Disclaimer: These guidelines were developed under contract using generally accepted secondary sources. The protocol used by the contractor for surveying these data sources was developed by the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA), and the Department of Energy (DOE). The information contained in these guidelines is intended for reference purposes only. None of the agencies have conducted a comprehensive check of the information and data contained in these sources. It provides a summary of information about chemicals that workers may be exposed to in their workplaces. The secondary sources used for supplements 111 and 1V were published before 1992 and 1993, respectively, and for the remainder of the guidelines the secondary sources used were published before September 1996. This information may be superseded by new developments in the field of industrial hygiene. Therefore readers are advised to determine whether new information is available.
OCCUPATIONAL SAFETY AND HEALTH GUIDELINE FOR ARSENIC, ORGANIC COMPOUNDS (as
As)
INTRODUCTION
This guideline summarizes pertinent information about the organic compounds
of arsenic for workers and employers as well as for physicians, industrial
hygienists, and other occupational safety and health professionals who may
need such information to conduct effective occupational safety and health
programs. Recommendations may be superseded by new developments in these
fields; readers are therefore advised to regard these recommendations as
general guidelines and to determine whether new information is available.
APPLICABILITY
The general guidelines contained in this document apply to all of the
organic compounds of arsenic. Examples of such compounds include arsanilic
acid and cacodylic acid. For illustrative purposes, the physical and
chemical properties of these organic arsenic compounds are presented below.
SUBSTANCE IDENTIFICATION
Arsanilic acid
* Formula
C(6)H(8)AsNo(3)
* Structure
(For Structure, see paper copy)
* Synonyms
p-aminobenzenearsonic acid, aminophenylarsine acid, atoxylic acid,
antoxylic acid, p-arsanilic acid
* Identifiers
1. CAS No.: 98-50-0
2. RTECS No.: CF7875000
3. Specific DOT number: None
4. Specific DOT label: None
* Appearance and odor
Arsanilic acid is a white crystalline powder that is essentially
odorless. It may also be in the form of needles.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 217
2. Boiling point: Decomposes.
3. Specific gravity: Data not available.
4. Vapor density: Data not available.
5. Melting point: 232 degrees C (450 degrees F)
6. Vapor pressure: Data not available.
7. Solubility: Very soluble in hot water; slightly soluble in cold water,
alcohol, and acetic acid; insoluble in acetone, benzene, ether, and
chloroform.
8. Evaporation rate: Data not available.
Cacodylic acid
* Formula
C(2)H(7)AsO(2)
* Structure
((CH(3))(2)AsOOH)
* Synonyms
Dimethylarsinic acid, hydroxydimethylarsine oxide, phytar, DMAA,
chexmate, ansar
* Identifiers
1. CAS No.: 75-60-5
2. RTECS No.: CH7525000
3. DOT UN number: 1572 53
4. DOT label: Poison
* Appearance and odor
Cacodylic acid is a colorless, odorless, and hygroscopic crystalline
solid. It is also commercially available in the form of soluble
concentrates. Water solutions of cacodylic acid are sometimes dyed
blue.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 138.01
2. Boiling point: Data not available.
3. Specific gravity: Data not available.
4. Vapor density: Data not available.
5. Melting point: 195 to 196 degrees C (383 to 385 degrees F)
6. Vapor pressure: Data not available.
7. Solubility: Very soluble in alcohol; soluble in water and acetic acid;
practically insoluble in ether.
8. Evaporation rate: Data not available.
* Reactivity
1. Conditions contributing to instability: Vary depending on the specific
organic arsenic compound.
2. Incompatibilities: Vary depending on the specific organic arsenic
compound. Arsenic is incompatible with oxidizers such as perchlorates,
peroxides, permanganates, chlorates, or nitrates, and strong acids such as
hydrochloric, sulfuric, or nitric.
3. Hazardous decomposition products: Vary depending on the specific
organic arsenic compound.
4. Special precautions: Vary depending on the specific organic arsenic
compound.
* Flammability
The flammability of each organic arsenic compound may vary. Arsenic
dust is a slight explosive hazard when exposed to flame.
The National Fire Protection Association has not assigned a
flammability rating to arsenic, cacodylic acid, or arsanilic acid.
1. Flash point: Data not available.
2. Autoignition temperature: Data not available.
3. Flammable limits in air: Data not available.
4. Extinguishant: Use an extinguishant that is suitable for the materials
involved in the surrounding fire.
Fires involving organic arsenic compounds should be fought upwind
from the maximum distance possible. Isolate the hazard area and deny access
to unnecessary personnel. Firefighters should wear a full set of protective
clothing and self-contained breathing apparatus when fighting fires involving
arsenic, organic compounds.
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for organic compounds arsenic (as As) is 0.5
milligrams per cubic meter (mg/m(3)) of air as an 8-hour time-weighted
average (TWA) concentration [29 CFR 1910.1000, Table Z-1].
* NIOSH REL
* The National Institute for Occupational Safety and Health has not
established a recommended exposure limit for arsenic, organic compounds.
* ACGIH TLV
The American Conference of Governmental Industrial Hygienists
(ACGIH) has not assigned organic arsenic compounds a threshold limit
value.
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to arsenic, organic compounds can occur through inhalation,
ingestion, eye or skin contact, and absorption through the skin.
* Summary of toxicology
1. Effects on Animals: Organic arsenic compounds can be irritants,
reproductive toxins, or kidney toxins in experimental animals. The toxicity
of arsenic compounds vary greatly with the chemical form and oxidation state
of the specific chemical involved. Oral LD(50) values in animal studies range
from 10 to 2,800 mg/kg, depending on the compound [IARC 1980]. The oral
LD(50) in rats for arsanilic acid and cacodylic acid are 216 and 1,350 mg/kg,
respectively [Sax and Lewis 1989; Parmeggiani 1983]. Rats receiving oral
doses of 2,260 mg/kg of cacodylic acid over a period of 4 weeks showed signs
of kidney, ureter, and bladder effects as well as weight loss [NIOSH 1995].
Long-term dietary feeding of 50 ppm monosodium methanearsonic acid
(equivalent to a dose of 1.5 mg arsenic per kilogram body weight) of rabbits
produced toxic hepatitis [IARC 1987]. In mice, oral doses of 3 gm/kg of
cacodylic acid on days 8 through 12 of the pregnancy produced effects on the
newborns (effects not further specified) [NIOSH 1995]. A study on the
developmental effects of cacodylic acid in mice reported positive results
following oral administration a 1,600 mg/kg dose on the eighth day of
pregnancy [NIOSH 1995]. The effects noted were developmental abnormalities
involving the musculoskeletal system. The International Agency for Research
on Cancer (IARC) reviewed the data on the carcinogenicity of organic
arsenicals to animals and determined that inadequate data was available to
make firm conclusions regarding the carcinogenicity of these compounds.
Arsenic was found to have limited evidence for carcinogenicity to animals
[IARC 1987].
2. Effects on Humans: Arsenic compounds are irritants, systemic toxins,
and carcinogens in humans. Acute exposures to arsenic compounds are
considered rare in industry; most poisonings are the result of ingestion of
contaminated food and drinks [Hathaway et al. 1991]. The trivalent arsenic
compounds are the most toxic to humans. Initial responses to acute poisoning
include burning of the lips, constriction of the throat, and dysphagia
[Hathaway et al. 1991]. This is followed by excruciating pain in the
abdominal region, severe nausea, vomiting, and diarrhea. Toxic effects on
the liver, blood-forming organs, both central and peripheral nervous systems,
and the cardiovascular system may also occur. Convulsions, coma, and death
may follow within 24 hours of severe poisonings [Hathaway et al. 1991].
Acute inhalation exposures to arsenic compounds may result in damage to the
mucous membranes of the respiratory system [Parmeggiani 1983]. Severe
irritation of the nasal mucosae, larynx, and bronchi have been observed
following exposures. In addition, exposed skin may become irritated; cases
of dermatitis have been reported following dermal contact with arsenic
compounds [Parmeggiani 1983]. Conjunctivitis, visual disturbances,
hyperpigmentation of the skin, and perforation of the nasal septum have been
described in the literature [Hathaway et al. 1991]. Chronic exposure causes
damage to the nervous system, cardiovascular system, and liver [Parmeggiani
1983]. Anemia and leukocytopenia have been reported to occur following
chronic exposures to arsenic compounds [Parmeggiani 1983]. Cancers of the
skin, lungs, larynx, lymphoid system, and viscera have been identified as
potential responses to arsenic poisoning [Hathaway et al. 1991]. IARC has
reviewed the available data and considers arsenic to be a Group 1 carcinogen
with sufficient evidence of carcinogenicity in humans [IARC 1987].
* Signs and symptoms of exposure
1. Acute exposure: Acute exposures to organic arsenic compounds by
ingestion may result in burning lips, throat constriction, abdominal pain,
dysphagia, nausea, vomiting, diarrhea, convulsions, coma, and death.
Irritation of the respiratory tract, skin, and eyes may result from
inhalation exposures.
2. Chronic exposure: Chronic exposure to organic arsenic compounds may
result in dermatitis, anemia, leukocytopenia, or the effects associated with
several forms of cancer.
EMERGENCY MEDICAL PROCEDURES
* Emergency medical procedures: [NIOSH to supply]
5. Rescue: Remove an incapacitated worker from further exposure and
implement appropriate emergency procedures (e.g., those listed on the
Material Safety Data Sheet required by OSHA's Hazard Communication Standard
[29 CFR 1910.1200]). All workers should be familiar with emergency
procedures, the location and proper use of emergency equipment, and methods
of protecting themselves during rescue operations.
EXPOSURE SOURCES AND CONTROL METHODS
The following operations may involve organic arsenic compounds and lead to
worker exposures to these substances:
* The manufacture and transportation of organic arsenic compounds *
Use as herbicides, pesticides, and defoliants * Use as additives for feed
and drinking water for animals * Use as a preharvest desiccant, sugarcane
ripener, soil sterilant, and for timber thinning * Use in warfare
Methods that are effective in controlling worker exposures to arsenic,
organic compounds, depending on the feasibility of implementation, are as
follows:
* Process enclosure * Local exhaust ventilation * General dilution
ventilation * Personal protective equipment
Workers responding to a release or potential release of a hazardous
substance must be protected as required by paragraph (q) of OSHA's Hazardous
Waste Operations and Emergency Response Standard [29 CFR 1910.120].
Good sources of information about control methods are as follows:
1. ACGIH [1992]. Industrial ventilation--a manual of recommended
practice. 21st ed. Cincinnati, OH: American Conference of Governmental
Industrial Hygienists.
2. Burton DJ [1986]. Industrial ventilation--a self study companion.
Cincinnati, OH: American Conference of Governmental Industrial Hygienists.
3. Alden JL, Kane JM [1982]. Design of industrial ventilation systems.
New York, NY: Industrial Press, Inc.
4. Wadden RA, Scheff PA [1987]. Engineering design for control of
workplace hazards. New York, NY: McGraw-Hill.
5. Plog BA [1988]. Fundamentals of industrial hygiene. Chicago, IL:
National Safety Council.
MEDICAL SURVEILLANCE
OSHA is currently developing requirements for medical surveillance. When
these requirements are promulgated, readers should refer to them for
additional information and to determine whether employers whose employees are
exposed to arsenic, organic compounds are required to implement medical
surveillance procedures.
* Medical Screening
Workers who may be exposed to chemical hazards should be monitored
in a systematic program of medical surveillance that is intended to prevent
occupational injury and disease. The program should include education of
employers and workers about work-related hazards, early detection of adverse
health effects, and referral of workers for diagnosis and treatment. The
occurrence of disease or other work-related adverse health effects should
prompt immediate evaluation of primary preventive measures (e.g., industrial
hygiene monitoring, engineering controls, and personal protective equipment).
A medical surveillance program is intended to supplement, not replace, such
measures. To detect and control work-related health effects, medical
evaluations should be performed (1) before job placement, (2) periodically
during the term of employment, and (3) at the time of job transfer or
termination.
* Preplacement medical evaluation
Before a worker is placed in a job with a potential for exposure to
organic arsenic compounds, a licensed health care professional should
evaluate and document the worker's baseline health status with thorough
medical, environmental, and occupational histories, a physical examination,
and physiologic and laboratory tests appropriate for the anticipated
occupational risks. These should concentrate on the function and integrity
of the eyes, skin, respiratory system, central and peripheral nervous
systems, and liver. Medical surveillance for respiratory disease should be
conducted using the principles and methods recommended by the American
Thoracic Society.
A preplacement medical evaluation is recommended to assess medical
conditions that may be aggravated or may result in increased risk when a
worker is exposed to organic arsenic compounds at or below the prescribed
exposure limit. The health care professional should consider the probable
frequency, intensity, and duration of exposure as well as the nature and
degree of any applicable medical condition. Such conditions (which should not
be regarded as absolute contraindications to job placement) include a history
and other findings consistent with diseases of the eyes, skin, respiratory
system, central and peripheral nervous systems, or liver.
* Periodic medical evaluations
Occupational health interviews and physical examinations should be
performed at regular intervals during the employment period, as mandated by
any applicable Federal, State, or local standard. Where no standard exists
and the hazard is minimal, evaluations should be conducted every 3 to 5 years
or as frequently as recommended by an experienced occupational health
physician. Additional examinations may be necessary if a worker develops
symptoms attributable to arsenic, organic compounds exposure. The
interviews, examinations, and medical screening tests should focus on
identifying the adverse effects of organic arsenic compounds on the eyes,
skin, respiratory system, central and peripheral nervous systems, or liver.
Current health status should be compared with the baseline health status of
the individual worker or with expected values for a suitable reference
population.
* Termination medical evaluations
The medical, environmental, and occupational history interviews, the
physical examination, and selected physiologic or laboratory tests that were
conducted at the time of placement should be repeated at the time of job
transfer or termination to determine the worker's medical status at the end
of his or her employment. Any changes in the worker's health status should
be compared with those expected for a suitable reference population. Because
occupational exposure to organic arsenic compounds may cause diseases with
prolonged latent periods, the need for medical surveillance may extend well
beyond the termination of employment.
* Biological monitoring
Biological monitoring involves sampling and analyzing body tissues
or fluids to provide an index of exposure to a toxic substance or metabolite.
Urine levels of arsenic can be measured at the end of the workweek. A
biological exposure index (BEI) of 50 micrograms/gram of creatinine should be
used to evaluate exposures to organic arsenic compounds.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne organic arsenic compounds
(as As) is made using a PTFE polyethylene-backed membrane filter, 1 micron
pore size. Samples are collected at a maximum flow rate of 2.0 liters/minute
until a minimum collection volume of 450 liters (or a maximum volume of 960
liters) is reached. Analysis is conducted by ion chromatography using atomic
absorption spectroscopy (IC-AAS). This method is described in the OSHA
Computerized Information System [OSHA 1994] and is not yet validated. This
method is also found in the NIOSH Manual of Analytical Methods (Method No.
5502) [NIOSH 1994].
PERSONAL HYGIENE PROCEDURES
If organic arsenic compounds contacts the skin, workers should flush the
affected areas immediately with plenty of water, followed by washing with
large amounts of soap and water.
Clothing contaminated with organic arsenic compounds should be removed
immediately, and provisions should be made for the safe removal of the
chemical from the clothing. Persons laundering the clothes should be
informed of the hazardous properties of organic arsenic compounds,
particularly their potential for causing irritation, and nevous system
effects.
A worker who handles organic arsenic compounds should thoroughly wash hands,
forearms, and face with soap and water before eating, using tobacco products,
using toilet facilities, applying cosmetics, or taking medication.
Workers should not eat, drink, use tobacco products, apply cosmetics, or
take medication in areas where organic arsenic compounds or a solution
containing organic arsenic compounds is handled, processed, or stored.
STORAGE
Organic arsenic compounds should be stored in a cool, dry, well-ventilated
area in tightly sealed containers that are labeled in accordance with OSHA's
Hazard Communication Standard [29 CFR 1910.1200]. Containers of organic
arsenic compounds should be protected from physical damage and should be
stored separately from oxidizers such as perchlorates, peroxides,
permanganates, chlorates, or nitrates, and strong acids such as hydrochloric,
sulfuric, or nitric. Specific organic arsenic compounds may have other
storage requirements which should be evaluated prior to storage.
SPILLS AND LEAKS
In the event of a spill or leak involving organic arsenic compounds, persons
not wearing protective equipment and clothing should be restricted from
contaminated areas until cleanup has been completed. The following steps
should be undertaken following a spill or leak:
1. Do not touch the spilled material; stop the leak if it is possible to
do so without risk.
2. Notify safety personnel.
3. Ventilate the area of the spill or leak.
4. For small dry spills, collect the spilled material in the most
convenient and safe manner possible and deposit it into containers for later
disposal or reclamation.
5. For small liquid spills, take up with sand or other noncombustible
absorbent material and place into closed containers for later disposal.
6. For large liquid spills, build dikes far ahead of the spill to contain
the arsenic, organic compounds for later reclamation or disposal.
SPECIAL REQUIREMENTS
U.S. Environmental Protection Agency (EPA) requirements for emergency
planning, reportable quantities of hazardous releases, community
right-to-know, and hazardous waste management may change over time. Users are
therefore advised to determine periodically whether new information is
available. In addition, the requirements for specific organic arsenic
compounds vary and it is therefore advisable to check the published
requirements for the specific compound in use. An example compound
(cacodylic acid) is used for the section below only to provide a
representative listing of the EPA requirements.
* Emergency planning requirements
Cacodylic acid is not subject to EPA emergency planning requirements
under the Superfund Amendments and Reauthorization Act (SARA) (Title III) in
42 USC 11022.
* Reportable quantity requirements for hazardous releases
A hazardous substance release is defined by EPA as any spilling,
leaking, pumping, pouring, emitting, emptying, discharging, injecting,
escaping, leaching, dumping, or disposing into the environment (including the
abandonment or discarding of contaminated containers) of hazardous
substances. In the event of a release that is above the reportable quantity
for that chemical, employers are required to notify the proper Federal,
State, and local authorities [40 CFR 355.40].
The reportable quantity of cacodylic acid is 1 pound. If an amount
equal to or greater than this quantity is released within a 24-hour period in
a manner that will expose persons outside the facility, employers are
required to do the following:
- Notify the National Response Center immediately at (800)
424-8802 or at (202) 426-2675 in Washington, D.C. [40 CFR 302.6].
* Community right-to-know requirements
Employers who own or operate facilities in SIC codes 20 to 39 that
employ 10 or more workers and that manufacture 25,000 pounds or more of
cacodylic acid per calendar year or otherwise use 10,000 pounds or more of
cacodylic acid per calendar year are required by EPA [40 CFR Part 372.30] to
submit a Toxic Chemical Release Inventory form (Form R) to EPA reporting the
amount of cacodylic acid emitted or released from their facility
annually.
* Hazardous waste management requirements
EPA considers a waste to be hazardous if it exhibits any of the
following characteristics: ignitability, corrosivity, reactivity, or
toxicity as defined in 40 CFR 261.21-261.24. Under the Resource Conservation
and Recovery Act (RCRA) [40 USC 6901 et seq.], EPA has specifically listed
many chemical wastes as hazardous. Cacodylic acid is listed as a hazardous
waste under RCRA and has been assigned EPA Hazardous Waste No. U136. This
substance has been banned from land disposal.
Providing detailed information about the removal and disposal of
specific chemicals is beyond the scope of this guideline. The U.S.
Department of Transportation, EPA, and State and local regulations should be
followed to ensure that removal, transport, and disposal of this substance
are conducted in accordance with existing regulations. To be certain that
chemical waste disposal meets EPA regulatory requirements, employers should
address any questions to the RCRA hotline at (703) 412-9810 (in the
Washington, D.C. area) or toll-free at (800) 424-9346 (outside Washington,
D.C.). In addition, relevant State and local authorities should be contacted
for information on any requirements they may have for the waste removal and
disposal of these substances.
RESPIRATORY PROTECTION
* Conditions for respirator use
Good industrial hygiene practice requires that engineering controls
be used where feasible to reduce workplace concentrations of hazardous
materials to the prescribed exposure limit. However, some situations may
require the use of respirators to control exposure. Respirators must be worn
if the ambient concentration of arsenic, organic compounds exceeds prescribed
exposure limits. Respirators may be used (1) before engineering controls
have been installed, (2) during work operations such as maintenance or repair
activities that involve unknown exposures, (3) during operations that require
entry into tanks or closed vessels, and (4) during emergencies. Workers
should only use respirators that have been approved by NIOSH and the Mine
Safety and Health Administration (MSHA).
* Respiratory protection program
Employers should institute a complete respiratory protection program
that, at a minimum, complies with the requirements of OSHA's Respiratory
Protection Standard [29 CFR 1910.134]. Such a program must include
respirator selection, an evaluation of the worker's ability to perform the
work while wearing a respirator, the regular training of personnel,
respirator fit testing, periodic workplace monitoring, and regular respirator
maintenance, inspection, and cleaning. The implementation of an adequate
respiratory protection program (including selection of the correct
respirator) requires that a knowledgeable person be in charge of the program
and that the program be evaluated regularly. For additional information on
the selection and use of respirators and on the medical screening of
respirator users, consult the latest edition of the NIOSH Respirator Decision
Logic [NIOSH 1987b] and the NIOSH Guide to Industrial Respiratory Protection
[NIOSH 1987a].
PERSONAL PROTECTIVE EQUIPMENT
Workers should use appropriate personal protective clothing and equipment
that must be carefully selected, used, and maintained to be effective in
preventing skin contact with organic arsenic compounds. The selection of the
appropriate personal protective equipment (PPE) (e.g., gloves, sleeves,
encapsulating suits) should be based on the extent of the worker's potential
exposure to organic arsenic compounds. There are no published reports on the
resistance of various materials to permeation by organic arsenic compounds.
However, readers are advised to inquire about information regarding
protection against exposure from the specific organic arsenic compounds in
use.
To evaluate the use of PPE materials with organic arsenic compounds, users
should consult the best available performance data and manufacturers'
recommendations. Significant differences have been demonstrated in the
chemical resistance of generically similar PPE materials (e.g., butyl)
produced by different manufacturers. In addition, the chemical resistance of
a mixture may be significantly different from that of any of its neat
components.
Any chemical-resistant clothing that is used should be periodically
evaluated to determine its effectiveness in preventing dermal contact. Safety
showers and eye wash stations should be located close to operations that
involve arsenic, organic compounds.
Splash-proof chemical safety goggles or face shields (20 to 30 cm long,
minimum) should be worn during any operation in which a solvent, caustic, or
other toxic substance may be splashed into the eyes.
In addition to the possible need for wearing protective outer apparel (e.g.,
aprons, encapsulating suits), workers should wear work uniforms, coveralls,
or similar full-body coverings that are laundered each day. Employers should
provide lockers or other closed areas to store work and street clothing
separately. Employers should collect work clothing at the end of each work
shift and provide for its laundering. Laundry personnel should be informed
about the potential hazards of handling contaminated clothing and instructed
about measures to minimize their health risk.
Protective clothing should be kept free of oil and grease and should be
inspected and maintained regularly to preserve its effectiveness.
Protective clothing may interfere with the body's heat dissipation,
especially during hot weather or during work in hot or poorly ventilated work
environments.
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