Glove permeation tests using novel microchemical techniques for 2,4- dichlorophenoxyacetic acid (2,4-D) derivatives

Article abstract of DOI:10.1007/PL00006621

The aim was to assess the permeation of different herbicide emulsion concentrate formulations of 2,4-dichlorophenoxyacetic acid (2,4-D) as 60.8 and 83.5% butoxyethy] ester (BEE) and 46.8% dimethyl amine salt (DMAS) through four types of glove materials (l

Full text of DOI:10.1007/PL00006621

Arch. Environ. Contam. Toxicol. 36, 485–489 (1999)
A R C H I V E S O F
E
Cnovnitraomnmineant tioanl
a n d
T
oxicology
1999 Springer-Verlag New York Inc.
௠
Glove Permeation Tests Using Novel Microchemical Techniques
for 2,4-Dichlorophenoxyacetic Acid (2,4-D) Derivatives
Y.-W. Lin, S. S. Que Hee
Department of Environmental Health Sciences and UCLA Center for Occupational and Environmental Health, UCLA School of Public Health,
10833 Le Conte Ave., Los Angeles, California 90095-1772, USA
Received: 8 July 1998/Accepted: 13 December 1998
Abstract. The aim was to assess the permeation of different
herbicide emulsion concentrate formulations of 2,4-dichloro-
phenoxyacetic acid (2,4-D) as 60.8 and 83.5% butoxyethyl
ester (BEE) and 46.8% dimethyl amine salt (DMAS) through
four types of glove materials (lined unsupported nitrile, unlined
unsupported butyl, Silver Shield laminate, and Viton). This
entailed the development of new microchemical techniques to
allow sensitive capillary gas chromatography/mass spectrom-
etry (GC/MS) of the permeated herbicide. The 2,4-D DMAS
was esterified to the methyl ester by boron trifluoride-methanol
complex with 99.2 Ϯ 3.7% efficiency using microwave heating
to minimize reaction time and to process microsamples. The
GC/MS detection limit was 5 ng/ml (ppb) of 2,4-D DMAS in
the collection medium. The permeates from the ester formula-
tions were analyzed directly for the ester above the detection
limit of 9 ng/ml (ppb) BEE. The permeation investigations
utilized the American Society for Testing Materials (ASTM)-
type permeation cells with liquid collection media. The results
showed that these gloves could provide at least 6 h protection
for these formulations.
clothing offer only tb and Ps for guidance for selection of
chemically protective clothing. Gloves are also characterized
by physical properties related to strength, flexibility, and wearer
comfort in addition to protectiveness. The correct initial choice
of gloves that are to be disposed of after the task is thus crucial.
The influence of workshift manual manipulations on perme-
ation properties requires separate study: if the gloves fail when
no stress is on them, this needs to be known before donning
them.
Although the permeation properties of commercially impor-
tant solvents are well documented, those for pesticides in their
formulations are not. A liquid pesticide like malathion can
permeate without assistance (Lin and Que Hee 1998a). In fact,
the presence of 12 xylene-fraction inert components moderated
the permeating properties of pure malathion in a liquid emul-
sion concentrate, and this has been modeled for nitrile and butyl
gloves (Lin and Que Hee 1998b, 1998c). The permeation of a
solid pesticide is wholly dependent on the liquid inert ingredi-
ents of emulsifiable concentrates, an area of ongoing research
for our research group. The permeation of solid organophos-
phates (Khan et al. 1997) and carbamates (Lu and Que Hee
1998) in their liquid emulsion concentrates has been already
reported in addition to earlier work with an emulsion concen-
trate of isooctyl ester of 2,4-dichlorophenoxyacetic acid (2,4-
D), the pure ester being a viscous, nonpolar liquid (Harville and
Que Hee 1989). The present study extends the latter investiga-
tion for a different ester and a salt form of the organochlorine
herbicide 2,4-D.
2,4-D is a phenoxy herbicide that on absorption (‘‘systemic’’)
is transported to its target sites (‘‘translocated’’) (Audus 1976).
It is usually applied as a salt or ester together with other inert
components. 2,4-D amine salt, alkali salt, and low-volatile ester
formulations are used to control broadleaf plants and weeds in
orange groves, lawns, golf courses, forests, roadways, parks,
playgrounds, playing fields, and agricultural land (Harris et al.
1992). 2,4-D butyl and octyl esters were the constituents of
Agent Orange, the Vietnam War defoliant (Que Hee and
Sutherland 1981). 2,4-D has been reported to cause convul-
sions, peripheral neuropathy, and brain damage in poisoning
cases (Watterson 1988). Acute effects include skin and mucous
membrane irritation. Workers have reported general weakness,
headache, dizziness, stomach pains, and nausea after occupa-
Protective clothing is an essential personal protective equip-
ment item for workers and for many others who require
shielding from the adverse effects of chemical, physical, and
biological agents. The transfer of a challenge agent through a
protective clothing barrier without degradation of the barrier is
permeation. Transfer through pinholes in the barrier present
originally or after chemical degradation of the barrier is
penetration. The time when the agent is detected in the
collection medium by permeation, penetration, or both pro-
cesses is termed the breakthrough time, tb, and is technique
dependent. When the rate of appearance of agent in the
collection medium is constant, the transfer process is said to be
in steady state, characterized by both the steady state transfer
rate, Ps, and the lag time, tl, the latter being the hypothetical
time when the steady state last shows zero transferred mass in
the collection medium. Manufacturers of gloves and protective
Correspondence to: S. S. Que Hee

486
Y.-W. Lin and S. S. Que Hee
tional exposure (Hayes 1982; Stevens and Sumner 1991).
Kansas farmers who used 2,4-D for more than 20 days per year
reportedly had a risk of lymphatic cancer six times higher than a
control group with no exposure to herbicides (Nadakavukaren
1990). Agricultural workers exposed to 2,4-D exhibited abnor-
mal spermatozoa as tetraspermia (Lerda and Rizzi 1991).
Suicides with 2,4-D dimethyl amine salt (DMAS) have been
documented (Keller et al. 1994). The major route of human
exposure to the semivolatile and nonvolatile forms of 2,4-D
currently sprayed is through the skin (Hayes 1982). Thus, the
wearing of personal protective equipment like gloves is neces-
sary (Grover et al. 1988). Studies of permeation through glove
materials are therefore essential.
were investigated in the present study with methods of about
equal sensitivity relative to 2,4-D acid equivalent.
Materials and Methods
Gloves and Reagents
Four types of glove barriers were tested: lined unsupported Sol-vex
nitrile from Ansell Edmont (Coschocton, OH, catalog No. 37-165, 0.56
mm thickness, 38 cm in length), unlined unsupported butyl (B131, light
weight, 0.36–0.38 mm thickness, 28 cm in length), Silver Shield
laminate (SS104M, 0.76 mm), and Viton (F124, 2.3 mm) from North
Hand Protection (Charleston, SC). The more expensive Silver Shield
and Viton gloves should be protective to 2,4-D ester formulations, and
the much less expensive nitrile gloves should be less protective
(Harville and Que Hee 1989). The inexpensive butyl gloves were
expected to offer about the same protection as nitrile, based on solvent
protection characteristics relative to nitrile. Weedone Brand LV4
(60.8% nominal weight percentage of 2,4-D BEE), Weedone Brand
LV6 (83.5% nominal weight percentage of 2,4-D BEE), and Weedar
Brand 64 (46.8% nominal weight percentage of 2,4-D DMAS) were
provided by Rhone-Poulenc (Research Triangle Park, NC). 2,4-D
(Kodak, Rochester, NY), 2,4-D BEE, 2,4-D DMAS, and 2,4-D methyl
ester (ME) (Chem Service, Westchester, PA) were used as the primary
standards. Methanol MeOH (Optima, Fisher Scientific, Fair Lawn, NJ),
anhydrous diethyl ether (Reagent A.C.S., Fisher Scientific), and boron
trifluoride (BF3)-MeOH complex BFM ϳ50% wt BF3 (Aldrich,
Milwaukee, WI) were used in 2,4-D DMAS esterification. Hydrochlo-
ric acid HCl (trace metal grade, 30.5–38.0 % w/w) and sodium
hydroxide NaOH (Fisher Scientific) facilitated pH adjustment.
Data on the permeation of some 2,4-D derivatives are
available. 2,4-D DMAS permeated through cotton coveralls
and a short-sleeved cotton T-shirt to farmers’ skins (Grover et
al. 1988). No breakthrough was observed when a 2,4-D Amine
96௡ formulation containing 2,4-D DMAS challenged neoprene,
natural rubber, polyvinyl chloride, and nitrile butyl rubber for 8
h and 16 h using the ASTM and AIDA test methods, respec-
tively, using a number of permeation cell types (Moody and
Ritter 1990). Killex௡, a 11.8% 2,4-D DMAS formulation,
showed no detectable permeation against nitrile rubber gloves
over a 24-h period (Moody and Nadeau 1994). The same
challenge concentration of 2,4-D DMAS in acetone permeated
through the same glove material during the 24-h testing period
(Moody and Nadeau 1994). Thus, the type of carrier solvent
was important. 2,4-D formulation emulsion concentrates and
aqueous solutions of Esteron௡ 99 containing 2,4-D isooctyl
ester had tb Ͻ 10 min for nitrile and neoprene glove materials
(Harville and Que Hee 1989; Que Hee 1989). Tyvek (laminated
Saranax) and unsupported nitrile protected up to 100 min.
Permeation of 2,4-D free acid in acetone through natural rubber
gloves was 3.2 Ϯ 3.5% after 48 h (Moody and Nadeau 1992).
The detection limits for the 2,4-D DMAS studies that did not
use radiolabeling were high because high-performance liquid
chromatography (HPLC) with ultraviolet (UV) detection was
utilized as the analytical technique to define the herbicide tb.
Therefore, a more sensitive technique might reveal shorter tb.
The polarity of the active ingredient may also modify the
permeation properties of the carrier solvent as evident for
malathion (Lin and Que Hee 1998b, 1998c). Indeed the higher
the concentration of the active ingredient, the more important
should this effect be on inert components that do not permeate
alone. The saline collection medium used to mimic sweat in
some studies might cause a salt effect that would reduce
solubility in the saline relative to water and keep a permeated
organic from desorbing into the saline collection medium. This
would cause long tb and low Ps.
Nitrogen (99.995%) from Alphagaz (Walnut Creek, CA) was passed
through a charcoal tube (20/40 mesh, Aldrich) before use in evapora-
tive concentrations. Optima grade hexane and 2-propanol from Fisher
Scientific were the collection media for permeation and dilution
purposes as appropriate (Table 1). American Society for Testing and
Materials (ASTM)-Type I distilled water was generated by a Millipore
Super-Q water filter system (Bedford, MA). Sodium dichromate
(Fisher Scientific) was used to produce an atmosphere of known
relative humidity (RH).
Apparatus
ASTM-type I-PTC-600 permeation cells (Figure 1) were from Pesce
Lab Sales (Kennett Square, PA). The moving tray shaker water bath
used for simultaneous immersion of three permeation cells was a Fisher
Scientific model 125 series No. 429 (Lin and Que Hee 1998a–c). A
torque wrench (Mechanics Products, Kent, WA) ensured equal tight-
ness of permeation cell nuts. A vortex mixer (Thermolyne type 16700
mixer, Dubuque, IA) facilitated liquid-liquid extraction. Kimax test
tubes of 15 ml and 10 ml with Teflon-septum screw caps contained
permeates for processing. An 850-W microwave oven (Gold Star,
model 1080M, Seoul, Korea) heated the samples.
The analysis utilized a Hewlett-Packard 5890A gas chromatograph
equipped with a Hewlett-Packard 5988A quadrupole mass spectrom-
eter in 70 eV positive ion electron impact mode. The fused silica
capillary column was a 30-m long ϫ 0.32-mm ID DB-1701 with 1.0
µm chemically bonded 14% cyanopropylphenyl film from J&W
Scientific (Alltech, Deerfield, IL). Carrier gas helium of 99.9999%
purity at flow rate 3.0 Ϯ 0.3 ml/min was from Alphagaz.
Though many methods are available for 2,4-D compounds to
create volatile derivatives for sensitive (pg sensitivity) gas
chromatography/mass spectrometry (GC/MS), there is still a
need for methods that can determine small quantities of
analytes without intensive sample preparation. In this study, an
efficient and reliable microchemical GC/MS method for the
esterification of 2,4-D DMAS microsamples was developed
based on the BF3/methanol (BFM) method (Horner et al. 1974;
Henshaw et al. 1975; Lee Choi et al. 1976). One DMAS salt
and two butoxyethyl ester (BEE) low-volatile formulations

Glove Permeation Tests for 2,4-D Derivatives
487
Table 1. Challenge formulations, glove materials, and collection
media used in the permeation tests
hydrolysis. All the hexane extraction samples were analyzed by
GC/MS to investigate nonpolar components. Concurrent sample pro-
cessing of water blank and 2,4-D DMAS aqueous solutions provided
reagent blanks and positive controls, respectively.
Weedone
Weedone
Weedar
Brand LV4
Brand LV6
Brand 64
Sol-vex Nitrilea
Butylb
Viton
Hexane
2-Propanol
Hexane
Hexane
2-Propanol
Hexane
Water
Water
Water
Water
Permeation Experiments
Silver Shield
Hexane
Hexane
The complete method has been described elsewhere (Harville and Que
Hee 1989; Lin and Que Hee 1998a–c). In summary, the glove was
equilibrated at least 24 h at RH 65 Ϯ 1% in a desiccator containing
saturated aqueous sodium dichromate at room temperature
(21.1 Ϯ 0.3°C). The material was placed between the two Teflon
gaskets of the permeation cell. The two Pyrex chambers were inserted
into the aluminum flanges, and the nuts were tightened to a torque of 16
in-lb. A volume of 10 ml of collection medium was added. The
collection media were selected depending on the types of challenge
solutions and glove materials (Table 1). After placing 15 ml of
challenge solution into the challenge chamber, the initial 100-µl
samples were taken from both sides, and the tray set to shake at 8.42 Ϯ
0.04 cm/s at 30.0 Ϯ 0.5°C. Precooled (Ϫ20°C) vials received the
100-µl samples from the collection side (Table 1). The initial and final
volumes of the challenge and collection sides were measured to assess
evaporation. The challenge headspaces were analyzed for hexane and
2-propanol as appropriate by deleting the GC/MS solvent delay. All
experiments were in triplicate.
a Average measured thickness was 0.80 Ϯ 0.08 mm, n ϭ 9
b Average measured thickness was 0.39 Ϯ 0.03 mm, n ϭ 9
c Average measured thickness was 1.05 Ϯ 0.06 mm, n ϭ 9
d Average measured thickness was 0.85 Ϯ 0.03 mm, n ϭ 9
The design of the permeation sampling time followed our previously
published protocol (Harville and Que Hee 1989; Lin and Que Hee
1998a). The initial testing was a 0-h and a 8-h screening test in
triplicate with samples taken in 1-h increments. The samples were then
analyzed in reverse time order. For kinetic permeation curves to be
defined at every 10 min as reported in the other publications of our
permeation research group (Mikatavage et al. 1984; Harville and Que
Hee 1989; Khan et al. 1997; Lin and Que Hee 1998a, 1998b, 1998c; Lu
and Que Hee 1998), a tb of at least 6 h was the cut-off to ensure enough
data points to define the steady state permeation period.
Fig. 1. ASTM type I-PTC 600 permeation cell
Esterification of 2,4-D Dimethyl Amine Salt
A mass of 0.1211 g 2,4-D DMAS was dissolved in 25 ml of Milli-Q
water to generate 4.84 mg/ml stock solution. 530 µl 10% (w/w) NaOH
aqueous solution was added to a 0.1-ml aliquot of the 2,4-D DMAS
stock solution to ensure a pH Ͼ 14. The aqueous alkaline solution was
then heated in the microwave oven at the lowest power level until
bubbles first appeared (about 90–120 s for a solution temperature of
about 80°C starting from room temperature). The solution was cooled
at room temperature. The pH of the solution was adjusted by HCl (530
µl) to ensure a pH Ͻ 2. 2,4-D was extracted by diethyl ether (0.5
ml ϫ 5) with vortexing for 1 min/extraction. The supernatants were
collected in Kimax test tubes. Excess diethyl ether was then evaporated
under a gentle stream of nitrogen. One milliliter MeOH and 0.5 ml
BFM (0.2 g/ml) were added to the concentrated solution. The solution
was then heated in the microwave oven at its lowest power level for
about 90–120 s and cooled. A 1-ml aliquot of Milli-Q water was added
and vortexed for 3 min. Hexane (2 ml ϫ 5) was added and the solution
was vortexed for 1 min/extraction to extract 2,4-D ME. The combined
extracts were concentrated using nitrogen to fit into the linear dynamic
range of 2,4-D ME. A 0.1-ml Milli-Q water reagent blank in triplicate
was processed in parallel.
GC/MS Analysis
A 1-µl aliquot from the 100 µl of thawed collection solution was
injected for GC/MS analysis. The MS was operated in the total ion
current (TIC) mode to acquire mass spectra. The selected ion monitor-
ing (SIM) mode was used at m/z 199 for the 2,4-D ME and at m/z 220
for 2,4-D BEE quantitations. The constant temperature zones were:
injector 250°C, transfer line 250°C, and ion source 250°C.
For analysis of the permeation samples for Weedone௡ LV4 and LV6,
the initial column temperature was 55°C for 2 min, then 25°C/min to
80°C and held there for 27 min, followed by 10°C/min to 100°C, and
then 30°C/min to the final temperature of 250°C until all peaks eluted.
The solvent delay time was 3 min.
The permeation samples of the Weedar 64 formulation were
analyzed as 2,4-D ME in hexane and neutral organics in hexane after
the alkaline hydrolysis. 2,4-D ME was determined with the following
temperature program: initial column temperature of 60°C for 2 min,
ramped at 25°C/min to 250°C, and then held for 5 min. The program
for the nonpolar inert components was: initial column temperature of
60°C for 2 min, ramped at 5°C/min to 250°C, and held for 10 min.
Breakthrough times (tb) were obtained from samples taken at a time
that yielded data with signal/noise (S/N) ratio of 2 for the specific m/z
ion. External standards of 2,4-D ME and 2,4-D BEE in hexane were
used in their defined linear dynamic ranges. The method detection
limits of 2,4-D ME and 2,4-D BEE were 5 ng/ml (ppb) and 9 ng/ml
(ppb), respectively, in the collection solution.
To esterify the 2,4-D DMAS from Weedar 64 formulation, 20-µl
aliquots of the formulation were diluted to 25 ml by Milli-Q water. A
volume of 0.1 ml of this aqueous solution was taken and an equal
volume of hexane was used to extract the neutral organics three times
each by vortexing for 1 min. The aqueous phase was then hydrolyzed
and esterified as described above. The same equal-volume-hexane
extraction for the neutral organics was also performed after the alkaline

488
Y.-W. Lin and S. S. Que Hee
Table 2. Summary of the permeation results of the systems
defined in Table 1
Results and Discussion
tb
mg
(ng)
Esterification
Formulations
Glove Material (h)
Five replicates for 2,4-D DMAS esterification showed 99.2 Ϯ
3.7% recovery. There was no significant difference at p Յ 0.05
relative to a reflux method of recovery 96.0 Ϯ 1.5% (Horner et
al. 1974). The sample processing time was only 20 min.
Szmigielska and Schoenau (1995) reported the esterification
of 1-ml aliquots of 2,4-D DMAS in a water bath heating step of
15 min. 2,4-D DMAS was extracted by diethyl ether and
esterified overnight by 2-chloroethanol/BCl3 with recovery of
98.5 Ϯ 4.8% for rat serum and 93.3 Ϯ 7.5% for rat brain tissue
(Oliveira and Palermo-Neto 1995). The sensitivity was about
250 ng/ml for serum and 300 ng/g for brain tissue. Mierzwa and
Witek (1977) reported the recovery of 2,4-D 2,2,2-trichloroetha-
nol ester formed after overnight reaction to be 92.1 Ϯ 3.4%
with detection limit of 96 ng/ml using GC/electron capture
detection (ECD). Roseboom et al. (1986) utilized 2,4-D esterifi-
cation by pentafluorobenzyl bromide (PFBBr), 2-naphthacyl
bromide, and 4-bromomethyl-7-methoxycoumarin for 2,4-D
esterification with recoveries of 91%, 99%, and 84%, respec-
tively. The esters were purified on a silica gel column after the
esterification to eliminate interferences. 2,4-D in sediments and
natural waters were also esterified by PFBBr by 3-h reaction
followed by silica gel column cleanup (Lee and Chau 1983; Lee
et al. 1986). The recoveries were from 71% to 108% for
sediments and from 73% to 108% for natural waters. The
GC/ECD detection limits were 10 µg/kg and 1.0 µg/L, respec-
tively. Fuming sulfuric acid-ethanol (1:20, v/v) was utilized for
2,4-D esterification with a detection limit of 20 ng/ml by
GC/ECD (Siltanen and Mutanen 1985). The reagent had to be
prepared daily. The limit of detection was 10 ng/ml by
GC/ECD. 2,4-D in water samples was esterified by 2,2,2-
trifluoroethanol (TFE) at 70°C for 60 min with 85.0 Ϯ 3.2%
recovery (Adolfsson-Erici and Renberg 1991). Lee et al.
(1995), who esterified 2,4-D by H2SO4/TFE at 60°C for 60 min,
reported 107.1 Ϯ 0.5% recovery and 50 ng/ml detection limit
by GC/MSD and GC/ECD. 2,4-D in acetone was also esterified
by H2SO4/TFE at 60°C for 120 min with 99.56 Ϯ 0.63%
recovery (Hong et al. 1996). All literature esterifications took
longer than the technique of the present study, which also had
acceptable sensitivity, but used commercially available re-
agents.
Weedone Brand LV4 (60.8% Sol-vex Nitrile
7–8 Ͻ60
2,4-D butoxyethyl ester)
Butyl
Ͼ8
Ͼ8
Ͼ8
Ͼ8
Ͼ8
Ͼ8
Ͼ8
Ͻ60
Ͻ60
Ͻ60
Ͻ60
Ͻ60
Ͻ60
Ͻ60
Viton
Silver shield
Weedone Brand LV6 (83.5% Sol-vex Nitrile
2,4-D butoxyethyl ester)
Butyl
Viton
Silver Shield
Sol-vex Nitrile
Butyl
Weedar Brand 64 (46.8%
2,4-D DMAS)
7–8 62.0 Ϯ 6.3
6–7 86 Ϯ 18
7–8 51 Ϯ 13
Viton
Silver Shield
Ͼ8
Ͻ50
Breakthrough at a trace level in one of the nitrile triplicates was
observed between 7 h and 8 h, with the other two at Ͼ8 h for LV4
tb: breakthrough time in h (S/N ϭ 2 for analyte); mg: cumulative
permeated mass of 2,4-D acid equivalent in ng for the active ingredient
at 8 h; mg is expressed as the arithmetic mean Ϯ standard deviation
when permeation was observed, and detection limits are denoted as Ͻ
quantities
within 8 h for Weedones LV6 and LV4. One run of Weedone
LV4 through nitrile did show permeation between 7–8 h,
suggestive of quality control variation for nitrile gloves. Silver
Shield showed no permeation of Weedar 64 within 8 h, but
butyl and nitrile showed respective tb of 6–7 h and 7–8 h.
No previous data are available in the literature for the
permeation of 2,4-D BEE formulations. Two herbicide formula-
tions containing 2,4-D DMAS have been reported as ‘‘no
permeation’’when nitrile gloves were challenged for 16 h using
a less sensitive HPLC analytical technique (Moody and Ritter
1990). However, the formulations differed from the one tested
in the present study, though the glove types were the same.
The observation of no breakthrough in an 8-h test implies
potentially complete protection should workers have a continu-
ous 8-h shift, subject to work practices. This is so for all Silver
Shield challenges, and also for the other three glove types when
challenged with the butoxyethyl ester formulations Weedone
Brand LV4 and LV6. Workers usually change their gloves
during the midshift or 2-h interval breaks without washing
them. For the challenge to the 2,4-D DMAS formulation
Weedar Brand 64, Sol-vex nitrile, butyl, and Viton gloves could
be redonned at 7 h in exposure time if little contact with the
formulation has occurred, as determined by an industrial
hygienist.
Microwave heating potentially allows quick and efficient
processing of many microsamples. GC/MS with SIM elimi-
nates background interferences should GC/ECD have interfer-
ences.
Weedar 64 formulation contained an average 2,4-D acid
equivalent of 42.7 Ϯ 1.5 µg or 48.7 Ϯ 1.7% (w/w). Compared
with the nominal content of 46.8% (w/w), this was not
significantly different at p Յ 0.05. No neutral organic peaks of
boiling point greater than hexane were detected by GC/MS after
alkaline hydrolysis. However, the major inert component for
this DMAS formulation should be water.
Acknowledgments. This work was supported by Grant RO1 OH02951
from the National Institute for Occupational Safety and Health of the
Centers for Disease Control and Prevention and by the UCLA Center
for Occupational and Environmental Health.
References
Permeation Studies
Adolfsson-Erici M, Renberg L (1991) Gas chromatographic determina-
tion of phenoxyacetic acids and phenoxypropionic acids as their
2,2,2-trifluoroethyl esters. Chemosphere 23:845–854
The results of the permeation experiments are summarized in
Table 2. No breakthrough of the four gloves was observed

Glove Permeation Tests for 2,4-D Derivatives
489
Audus LJ (ed) (1976) Herbicides: Physiology, biochemistry, ecology,
2nd ed. Academic Press, New York, vols 1 and 2
Lin Y-W, Que Hee SS (1998b) Permeation of a malathion formulation
through nitrile gloves. Appl Occup Environ Hyg 13:286–298
Lin Y-W, Que Hee SS (1998c) Permeation of a malathion formulation
through butyl gloves. J Haz Mat 60:143–158
Lu X, Que Hee SS (1998) Permeation of methomyl in Lannate L
through nitrile gloves. J Haz Mat 59:279–285
Mierzwa S, Witek S (1977) Gas-liquid chromatographic method with
electron-capture detection for the determination of residues of
some phenoxyacetic acid herbicides in water as their 2,2,2-
trichloroethyl esters. J Chromatogr 136:105–111
Mikatavage M, Que Hee SS, Ayer HE (1984) Permeation of chlorinated
aromatic compounds through Viton and Acrylonitrile polymer
glove materials. Am Ind Hyg Assoc J 45:617–621
Moody RP, Nadeau B (1992) Effect of the mosquito repellent DEET
and long-wave ultraviolet radiation of the herbicide 2,4-D and the
insecticide DDT in natural rubber gloves. Am Ind Hyg Assoc J
53:436–441
Moody RP, Nadeau B (1994) Nitrile butyl rubber glove permeation of
pesticide formulations containing 2,4-D-amine, DDT, DEET, and
Diazinon. Bull Environ Contam Toxicol 52:125–130
Moody RP, Ritter L (1990) Pesticide glove permeation analysis:
comparison of the ASTM F739 test method with an automated
flow-through reverse-phase liquid chromatography procedure. Am
Ind Hyg Assoc J 51:79–83
Nadakavukaren A (1990) Man and environment: a health perspective,
3d ed. Waveland Press, Prospect Heights, IL
Oliveira GH, Palermo-Neto J (1995) Toxicology of 2,4-dichlorophen-
oxyacetic acid (2,4-D) and its determination in serum and brain
tissue using gas chromatography-electron-capture detection. J
Anal Toxicol 19:251–255
Que Hee SS (1989) Permeation of some pesticidal formulations
through glove materials. In: Perkins JL, Stull JO (eds) Chemical
protective clothing performance in chemical emergency response.
ASTM STP 1037, ASTM, Philadelphia, PA, pp 157–164
Que Hee SS, Sutherland RG (1981) The phenoxyalkanoic herbicides,
vol 1. CRC Press, Boca Raton, FL
Roseboom H, Herbold HA, Berkhoff CJ (1986) Determination of
phenoxy carboxylic acid pesticides by gas and liquid chromatogra-
phy. J Chromatogr 249:323–331
Siltanen H, Mutanen R (1985) Formation of derivatives of chlorophe-
noxy acids and some other herbicides. Chromatographia 20:685–
688
Stevens JT, Sumner DD (1991) Herbicides. In: Hayes WJ Jr, Laws ER
Jr (eds) Handbook of pesticide toxicology, vol. 3. Academic Press,
San Diego, CA, pp 1319–1325
Grover R, CessnaAJ, Muir NI, Riedel D, Franklin CA(1988) Pattern of
dermal deposition resulting from mixing/loading and ground
application of 2,4-D dimethylamine salt. In: Mansdorf SZ, Sager
R, Nielsen AP (eds) Performance of protective clothing: second
symposium. ASTM STP 989, ASTM, Philadelphia, PA, pp 625–
629
Harris SA, Solomon KR, Stephenson GR (1992) Exposure of homeown-
ers and bystanders to 2,4-dichlorophenoxyacetic acid (2,4-D). J
Environ Sci Health 27B:23–28
Harville J, Que Hee SS (1989) Permeation of a 2,4-D isooctyl ester
formulation through neoprene, nitrile, and tyvek protection materi-
als. Am Ind Hyg Assoc J 50:438–446
Hayes WJ (1982) Pesticide studies in man. Williams and Wilkins,
Baltimore, MD
Henshaw B, Que Hee SS, Sutherland RG, Lee CC (1975) Gas-liquid
chromatography and gas-liquid chromatography combined with
mass spectrometry of a butyl ester formulation of (2,4-dichlorophen-
oxy)acetic acid. J Chromatogr 106:33–39
Horner J, Que Hee SS, Sutherland RG (1974) Esterification of
(2,4-dichlorophenoxy)acetic acid—a quantitative comparison of
esterification techniques. Anal Chem 46:110–112
Hong M, Kim M, Smith AE (1996) Simultaneous determination of
2,4-D, dicamba, and mecoprop in soil leachates by gas chromatog-
raphy with electron capture detection. J Assoc Off Anal Chem Int
79:988–1004
Keller T, Skopp G, Wu M, Aderjan R (1994) Fatal overdose of
2,4-dichlorophenoxyacetic acid (2,4-D). Foren Sci Int 65:13–18
Khan AA, Chen X, Que Hee SS (1997) Permeation of chlorpyrifos and
endosulfan formulations through protective materials. Appl Occup
Environ Hyg 12:413–417
Lee AS, Hong M, Smith AE (1995) Analysis of 2,2,2-trifluoroethyl
derivatives of carboxylic acid herbicides by gas chromatography
with mass-selective and electron capture detection. J Assoc Off
Anal Chem Int 78:1459–1464
Lee Choi K, Que Hee SS, Sutherland RG (1976) 2,4-D levels in the
south Saskatchewan River in 1973 as determined by a GLC
method. J Environ Sci Health 11B:175–183
Lee H, Chau ASY (1983) Analysis of pesticide residues by chemical
derivatization. VI. Analysis of ten acid herbicides in sediment. J
Assoc Off Anal Chem 66:1023–1028
Lee H, Stokker YD, Chau ASY (1986) Chemical derivatization
analysis of pesticide residues. X. Analysis of ten acid herbicides in
natural waters. J Assoc Off Anal Chem 69:557–560
Szmigielska AM, Schoenau JJ (1995) Determination of 2,4-D amine in
soils using anion exchange membranes. J Agric Food Chem
43:151–156
Watterson A (1988) Pesticide users’ health and safety handbook: an
international guide. Van Nostrand Reinhold, New York, NY, pp
162–163
Lerda D, Rizzi R (1991) Study of reproductive function in persons
occupationally exposed to 2,4-dichlorophenoxyacetic acid (2,4-
D). Mutation Res 262:47–50
Lin Y-W, Que Hee SS (1998a) Permeation of malathion through glove
materials. Appl Occup Environ Hyg 13:158–165