M01-CR02 (formerly M01-B02)

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TITLE Improving the Understanding and Acceptance of Personal Protective
Equipment (PPE) M01-CR02 (formerly M01-B02)
Team Leader S. Kay Obendorf, Department of Textiles and Apparel, Cornell University,
Ithaca, NY
Students Dennis Maneefuangfoo (undergraduate) and Seungsin Lee (graduate)
URL: http://www.human.cornell.edu/units/txa/research/ntc/M01-CR02-02.pdf

GOAL STATEMENT
Study the use of synthetic membrane to evaluate the kinetics of pesticide transport from con-
taminated clothing through human skin and develop a mathematical model. · Objectives are:
(1)Develop a model using principal factor analysis to serve as the basis for recommendation of
textile material selection and/or product development for full body coverage PPE when using
existing and/or new pesticide products. (2)Improve understanding of the complex interactions
between pesticide chemicals and textile surfaces. · Use the manipulation of the surface tension of
the textile relative to the chemical challenge to develop a fabric with “idea” behavio r of high pro-
tection and high air permeability for thermal comfort in hot, humid weather.

ABSTRACT

Most protective clothing research for workers exposed to pesticides has focused on primary der-
mal exposure that results from direct contact with the pesticide and on barrier protective materi-
als to limit this exposure. The function of traditional clothing materials in reducing pesticide ex-
posure through non-barrier mechanism has received less attention. This project investigates the
transfer of pesticides from contaminated work clothing to human skin with the goal of furthering
our understanding of the role of non-barrier clothing in minimizing risk. Our objective was to
study the use of synthetic membrane to evaluate the kinetics of pesticide transport from contami-
nated clothing through human skin. Data have been collected for transport of pesticide through
the synthetic membrane system with and without the presence of shirt-weight fabric and for hu-
man skin with and with denim (pant-weight) fabric. Data will be analyzed to develop a mathe-
matical model for transport of pesticide from the contaminated fabric. Statistical analyses will
test fabric- finishing differences for cotton fabrics finished by bleaching, mercerization, car-
boxymethylation, and starching.

Introduction
Exposure to sunlight and pesticides increases the risk of contracting several types of cancer, and
pesticide absorption is mainly through the skin with most exposure (70-80%) occurring through
the hands. Clothing is a primary means of protection. Chemically resistant clothing ranges from
everyday clothing used in conjunction with rubber gloves and boots to totally encapsulated suits.
Data on barrier properties of glove materials were used to develop the Chemical Resistance
Category Selection Chart of the Environmental Protection Agency. Although most workers rec-
ognize that clothing provides some degree of protection, they have long resisted wearing full
body garments because they are physically and thermally uncomfortable. As the level of protec-
tion is increased, thermal and moisture transport are reduced making the garment less comfort-
able for work in hot, humid environments.

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Protective clothing functions as a protective layer or barrier between the worker and the chemical
contaminate. Protection can be provided through more than one mechanism such as prevention
of chemical penetration through barrier properties or through absorption and retention of the
chemical in the fabric. Chemical penetration is defined as flow of a chemical through pores, clo-
sures, porous or imperfection in the material, and permeation is molecular diffusion through a
solid-state material. Thus penetration is a macroscopic event, while permeation is a microscopic
event; both of which can occur in chemical protective clothing. A main difference between the
two phenomena is that applied force increases penetration, while permeation is a material prop-
erty driven by time. Penetration of a liquid through a material can be determined by subjecting
the material to the liquid at low pressure. When visible signs of the liquid appear, penetration
has occurred and can be measured in terms of the length of time to penetration. Recording the
time after the initial penetration time and measuring the amount of pesticide penetrated allows
calculation of penetration rate through fabric.

The basic process of chemical permeation can be described by three consecutive steps: absorp-
tion of molecules, diffusion of the absorbed molecules, and desorption of the molecules. By
definition, the permeation time of a pesticide through a material is equivalent to the sum of ab-
sorption, diffusion, and desorption time. However, in practice, one often finds that one of the
steps takes much longer than the other two steps, known as the rate- limiting step. Determination
of the permeation rate- limiting step for particular protective clothing provides insight useful for
improvement of the chemical protective by clothing. Various mathematical models have been
developed in an attempt to fully explain the mechanism by which pesticides penetrate mono-
lithic, microporous, and porous materials.

The American Society of Testing and Materials Committee on Protective Clothing established
the Test Method for Resistance of Protective Clothing Materials Permeation by Liquids or Gases,
which quantifies the permeation of liquids through protective clothing materials under conditions
of continuous contact (Henry and Schlatter 1981). The size of the cell can vary depending on the
size of the tested material. In the test cell, the subjected material is placed in the center of the
cell. One side is charged with the chemical to be tested. The collection side is then sampled
continuously by automated, continuous-detection monitors, or by hand. Termination occurs
when a cons tant rate of permeation, better known as steady state, is attained. Once steady state is
reached, the constant rate of penetration and the time it takes to reach steady state are recorded.

This research focused on the use of a synthetic membrane system to mathematically model the
kinetic transport of pesticide from a contaminated clothing fabric through human skin. We will
compare the behavior of the synthetic membrane to that of excised human skin. In addition, we
are studying cotton shirt-weight fabrics that varied in chemical finishing, as well as pant-weight
fabric.

MATERIALS AND METHODS

Pesticide
Methyl parathion, MeP, [O,O-dimethyl O-4-nitrophenyl phosphorothioate] 98% pure crystal,
obtained from Chem Service, West Chester, PA, was combined with toluene to form an 80% so-
lution. A 14 C-labeled MeP (Sigma Chemical, St. Louis, MO) was added to the soiling solution to
allow radiotracer analysis. The contaminating solution contained 2.3 × 10-6 µCi/mg MeP.

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Fabrics
Bleached and bleached/mercerized cotton fabrics were supplied by Testfabric Inc. (West Pitt-
ston, PA). Print cloth fabric weight was 102-107 g/m2 (shirt-weight), and the denim fabric was
much heavier weight, 274 g/m2 (pant-weight). Fabric characteristics are in Table 1.

Table 1 Fabric characterization and starch levels

Fabric Weave Fabric Weight Starch Add On

(g/m2 ) (%)
Bleached print cloth Plain 102 10.6 (1.7)

Mercerized print cloth Plain 107 6.6 (0.9)

CMC print cloth Plain 102 10.6 (1.1)

Denim Twill 274 --------------

Carboxymethylation finish
Carboxymethylation (CMC) treatment conditions were selected from the previous work by Rácz,
Borsa, and Bodor (1996). Solutions of sodium hydroxide and monochloroacetic acid were mixed
(C NaOH=5 mol/kg, CMCAA=0.66 mol/kg) and cooled, then used 20 min after mixing. Bleached cot-
ton fabric was padded by mixed solution with two dips (each for 1 min) at room temperature.
Fabric sealed in polyethylene foil was put in an oven set at 70 °C, the optimum temperature of
the reaction, for 20 min. The cloth was then washed in tap water, soaked with diluted HCl solu-
tion (8 cm3 of concentrated hydrochloric acid in 1 l distilled water) for 60 min, neutralized with
distilled water, and air dried at room temperature.

Starch finish
A 4 % solution (w/v) of Mallinckrodt® acid- modified soluble starch was made. Six shirt-weight
fabric samples (6 cm x 6 cm) were soaked in 500 ml starch solution at 60 °C for 1 minute. Sam-
ples were then removed and passed through a Kenmore® wringer, with 3 samples at a time and
then put back into the starch solution for 1 min, followed by a final run through the wringer.
Starched samples were then dried at 21 °C, 65 % relative humidity and cond itioned for 24 h. The
fabrics had a starch add-on of 7 to 10 % of the fabric weight (Table 1).

Human skin
Human skin was obtained from Community Tissue Services, Dayton, OH. Split thickness skin
was used, approximately 0.381 mm thick. Samples were taken at autopsy, wrapped in gauze,
sealed in plastic and frozen until use.

Synthetic membrane system

A synthetic membrane system was used as a model for initial test method development. One
layer of silicone elastomer (PharmElast, SF Medical, Hudson, MA) was sandwiched between
two layers of cellulose acetate (Sartorious Membrane Filters, Curtis Matheson Scientific, Morris

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Plains, NJ). This system has been shown to closely replicate the barrier properties of skin (Nacht
and Young 1985).

Receptor solution
A 6% solution of polyoxyethylene 20 oleyl ether (Sigma Chemical, St. Louis, MO) in distilled
water was used as the receptor fluid. This solution has been demonstrated to allow partitioning of
lipophilic compounds, such as MeP, from membranes (Scott et al. 1993).

Diffusion cell
A Franz diffusion cell with magnetic cell drive purchased from Crown Glass Company, Somer-
ville, NJ, was selected as the test apparatus. The chamber of the diffusion cell was filled with re-
ceptor solution, the skin/synthetic membrane was placed on top of the receptor chamber, then the
fabric was placed on the skin, and finally the chimney top was secured.

Sample Skin
Fabric

Receptor
Solution Experimental Cell

Fig. 1 Side-view drawing of experimental cell

The experimental setup consisted of diffusion cell containing a receptor solution. A circular
piece of synthetic membrane 2.54 cm in diameter was placed on top of the receptor chamber, fol-
lowed by a circular piece, of cotton fabric. The top was then sealed in order to secure the ex-
perimental setup from external interference. Figure 1 shows the side view image of the setup.
The experiment was carried out by applying pesticide solution to the center of the fabric sample.
The contamination level is comparable to a spill that might occur during daily work. The
amount of pesticide in the fabric sample and in the receptor solutions was measured by radio-
tracer analyses. The amount retained in the skin then was obtained using subtraction in order to
obtain a mass balance. Diffusion tests using the synthetic membrane system were run for 1 to 72
h at 37 °C. Evaluation of human skin was performed with and without denim fabric (pant-
weight, Table 1), with data collected for a time period of 3 to 144 h.

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Contamination for diffusion experiment
Circular samples, 2.54 cm in diameter, were cut from the fabric and the synthetic membrane or
human skin. The skin was placed on the test apparatus at the start of the test run; the test fabric
was placed on top of the skin. After assembling the specimen in the diffusion cell, it was con-
taminated by applying 20 µl of labeled MeP solution to the center of the specimen, using an Ep-
pendorf® micropipette. This resulted in soiling with 16 mg of MeP per specimen. Five repli-
cates were used for the bleached print cloth, and six replicates were used for the other print cloth
fabrics.

Experimentation with the synthetic membrane was carried out using shirt-weight fabrics with
different chemical finishing. The three chemical finishes applied to the fabrics were bleaching,
mercerization (a finishing process using a strong sodium hydroxide solution to increase the water
and dye absorption capability of the fabric), and carboxymethylation. For each type of fabric
finish, the effect of starching was also tested. For each type of fabric, both starched and non-
starched samples, six runs were carried out using three different experimental Franz diffusion
cells.

Radiotracer analysis
From the skin/fabric system, a 200-µl aliquot of receptor solution was placed in 20 ml of biode-
gradable counting scintillation (Amersham, Arlington Heights, IL). Radioactivity of each sample
was then measured according to standard procedures using a Beckman® LS-7000 Liquid Scintil-
lation counter.

Results

Several goals were established for statistical analysis of the data. The first is to determine a ge-
neric equation, which would be capable of explaining the data. The second is to determine
whether the synthetic membrane can be used to predict transport of pesticide from contaminated
clothing fabric through human skin. A third goal is to test the effect of fabric and finishing had
on the pesticide penetration rate using the general linear model.

Figure 2 plots data for percent of pesticide penetrated through both the shirt-weight fabrics and
the synthetic membrane into the receptor solution as a function of time. For all experimental
runs, the amount of pesticide penetrating both the fabric and the synthetic membrane approaches
a limiting value with increasing time, agreeing with the expectation that a single mathematical
model could be used to represent the experimental data and to explain the mechanism of pesti-
cide transport. Figure 3 is a plot of the data for excised human skin and denim.

Fitting Equation

We observe that the data followed a non- linear pattern with asymptotic, or limiting va lues. Data
points with such behavior generally follow the equation of the form:

y = a(1-e-bt)+c (3)

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where the value of a+c represents the asymptotic value of the equation and t is time. The pa-
rameters a, b, and c will be estimated using the statistical program SIGMAPLOT® (SPSS Inc.
Chicago, IL).

Pesticide penetration (%)

16

12
without fabric
bleached
8
mercerized
cmc
4

0
0 20 40 60 80
Time (h)

Fig. 2 Transport of pesticide through synthetic membrane with and without shirt-weight fabric
Pesticide penetration (%)

4 with denim
3 no fabric
2

0
0 50 100 150
Time (h)

Fig. 3 Transport through human skin with and without denim fabric

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Statistical Analysis
Data from the fitted equations for each fabric for each of three diffusion cells will be used to
evaluate effect of fabric, fabric finish type, and starching on transport of the contaminate through
the synthetic membrane. Further, we will compare the synthetic membrane to that of excised
human skin.

Using SAS® (SAS Institute Inc., Cary, NC), a linear model will be constructed with the follo w-
ing dependent variables: (1) time for two percent of the applied pesticide to be transported
(threshold value), (2) amount of pesticide transported from the contaminated fabric through the
membrane in 8 h, (3) maximum amount of pesticide expected to be transported in infinite time
(asymptotic value), (4) rate of transport of pesticide from contaminated clothing fabric through
the synthetic membrane (slope of pesticide penetration for ln [t]). The explanatory variables are:
(1) binary variable indicating existence of fabric finishing, (2) binary variable indicating pres-
ence of starch, (3) variable indicating type of fabric, (4) variable indicating which diffusion cell
was used to run the test.

Continuing work:
Woven fabrics are being evaluated and a preliminary model will be developed. Twist factor and
cover factor will be considered as independent variables in the performance model. · Use the ma-
nipulation of the surface tension of the textile relative to the chemical challenge to develop a fab-
ric with “idea” behavior of high protection and high air permeability for thermal comfort in hot,
humid weather.

Acknowledgements: Professors Emília Csiszár, Judit Borsa, and Charles E. McCulloch;, Dr.
Pauline Ukpabi

References
Henry NW, Schlatter CN (1981) The development of a standard method for evaluating chemical
protective clothing to permeation by hazardous liquids. Am Ind Hyg Assoc J 42:202-207
Nacht S, Yeung D (1985) Artificial membranes and skin permeability. In: Bronaugh RL, Mai-
bach HI (eds) Percutaneous Absorption. Marcel Dekker, New York, NY p 373-386
Rácz I, Borsa J, Bodor G (1996) Crystallinity and accessibility of fibrous carboxymethylcellu-
lose by pad-roll technology. J Appl Poly Sci 62:2015-2024
Scott RC, Carmichael NG, Huckles KR, Needham D, Savage T (1993) Methods for measuring
dermal penetration of pesticides. Food Chem Toxicol 31:523-529

National Textile Center Annual Report: November 2002