2.01.08
Safety Review: Ingredients in Checkmate
LBAM-F
[DRAFT - authors' names have been removed pending final edits and review]
Checkmate
LBAM-F is a biochemical pesticide designed for mating disruption of the light
brown apple moth (LBAM). In early November 2007 aerial spraying of the pesticide
was conducted over residential areas in
The
Checkmate LBAM-F formulation includes two types of synthetic moth pheromones,
as well as a variety of ìinertî ingredients. Though safety data sheets for the inert ingredients in the formulas have
raised many serious health and safety concerns, materials presented by the CDFA
(CDFA 2007; DPR/OEHHA 2007) have consistently focused on the safety of only the
pheromone constituents, failing to address the preponderance of known toxicity
data for the inerts. A 2007 CDFA Questions and Answers document on the
LBAM states that ìthe ingredients in the formulation are water and
biodegradable elements used to delay the release of the active ingredientî and
that ìthe basic biodegradable building block is urea, a normal constituent of
the human body that is derived from the breakdown of proteins that we
eat.îÝ However a review of the available
research data as well as the MSDS sheets (Material Safety Data Sheets) for
these chemicals indicates a high level of toxicity for many of the inerts.
The
word ìinertî as used on a pesticide label is commonly mistaken to mean inactive
or benign. However the EPA states that ìalthough the term ìinertî may connote
physical, chemical or biological inactivity, use of the word ìinertî to
describe a component in a pesticide product means only that the substance is
not intended to exert a pesticidal effect Ö in that product. The ìinertî
ingredient may have biological activity of its own, it may be toxic to humans,
and it may be chemically activeî (EPA
2002). Though typical pesticide formulations are comprised largely of inerts (a review of 100 agricultural
pesticide products found that the formulations contained on average 50% inert
ingredients, with many containing 90% or more ìinertsî; NCAP 2006) the majority of safety tests required to register a
pesticide are performed with the active ingredient alone, not the complete
formulation (Cox & Surgan 2006).Ý
Numerous
studies have shown that inerts can
increase the toxicity of pesticides to body systems such as the nervous,
cardiovascular, and hormonal systems, the mitochondria, and genetic material. Inerts can also interact with other
chemicals in pesticide formulations, to increase human exposure levels to the
pesticide. Additionally, inerts have
been shown to raise the ecotoxicity of pesticide formulations; increasing the
severity of toxic effects to plants, animals, and non-target microorganisms (Cox & Surgan 2006).Ý
A
comparison of potential health effects listed for the inert ingredients in the Checkmate formulas, with the actual
adverse effects reported following the sprayings, indicates a remarkable
consistency between the two. In fact a DPR/OEHHA
(2007) consensus document provided by
the CDFA states the following:
…
ìThe toxicity data on the pheromone active ingredients as well as
on microencapsulated pheromone product formulations suggest that exposure to a
high dose of airborne Checkmate microcapsule particles could cause eye, skin,
or respiratory irritation.î
…
ìThe toxicological information on the Checkmate product indicates
that exposure to high levels of the applied material would be consistent with
many of the reported symptoms. However, because the application rate was
extremely low, it is likely that exposure occurred at levels below those that
would be expected to result in health effects.î
643
adverse reactions reported following the sprayings in
v
asthma attacks
v
bronchial irritation
v
lung congestion and soreness
v
difficulty breathing and shortness of breath
v
coughing or ìwheezingî
v
skin rashes (sometimes severe)
v
vision blurred
v
eye irritation
v
sore throats
v
nasal congestion
v
sinus bleeding
v
chest pains and tightness
v
heart arrhythmia and tachycardia (irregular and rapid heartbeat)
v
headaches (sometimes debilitating)
v
an inability to concentrate and focus
v
dizziness
v
muscle aches
v
body tremors
v
intestinal pain and diarrhea
v
nausea
v
swollen glands and lymph nodes in neck and under arms
v
feelings of lethargy and malaise
v
menstrual cramping, an interruption to menstrual cycles, and in
some cases a recommencement of menstrual cycles after menopause
(HOPE
1/3/08)
The
particle size of the microcapsule shell is another issue that has raised
serious health concerns. A consensus document provided by the CDFA in regard to
the microencapsulated spray lists the particle size as 25 micrometers (microns)
or larger (DPR/OEHHA 2007), however a
UC Davis study on the spray discovered a wide range of particle sizes down to
the 10 micron size (Werner et al 2007).
The EPA classifies particles 10 microns in size or smaller as ìparticle
pollutionî, cautioning that this size particle can get deep into the lungs and
cause or aggravate a variety of health problems including coughing, difficulty
breathing, asthma, and other respiratory symptoms (EPA website). The sprayings in Monterey and Santa Cruz counties
were followed by numerous reports of mild to severe respiratory and asthma-like
symptoms (HOPE 1/03/08). Ý
Checkmate LBAM-F
Product Description
Toxicity
As
stated on Suterra MSDS Product Sheet: the toxicity of the product is determined
by the toxicity of the pheromone active ingredient. The toxicity of this
pheromone will be similar to the toxicity of other lepidopteran pheromones, ie:
Potential Health Effects (Warnings)
Ecological Toxicity
ENVIRONMENTAL HAZARD
For terrestrial uses: For purposes of this
Section 18 use only, this product may be applied in Riparian habitats, over
water that is covered or partially covered by tree canopies, or over uncovered
water that is close to such water bodies. Otherwise, do not apply directly to
water, or to areas where surface water is present, or to intertidal areas below
the mean high water mark. Do not contaminate water when cleaning equipment or
disposing of equipment washwaters or rinsate.
(E)-11-Tetradecenyl
Acetate
(E)-11-Tetradecen-1-YL
Acetate (As Listed on Checkmate LBAM-F
MSDS)
CAS Number - 33189-72-9
Class
Toxicity
Potential Health Effects (Warnings)
Ecological Toxicity
(E,E)-9,11-Tetradecadienyl Acetate
(E,E)-9,11-Tetradecadien-1-YL Acetate (As Listed on Checkmate LBAM-F MSDS)
CAS Number - 54664-98-1
Class
Toxicity
Potential Health Effects (Warnings)
Ecological Toxicity
Crosslinked Polyurea
Polymer
(generic
term - actual chemical name unknown. According to Checkmate manufacturer
Suterra, polymethylene polyphenyl isocyanate is used to create the
encapsulation polymer, however they say that the PPI starter compound is used
up during the reaction [Renner 12/5/07])
CAS Number ñ information not
available
Crosslinked Polyurea
Polymer
is a component of the microcapsule shell. A DPR /OEHHA (Department of Pesticide
Regulation/Office of Environmental Health Hazard Assessment) consensus document
states that the polyurea shell biodegrades into urea. Research has linked urea
to the occurrence of harmful algal blooms (HABís), also known as red tides.
Following the spraying, a harmful algal bloom (red tide) described by a water
specialist with the Santa Cruz County Environmental Health Services as ìone of
the more dramatic ones in recent memoryî, hit the Monterey Bay (Ragan 11/13/07).
Class
Toxicity
Potential Health Effects (Warnings)
Ecological Toxicity
Polymethylene Polyphenyl
Isocyanate (PPI)
synonym ñ polymeric MDI (PMDI)
CAS Number ñ 9016-87-9
According
to a Suterra representative, PPI is used to create the encapsulation polymer
but reacts into different chemicals by the time the product is ready to use.
The company maintains that the PPI starter compound is used up during the
reaction (Abraham 10/18/07; Renner 12/5/07).
The MSDS sheet on this chemical states that ìthe product reacts with water at
the interface, forming CO2 and a solid insoluble product with high
melting point (polyurea). This reaction is accelerated by surfactants (e.g.
detergents) or by watersoluble solvents.î (Pagel
MSDS)
Polymethylene Polyphenyl
Isocyanate (PPI) is classified as harmful by inhalation, and as an irritant
to the eyes, respiratory system, and skin under European classification. MSDS
sheets warn against breathing the vapor or spray and caution individuals with
asthma and other known respiratory problems to avoid exposure to the product.
PPI is a known respiratory irritant associated with occupational asthma (Carlisle MSDS; HAZ-MAP; IRIS data sheet; Seguin et al. 1987). An EPA document from
IRIS (Integrated Risk Information System) indicates that ìexposure to
isocyanates is a leading cause of occupational asthma worldwideî. The document also cites a number of case
reports describing occupational asthma
and hypersensitivity pneumonitis, related to PMDI exposure (IRIS data sheet).
Following
the sprayings in Monterey and Santa Cruz Counties there were numerous reports
of respiratory symptoms including asthma, bronchial irritation, difficulty
breathing, shortness of breath, coughing and wheezing, and lung congestion.
Blurred vision, eye irritation, and skin rashes were also reported (HOPE 1/03/08).
Class
European Classification
WHMIS Classification (Canada)
WHMIS Health Effects Criteria Met by this Chemical (Canada)
Toxicity
Acute
toxicity - no available weight-of-the-evidence summary assessment (PAN Database).
Potential Health Effects (Warnings)
Ecological Toxicity
Butylated Hydroxytoluene
(BHT)
synonym ñ
2,6-Di-tert-butyl-p-cresol
CAS Number ñ 128-37-0
Butylated Hydroxytoluene
(BHT)
is classified as irritating to the eyes, respiratory system, and skin under
European classification. Allergic contact dermatitis and contact urticaria are
associated with exposure to BHT (HAZ-MAP).
It is currently listed as ìunclassifiableî in regard to itís carcinogenicity in
humans (due to limited human test data), however a variety of in vitro and animal studies have shown
it to have carcinogenic, tumorigenic, mutagenic, and teratogenic effects in
animals as well as in human cells (Sigma-Aldrich
MSDS). Studies have also confirmed BHT to have estrogenic activity (Miller et al. 2001; Wada et al. 2004)
and MSDS sheets state that chronic
exposure to BHT may cause reproductive and fetal effects (Acros MSDS).
Following
the sprayings in Monterey and Santa Cruz counties, several women reported
unusual menstrual symptoms including cramping, interruption of menstrual cycle,
and postmenopausal recommencement of the menstrual cycle (HOPE 1/03/08). A wide variety of respiratory symptoms, as well as
blurred vision and eye irritation, and skin rashes were also reported (HOPE 1/03/08).
Class
European Classification
WHMIS Classification (Canada)
Toxicity
Acute
toxicity ñ slight (PAN Database)
Potential Health Effects (Warnings)
Ecological Toxicity
Polyvinyl Alcohol (PVA)
CAS Number ñ 9002-89-5
Polyvinyl Alcohol is currently listed as
ìunclassifiableî in regard to itís carcinogenicity in humans (due to limited
human test data), however animal test data has shown it to be tumorigenic (Science Lab MSDS). Inhalation or
ingestion of PVA for a prolonged period of time may affect blood and
metabolism, and behavior (Science Lab
MSDS). Symptoms of PVA exposure include digestive tract irritation,
respiratory irritation or cough, and red/irritated eyes.
Following
the sprayings in Monterey and Santa Cruz counties there were numerous adverse
effects reported, including nausea, diarrhea, coughing, wheezing, and eye
irritation (HOPE 1/03/08).
Class
European Classification
WHMIS Classification (Canada)
Toxicity
Acute
toxicity ñ not acutely toxic (PAN
Database)
Potential Health Effects (Warnings)
Ecological Toxicity
Tricapryl Methyl
Ammonium Chloride
Tricaprylyl
Methyl Ammonium Chloride (as reported by CDFA)
synonym ñ methyl trioctyl
ammonium chloride
CAS Number - 5137-55-3
Tricapryl Methyl
Ammonium Chloride is classified as irritating to the skin and risk of serious
damage to eyes under European classification. Under Canadian classification it
is listed as ìmaterial causing immediate and serious toxic effectsî. MSDS
sheets warn that the substance is extremely hazardous in case of ingestion,
inhalation, skin contact, and eye contact and that it causes severe skin and
eye burns. Symptoms of inhalation exposure include irritation of the
respiratory tract, burning pain in the nose and throat, coughing, wheezing,
shortness of breath, and pulmonary edema. Symptoms of eye exposure include redness,
watering, itching, eye burns, and possible corneal injury. Symptoms of skin
exposure include inflammation characterized by itching, scaling, reddening, and
occasionally blistering.
Respiratory
symptoms reported following the sprayings in Monterey and Santa Cruz counties
included asthma, bronchial irritation, difficulty breathing, shortness of
breath, coughing and wheezing, sore throat, nasal congestion, sinus bleeding,
lung soreness, lung congestion, and chest pain and tightness. Intestinal pain,
diarrhea, nausea, blurred vision, eye irritation, and mild to severe skin
rashes were also reported (HOPE 1/03/08).
Tricapryl Methyl
Ammonium Chloride is classified as dangerous to the environment, and very
toxic to aquatic organisms under European classification. European labeling
warns against releasing the substance into the environment, cautioning that it
may cause long-term adverse effects in the aquatic environment. Also known by the trade
name Aliquat 336 (Acros MSDS; de Oliveira
& Bertazzoli 2007; Sigma-Aldrich MSDS) tricapryl methyl ammonium chloride is a surfactant (de Oliveira
& Bertazzoli 2007; Gyenge & Oloman 2001) which could change the
surface tension of water and affect zooplankton (Abraham 10/25/07).
Following
the sprayings in Monterey and Santa Cruz counties, hundreds of seabirds found
dead or dying in the Monterey Bay were found to be covered with a waxy
substance, which was determined by testing to be a surfactant protein.
According to SIMoN (Sanctuary Integrated Monitoring Network for the Monterey
Bay) surfactants act like a detergent to reduce the waterproofing ability of
feathers. This same protein has also been associated with the recent red tide
in the Monterey Bay (SIMoN website).
Class
European Classification
WHMIS Classification (Canada)
Toxicity
Potential Health Effects (Warnings)
Ecological Toxicity
Sodium Phosphate
(type
of sodium phosphate not specified, PAN database lists 7 compounds with sodium
phosphate in the name, could be any of the following or others)
Sodium
Phosphate (Disodium Phosphate): CAS
Number - 7558-79-4
Sodium
Acid Phosphate (Monosodium Phosphate): CAS
Number ñ 7558-80-7
Trisodium
Phosphate (Sodium Phosphate): CAS
Number ñ 7601-54-9
Sodium Phosphate (various types) -The exact type of
sodium phosphate used in the Checkmate formulas is currently unspecified, and
therefore itís not possible to give a precise description of potential adverse
effects. However, it would be expected that the range of exposure symptoms
would vary from mild to severe depending on the specific type of sodium
phosphate used in the formula. Symptoms of exposure to the various kinds of
sodium phosphate would range from mild to severe gastrointestinal effects
(varying degrees of gastrointestinal irritation, abdominal pain/cramping,
vomiting, diarrhea, nausea, abdominal discomfort, burning sensation), mild to
severe respiratory symptoms (throat irritation, respiratory tract/mucous
membrane irritation, coughing, sneezing, choking, difficulty breathing, pulmonary
edema), mild to severe effects on the eye (irritation, redness, pain, conjunctival
edema and corneal clouding [later cataract formation could occur], eye burns),
and mild to severe skin symptoms (skin/mucous membrane irritation, dermatitis, local
skin destruction, burning pain, skin burns, blisters), depending on the
specific type of sodium phosphate to which an individual was exposed.
Sodium Phosphate is a pH buffer, which
could lead to algal blooms if runoff concentrations are high enough (Abraham 10/25/07). Increased phosphate
levels are known to be a contributing factor in the occurrence of red tides (Feyzioglu
& Ogut 2006; Wikipedia).
Following
the sprayings in Monterey and Santa Cruz counties, a harmful algal bloom (red
tide) described by a water specialist with the Santa Cruz County Environmental
Health Services as ìone of the more dramatic ones in recent memoryî, hit the
Monterey Bay (Ragan 11/13/07).
Class
European Classification
WHMIS Classification (Canada)
Toxicity
Potential Health Effects (Warnings)
Ecological Toxicity
Ammonium Phosphate
(type
of ammonium phosphate not specified, could be either of the following)
Monoammonium
Phosphate: CAS Number ñ
7722-76-1
Diammonium
Phosphate: CAS Number ñ
7783-28-0
Ammonium Phosphate - The exact type of
ammonium phosphate used in the Checkmate formulas is currently unspecified, and
could be either monoammonium phosphate
or diammonium phosphate. Monoammonium is not listed under
European classification however diammonium
is classified as irritating to the eyes, respiratory system, & skin.
Symptoms
of inhalation exposure include:
Symptoms
of eye exposure include:
Symptoms
of skin exposure include:
Following
the sprayings in Monterey and Santa Cruz counties there were numerous reports
of respiratory symptoms including asthma, bronchial irritation, difficulty
breathing, shortness of breath, coughing and wheezing, lung
congestion/soreness, and chest pain/tightness. Nausea, blurred vision, eye
irritation, and skin rashes were also reported (HOPE 1/03/08).
Ammonium Phosphate is a pH buffer, which could lead to algal blooms if runoff
concentrations are high enough (Abraham
10/25/07). Increased phosphate levels are known to be a contributing factor
in the occurrence of red tides (Feyzioglu & Ogut 2006; Wikipedia).
Ammonium phosphate has also been implicated in fish die-offs, including one
that killed 20,000 fish following the accidental dropping of an ammonium
phosphate based fire retardant in an Oregon river (Barnard 2007).
Following
the sprayings in Monterey and Santa Cruz counties, a harmful algal bloom (red
tide) described by a water specialist with the Santa Cruz County Environmental
Health Services as ìone of the more dramatic ones in recent memoryî, hit the
Monterey Bay (Ragan 11/13/07).Ý
Class
European Classification
WHMIS Classification (Canada)
Toxicity
Acute
toxicity ñ
Acute
oral toxicity LD50
Potential Health Effects (Warnings)
Ecological Toxicity
1,2-benzisothiazolin-3-one
1,2-benzisothiozoli-3-one
(as reported by CDFA)
synonym ñ BIT (trade name)
CAS Number -2634-33-5
1,2-benzisothiazolin-3-one is a preservative
associated with occupational asthma. Multiple accounts of occupational
dermatitis have also been reported with exposure to the chemical.
Under
European classification it is classified as irritating to the skin and risk of
serious eye damage. Canadian classification lists it as causing skin
sensitization in humans. BIT is a known irritant at the 1% level, and studies
have confirmed the irritant effect even down to the 0.1% level. Individuals
with chronic pulmonary or asthmatic conditions or chronic skin conditions are
warned to avoid repetitive exposure to the chemical. According to data compiled
by OSHA it has been shown to cause genetic damage in human cells. Symptoms of
exposure include respiratory tract and mucous membrane irritation, severe eye
irritation, skin irritation, and dermatitis.
Following
the sprayings in Monterey and Santa Cruz counties a wide variety of mild to
serious respiratory symptoms, as well as eye irritation and skin rashes were
reported (HOPE 1/03/08).
1,2-benzisothiazolin-3-one
is
classified as dangerous to the environment and very toxic to aquatic organisms
under European classification. European labeling warns against releasing the
substance into the environment. It is classified as ìhazardous wasteî under the
European Waste Catalogue Ordinance. It is classified as a ìhazard to watersî
under the European Administrative Regulation of Substances Hazardous to Water,
and MSDS sheets for the chemical warn that water polluted with the substance
should not be discharged into sewage or natural areas. EPA documents on the
chemical state that it is highly toxic to green algae and other invertebrate
species. The EPA also states that if it is used outdoors, BIT may possibly move
with soil during rainfall events and potentially reach surface waters. The
Santa Cruz county sprayings on November 8th & 9th
were followed by a significant rainfall event on November 10th &
11th (Weather Underground
website).
Class
European Classification
WHMIS Classification (Canada)
Toxicity
Acute
toxicity - no available weight-of-the-evidence summary assessment (PAN Database).
Potential Health Effects (Warnings)
Ecological Toxicity
2-hydroxy-4-n-octyl
benzophenone
2-hydroxy-4-n-octyloxybenzophenone
(as reported by CDFA)
synonym ñ benzophenone 12
CAS Number ñ 1843-05-6
2-hydroxy-4-n-octyl
benzophenone is a UV light absorber of
unknown health impact, however related compounds in the benzophenone family
have been shown to form estrogenic photoproducts, upon exposure to UV or
sunlight (Hayashi et al. 2006). Under
European classification it is classified as irritant, as may cause
sensitization by skin contact, and as irritating to eyes, respiratory system
and skin. Symptoms of exposure include reddening and irritation of the skin and
eyes, mucous membrane irritation, and upper respiratory tract irritation.
Following
the sprayings in Monterey and Santa Cruz counties, several women reported
unusual menstrual symptoms including cramping, interruption of menstrual cycle,
and postmenopausal recommencement of the menstrual cycle (HOPE 1/03/08), which would be consistent with exposure to endocrine
disrupting/estrogenic compounds. A wide variety of mild to serious respiratory symptoms,
as well as eye irritation and skin rashes were also reported.
2-hydroxy-4-n-octyl
benzophenone is classified as harmful to aquatic organisms and may cause
long-term adverse effects in the aquatic environment, under European
classification. European labeling warns against releasing the substance into
the environment. It is classified as hazardous by OSHA.
Class
European Classification
Canadian WHMIS
Classification
Toxicity
Acute
toxicity - no available weight-of-the-evidence summary assessment (PAN Database).
Mammalian
toxicity
Potential Health Effects (Warnings)
Ecological Toxicity
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