residue on aluminum foil
b Spiked amount was determined from the mean of the analysis of three replicates each of two solvent spikes
c Corrected for mean elution efficiency of 103.2% = M^/l.032
d Corrected for mean isopropanol SOF-W1CK® gauze extraction efficiency of 96.9% during Experiment 4 =
(Mwipe-0.OugVO.969
71
-------
Table 45. Comparison ofTran.ifeni of Chlorpyrifos Residues from I'lush Cirpct in Experiment 6A hy Drug Sled. PUI: Roller
Deposition Drag Sled
Block
Coupon
Amount
MR
Surface Transfer
leading Amount
ng/cm* up
Transfer
Rale
ng/cmj
I'UF Roller
Transfer Transfer
Amount Rate
MR ng/cm*
and Human Hand Press
llumnn llnml Press
Subject
Mnnd
6- 16-93 (Application)
NE
NW
6-17-93
CE
CW
6-18-93
SE
SW
No. samples, n
Mean, X
Std. dev.. s
Coef. of variation
a Net amount -
1.240
970
1,510
1,360
940
1,200
6.020 8.49
4,680 5.77
7,320 I.RO
6.590 2.51
4,530 3.66
5,790 3.31
6
5.820
1,080
0.19
Crude handwipe amount - mean handwipe background =
11.17
7.60
2.37
3.30
4.82
4.35
6
5.60
3.25
0.58
X-0.26ug
1.60 2.10
2.64 3.47
1.26 1.66
0.68 0.89
0.68 0.90
1.50 1.98
6
1.83
0.%
0.52
AR
BR
CR
AL
Dl.
C:L
AL
Bl.
CL
AR
BR
CR
AR
BR
CR
AL
BL
CL
Net Transfer
Amount"
MR
I.Bh
0.03
I.B
LB
LB
0.06
r
Ti»
LB
LB
LB
0.04
LB
LB
LB
c
IB
LB
b LB = crude amount is less than background amount
c Sample lost
-------
Table 46. Comparison of Transfers of Piperonyl Huloxidc Residues front Plush (
'arnel in 1
Deposition Drag Sled
Block
6- 16-93 (Application)
NE
NW
6-17-93
CE
CW
6-18-93
SE
SW
No. samples, n
Mean,*
Std. dev., s
Coef. of variation
Coupon Surface Transfer
Amount Loading Amount
ug nf/cm' ug
1.240 6,020 11.19
960 4.670 4.96
1.520 7.370 2.R3
.
I.3RO 6.660 3.25
810 3,940 5.52
1.220 5.920 4.27
6
5.760
1.260
0.22
Transfer
Rntc
ng/cm*
14.72
6.53
3.72
4.2R
;.26
5.62
6
7.02
4.00
0.57
xperimcnl 6A by Drop Sled. Pill-'
I't !!• Holler
Transfer Transfer
Amount Rale
ug ng/cm?
1.64 2.15
3.04 4.00
1.64 2.16
O.R2 1.08
0.71 0.94
2.13 2.81
6
2.19
1.14
0.52
Roller, and Muinnn
Hand Press
llumnn llnml Press
Subject
llnml
AR
IIR
CR
AL
BL
CL
AL
BL
CL
AR
BR
CR
AR
BR
CR
AL
BL
CL
Net Transfer
Aniounl"
I'K
0.14
«).2
<0.2
0.07
<0.2
<0.2
b
~0.05
O.OR
<0.05
<0.05
0.06
<0.03
<0.03
<0.03
b
~<0.03
<0.03
a Since handwipe field blank amounts were <0.05 pg. no background is subtracted
b Sample lost
-------
Table 47. Comparison of Transfers of Pyrclhrin 1 Residues from Plush Carpet in 1
xpcrimcnl 6A by
Deposition Drag Sled
Block
6- 16-93 (Application)
NE
NW
6-1 7-93
CE
CW
6-18-93
SB
SW
No. samples, n
Mean, X
Std. dev., s
Coef. of variation
Coupon Surface Transfer
Amount Ixtading Amount
ug ng/cnr ug
197 954 2.12
152 736 0.66
153 741 0.36
100 484 0.50
29 140 0.55
56 274 0.54
6
555
311
0.56
Transfer
Rale
ng/cmj
2.79
0.87
0.48
0.65
0.73
0.71
6
1.04
0.87
0.84 .
Drag Sled. PI ir Roller, and
PI II- Roller
Transfer Transfer
Amount Rate
MR ng/cm'
O.IH7 0.25
0.336 0.44
0.194 0.26
0.113 0.15
0.072 0.10
0.167 0.22
6
0.23
0.12
0.51
Human Hnnd Press
Human Hand Prrs*
Subject
Hand
AR
BR
CR
AL
BL
CL
AL
BL
CL
AR
BR
CR
AR
BR
CR
AL
BL
CL
Net Transfer
Amount"
MR
<0.2
INI*
<0.2
<0.2
INT
<0.2
c
INT
<0.05
INT
INT
INT
<0.05
<0.05
<0.05
c
~<0.05
<0.05
a Since handwipe field blank amounts were <0.05, no background is subtracted
b INT = Elevated background due to interference
c Sample lost
-------
Table 48. Comparison of Transfers of Chlorpyrifos Residues* from Plush Carpel in Experiment 61! by Drag Sled, PUI: Roller, and Human Hand Press
Block
6-22-93
NE
NW
6-23-93
CE
cw
6-24-93
SE
SW
No. samples, n
Mean, X
Std. dev., »
Coef. of variation
a No chlorpyrifos
Deposition* . Drag Sled Pill
Coupon Surface Transfer Transfer Transfer
Amount Loading Amount Rate Amount
Mg ng/cm* Mg ng/cm2 MR
7.84 10.32 2.03
5.80 7.63 2.45
11.35 14.94 2.50
6.97 9.18 2.11
7.31 9.61 2.04
2.60 3.42 3.27
6
9.18
3.75
0.41
was applied for Experiment 6B, but chlorpyrifos had been applied on 6-16-93
•Roller
Transfer
Rale
ng/cm7
2.67
3.22
3.29
2.78
2.69
4.30
6
2.93
0.30
0.10
for Experiment 6A
Human Hand Press
Subject
Hand
AR
BR
CR
AL
BL
CL
AL
BL
CL
AR
BR
CR
AR
BR
CR
AL
BL
CL
Net Transfer
Amount*1
Mg
0.22
0.49
0.20
0.38
0.83
0.22
1.24
0.51
0.87
1.07
0.95
1.28
0.46
0.74
0.52
0.31
0.09
0.73
Transfer
Rate
ng/cm
0.45
1.03
0.42
0.80
1.73
0.45
2.58
1.06
1.82
2.23
1.98
2.66
0.97
1.54
1.09
0.64
0.18
1.53
18
1.29
0.76
0.59
b Net amount = crude handwipe amount - mean handwipe background = X - 0. 1 6 Mg
-------
Table 49. Comparison of Transfers of Methoprcne Residues* from Plush Carpet in Experiment 6B by Drag Sled. PDF Roller, nnd Human Hand Press
Block
6-22-93 (Application)
NE
NW
6-23-93
CE
CW
6-24-93
SE
SW
No. samples, n
Mean, X
Std. dev., s
Coef. of variation
Deposition
Coupon Surface
Amount Loading
ug ng/cm'
20.0 96.7
24.2 117.0
13.0 62.9
11.6 56.1
16.8 8l.3b
16.8 8l.4b
4b
83.2b
2R.7b
0.34b
a Since handwipe field blank amounts were <0.03
b Excluded from summary statistics
Drag Sled
Transfer
Amount
Mg
2.25
2.45
1.71
1.23
0.13
0.15
Transfer
Rnte
ng/cm2
2.96
3.22
2.25
1.62
O.I7b
0.20b
4b
2.5lb
0.72b
0.29b
PUF Roller
Transfer
Amount
Mg
0.92
0.92
0.2R
0.37
0.41
0.32
-
Transfer
Rate
ng/cm2
1.20
1.20
0.36
0.49
0.53b
0.42b
4b
O.R2b
0.45b
0.56b
Subject
Hand
AR
BR
CR
AL
BL
CL
AL
BL
CL
AR
BR
CR
AR
BR
CR
AL
BL
CL
Human Hand
Net Transfer
Amount"
Mg
0.09
0.19
0.13
0.30
0.45
0.23
0.15
0.06
0.06
0.10
0.10
0.10
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
Press
Transfer
Rntc
ng/cm7
O.IR
0.39
0.27
0.63
0.93
0.4R
0.32
0.13
0.13
0.21
0.22
0.22
<0llb
<0.llb
<
-------
Table SO. Comparison of Transfers of Pipcronyl Butoxidc Residues from Plusli Carpet in Experiment 61) by Drag Sled
Deposition Dreg Sled
Coupon Surface Transfer Transfer
Block
6-22-9.1 (Application)
NE
NW
6-23-93
CE
CW
6-24-93
SE
SW
No. samples, n
Mean. X
Std. dev.. s
Coef. of variation
Amount Loading Amount
ug ng/cm* ug
1,029 4.980 126.6
1,200 S.RIO I3S.6
593 2.870 121.8
Sll 2.480 88.1
8SO 4,120 8I.S
826 4,000 29.6
6
4.040
1,250
0.31
a Net amount = crude handwipe amount - mean handwipe background
Rate
ng/cm2
167
I7R
160
116
107
39
6
127.9
S2.I
0.41
= X-0.lMg
PUF Roller
Transfer Transfer
Amount Rale
ug ng/cm2
51.0 67
56.8 75
31.4 41
36.3 48
46.6 61
40.6 53
6
57.6
12.5
0.22
PUP Roller, and Human Hand Press
Human Hand Press
Subject
Hnnd
AR
RR
CR
AL
RL
CL
AL
RL
CL
AR
RR
CR
AR
RR
CR
AL
BL
CL
Net Transfer
Amount*
MR
6.0
R.5
6.1
20.3
18.7
10.2
12.3
5.9
4.8
9.1
8.2
6.5
8.3
6.1
5.2
4.1
2.5
7.8
Transfer
Knte
np/cm2
12
18
13
42
39
21
26
12
10
19
17
14
IV
13
II
9
5
16
18
17.4
9.7
0.56
-------
-J
00
Table 51. Comparison of Transfers of Pyrcthrin 1 Residues from Plush Carpet in P.xpcrimcnt 6B by Drag Sled, PDF Roller, and Human Hnnd Press
Deposition Drag Sled PUF Roller
Coupon
Amount
Block ug
6-22-93 (Application)
NE 339
NW 415
6-23-93
CE 173
CW 146
6-24-93
SE 175
SW 183
No. samples, n
Mean, Jk
Std. dev., s
Coef. of variation
Surface Transfer
leading Amount
ng/cm |ig
1,640 39.7
2,010 42.2
836 44.2
707 31.9
846 5.2
886 9.1
6
1155
536
0.46
Transfer Transfer Transfer
Rate Amount Rate
ng/cm2 ug ng/cm2
52.3 11.6 15.2
55.5 16.1 21.2
58.2 8.7 11.5
42.0 11.0 14.5
6.8 14.0 IR.4
12.0 11.5 15.1
6 6
37.8 16.0
22.7 3.4
0.60 0.21
Human Hnnd Press
Subject
Hand
AR
BR
CR
AL
BL
CL
AL
BL
CL
AR
BR
CR
AR
BR
CR
AL
BL
CL
Net Transfer
Amount*
MR
INT*
INT
INT
INT
INT
INT
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
Transfer
Kate
ng/cm2
<0.10
«).IO
-------
T«hlc 52. Compari»on of Tnn«frn of Chlorpynfo* Residue* from Shrrt
Vinyl Hooting in Hpenmenl 7 hy I>MR Slc«l,
IVpcwiliofi Drag Sled
.
Rlock
8- 10-93 (Application)
Nl:.
NW
8-11-93
CE
cw
8-12-93
SW
SE
No. samples, n
Mean.*
Std dev., a
Coef. of variation
Coupon SuifiKf Transfer
Amount loading Amounl
Mg ng/cm' Mg
1.780 8.660 920
1.640 7,990 1.iS50
2.000 9.770 1.0 10
2,700 13,170 1.040
580 2.800 1.080
1,170 5.700 940
A
8.010
.1.540
0.44
a Net amount » Crude handwipe amount - mean handwipe background
liwwfcr
Rme
ng/cmj
1.210
4.800
1.1.10
1.160
1.420
1.240
6
1.890
1.430
0.75
= X-0.1ug
Pill : Roller
Tran\fcr 1 runsfcr
Amount Rule
Mg np/rnt
115 440
%1 1.270
560 740
291 190
.141 450
1.046 1.380
6
778
442
057
(Mil •Rolln.an
-------
00
o
table 51 Compattmn of f rannfrr* of Pipctonyl liulotnk RfMitur* ftnm Shrri Vinyl 1 Inonnp in l-tprnmrni 7 by Dt»R Slnl. PI l|; Ritlln. ami llutrmn llnrnl
Prt>«
Block
R. 10-91 (Application)
NK
NW
R-ll-91
CK
CW
R-12-91
SW
SE
No. samples, n
Mean.*
Std. dev.. s
Coef. of variation
(Vpmilinn
Coupon Surface
Amount I jtarfine
ug ng/cm'
1.670 R.1 10
.
I.UO 6.1RO
I.H80 9.150
2.790 11.610
720 .1.5.10
960 4.680
6
7.5RO
.1.620
0.4R
a Since handwipe field blank amounts were
-------
00
Table 54. Companion of Transfer* of Pyrelhrin 1 Revdue* fnmi Sheet Vmyl Mwnng in l-tpenmenl 7 hy Dinp Slnl. PHI-
Block
8- 10-91 (Application)
Nl-
NW
8-11-91
CK
cw
8-12-91
SW
SB
No. sample*, n
Mean. \
Sid. dev., •
Coef. of variation
Oepmilion IVtg Sled PHIKolln
Coupon. Surface Transfer 1r»mfcr li»n\fef tiimfrr
AmiHini londinp. Amminl Rule Amntinl Rule
- * 1 1
MR ng/cm' |IR ng/cm' IIR ng/cm'
284 1.180 101 111 68 <. V(l
288 (.190 168 221 1110 149
261 1.260 121 159 715 97
.111 1.510 127 167 458 60
122 .590 201 26* 48 1 61
229 I.IIO 160 210 1820 240
66 6
1.210 192 116
.130 49 68
027 0.25 059
Roller. «nd Human lUml
Subject
Hurnl
AR
IIR
CR
Al.
m.
C|.
Al.
m.
Cl.
AR
RR
CR
Al,
Bl.
CL
AR
DR
CR
Munun Muni) l'i
Net Tr*n\f'ei
Anwninl"
MR
148
191
414
.100
86.7
269
109
91
7.1
184
26.2
16
86
42
3.8
22.3
5.)
1.1
Prrs
-------
Tar.e 55 Com*>inson of Transfer of Fresh Dried Formulated Pesticide Residues from Flooring b> Drag Siei
PL'F Roiier. and H^-nac Hand Presses*
Applied Active
Ex^ervr .rr.r Flooring Ingredient
6A Piusb carpet (used)
Qiiorpynfoi
Piperonyl binoxide
Pymhnn 1
6B Plash carpet ( used i
Cfciorpvnfos*
Metboprene
PiperorAl butoxde
rS-rethnnl
S.Ser v tr> ! (neu i
Chtorpynfos
Piperocv ' bmoxidc
PNTethnr. !
Transfer
Drag Sled
(0=6)
5.6 * 32
7.0x4.0
1.0x0.9
9.2 * 3.7
2.5 x 0.7
128 x52
38 x22
1890 x 1430
1660 *990
192 *49
Rate (\ x tf. ng cm*. Using
Ten Hand
PUF Roller Presses
(n«6» (n=lg>
.4
1.8x1.0 '
2^x1.1 d
OJ2 x 0 1
2.9x03 1.3x0.8
OS x 05 0.3 x 0.2
58 x 12 17.x 10
16 at 3
780 x 440 250 x 200
630 x 390 300 x2lO
116 x68 39 x42
• Transfer b> s:ngie PASS over flooring jstng dr> cootaci medium
b Mean and standard dev uoon of transfer rates from 0 to 2 d*>i after applicaoon
c Transfer rates from 6 10 8 davs after appicaoon
6 Single hand pre*>
82
-------
Tab.s 5* Perces: Mear. Transfer* of Fresh Cblorpynfos Residues b> Floonng and Transfer Method*1
Mean Transfer. *,'
Cloth Human
Eiperg-icr:: Flooring Roller Drag Sled PIT Roller Hand Press
I Piush carpet (neu) 49C 1.3 0.9s
2 Level-loop carpet 2.7* 1.7 1.5*
(neu)
3 Piusb carpel (ne*) 0.41
5A
5B
SC
5D
5E
6A
-
SB
• •-• mean
K T rm f%e /«r
Piush carpet (used*
Piusfc carpet (used/
Piuse carpet (used)
Plush carpet (used)
Piusb carpet (used )
Piush carpet (used)
Sbeei vinvl (neu)
PI j»b carpet (used i
transfer = 100 » (mean (ransfer rate, og cr
n^ Af\. r*«tj4i*« AM ttm\. ftf ftMMlk^hlinM fttk cti
0063
013
0092
0.23
0044
OIS
36.1
0.31
rr > (.Ttean surface
%•!« ft*£4 A«.*«V AlWI
0052
10.3 4.6
013
loading, ng cm* )
mta netnA «t*v ^^ijit^^f f-MA^tiin-i
c 20 passes o»~ floonog
d 2 passes over flooring
83
-------
Taric 5' Percent Vicar Transfer* of First Dned Residues by Flooring. Active Ingredient, and Transfer
MetrxxJ-
Mean Transfer. •••*
6A
6B
7
m: Flooring
Plusb carpet (used)
Plush carpet (used)
Sheet vinyl (ne»)
Application
Method
Broadcast
Aerosol can
Broadrast
Active
Ingredient
Cblorpyrifos
Piperonyl butoxide
Pyrohnn!
M I
U-^ ^^ 'b*rwi
Pipenxryl buunide
Pyicuinn 1
Chlorpynfos
Piperonyl butoxide
Pymhnn 1
Drag
Sksd
0.10
0.12
0.19
3.0
3^
3.3
24
22
16
PUF
Roller
0.03
0.04
0.04
1.0
1.4
1.4
9.7
8.3
9.6
Human
Hand Press
0.4
0.4
3.2
4.0
3.2
a •/• mean transfer = 100 » (mean transfer rate, ng cm* Mmean surface loading. ng'Cirr). Mean of transfer rates
and surface loadings from 0 to 2 days after application
b Transfer bv single pass over flooring using dry contact medium
84
-------
lar.e 5r Sus
EV D»'f
6B 6-IT-93
6-23-93
6-24-9?
8-10-93
8-11-93
8-12-93
So ratios, n
Mean! n
Std 6e\ .. s
Coef of \ananon
a Transfer ratio
.i.r. o: the R*!ic oflransfcrs r> Drag Siec and PUF Rt l;er to Transfers b> the Human Hand Press
Mear. Transfrr R»:r. nr nrr Transfer Ratio*
Pesticide
ChJorpyrifos
Meihoprene
Pipcrooyl buioxide
CWorpynfos
Metboprene
Piperonyl butcxide
Chlorpynfos
Piperon) ! butoxide
Chlorpynfos
Piperony! bu:oxide
Pyrethnnl
Chlorpynfos
Piperor> 1 buioxide
P>Tethnnl
Chlorp>-nfos
Piperonv 1 butoxide
P>TcthnnI
s Mean transfer rate by
Drag Sied
tn=2>
90
31
12 1
1.9
138
65
3000
2300
1350
12?0
163
1330
1400
238
PIT Roller Human HanJ
(D=2t
29
1.20
71
3.0
0.42
44
35
5-
860
570
119
560
470
78
920
840
152
Press(D=6>
081
048
24.2
2.06
0.20
16.2
099
11.8
384
426
76
236
280
25.4
144
198
157
mechanical method ing CRT (Mean transfer rate by
Draf Sifd
Hand Press
110
6.5
71
5.9
9.5
8.5
66
6.2
54
23
57
45
64
93
Tl
17
7.35
2.84
039
PUT Roller
Hand Press
36
2.5
29
1.5
2.1
J 5
49
1 3
16
24
1 7
31
64
42
96
17
3.31
2 10
0.63
human hand press (ng cnr )
85
-------
APPENDIX A
PROTOCOL FOR THE DETERMINATION OF WIPE REMOVAL
EFFICIENCY OF CHLORPYRIFOS AND PYRETHRINS FORMULATED
MIXTURE RESIDUES FROM HANDS (EXPERIMENT 4)
-------
PROTOCOL FOR THE DETERMINATION OF UTPE REMOVAL EFFICIENCY OF
CHLORPYRIFOS AND PYRETHRINS FORMULATED MIXTURE RESIDUES FROM RANDS
(EXPERIMENT 4)
BY
PAUL W GENO
NICHOLAS J. GlARDINO
DAVE) E. CAMANN
SOUTHWEST RESEARCH INSTITUTE
POST OFFICE DRAWER 28510
SAN ANTONIO, TX 78228-0510
Revised November 5.1993 u Performed
-------
TITLE: Protocol for the Deierminarioc of Wipe Remova! Efficiency of Chlorpyrifos and
Pyreririns Residues from Hands (Experiment 4)
TESTING
FACILITY: Southwest Research bsrimtf
Department of Environmental Chemistry
6220 Culebn Rd.
Post Office Drawer 28510
San Antonio. TX 78228-0510
Phone:(210)522-5947
FAX: (210)522-3649
AUTHORIZATION: SWRI Project 01-5164-202
Work Assignment f33
Banelk Subcontract
EPA Contract 68-DO-0007
SPONSORS: BATTELLE
505 King Avenue
Columbus. OH 43201-2693
U.S. Environmental Protection Agency
Aonosphe-ic Research and Exposure Assessment Laboratory
Research Triangle Park. NC 27711
PROJECT PERIOD: December 21.1992 - January 29, 1993
-------
Page 3
L INTRODUCTION AND OBJECTIVES
This is the fourth experiment of a study 10 compare sampling methods for the estimation of
transfer of chemicals from coocaminated surfaces (Le. carpeting) to the skin. The methods are the
Dou drag sled, the California doth roller, and the Southwest Research Institute (SwRI) polyurethane
foam (FUF) roDer. These methods must be compared with each other, then with human sJdn pick-up
before standardized methods can be established Prior to the measurement of efficiency of the pick-
up of chemicals by human fi™. controlled experiments must be performed in order to determine the
efficiency of removal of each rh^™"**1 by the handwipe procedure and the efficiency of extraction
of pesticides from the handwipe.
This experiment consists of three tasks. The experiment win be performed using pesticides
at the lowest levels feasible to obtain meaningful analytical results. The specific tasks are:
A. Determine the elution efficiency of chlorpyrifos and pyrethrins formulated products from
aluminum foil deposition squares.
B. Determine the extraction efficiency of chlorpyrifos and pyrethrins from isopropanol
handwipes.
C. Determine the efficiency of removal of chlorpyrifos and pyrethrins from human hands by
isopropanol wipes.
IL MATERIALS AND METHODS
A. Facilities Preparation.
All t»tic« will be conducted in the PV
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Page 4
C. Hand-press Method
Since the purpose of this study is to investigate the wipe removal efficiency of the handwipe
and not die uptake of pesticides onto the hand, a precise and reproducible procedure for the hand
press is not necessary. However, a method is needed that wfll efficiently transfer most of the
pesticide from me foil to the hand. Prior to f4r^ hand press, each subject will be requested to
thoroughly wash his or her hands with soap and water. The subject will be cautioned to avoid
touching any surfaces prior to the handwipe procedure. Each subject will men place a powder-free
vinyl glove over one hand to prevent contamination while performing the wipe procedure on the first
hand and to prevent the isopropanol from drying out the skin prior to the handwipe resulting in an
abnormal skin condition ma: could affect wipe removal efficiency. Each subject will then be asked
to initially to press and rotate the palm of the hand to the 2" dia. area of pesticides with fingers held
off of the surface. The subject wfll then be asked to press and rotate the front and back of the fingers
on the foil
D. Isopropanol Handwipe Method
Following deposition of the target pesticides onto the hand, an isopropanol handwipe of the
hand will be performed. The handwipe procedure wfll be that described by Camann et aL (1992).
The handwipe will consist of two SOF-W1CK 4" x 4M 6-ply dressing sponges which have been pre-
cleaned prior to use. Each sponge will be laced with 10 mL of OPTIMA grade isopropanoL The
subject will be asked to perform a general wipe of each hand with the first sponge. The second
sponge will be used to wipe around and between each digit. Bom sponges wfll then be placed in t
single container and an additional 50 mL of isopropanol wfll be added. The subject will perform all
actual handling of the sponges from preparation to placement in the sample container. Immediately
following each handwipe procedure, the subject will thoroughly wash his hands to remove any
remaining pesticides residues.
E. Extraction of Pesticides from Aluminum Fofl Deposition Squares
Following die deposition of die pesticide formulated mixture (in the case of control samples)
or following die hand-press procedure, die 6" x 6" aluminum fofl squares will be placed in solvent
washed and oven dried 1 Ib wide-mouth jars fined with teflon lined Eds. Any tape used to hold die
squares to the board will be removed prior to extraction. A 300 mL volume of 1:1 etherhexane will
be added to each jar. Terphenyl-d14 wfll be added as a surrogate in sufficient quantity to result in a
concentration of 1.0 ng/uL in me final extract. The jars wfll then be shaken for 30 mm. The ether-
hexane extract wfll dxn be concentrated to a volume of 1.0 mL in hexane for GC/MS analysis.
F. Extraction of Pesticides from Isopropanol Handwipes
Following the hand-press and handwipe procedures, me handwipes wiD be extracted for die
target pesticides using the method described by Camann et aL (1992). Immediately prior to
extraction, terphenyl-4,« surrogate will be added and die jars wfll be shaken for five minutes. The
isopropanoi wfll dien be drained from the jar into a 250 mL flat bottom flask. The handwipes win
be extracted twice with two 50 mL portions of 1:1 diethyl etherhexane by shaking for one minute.
The gauze pad wfll dien be squeezed to remove solvent and die jar wfll be rinsed three times with
-------
PageS
boons. All rinsares and extracts will then be combined in the 250 mL round bottom flask. The
ether/toe xane/isopropaDo] extracts will then be concentrated to a volume of 1.0 *"L in bexane for
GC/MS analysis.
C. Analysis of Pesticides Extracts
Each handwipc and aluminum fofl extract will be analyzed for chlorpyrifos and pyrethrins on
a fisons MD800 gas chronuaognph/mass spectrometer (GC/MS) operating in a selected ion recording
mods. A primary quantitarion ion and secondary confirmation ion will be selected for chlorpyrifos
and each of die six pyrethrins. The GC/MS will be calibrated from 0.05 to 1.0 ng/uL for chlorpyrifos
and 1.0 ng/uL to 20 ng/uL for total pyrethrins. This corresponds to a quantitarion limit of 50 ng per
handwipe for chlorpyrifos and 1 pg per handwipe for pyrethrins. Sample extracts containing target
analytes at levels beyond the calibration range will be diluted and reanalyzed.
ID. EXPERIMENTAL DESIGN
A. Task 4A. Determination of Aluminum Fofl Elution Efficiency
In order to determine the efficiency of removal of me target pesticides from aluminum fofl
squares, seven foils will be spiked with 250 uL of ±e diluted formulated mixture. An additional
seven foils will be spiked with 25 uL of the formulated mixture. The factor of ten difference in spike
levels will determine if aluminum fofl ehnion efficiency is independent of the amount of pesticide
spiked. Two additional foils will be extracted without spiking to serve as control blanks. In order
to verify the level of the pesticides in the spike solution, two 300 mL portions of 1:1 etherhexane
wiD be spiked with 250 uL of the diluted formulated mixture and two ad^o**) portions of
etherhexane will be spiked with 25 pL of the diluted formulated mixture. All foils, control blanks
and solvent spikes will be extracted and analyzed as described above.
B. Task 4B. Determination of Handwipe Extraction Efficiency
Efficiency of the extraction method for removal of the target pesticides from the handwipes
wiD be evaluated by spiking seven moistened, precleaned handwipes with 250 uL of the diluted
formulated mixture. An additional seven wipes will be spiked with 25 uL of the dihuM formulated
mixture. The factor of ten difference in spike levels will determine if the handwipe extraction
efficiency is independent of the amount of pesticide spiked. Two handwipes will be extracted without
spiking and will serve as control blanks, two aliquot* of tsopropanol will be spiked with 250 nL of
die diluted formulated mixture and two abquots win be spiked with 25 uL of die diluted formulated
mature. All handwipes and spikes will be extracted and analyzed as described above.
C Task4C Determination of Handwipe Removal Efficiency
Handwipe removal efficiency experiments wiD be performed using two human subjects
volunteers over a three day period. Mr. David E Camann and Dr. Paul W. Geno of the Department
of Environmental Chemistry at SwRI wiD serve as the subjects. On each day prior to sampling, the
subject's handr wiD be inspected by Dr. Nicholas Giardmo for rashes, abrasions or cuts in the skin.
-------
Page 6
When ar> such sores exist, the experimcn: will be postponed unri! the hand heals. On Days 1 and
2. five aiun^narc foil squares will be spiked with 50 uL of the diluted formulaied mixture as
described above, one aluminum foil square will be spiked wiib 25 uL of the diluted formulaied
product and one foil square will serve as a control blank. Hand presses will be performed on four
of the 50 uL spiked aluminum squares, corresponding to each hand of each of the two subjects. The
order in which the two hands are sampled wil! alternate on the two days. On Day 3. three aluminum
foil squares will be spiked with 50 uL of the diluted formulated mixture and one aluminum foil
square wCJ be spiked with 25 uL of diluted formulated mixture. Hand presses will be performed on
two of the 50 uL spiked squares. Isopropanol handwipes will be immediaie performed following the
hand presses. On each day, one addinonal handwipe will be spiked directly with 50 uL of the diluted
formulaied mixture, one handwipe will be spiked with 25 uL of the diluted formulated mixture and
one nanciwipe will serve as a control blank. In order to verify the level of the pesticides in the spike
solution, one 300 mL portion of 1:1 ether-hexane will be spiked wixh 50 uL of the diluted formulated
mixture, one additional portion of etherhexane will be spiked with 25 uL of the diluted formulated
mixture and one portion will serve as an extraction blank. All handwipes and foils will be extracted
as described above urmediaiely following the handwipe procedure. A summary- of samples for the
three Described tasks is given in Table 1.
IV. CALCULATIONS
Following completion of Task 4A, me elubon efficiency (E^) of the aluminum foil extraction
procedure for each pesticide will be f»inii«™H by:
where Mj^ is the amount of each pesticide determined to be extracted Jrom each foil by analysis and
M^ is the amount of each pesticide applied from the foil The mean (£„) and coefficient of variation
of the elution efficiency will then be raH'Ty** over the ten replicates at each level
Following the completion of Task 4B. the extraction efficiency of the handwipe extraction
method (£.„) will be f*\r*t\MvA by
where M^, is the amount of each pesticide determined to be extracted from each handwipe by
analysis and M^ is the amount of each pesticide applied to the handwipe. The mean (E^ ) and
coefficient of variation of the extraction efficiency will then be ^'Tfrnif over the ten replicates at
each level
The wipe removal efficiency (RE) can then be r*i*n\*M*i for each replicate handwipe of Task
4C using the following equation:
RE =
where M^, is the analytically determined amount of each pesticide wiped from the hand, E— is the
mean extraction efficiency of the handwipe extraction method determined in Task 4B for the low
level spike. M^ is the known amount of each pesticide applied to the foil prior to hand press. M^
is the analytically determined amount of each pesticide remaining on the foil following hand press
-------
Page?
and £.. is ihz py^n eluuoo efficiency of ibe ^himin^m foil extraction determined in Task 4A for the
leu level spike. The rofan removal efficiency end coefficient of variation for each subject, and the
removal efficiency and coefficient of variation for all samples will be calculated.
V. ESTIMATION OF HUMAN EXPOSURE
The T"«*M*»"" exposure to subjects is 5 pgAiand of chlorpyrifos and 100 pg/hand for
pymhrins. This estimaie *yttp"« 100% of the pesticides applied to the foil are picked-up by the
hand and absorbed through the «>"» According to our modeled resuhs for flux through the dermal
layer of the h*"dt we determined for each hand press that 0.09 ng of pyrethrins and 1 pg of
chlorpyrifos will be absorbed (Droz, «. al (1991) and Fiserova-Beberova, «. al (1989)). It is assumed
the total surface area of the hand is 900 cm3 (within the range of surface areas provided by the EPA
Interim Repon on Derma] Exposure. January 1992). and thai the exposure rime is 5 minutes. The
model assumes thai a completely saturated water tohitiCT) of the f**^tnir»i is applied to the skin of
the Kffui
In these experiments the dried pesticide residue will be wiped from the hands using
tsopropanol. This solvent is likely to enhance the absorption of the pesticides into the skin.
One must be cautious whenever using and interpreting modeled results. However, this model
has been used and extensively tested by others (see above references) and was a good predictor for
dermal absorption of chemicals with molecular weights below 500. According to the modeled results
the absorbed amount of pyrethrins for the entire experiment is negligible. The predicted absorption
of chlorpyrifos is higher, but is still low.
The rabbit LDM dermal for chlorpyrifos is 2000 mg/kg and rat dermal LDM for pyrethrins
greater than 1800 mg/kg (Farm Chc**^*** Handbook *92). There is very fo»V chance for severe
adverse health effects to occur.
For short-term exposures, pyrethrins are contact aUergenic compounds, can cause dermatitis.
and may mildly irritate the eyes, nose, and throat. Long-term exposure can lead to organ toxiciry.
excluding the nervous, respiratory, hematological, or reproductive systems. Chlorpyrifos can cause
nervous system disturbances, and represents an acute and chronic hazard. These health advisories
were taken from Patty's Industrial Hygiene And Toxicology. Volume IDA (1985) and concern
workplace exposures. It is expected diat these workplace exposures are substantially big n than
those predicted during this set of experiments.
The acme exposures predicted to be received during this experiment for chlorpyrifos are 1
ugAand for a total of 2 pg. and for pyrethrins 0.09 ngAiand for a total of 0.18 ng. Since all the
recognized industrial hygiene organizations (ACGIH, OSHA, NIOSH, MAK)have a skin notation tor
cnlfcW |>y » *f o», those pan icipanng B the experiment wiD wash their *|*>inf immediately after exposure
to either of the pnriridfs. The skin notation for healthy workers addresses adverse health effects
ocoirr^g if a worker cotnesmtocomaa with the ptnrdteinuaL Industrial and agricultural exposures
(Camann et al (1992)) would be several orders of •Mgmtnd* above what the participants in this
will receive.
Lastly, those with any abnormal skin condition such as •*•*>''"• a rash, abrasions, cuts, or any
breaks in the skin will not be eligible to participate in the experiment.
-------
PageS
\1. REFERENCES
r*~»y- D.E.. Gene. P.W., Harding. HJ., Clothier. J.M.. and Giardino. NJ (1992). Evaluation of
Environmental Exposure Assessment Methods for the NCI/EPA Finn Occupation Exposure Study
(NEOFOS) EPA Conn-act Number 68D10150. Southwest Research Institute Project 01-5278.100. San
Antocio, TX.
Droz, P.O. Benxlc. M., and Wu, M.M (1991). Appl. Occup. Environ. Hyg., 465-47-.
Fiserova- Berberova. V^ and Pierce. J.T. (1989). Appl. Indus. Hyg. 8: F-14 - F-21.
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Page 9
Table 1. Experimental Design for the handwipe removal efficiency study.
Task4A.
Al Fofl Sq. (FS)
Extraction Solvent
Spikes (SS)
Task4B.
Isopropanol
Handwipes (HW)
Extraction Solvent
Spikes (SS)
Task 4C Dav 1.
Al Fofl Sq. (FS)
Hand presses
Subj. A (HA UR)
Subj. B (HB UK)
Isopropanol
Handwipes (HW)
Extraction Solvent
Spikes (SS)
Task 4C Dav 2.
Al Fofl Sq. (FS)
Hand presses
Subj. A (HA UR)
Subj. B (HB UR)
IMMMI^..«J
250 uL Formulated
Mixture (Hi
7
2
250 uL Fonnulated
Mixture (Hi
7
2
50 uL Fonnulated
Mixture (H)
5
2
2
4+1
1
5
2
2
25 uL Fonnulated
Mixture CL)
7
2
25 uL Fonnulated
Mixture fl^
7
2
25 uL Fonnulated
Mixture (L\
1
1
1
1
Blank
-------
Page 10
Table 1. Coot
Task 4C Dav 3
AJ Fofl Sq. (FS) 3 1 . 1 5
Hand presses
Sub}. A (HA L/R) 1
Subj. B{HBL/R) 1
IsopropaDoI
Handwipes (HW) 2+1 1 15
Extraction Sofvent
Spikes (SS) 11 13
Toul Analyses 91
Sample ID. wfll be the task number followed by the medium followed by the spike level
followed by the replicate (or the day for Task 4C). e^. the foil square for the right hand
replicate of Subject B hand press on Day 2 would be labeled 4C-FS-HBR-H-2.
-------
APPENDIX B
PROTOCOL FOR THE COMPARISON OF TRANSFERS BY THE DRAG
SLED, PUF ROLLER, AND HUMAN HAND PRESS OF CHLORPYRIFOS
AND PIPERONYL BUTOXTOE FORMULATED MIXTURE RESIDUES
FROM SHEET VINYL FLOORING (EXPERIMENT 7)
-------
PROTOCOL FOR THE COMPARISON OF TRANSFERS BY THE DRAG SLED, PUF
ROLLER, AND HUMAN HAND PRESS OF CHLORPYRIFOS AND PIPERONYL BUTOXIDE
FORMULATED MIXTURE RESIDUES FROM SHEET VINYL FLOORING (EXPERIMENT 7)
BY
DAVID E CAMANN
R JAC HARDING
NICHOLAS J. (HARDINO
SOUTHWEST RESEARCH INSTITUTE
POST OrFICE DRAWER 28510
SAN ANTONIO. TX 78228-0510
JULY 30.1993
-------
TITLE:
TESTING
FAOLTTY:
Protocol for the Comparison of Transfers by the Drag Sled, PUP Roller, and Human
Hand Press of Chlorpyrifos and Piperonyl Butoxide Formulated Mixture Residues
from Sheet Vinyl Flooring (Experiment 7)
Southwest Research Institute
Department of F-r>vtir>nTn>^>f>>^ Cbemistxy
6220 Cuk bra Rd
Post Office Drawer 2&510
San Antonio, T\ 78228-0510
Phone: (210)522-2673
Fax: (210)522-3649
AUTHORIZATION:
SPONSOR:
SwRJ Project 01-5164-20X
Work Assignment #33
Banelle Subcontraa 34501 (2173>2135
EPA Contract 6S-DO-OOC7
Banelk
505 King Avenue
Columbus, OH 43201-2693 ,
U.S. Eovmnmental Piotccuon Agency
Atmospheric Research and Exposure Ass
.Research Triangle Park, NC 27711
ory
PROJECT PERIOD: August 4.1993 - September 15.1993
-------
L INTRODUCTION
Dermal contact with residues of pesticides applied to carpets and subsequent skin absorption
or jngestion through hand-to-mouth activity are routes of human exposure which naed beoer
evaluation, especially for young children. The Dow drag sled, the California doth roller, and the
Southwest Research Institute (SwRI) polyuremane foam (PUF) roller (SwRI invention disclosure
#2061, paw pending) are dislodgeable residue sampling methods which have recently been
developed to estimate the transfer of a cbfF"^ from a cc"^^"^?^ surface to the «irm These
methods need to be compared to determine which provides the most accurate, reproducible.
economical, and facile performance. Precision and bias relative to human skin pick-up must also be
before ft»nrii>Tffi»xj methods can be fstflbliyhf^ for use by registrants and researchers.
After chlorpyrifos which was broadcast-sprayed on carpet had dried, transfers by the drag sled,
the cloth roller, and the PUF roller were compared in Experiments 1 to 3 (Camann et aL, 1993). On
plush nylon carpet, mean chlorpyrifos transfers were 4.5% by the cloth roller, 1.1% by the drag sled,
and 0.65% by the PUF roller (Experiment 1). On level-loop polypropylene carpet, mean transfers
were 2 .5% by the doth roller, 1.4% by the drag sted, and 12% by the PUF roUer (Experiment 2).
The cloth roller was found to be less suitable than the other methods because its transfers exhibited
greater variability and were altered by orientation of the roll relative to the lay of the carpet fibers.
Moistening the sampling media increased the transfer by the drag sled and the PUF roller, but
substantially increased the measurement variabiliry of both methods (Experiment 3).
Experiment 4 determined the removal efficiency of two pesticides (chlorpyrifos and
pyrethrins) that had been applied to human skin. Experiment 5 evaluated the effects of sampling
pressure, traverse distance, number of repeat passes over the same section of carpet, speed, and air
temperature on dislodgeable residue transfer of chlorpyrifos by the PUF roller and drag sled.
Preliminary results indicate that air or carpet temperature had a marked effect on transfer, especially
by the drag sled, but this effect was deduced from a series of tests performed on different days.
Experiments are being conducted to compare human hand presses and mechanical dislodgeabiliry of
several pesticide residues (chlorpyrifos, pyremrins and piperonyl butoxide) from plush carpet
(Experiment 6), and to determine the direct effect of the temperature of the air and carpet on transfer
of chlorpyrifos. pyremrins, and piperonyl butoxide residues from plush carpet using both the drag sled
and the PUF roller in tests performed on the same day (Experiment 8).
This protocol describes Experiment 7, in which comparisons will be made between hand
presses and both the drag sled and the PUF roller in die transfer of chlorpyrifos and piperonyl
butoxide residues from new sheet vinyl flooring.
IL MATERIALS AND METHODS
A. Facility Preparation
An empty room (9* x 15*) in a 42* x IO'3-room trailer on the SwRI Campus will be used to
do the experiment. The push cut-pile nylon carpet and pad will be removed and Armstrong Explorer
Solarian sheet vinyl in«aiic
-------
B. Dislodgeable Residue Methods
Relevant characteristics of the dislodgeable residue methods (Le., the Dow drag sled and the
SwRI PUF roller) and the human hand press are summari**** and contrasted in Table 1.
TABLE 1. CHARACTERISTICS OF DISLODGEABLE RESIDUE AND HAND PRESS METHODS
Sampling Medium
Surf ace of
Sampling Medium
Cjnun Motion
Face (Instantaneous
Pressed Contact
Area through
Sampling Medium)
Mass Exerting
Pressure Through
Sampling Medium
Pressure Exerted
Through Sampling
Medium
Sampled Carpet
Area
Number of Passes
over Sampled
Carpet Area
Sampling Speed
over Carpet
DOW DRAG SLED
Denim weave cloth
(predominantly cftflo*))
Square (102 cm)2
Drag
7.6 cm x 7.6 cm « 58 cm2
3.46kg
5.900 Pa -
(3.46 kgX9.8 mW(0.076
a)2
7.6 cm z 1.0 m « 0.076
m2
1
0.07 m/s
SWRI PUF ROLLER
(October 1992 Model)
Polyurethane foam (PUF)
ring (0.029 g/cm*. polyether)
Carved exterior of ring(OD «
8.9 cm, length * 7.6 cm)
RoD
7.6 cm x 5.1 cm » 38.6 cm2
3.10kg
8.000 Pi-
(3.10 kgX9.8 nVs*y[(Q.076
mX0.05 m)]
7.6 cm x 1.0m « 0.076 m2
1
0.10 m/s
HUMAN HAND PRESS
Skin oo p»>rn of ^«n/i .
Palm (ca. 8 cm x 8 cm)
Ten Presses (for Is)
7.6 cm x 7.6 on « 58 cm2
NA
6.900 Pa « 1.0 psi
10 x 7.6 cm x 6J cm •
0.048m2
1
NA
The drag sled method wiD be performed using the initial configuration described by Vaccaro
and Cranston (1990). Briefly, a precleaned dry 4" x 4" denim weave cloth supplied by B. Shurdut,
Dow Chemical Company, is attached beneath foil under a 3" x 3" plywood block on which an 8-lb.
weight is mounted (Figure 1). From a stationary position on »h«mnmi> foil, the sled is dragged once
over a 3" x 1 m carpet strip at 6-8 cm/s. After the single pass, the denim cloth is removed far
analysis. Except for the weighted plywood block (current model unavailable since in use at Dow),
Dow still performs its drag sled method as initially described (personal communication, B. Shurdut,
July 1992).
-------
' The new (October 1992) model of the PUF roller sampler (Camann et aL, 1993b) will be used
instead of me original PUF roller sample" (Hsu, et al., 1990). A precleaned dry PUF ring (3" length.
3.5" OD, 1.62" ID) is secured on the 3" length x 1.75" OD cylindrical 037 kg aluminum roller
(Figure 2). From a stationary position on Aluminum foil, the PUF roller is rolled once over a 3" x
1.0 m carpet strip at 10 cm/s. After the pass, the PUF ring is removed from the roller for analysis.
C. Hand Press and Wipe Methods
A set of ten presses of the treated vinyl will be made with each hand by three subjects on
three days in a reproducible manner Prior to each daily pair of hand presses, each subject will be
requested to thoroughly wash his hands with soap and water. The subject will be cautioned to avoid
touching any surfaces during the hand press and wipe sequence. The subject will then place a
disposable nitrile glove over the non-test hand. The second hand is gloved to prevent contamination
while performing the press and wipe procedure on the first hand and to prevent the isopropanol fror
drying out the skin of the second hand prior to the band press (avoiding an abnormal skin condition
that could afreet hand press transfer efficiency). A card-stock template will be planed over the
designated area for vinyl sampling to expose a 3 in (7.6 cm) x 25 in (63.5 cm) vinyl strip. Whik
kneeling on a cardboard mat, each subject will perform a series of ten presses of the palm of the test
hand to adjacent sections of vinyl exposed by the template at a pressure of ca. 1.0 psi for 1 sec each
with fingers held off of the surface. An isopropanol handwipe of the hand will be performed as
described by Camann et aL (1992) in a clean area away from the trailer. After washing bom hands
with soap and water, the glove will be removed from the second test hand and a clean glove placed
over the second non-test hand. The press and wipe procedures described above will then be repeated
using the second hand.
The handwipe will utilize two SOF-WICK* 4" x 4" 6-ply dressing sponges which have been
pre-cleaned prior to use. Each sponge will be laced with 10 mL of OPTIMA grade isopropanol. The
subject will be asked to perform a general wipe of each hand with the first sponge. The second
sponge will be used to wipe around and between each digit Both sponges will then be placed in a
single container and an additional 50 mL of isopropanol will be added. The subject will perform
all direct handling of the sponges from preparation to placement in the sample container, although
handling via forceps is also permitted. Immediately following each handwipe procedure, the subject
will thoroughly wash his hands to remove any remaining pesticides residues.
D. Broadcast Application of Chlo^yrifos/Pyrethrins/Piperonyl Butoxide Formulated
Mixture and Ventilation Whik Drying
Broadcast application of a cUoipyrifos/pyrethrins/piperonyl butoxide formulated mixture to
test vinyl flooring will be conducted by a licensed pest control applicator according to label
instructions to control a light infestation of fleas. The formulated emulsifiable conrymraif products,
Dursban* L.O. (EP.A. Registration No. 62719-55), which contains 41.5% chlorpyrifos (O,O-diethyl
O-[3^,6^tricUoro-2-pyridyl]phosphoromioate), and Kicker* (EPA Registration No. 4816-707AA),
which ?nnq«mf 6.0% pyrethrins and 60.0% t*rfMfo^i piperonyl butoxide will be tank nwtfd at 2/3 fl.
02. (20 mL) Dursban* L.O. and 0.5 fl. oz. (15 mL) Kicker* per gallon of water to yield 025 %
chlorpyrifos, 0.025% pyrethrins, and 025% piperonyl butoxide in the aqueous spray. The mixture
wiU be appb'ed approximately 40 cm above me vinyl at a rate of 1 gallon of diluted mixture per 1600
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square feet with a hand-held fan broadcast nozzle attached to an air pressurized tank. Application
will be accomplished in ca. 2
The trailer will be ventilated f or 2 h immediately after application. All windows will be
opened and window air conditioning units operated in fresh return air mode. During the first 30 min
and last 15 min of the ventilation period, both doors will be opened and a box fan operated outside
the test room doorway to allow TnaTitmmi cross ventilation. Air conditioner units will be returned
to the usual recirculated air moor just prior to sampling and remain on throughout the sampling
period.
E.- Expei iinenral Design
Adjacent samples using both dislodgeable residue methods, a hand press by each subject, and
two deposition coupons will be collected sequentially within a rectangular block of treated vinyl Six
replicate blocks will be sampled over three days so that each hand is pressed and wiped only once
per day (to limit dermal exposure and to allow return of normal levels of natural oils to the skin
before each hand press). The experimental design is presented in Table 2 and the physical layout for
sampling is shown in Figure 1. Sampling will be performed at approximately the same floor
temperat je (-25 °C) and room air temperature each day.
Deposition coupons, consisting of Teflon squares (4 in. x 4 in.) will be placed on the vinyl
prior to the pesticide application and picked up before the adjacent dislodgeable residue samples from
the block are collected. Residues measured on the coupon pair give an estimate of the surface
loading of residue remaining on adjacent vinyl flooring during sampling in the block.
Field blank wipes of bom hands of each subject wfll be made in the clean area after a set of
ten presses with the hand on the untreated vinyl on Days 1 and 2. Two field blanks of both
mechanical methods will be obtained by sampling on the vinyl on the day prior to the pesticide
application (Day 2). The field blanks will yyscss residues transferred via air and contamination
potential during sampling and handling. Deposition coupons will be placed at two designated locations
in each sampling block shortly before the application commences on Day 3. Field samples will be
collected in two blocks each on the afternoons of Days 3, 4, and 5 after label allowed re-entry on Day
3 (Le., when the vinyl is dry). The dislodgeable residue and hand press samples of a block will be
collected from specified locations in the block after the deposition coupons are picked up (see Figure
1). All samples will be collected in one block before proceeding to the next block. Spikes of the
precleaned dislodgeable residue and wipe matrices and of a deposition coupon pair will be made bom
before (Day 3) and after pay 5) the replicate block sample sets are collected; these field spikes will
be used to assess and adjust for losses during transport, storage, and extraction.
F. Sample Analysis
Dislodgeable residue samples win be Soxhlet-extracted with 6% ethyl ether/94% nexane;
extraction will commence within 24 hours after sampling. The pair of deposition coupons from a
block will together be rinsed with 6% ether-hexane as a single sample. Isopropanol-saturated
handwipes will be shake extracted with 1:1 diethyl ethrrhffxane (Camann et aL, 1992). Extracts will
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be analyzed for cblorpyrifos, pyrethrins and piperonyl buTcwodf on a Fisoos MD 800 GC/MS
operating in selected ion monitoring modr.
G. Data Adjustment
Crude wipe results win be adjusted for wipe removal efficiency from the hand by dividing
by the mean removal efficiency determined in Experiment 4. It is anticipated that hand wipe results
for pyrethrins may be less than the detection limit. The wipe removal efficiency for piperonyl
butoxidf will be assumed to be between the mean removal ffficiffifs deter1""1*** for chlorpyrifos and
pyrethrins.
Crude resuhs (mg/sample) from each field sample win be adjusted for contamination and
extraction inefficiency by subtracting the field blank mean and dividing die difference by *he mean
recovery proportion of the field spikes for that method. The adjusted result wfll be divided by the
vinyl area (see Table 1) to determine the measured transfer rate (mg/m2 of vinyl contacted) for
dislodgeable residue and hand wipe samples and the measured surface loading (mg/m2) for coupon
samples.
EL ESTIMATION OF HUMAN EXPOSURE
A. Selection and Recruitment of Subjects
Three normal male subjects. 35 to 49 years of age, have volunteered to perform the hand
presses of treated vinyl as described herein, They are Mr. David E C**n^n. principal investigator,
Dr. Paul W. Geno, investigator, and Dr. Jong-Pyng Hsu, Director, Department of Environmental
Chemistry. Informed consent will be obtained from each subject b> Mr. CV»ff*" before the
experiment commences; the consent forms will be kept in Mr. Camann's office in Bldg. 70, Office
17.
Those subjects wiA any abnormal skin condition such as *r?f"Mi. a rash, abrasions, cuts, or
any breaks in the skin will not be eligible to participate in the experiment, until the condition heals.
B. Estimated Exposure of Subjects
In Experiment 1, broadcast application of a 0.5% aqueous spray of chlorpyrifos at 1 gal/1600
ft2 during summer produced a loading of 154 mg/m2 on the plush cut-pile nylon carpet (Camann et
aL. 1993b). Thus, an aqueous spray of 025% chlorpyrifos, 0.025% pyrethrins, and 025% piperonyl
butoxide in Experiment 7 applied by the same application method at the sure raff in the *?"** reason
should produce loadings of approximately 77 mg chlorpyrifos/m2,7.7 mg pyrethrins/m2, and 77 mg
piperonyl butoxjde/m2 during sampling on the application day. Day 3. Fenske et al (1991) found mat
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TABLE 2. EXPERIMENT 7: COMPARISON OF CHLORPYRIPOS AND PIPERONYL BUTOXIDB RESIDUE TRANSFERS FROM
SHEET VINYL FLOORING BY DRAO SLED SAMPLER. PUF ROLLER SAMPLER, AND1 HAND PRESS BY THREE
HUMAN SUBJECTS
Simple Analyses
Dayd Sample Category
1 Field Blank!
2 Field Blank!
3-AM Pesticide application
3-AM Field Matrix Spikes
3-PM DR Samples'
4-PM DR Samples'
5PM DR Samplei'
5-PM Field Matrix Spike
Total DR Sample!
Toul Field Blank!
Total Field Matrix Spikes
Total Samples
a The two Teflon coupons in
b The samples collected from
Deposition
Coupon
0
0
I"
T
T
T
r
6
0
JL
8
a block are
Draft Sled
0
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1
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10
combined and
„ PUF Roller
0
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1
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1
6
2
JL.
10
Subject
A
JL R
I l
1 1
1
1 1
I 1
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12
Hand Press
Subject
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1 1
1 1
1 1
1 1
6
4
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10
Told
6
10
5
12
12
12
5
36
16
_m_
62
extracted together as a single sample.
different treated vinyl areas within each block
are two deposition coupons,
one drag sled, on
PUF roller,
and one press/wipe by each subject of the same hand.
-------
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• 2 FUF nU0 umptas (with, toon)
2 Dow dotfi HRijte (witt. aoDH)
6 tMd pteae* (brtfc taadi of iibjicii A. B. It O
VajJ Stact Fteeraf
Figure 1. Sampling Layout for Experiment 7.
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mean chloipyrifos wipe residues from treated carpet after 24 hr were only 30-40% of the wipe
residues 1-7 hr post-application. In two recent experiments, the mean amount of chlorpyrifos
transferred from a plush nylon carpet three days after application was 15% and 25% of the amount
transferred by the PUF roller after drying on the application day. Hence the loadings for Days 4 and
5 of Experiment 7 can be anticipated to be about 35% and 27% of the Day 3 loadings, respectively:
Chlorpyrifos: 27 mg/m2 on Day 4; 21 mg/m2 on Day 5
Pyrethrins: 2.7 mg/m2 on Day 4; 2.1 mg/m2 on Day 5
Piperonyl butoxide: 27 mg/m2 on Day 4; 21 mg/m2 on Day 5
The percentages of analytical standard residues of 13 pesticides (including chlorpyrifos) on
aluminum foil which were transferred to skin by a series of ten sequential Is hand heel presses by
two of the study subjects were nearly equivalent to the mean percentage transfers by the PUF roller
(e.g., 7.7% by Subject 1 and 8.9% by Subject 2 vs. 7.1% mean by PUF roller for chlorpyrifos) (Hsu
et aL, 1990). Thus, hand press transfers from sheet vinyl in Experiment 7 can be expected to be
similar to, or less man, the mean 83% transfer of chlorpyrifos from aluminum foil by the two
subjects. To be conservative, a transfer of 10% wOl be assumed. Using an exposed palm area of the
hand of 0.0058 m2, the residue on both palms of each subject after the hand presses on Day 3 can
be estimated as:
Chlorpyrifos: (77 mg/m2) x (0.10 transfer/press) x (10 presses) x (0.0058 mVpress)
x (2 palms) = 890 pg
Pyrethrins: (7.7 mg/m2) x (0.10 transfer/press) x (10 presses) x (0.0058 nrVpress)
x (2 palms) = 89 pg
Piperonyl butoxide. (77 mg/m2) x (0.10 transfer/press) x (10 presses) x (0.0058 mVpress)
x (2 palms) - 890 pg
The residues on both palms of a subject after the hand presses on Days 4 and 5 are estimated
as 310 pg and 240 pg of chlorpyrifos, 31 pg and 24 pg of pyrethrins, and 310 pg and 240 pg of
piperonyl butoxide.
C. Subject Monitoring
Since chlorpyrifos is a cholinesterase - inhibiting organophosphate insecticide, the American
Conference of Governmental Industrial Hygienists recommends monitoring cholinesterase activity in
red blood cells (RBC) as an index of biological exposure (ACGBi, 1991). Accordingly, blood samples
were collected from each subjec twice (except Dr. Hsu, who declined) at an interval of at least 24 hr
prior to Experiment 6, and wii'. be collected once before and after Experiment 7, for RBC
cholinesterase activity determination. The ACGIH criterion of post-exposure activity <70% of
baseline activity will be used to monitor if excess exposure occurred.
8
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Linle reduction in RBC cholinesterase activity is expected in the post-«xposure sample.
Handwipes of fair-ers following single mixing/application evem show thai residues of the applied
analyte of 100 pg to 15 mg (n=ll) were wiped from both hands (Camann et aL, 1993a). However,
an RBC cholinesterase drop exceeding 20% was observed in only 30% (3 of 10) fanners who applied
organophosphate insecticides at least 10 days over the course of an application season (Potter et aL,
1993).
D. Evaluation of Risk
Pyrethrins kill insects by acting as a neurotoxin and causing paralysis. Most humans can
metabolize pyrethrins to nomoxic compounds in their liver, rendering harmless mis knock down effect
seen in insects. There are a very few individuals with a disease known as motor neuron disease or
MND. Persons suffering from MND have an incapacity to breakdown pyrethrins through liver
enzymatic action (Steventon and Wadding, 1990).
Pyrethrins are used in a synergistic mix with piperonyl butoxide, both in undiluted form, to
treat head lice in children. This is one of the most susceptible subgroups of our population and no
adverse health effects were reported in a study involving 92 children, both boys and girls. 3 to 15
years of age (Fusia, et aL. 1987). The pyrethrin synergistic mixture was applied thoroughly so as to
soak the scalp and then allowed to dry for 10 minutes. This treatment was followed by a regular
shampooing and combing.
Wester et al. (1984) showed mat if pyrethrins and piperynol butoxide were applied to the
foreman of individuals in formulated mixtures, the rate of absorption for pyrethrins was 1.9% and for
piperonyl butoxide 2.1% judging by a seven day urinary collection following dose application. It is
evident from the above facts that neither natural pyrethrins nor piperonyl butoxide pose any adverse
health threat to the participants in mis experiment.
Chlorpyrifos has been shown to be absorbed through the dermal layer of the forearm at ante
of 3% (Nolan et al., 1984). Chlorpyrifos and its principal metabolites were quickly fli*™n««*fd and
shown to have a low potential to ftftmtniiiw' in the human body. This study also showed mat the
six healthy male volunteers involvsd did not show any signs of toxiciry nor any depression of plasma
or RBC cholinesterase after a single dermal dose of 5 mg/kg.
In Experiment 7, the dried pesticide residue will be wiped from the hands using isopropanoL
This solvent is likely to enhance the absorption of the pesticides through the «i™.
The maximum dose to subjects will be 27 ug/day of Chlorpyrifos, 2 ug/day of pyrethrins, and
18 ug/day of piperonyl butoxide. These estimates are based on conservative, but realistic estimates
of the amounts of each pesticide absorbed through the skin of the palm (3% for Chlorpyrifos and 2%
for pyrethrins and piperonyl butoxide).
The rabbit dermal LDM for Chlorpyrifos is 2000 mg/kg (Farm rhr^irals Handbook, 1993).
This high LDM means mere is little chance of an adverse health effect to occur to the subjects in this
experiment
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Since all the recognized industrial hygiene organizations (ACGIH, OSHA, NIOSH, MAK)
have a skin notation for chlorpyrifos, those participating in this experiment will wash their hands
immediately after exposure to the pesticide formulation. The skin notation for healthy workers
addresses adverse health effects occurring if a worker comes into contact with pure chlorpyrifos.
Industrial and agricultural exposures (Ca""nn. et al, 1993) would be one to several orders of
magnitude above what the participants in this experiment will receive.
IV.
American Conference of Governmental Industrial Hygienists (1991). Threshold I ., Camann, DJi, Schanenberg, HJ. Wheeler, H.G., Villalobos, K., Kyle, M.,
Quarderer, S., Lewis, R.G.(1990). New Dermal Exposure Sampling Technique. IN: Proc.
Measurement of Toxic and Related Air Pollutants, Air And Waste Management Association,
VP-17 Pittsburgh, PA, 489-497.
Nolan, RJ., Rick, DJ-, Freshour, NJ., and Saunders, JJi (1984). Chlorpyrifos:
Pharmacokinetics in Human Vohmteers. Toxicology and Applied Pharmacology 73,8-15.
Potter, W.T., Gaxry, V J., Kelly, J.T., et al. (1993). Radiometric assay of red cell and plasma
cholinesterase in pesticide appliers from Minnesota, Toxicol Appl PharmacoL 119:150-55.
10
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Steventon, GJJ., and Wadding, ILM. (1990). Pesticide toxicity and motor neuron disease.
Neurology. Neurosurgery and Psychiatry, 53(7), 621-622.
Vaccaro, JJL, Cranston, RJ.(1990). Evaluation of Dislodgeable Residues and Absorbed
Doses of Chloipyrifos Following Indoor Broadcast Applications of Chloryrifbs-Based
Enmlsifiable Concentrate. inti»rnal Report, Dow Chemical Co., Midland, MI
Wester, R.C., Bucks, D.A.W., and Maibach, RL (1984). Human in vivo percutaneous
absorption of pyrethrins and piperonyl butoxide in RID formulation. Neurotoxicology, 5(4),
72.
11
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SUBJECT CONSENT TO TAKE PART IN A STUDY OF Page 1
COMPARISON OF TRANSFERS BY THE DRAG SLED, PUF ROLLER, AND
HUMAN HAND PRESS OF CHI 0RPYRIFOS AND PPERONYL BUTOXIDE FORMULATED
MIXTURE RESIDUES FROM SHEET VINYL FLOORING (EXPERIMENT 7)
Southwest Research Institute, Department of Environmental
Chemistry, &>?Q Culebra Road, San Antonio, TX 78228
We are asking you to take part in a study of die transfer by human hand press of a pesticide
formulated mixture residue (chlorpyrifos, natural pyredirins, and piperonyl butoxide) from vinyl
flooring. We want to compare the transfer by hand press to the Dow drag sled and the SwRI PUF
roller. We are asking you to take pan because you are a healthy adult male employee of the Division
of Chemistry and Chemical Engineering who has expressed an interest in being a subject for this
study.
If you decide to take pan, we wfll require that you expose me palms of both hands to an
estimated total of 1.4 mg chlorpyrifos, 140 pg pyrethrins, and 1.4 mg piperonyl butoxide over three
days. The procedure for the study requires each individual's hands be inspected for any cuts,
abrasions, or breaks in the skin by Nicholas J. Giardino. Any volunteer with a lesion on his hands
will have to wait for it to heal Hand washing with soap and water will be done prior to and after
the hand presses. You wfll place a vinyl glove on one hand and then do ten presses of the palm of
the ungloved hand on an exposed 3 in. x 25 in. strip of the treated vinyL You will do two hand
presses (one with each hand). Each hand press wfll be done on each of three consecutive days on
the carpet that was oratec with die pesticide mixture on the first day. After each hand press, you will
walk a short ffgr»"Cf to an ""cn1"^"1^ ^ ^ area «nj wipe your h*i*dc with an isopropanol-saturated
gauze pad. The total elapsed time for die completion of hand presses and wipes wfll be
approximately thirty minutes each day. We will also require diat you perform wipes of bom hands
after doing hand presses on clean untreated vinyl on two days before the pesticide applicariott. If you
are injured as a result of die research procedures, medical care wfll be provided,
We do not expect you wfll experience any discomfort during the study. We also expect that
no adverse health effects wfll occur.
Reduced cholinesterase activity in zed blood cells (RBC) is one biological indicator of
exposure to pesticides (recommended by the American Conference of Governmental Industrial
Hygienists). Therefore, as a means of monitoring the condition of your health (ie., keeping your
exposure to a minmmrn) we have arranged to have your blood monitored for RBC cholincstense
activity. Initially on two days before exposure begins and once after the hand press experiments, five
samples win be collfctfd by a registered nurse at die SwRI T^f^r*! eimi^ Blood drawing
sometimes involves mfld pain, or bruising, and may rarely cause infection at the place of the ntedlf
stick.
Consenting to tbe blood draw involves mimmgi risk; however, there is a possible benefit to
you. In the event that your cholinesterase activity suggests an unhealthy condition of exposure,
additional steps wfll be taken to limit the exposure of you and other subjects in similar future
experiments. We do not guarantee that yon wfll benefit from taking pan in mis study.
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SUBJECT CONSENT TO TAKE PART IN A STUDY OF Page 2
COMPARISON OF TRANSFERS BY THE DRAG SLED, PUF ROLLER, AND
HUMAN HAND PRESS OF CHLORPYRIFOS AND PIPERONYL BUTOXIDE
FORMULATED MDCTURE RESIDUES FROM SHEET VINYL FLOORING (EXPERIMENT 7)
Southwest Research Institute, Department of Environmental
Chemistry, 6220 Cukbra Road, San Antonio, TX 78228
Everything we If*™ about you in the study will be confidential. If we publish the results of
the study in a scientific magarinc or book, we. will not identity you in any way.
Your decision to take pan in the study is voluntary. You are free to chocs; not tr take pan
in the study or stop taking pan at any time. If you choose not to take pan ox to stop at any time, it
will not affect your status in the Department of Environmental. Chemistry, Southwest Research
Institute.
If you have any questions at any time, contact David Camann at 522-2673. The University
of Texas Health Science Center committee that reviews research on human subjects (Institutional
Review Board) will answer any questions about your rights as a research subject (567-2351).
We will give you a signed copy of mis form to keep.
YOUR SIGNATURE INDICATES THAT YOU HAVE DECIDED TO TAKE PART IN THIS
RESEARCH STUDY AND THAT YOU HAVE READ AND UNDERSTAND THE
INFORMATION GIVEN ABOVE AND EXPLAINED TO YOU.
SIGNATURE OF SUBJECT:
SIGNATURE OF WITNESS:
SIGNATURE OF INVESTIGATOR:
DATE: /TIME:
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