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Chapter Two

PESTICIDES

BACKGROUND
What Are Pesticides?
Pesticides are natural or synthetic agents that are used to kill unwanted plant or
animal pests. While the term pesticide is now often associated with synthetic
chemical compounds, it was not until relatively recently that synthetic pesti-
cides came into use. Naturally occurring compounds or natural extracts have
been used as pesticides since ancient times. The earliest pesticides were most
likely salt, sulfurous rock, and extracts of tobacco, red pepper, and the like. It is
rumored that the Napoleonic army used crushed chrysanthemums to control
lice, with limited effectiveness. Petroleum oils, heavy metals, and arsenic were
used liberally to control unwanted pests and weeds until the 1940s, when they
were largely replaced for many uses by organic synthetic pesticides, the most
famous of which is DDT.

Because the broad term pesticide encompasses a diverse collection of sub-


stances, an explanation of pesticide taxonomy and nomenclature is warranted.
Pesticides can be classified either by target pest or by chemical identity.1 Clas-
sification by target pest is perhaps the most familiar. For example, insecticides
are pesticides that target insects, and herbicides target plants. There are many
more examples (acaricides target ticks, nematocides target nematodes, etc.),
but it is important for the purposes of this report to note that 11 of the 12 pesti-
cides of concern identified by OSAGWI are insecticides and/or acaricides. The
twelfth, DEET, is also directed against insects and ticks, but it is unique in that it
is considered a repellent rather than an insecticide. To avoid confusion, the
term pesticide is used in lieu of subclassification alternatives in this report.

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1Certainly there exist other bases for classification, for example, by formulation (emulsions, pow-
ders, etc.) or by mode of toxic action (cholinesterase inhibition, etc.). However, target pest and
chemical identity are most often used—and are frequently a source of confusion.

5
6 Pesticides

Pesticides can also be organized by their chemical class. A pesticide class is a


group of pesticidal compounds that share a common chemistry. For example,
all pesticides in the class organophosphate (OP) are derivatives of phosphoric
acid, and all pesticides in the class organochlorine are composed of carbon, hy-
drogen, and chlorine. There are also chemical subclasses of pesticides, but
these are beyond the scope of this discussion. This report considers four
chemical classes of insecticides, as well as the repellent DEET, which is more
conveniently identified by its mode of use.

When discussing a pesticide, it is possible to refer to the pesticidal compound


itself or to the pesticide product or formulation. The compound itself is also
known as the active ingredient—the chemical responsible for killing the target
pest. The formulation is the manner in which the active ingredient is delivered.
Typical formulations include liquids, dusts, wettable powders, and emulsifiable
concentrates. The pesticide formulation includes the active ingredient as well
as other ingredients. These other ingredients may be inert, such as talcum
powder, or they can act to enhance the pesticidal properties of the active ingre-
dient. For example, some pesticide formulations include a synergist that
enhances the toxic activity of the active ingredient. Other ingredients in many
pesticide formulations are solvents. When considering the potential health ef-
fects of pesticides, it is important to consider the toxicity of the active ingredi-
ent as well as the other ingredients in the formulation. This is often a daunting
task. Clinical reports of pesticide poisoning provide clues about the toxicity of
the pesticide formulation or product, while controlled experiments involving
laboratory animals may include the formulation or just the active ingredient
alone.

Pesticide Regulation

The EPA regulates both active ingredients and pesticide formulations under the
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA).2 FIFRA gives the
EPA the authority to regulate pesticides to ensure that their use does not have
unreasonable adverse effects on humans and the environment. The registrant
of a pesticide must submit specific data to the EPA to support the conclusion
that the product meets this standard before the EPA will grant a registration
that allows the pesticide to be marketed and sold. This can be a lengthy and ex-
pensive process. It includes approval of a pesticide label that provides informa-
tion on the use and safety precautions related to the product. Under FIFRA, this
label is legally binding. For example, it would be illegal to use a pesticide prod-
uct in a food service establishment if the product is not specifically labeled for

______________
2Despite its name, FIFRA governs all pesticides, not just those targeted against insects, fungi, and
rodents.
Pesticides 7

that use. Following approval by the Armed Forces Pest Management Board
(AFPMB), the U.S. military can procure pesticide products registered by the EPA
and must follow the label instructions.

As part of the registration process, the EPA differentiates between general-use


and restricted-use pesticides (GUPs and RUPs), primarily on the basis of EPA
toxicity class. GUPs can be sold to the public for unrestricted use, while RUPs
can be sold to and used only by certified applicators.3 The distinction between
GUPs and RUPs can be somewhat confusing, because the classification can
refer to either the active ingredient or the formulation. For example, the
inclusion of some active ingredients makes any pesticide product an RUP, while
in other cases, the distinction between GUP and RUP is made by pesticide
formulation. Consider two pesticide products containing the same active
ingredient but different formulations. If the EPA does not consider all products
with this active ingredient to be RUPs, one of those products can be for general
use and the other restricted, because their formulations might be considered to
present different risks to humans or the environment.

Related to the distinction between GUP and RUP on a pesticide label is the EPA
toxicity class. This classification is based on acute human toxicity, hazard to
applicators, and ecological effects. The acute human toxicity is assessed via
animal tests, and ecological effects include the potential for groundwater con-
tamination. Each toxicity class is associated with a signal word, which must ap-
pear on the pesticide label. The toxicity classes are shown in Table 2.1.

PESTICIDE IDENTITY AND PROPERTIES

Tables in Chapters Four through Seven present the identity and chemical and
physical properties of each pesticide of concern. This information is intended
to enable cross-referencing regarding the chemical identity of the pesticides as
well to provide data that may be useful in characterizing their environmental
behavior and potential health effects. References for these tables include the

Table 2.1
EPA Pesticide Toxicity Classes

Toxicity Class Toxicity Rating Signal Word on Label


I Highly toxic DANGER-POISON
II Moderately toxic WARNING
III Slightly toxic CAUTION
IV Practically non-toxic CAUTION

______________
3Or in some cases, applicators directly under their supervision.
8 Pesticides

Merck Index (10th ed., 1983), the EPA Integrated Risk Information Service (IRIS)
database (http://www.epa.gov/iris), the EPA Pesticide Product Information
System Databases (http://www.epa.gov/opppmsd1/PPISdata/index.html), the
EXTOXNET database,4 and pesticide labels graciously provided by the Entomo-
logical Sciences Division of the U.S. Army Center for Health Promotion and
Preventive Medicine (USACHPPM). Original references were obtained for veri-
fication. Occupational exposure values (standards and recommendations)
were obtained from the American Conference of Governmental Industrial Hy-
gienists (ACGIH, 1999); 5 reference doses and concentrations (RfD and RfC)
were obtained from the IRIS database. In addition, Cheremisinoff and King
(1994), Hornsby et al. (1996), and Kamrin (1997) provided references and direc-
tions to original sources.

The characteristics summarized in the physical and chemical properties tables


for each pesticide of concern are described below.

Molecular Weight, Color, Form, and Odor. These entries are self-explanatory
and are presented as the range of values reported in the referenced sources,
where appropriate. The color, form, and odor of pesticides are generally
restricted to the active ingredients and are given here because they may assist
recall efforts of veterans being surveyed about their potential exposure to
pesticides. It should be noted, however, that these values could be substantially
different for pesticide formulations used during ODS/DS.6

Water Solubility. The water-solubility value is given for the active ingredient at
room temperature, either 20°C or 25°C. Values are presented as milligrams of
solute per liter of water (mg/L); in most cases, mg/L can also be reported as
parts per million (ppm), even for very soluble compounds (Hornsby et al.,
1996). Generally, the higher the value, the more readily the compound dis-
solves in water.

Partition Coefficient (Kow). The octanol-water partition coefficient indicates


how a chemical is distributed at equilibrium between organic (octanol) and
aqueous (water) phases. This coefficient is primarily used in predicting the en-
vironmental fate of organic chemicals such as pesticides. The higher the coef-

______________
4 http://ace.ace.orst.edu/info/extoxnet. EXTOXNET is a cooperative effort of the University of
California, Davis; Oregon State University; Michigan State University; Cornell University; and the
University of Idaho. Primary files are maintained and archived at Oregon State University.
5 This reference, published as a CD-ROM, includes the most recently published occupational
exposure values from the ACGIH, the Occupational Safety and Health Administration (OSHA), and
the National Institute for Occupational Safety and Health (NIOSH), and the carcinogenicity
classifications given in this report.
6 A separate, concurrent effort by RAND that surveyed some 2,000 PGWV addresses the formu-
lations more specifically (Fricker et al., 2000).
Pesticides 9

ficient, the greater the propensity for the chemical to be partitioned to organic
phases. This generally means that the chemical will tend to adhere to organic
matter in the soil (e.g., organocolloids), but it may also indicate a tendency to
accumulate in fat, although this behavior depends on other biological factors in
the body. The partition coefficient is included in this report primarily because
it is often used to estimate other chemical and physical properties.

Soil Sorption Coefficient (Koc ). This coefficient is sometimes called an adsorp-


tion coefficient. The distinction between adsorption and absorption is that the
latter requires the movement of a chemical across a barrier such as tissue or a
cell membrane. The soil sorption coefficient more accurately measures the
chemical’s propensity to “attach,” or adsorb, to soil particles. The term soil
sorption coefficient is used to avoid confusion. The utility of this measurement
is that it assists in predicting whether a pesticide will remain dissolved in solu-
tion or will become adsorbed to soil particles after its application (or following a
spill). If a pesticide is adsorbed to soil particles, it may be less available for
biodegradation or for runoff or leaching. This assessment could be useful in
estimating the potential for pesticide exposure. Generally, Koc values below 500
indicate little or no adsorption of the pesticide to soil (indicating a high possi-
bility of runoff or leaching).

Vapor Pressure. This value is given in millimeters of mercury (mm Hg), the unit
of measure most often used. To convert to millipascals (mPa), one divides this
value in mm Hg by 7.52 x 10-6 (Hornsby et al., 1996). Vapor pressure is a mea-
sure of the tendency of a pesticide to volatilize, a phase change that can affect
estimations of exposure. Generally, the lower the vapor pressure, the lower the
volatilization tendency of the chemical. Vapor pressure values are given for ac-
tive ingredients of pesticides in this report.

EPA Toxicity Classification. The EPA toxicity classifications presented in this


report were discussed above (Table 2.1).

ACGIH Threshold Limit Values–Time-Weighted Average (TLV–TWA). These


values are developed by ACGIH as guidelines to assist in the control of health
hazards and are not legal standards. TLVs refer to airborne concentrations of
substances and represent conditions under which it is believed that nearly all
workers may be repeatedly exposed day after day without adverse health ef-
fects.7 TLV–TWA represents these concentrations as the time-weighted average

______________
7This definition is provided by ACGIH (1999), which explains that, “Because of wide variation in
individual susceptibility . . . a small percentage of workers may experience discomfort from some
substances at concentrations at or below the threshold limit; a smaller percentage may be affected
more seriously by aggravation of a pre-existing condition or by development of an occupational
illness. . . . Individuals may also be hypersusceptible or otherwise unusually responsive to some
10 Pesticides

concentration for a conventional eight-hour workday and a 40-hour workweek.


Substances listed with the designation “skin” refer to the potential significant
contribution to overall exposure by the cutaneous route. TLVs are based on
available information from industrial experience and from experimental animal
and human studies, and, when possible, from a combination of the three.

NIOSH Recommended Exposure Limits (REL–TWA, REL–STEL, and IDLH).


These values are recommended by the National Institute for Occupational
Safety and Health (NIOSH), Centers for Disease Control and Prevention (CDC).
Acting under the authority of the Occupational Safety and Health Act (OSHAct)
of 1970 (29 USC Chapter 15) and the Federal Mine Safety and Health Act of 1977
(30 USC Chapter 22), NIOSH develops recommended exposure limits (REL) for
hazardous substances or conditions in the workplace. The REL–TWA values are
time-weighted average airborne concentrations for up to a 10-hour workday
during a 40-hour workweek. Short-term exposure limits (REL–STEL) are 15-
minute TWA exposures that should not be exceeded at any time during the
workday. For most substances with a TLV–TWA, there is currently not enough
toxicological information available to warrant a STEL, as evidenced by the lim-
ited availability of STELs reported here. IDLH values are concentrations that
are immediately dangerous to life or health.

OSHA Permissible Exposure Limits (PEL–TWA). These regulatory limits are es-
tablished by the Occupational Safety and Health Administration (OSHA) and
have the force of law in occupational environments where OSHAct is applica-
ble. PELs are also time-weighted averages and assume exposures of eight hours
a day for a 40-hour workweek. PELs are based on human and animal studies,
allowing for scientific uncertainty.

EPA Oral Reference Doses (RfD) and Inhalation Reference Concentrations


(RfC). The RfD and RfC can be used to estimate a level of environmental expo-
sure at or below which no adverse effect is expected to occur. The RfD or RfC is
an estimate (with uncertainty spanning perhaps an order of magnitude) of a
daily exposure that is likely to be without appreciable risk of deleterious effects
to humans, including sensitive subgroups, over a lifetime. These values are
based on lifetime exposure.8

Carcinogenicity. Carcinogenicity classifications are provided as reported by


the ACGIH, the EPA, and the International Agency for Research on Cancer
(IARC). These classifications are summarized in Table 2.2. They are generally

________________________________________________________________________
industrial chemicals because of genetic factors, age, personal habits (e.g., smoking, alcohol, or other
drugs), medication, or previous exposures.”
8http://www.epa.gov/iris/limits.htm.
Pesticides 11

Table 2.2
Carcinogenicity Classifications

Agency/Categories Classification
ACGIH
A1 Confirmed human carcinogen
A2 Suspected human carcinogen
A3 Confirmed animal carcinogen with unknown relevance to humans
A4 Not classifiable as a human carcinogen
A5 Not suspected as a human carcinogen a
EPA – 1986b
A Human carcinogen
B Probable human carcinogen
B1 subgroup Limited evidence from epidemiological studies
B2 subgroup Sufficient evidence from animal studies; inadequate or no evidence from
epidemiological studies
C Possible human carcinogen
D Not classifiable as to human carcinogenicity
E Evidence of non-carcinogenicity for humans
EPA – 1996
K Known human carcinogen
L Likely to produce cancer in humans
CBD Cannot be determined
NL Not likely to be carcinogenic in humans
IARC
1 Carcinogenic to humans
2A Probably carcinogenic to humans
2B Possibly carcinogenic to humans
3 Unclassifiable as to carcinogenicity in humans
4 Probably not carcinogenic to humans
aThe categories A4 and A5 can be confusing. The basic difference is that A4 substances cause con-
cern that they could be carcinogenic for humans but cannot be assessed conclusively because of a
lack of data; A5 substances are not suspected to be human carcinogens, based on human epidemio-
logic studies, or because the evidence suggesting a lack of carcinogenicity in experimental animals
is supported by mechanistic data.
b As found in the 1986 Risk Assessment Guidelines (EPA/600/8-87/045). New guidelines for carcino-

gen risk assessment were proposed in 1996 (1996 Proposed Guidelines for Carcinogen Risk Assess-
ment, Federal Register: 61[79]:17960-18011). These new guidelines were proposed due to advances
in toxicological science. One significant limitation of the old guidelines is that a compound was
considered carcinogenic if there was evidence of carcinogenicity from one exposure pathway, even
in the absence of such evidence from other pathways. None of the pesticides of concern have been
classified under the 1996 system; the old classifications are presented here for future comparisons.

based on the availability and weight of evidence of carcinogenicity from prop-


erly designed animal and human studies.

PESTICIDE USE IN ODS/DS

In every war and military conflict, combat effectiveness has been significantly
reduced by disease, and a large number of diseases can be directly linked to
12 Pesticides

disease-carrying organisms such as arthropods and rodents.9 Not only can


these organisms transmit disease, their bites can result in distracting and de-
moralizing conditions and can cause serious secondary infections and allergic
reactions. For these reasons, pest control is of significant military importance,
affecting not only troop morale and welfare but also overall unit combat effec-
tiveness and strength.

During ODS/DS, insects and rodents were of particular concern as potential


disease vectors. The primary focus for pest management was on ground
troops.10 With roughly one-half million personnel deployed to the region in a
very short time, under widely varying living, working, and threat conditions,
this logistical challenge was large.

Pests of concern in the Persian Gulf region included arthropods such as sand
flies, “filth flies,” black flies, mosquitoes, cockroaches, lice, ticks, scorpions, spi-
ders, and centipedes. These vermin are capable of transmitting major diseases
such as viral encephalitis, malaria, sand fly fever, and leishmaniasis, as well as
being an extreme nuisance because of their overabundance.11 Rodents such as
rats, mice, and voles were also of concern as disease vectors and contaminants
of food supplies.

During ODS/DS, military authorities recommended various pesticides to con-


trol a variety of pests. The pesticides recommended for use by U.S. forces were
listed by the AFPMB and approved for use by the EPA. Table 2.3 lists the pesti-
cides used or potentially used by U.S. military units during ODS/DS. As de-
tailed in Chapter One, OSAGWI has identified 12 pesticides that it considers to
be of particular concern either because of toxicity or expected exposure; these
pesticides are identified in bold type in Table 2.3.

More than 35 types of pesticides and pesticide products were used by military
personnel during ODS/DS. None of the pesticides used was unique to the
military; all are, or were at the time, legally available for civilian uses in the
United States or other countries. When the provided quantities of pest-control
products ran very low, purchases were made from the local economy in Saudi
Arabia. For example, insecticide bait containing the active ingredient azame-
thiphos was reportedly purchased in Saudi Arabia and used by U.S. units. This

______________
9Personal Protective Techniques Against Insects and Other Arthropods of Military Significance, U.S.
Army Technical Information Memorandum No. 36, Armed Forces Pest Management Board.
10 Indigenous pests were not considered a significant threat to personnel remaining on naval
vessels. It was expected that their exposure was no different from that of personnel afloat in any
other part of the world; therefore, no special studies of that group have been performed.
11See note 9 above.
Pesticides 13

Table 2.3
Pesticides Used or Potentially Used During ODS/DS

Active Ingredient Product Synonyms, Trade Names Target Pests


Allethrin d-trans-Allethrin Insects
Aluminum phosphide Phostoxin, Fumitoxin, AlP Stored product pests
Amidinohydrazone Combat Insects
Azamethiphos Snip Flykiller, Alfacron Flies
Bacillus thurengiensis Teknar Mosquito larvae
Bendiocarb Ficam W Roaches, fleas, ticks, mos-
quitoes, other arthropods
Boric acid Whitmire (PT 240) Perma-dust Insects
Brodifacoum Talon G Rodents
Bromadiolone Maki Rodents
Carbaryl Sevin Ants, fleas, other insects
Chlorophacinone Rozol Rodents
Chlorpyrifos Dursban Mosquitoes, other insects, ticks,
mites
Cypermethrin Demon Insects
Deltamethrin Insects
Diazinon Insects
Dichlorvos DDVP, Insects
Diethyl-m-toluamide DEET, 3M Insect/Arthropod and Sand flies, other insects, ticks
Cutter Insect Repellents
Diphacinone P.C.Q., Rodent Cake, Di-Blox Rodents
Ethyl hexanediol Insects
Lindane Lice
Malathion Insects
Methomyl Flytek Flies
Pentachlorophenol Fungi
Permethrin Permanone Insects
Pet flea and tick collars Amitraz, carbaryl, chlorpyrifos, Insects, ticks
methoprene, permethrin,
phosmet, propoxur, tetra-
chorvinphos
d-phenothrin Insects
Pindone Rodents
Propoxur Baygon Flies, roaches, other insects
Pyrethrum/pyrethrins Pyrenone Mosquitoes, flies
Resmethrin Insects
Sulfur Chigg-Away Chiggers (mites)
Valone
Warfarin O-R-500, Rodex, Final, Erase Rodents
Source: Provided by OSAGWI.

product, manufactured by Ciba Geigy, is not available in the United States.12


Local firms provided pest control services in selected areas, and around some
industrial camps they applied pyrethroid insecticides and malathion on

______________
12CDR T. Wayne Gale, presentation at the 137th Armed Forces Pest Management Board Meeting,
July 18, 1991. CMAT Control #1997269-0000-014.
14 Pesticides

portable latrines. The actual total usage of pesticides by U.S. forces during
ODS/DS is unknown, but estimates for pesticides acquired within the military
supply system have been made from records indicating the amounts sent to the
Gulf region minus the amounts returned (see Fricker et al., 2000). Total usage
does not include any pesticides in the possession of units at the outset of
ODS/DS or pesticides acquired outside the military supply system. Thus, it
does not include any pesticides acquired from the local economy or any that
personnel obtained on their own—factors that could lead to underestimates of
pesticide use. There is anecdotal information that some troops obtained pest-
control products such as citronella candles from private sources. And some
service members brought or had mailed to them unauthorized pesticides such
as pet flea and tick collars that were designed to protect pets. During ODS/DS,
a popular actor who visited the area advised the viewing audience of a televi-
sion show to send these pet collars to U.S. service personnel.13 Other practices
could have led to overestimates of pesticide use. These practices include units
keeping pesticides received during ODS/DS and returning them to their units’
supply stocks rather than the supply system, and giving pesticides to coalition
partners. Both practices would result in overestimations of pesticide use when
the “supplies in minus supplies out” method of estimating is employed.

______________
13 CAPT Herbert T. Bolton, “Pesticide Use by U.S. Forces During Operations Desert Shield and
Desert Storm,” AFPMB Testimony to the National Institutes of Health Technology Assessment
Workshop on the Persian Gulf Experience and Health, April 27, 1994.

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