HYDRAZINE: Nuclear Waste
CASRN: 302-01-2
Hydrazine is employed during nuclear
power plants start-up operations to ensure
that oxygen is not present to induce the stress-corrosion reaction
Cleanup Methods :
Hydrazine removal from nuclear power plant
wastewater using activated carbon and copper ion catalysts.
Probable Routes of
Human Exposure :
An industrial hygiene assessment of the extent of exposure to hydrazine
compounds was carried out due to the growing number of such compounds shown to
be animal carcinogens in laboratory studies. The report summarizes production
and uses of hydrazine compounds, the toxic effects of such compounds, relevant
exposure standards, sampling and analytical methods relevant to exposure
assessment, and observations made during surveys conducted at eight facilities
in the United States where these compounds were either prepared or used. The
sites visited for the survey were of four basic types: those which used
hydrazine compounds as propellants, those which manufactured the compounds,
those which used hydrazine as an aircraft emergency power unit
fuel, or sites where hydrazine was used in boiler water treatment. Personal
exposures measured were generally within the range from below the limit of
detection to 1.0 ppm as an 8 hour time weighted average. The OSHA permissible
exposure limits for the hydrazine compounds of interest ranged from 0.5 to 5 ppm.
The number of workers exposed was found to be low. Large scale propellant and
emergency jet power unit usage was relatively new, and the
manufacturing methods had not been used until recently. /Data indicated/ that
the accumulated person years of exposure are relatively low; it is unlikely that
suitable cohorts exist for retrospective exposure studies.
Major Uses :
Reducing agent for many transition metals and some nonmetals (arsenic, selenium,
tellurium), as well as uranium and plutonium; nuclear fuel
reprocessing; redox reaction; polymerization catalyst; short stopping agent;
component of high-energy fuels; corrosion inhibitor in boiler feedwater &
reactor cooling water; wastewater treatment; electrolytic plating of metals on
glass & plastics; rocket propellent; manufacture of drugs & agricultural
chemicals (maleic hydrazide); scavenger for gases; fuel cells; blowing agent.
General Manufacturing
Information :
A century after its discovery, hydrazine is still difficult to synthesize,
mainly for thermodynamic reasons. Most hydrazine is produced by variations of
the Raschig process, the oxidation of ammonia by hypochlorite. However, the new plants
built since 1980 are based on the PCUK process, which uses hydrogen peroxide as
oxidant.
MORE ABOUT HEALTH EFFECTS
Evidence for Carcinogenicity:
Evaluation: There is inadequate evidence in humans for the carcinogenicity of
hydrazine. There is sufficient evidence in experimental animals for the
carcinogenicity of hydrazine. Overall evaluation: Hydrazine is possibly
carcinogenic to humans (Group 2B).
CLASSIFICATION: B2; probable human carcinogen. BASIS FOR CLASSIFICATION: Tumors
have been induced in mice, rats and hamsters following oral, inhalation or
intraperitoneal administration of hydrazine and hydrazine sulfate. Hydrazine is
mutagenic in numerous assays. HUMAN CARCINOGENICITY DATA: Inadequate. ANIMAL
CARCINOGENICITY DATA: Sufficient.
A3; Confirmed animal carcinogen with unknon relevance to humans.
Human Toxicity Excerpts:
/SIGNS AND SYMPTOMS/ Skin contact with anhydrous hydrazine leads to caustic-like
burns and dissolves hair ...
/SIGNS AND SYMPTOMS/ The liquid is corrosive, producing penetrating burns &
severe dermatitis.
/SIGNS AND SYMPTOMS/ In cases of acute human poisoning, vomiting, severe
irritation of the respiratory tract with the development of pulmonary edema,
central nervous system depression, and hepatic and renal damage have been
reported.
/SIGNS AND SYMPTOMS/ Toxic effects of hydrazine /routes not specified/ include
conjunctivitis, pulmonary edema, anemia (hemolytic), ataxia, convulsions, kidney
toxicity, and liver toxicity. /from table/
/SIGNS AND SYMPTOMS/ Skin and eye irritation has occurred in humans, and
allergic contact dermatitis has been reported. No systemic responses were
described in any of these reported exposures. Several incidents of systemic
poisoning have been reported, mainly showing effects on the CNS, respiratory
system, and stomach. Vomiting, weakness, and irregular breathing, with recovery
in 5 days, occurred following ingestion of 20-30 mL of a 6% aqueous solution.
/SIGNS AND SYMPTOMS/ Exposure to the eyes can produce temporary blindness.
Liquid splashes to the eyes can produce corneal injury and burns. Liquid
splashes to the skin can also produce severe burns. Hydrazine can also produce
dermatitis and skin sensitization.
/CASE REPORTS/ An occupational exposure (both skin contact and inhalation) at an
unknown concentration over a 6-month period produced conjunctivitis, tremor, and
lethargy. Lung and liver damage occurred, and the individual died 21 days after
the last exposure.
/CASE REPORTS/ A case of residual neurobehavioral impairment possibly related to
occupational exposure to hydrazine was described. A 38 year old Israeli male was
treated for repeated complaints of sore throat and colds. His wife noticed that
he had difficulties remembering things that she had asked him to do. He became
impotent. He had similar difficulties at work in performing tasks that he had
previously done effortlessly. He had been employed as a water technician at a
hospital for 7 years. His job activities involved monitoring water quality,
adding hydrazine mixtures when necessary, and overseeing the workings of the
hospital pumping system. He had intense intermittent inhalation and skin
exposure to hydrazine while mixing and pouring hydrazine preparations, and
almost constant inhalation exposure to hydrazine vapors in his workplace. He
developed thrombocytopenia which was treated with steroids. He returned briefly
to work, but had to be discharged because of recurring episodes of colds and
malaise. His memory and concentration problems persisted and he became unable to
work or understand and remember material he had read. Neuropsychological testing
revealed deficits in specific task performance, memory, concentration, learning,
judgment, and abstraction and mood problems. A computed tomographic examination
showed no signs of brain damage. Over the next 4 years the patient showed a
gradual improvement in his general well being, mood status, and ability to carry
out some tasks. He was unable to hold down jobs or perform tasks commensurate
with his previous level of technical and organizational skills. He eventually
found work as a part time gardener. /It was/ concluded that exposure to
hydrazine during his work as a water technician is the most likely explanation
for the neurobehavioral impairment. The case illustrates the need to be aware
that exposure to hydrazine can cause neurobehavioral problems as sequelae.
/CASE REPORTS/ A case of an epithelioid sarcoma developing in the thumb of a
patient after repeated exposure to hydrazine fuel /is presented/. /The authors/
hypothesize that the epithelioid sarcoma is a consequence of cutaneous exposure
to hydrazine fuel.
/CASE REPORTS/ One person accidentally drank "between a mouthful and a
cupful." He immediately vomited and lost consciousness. Hospitalized, he
was flushed, but afebrile, unconscious, and vomiting; pupils were dilated but
central and light reactive. Within 12 hr vomiting ceased ...and he was
sporadically violent. Later, his memory and voluntary movements were normal but
he was ataxic and unable to write. There was lateral nystagmus to the right and
his ability to sense vibration was lost.
/CASE REPORTS/ ...Worker handled hydrazine hydrate once a week for 6 months.
Early signs were lethargy, conjunctivitis, and tremors. On last day of exposure
he developed fever, vomiting, and diarrhea. Later he developed abdominal
pains... and became incoherent. His abdomen was enlarged and liver was palpable
and tender. There was fluid in chest cavity and lung shadowing. Bilirubin and
creatinine levels were increased. ...He ...died 20 days after the last exposure
to hydrazine. Autopsy revealed severe tracheitis, bronchitis, lungs filled with
exudate, enlarged kidneys with... necrosis and granular cytoplasmic
degeneration, and enlarged heart with muscle fiber degeneration and hyperemia.
/Hydrazine hydrate/
/CASE REPORTS/ Choroidal melanoma was observed in one man who had been exposed
to hydrazine for six years.
/CASE REPORTS/ After a laboratory technician had drunk 20-30 mL of a 6% aqueous
solution of hydrazine (free base), he immediately vomited. Four hours later,
weakness, somnolence, and arrhythmia were observed. Laboratory findings showed a
slight but persistent leukocytosis. The serum-albumin fraction was decreased
with an increase in the urine noted, while the patient showed irregular
breathing. Five days after exposure, the patient had recovered.
/CASE REPORTS/ The case of a 24-yr-old man who accidentally ingested a mouthful
of hydrazine successfully treated with megadoses of intravenous pyridoxine
hydrochloride (vitamin B6) injection, 10 g over a few hr, who subsequently
developed sensory polyneuropathy, is reported. The neuropathy spontaneously
resolved over the next 6 months. It was concluded that although part of the
peripheral neuropathy could have been due to hydrazine toxicity, the
predominantly sensory neuropathy with axonal degeneration and spontaneous
recovery is due to pyridoxine hydrochloride (vitamin B6) induced peripheral
neuropathy.
/CASE REPORTS/ Contact dermatitis caused by hydrazine was reported in two
patients who worked in a gold plating factory. The workers wore gloves when
carrying baskets between the different plating baths, but they had frequent
spills over their hands and arms and were exposed to the vapor. The first case
was a 54 year old man who worked for 20 years in the plating industry. After
three weeks in the gold plating department the worker developed a recurrent hand
eczema. It was located on the dorsal side of the hands and spread to the
forearms. The patient recovered completely after changing his work
responsibilities. The second case was a 23 year old worker in the same gold
plating department who developed periorbital eczema four months after starting
work in the gold plating department. The worker recovered completely after
changing the working environment. The standard ICORG test procedures was used in
performing the patch testing. In both workers, 1% hydrazine sulfate, and 1 and
10% gold plating stabilizer gave positive epicutaneous test reactions and
potassium dicyanoaurate gave a negative reaction. /Observations indicated that/
there was evidence that hydrazine in the gold plating baths caused the
dermatitis.
/CASE REPORTS/ An accidental swallowing of a mouthful of hydrazine led to
confusion, lethargy, and restlessness in a 24-yr old man. Clinical liver damage
was detected, but other signs of systemic toxicity appear to have been masked by
the aggressive management of the patient.
/CASE REPORTS/ A male worker sustained severe chemical burns (involving 22% of
the body surface) following a hydrazine explosion. After a comatose period and
with biochemical indicators of liver malfunction, recovery was seen in 5 weeks.
/EPIDEMIOLOGY STUDIES/ Hydrazine was produced at a factory in the East Midlands
of the United Kingdom between 1945 and 1971. The cohort of all 427 men who were
employed there for at least six months with varying degrees of occupational
exposure to hydrazine was followed up until the end of January 1992. By the end
of July 1982 49 deaths had occurred and the observed mortality was close to that
expected at each level of exposure. By the end of January 1992 a further 37
deaths had occurred. Again the observed mortality was close to that expected for
all causes and also for lung cancer, cancers of the digestive system, other
cancers, and all other causes, respective of the level of exposure. The results
weigh against there having been any material hazard of occupational exposure to
hydrazine. The small number of men studied means, however, that a relative risk
as high as 3.5 for lung cancer cannot confidently be excluded.
/EPIDEMIOLOGY STUDIES/ A study of men engaged in hydrazine manufacture comprised
423 men, with 64% ascertainment of vital status. None of the five cancers
reported (three gastric, one prostatic and one neurogenic) occurred in the group
with the highest exposure. A follow-up of this cohort extended the observations
to 1982. Mortality from all causes was not elevated (49 observed, 61.5 expected)
and the only excess was two lung cancer cases within the highest-exposure
category, with a relative risk of 1.2 (95% confidence interval, 0.2-4.5).
Skin, Eye and Respiratory Irritations:
Vapors are very irritating to the mucous membranes, nose, throat, and upper
respiratory tract.
Drug Warnings:
...The presence of this compound in inadequately purified or aged medicinal
drugs can expose a section of the human population to hydrazine. Two drugs that
exemplify this exposure risk are isoniazid and hydralazine. Hydrazine can also
be formed during the metabolism of these drugs. Recently, hydrazine was detected
in the plasma of 8 healthy male volunteers taking isoniazid for 2 weeks and in
the plasma of 8 out of 14 hypertensive patients treated with, among others,
hydralazine. After 2 weeks of dosing with isoniazid, the average level of
acid-labile hydrazine in men of a slow acetylator phenotype was 2.7 times higher
than in men of a rapid acetylator phenotype.
Medical Surveillance:
Based partly on exptl data, placement should incl a history of exposure to other
carcinogens, smoking, alcohol, medications, & family history. The skin, eye,
liver, kidney, blood & CNS should be evaluated. Sputum or urine cytology may
give useful information. Hydrazine may be detected in blood.
A cross-sectional study evaluating the most common rocket fuels such as
hydrazine; 1,1-dimethylhydrazine (UDMH); mono-methylhydrazine (MMH); and
Aerozine-50 against the most commonly suggested therapies, such as pyridoxine,
traditional antiseizure therapies, and arginine is needed to clarify the
treatment implications for human exposure. Treatments that have been useful for
hyperammonemic states, such as those for the six inherited urea cycle defects,
have significant potential for the improvement of hydrazine exposure treatment.
Populations at Special Risk:
The effects of acetylation phenotypes on the metabolism of hydrazine /were
investigated/. Genotypes of N-acetyl transferases, NAT2*, were determined using
polymerase chain reaction for 297 male workers. Biological and exposure
monitoring were also conducted. The rapid and intermediate acetylators accounted
for 45% each, and the slow acetylators accounted for 10%. Biological half-lives
were significantly different among the three acetylation phenotypes (analysis of
variance, P < 0.05): 3.94+/-1.70 hours for slow acetylators, 2.25+/-0.37
hours for intermediate acetylators, and 1.86+/-0.67 hours for rapid acetylators.
Among Japanese, rapid and intermediate acetylators are the major phenotypes,
which is in sharp contrast with those among Caucasians./The authors/ conclude
that biological monitoring should take genetic factors, which may vary
dramatically among different populations, into account.
Probable Routes of Human Exposure:
THE SMOKE FROM A BLENDED US CIGARETTE CONTAINED 31.5 NG HYDRAZINE.
An industrial hygiene assessment of the extent of exposure to hydrazine
compounds was carried out due to the growing number of such compounds shown to
be animal carcinogens in laboratory studies. The report summarizes production
and uses of hydrazine compounds, the toxic effects of such compounds, relevant
exposure standards, sampling and analytical methods relevant to exposure
assessment, and observations made during surveys conducted at eight facilities
in the United States where these compounds were either prepared or used. The
sites visited for the survey were of four basic types: those which used
hydrazine compounds as propellants, those which manufactured the compounds,
those which used hydrazine as an aircraft emergency power unit fuel, or sites
where hydrazine was used in boiler water treatment. Personal exposures measured
were generally within the range from below the limit of detection to 1.0 ppm as
an 8 hour time weighted average. The OSHA permissible exposure limits for the
hydrazine compounds of interest ranged from 0.5 to 5 ppm. The number of workers
exposed was found to be low. Large scale propellant and emergency jet power unit
usage was relatively new, and the manufacturing methods had not been used until
recently. /Data indicated/ that the accumulated person years of exposure are
relatively low; it is unlikely that suitable cohorts exist for retrospective
exposure studies.
NIOSH (NOES Survey 1981-1983) has statistically estimated that 59,147 workers
(2,840 of these are female) are potentially exposed to hydrazine in the US(1).
About 2000 Finnish employees were exposed to hydrazine between the years
1980-1989(2). Occupational exposure may be through inhalation and dermal contact
with this compound at workplaces where hydrazine is produced or used(SRC). The
general population will be exposed to hydrazine via inhalation of cigarette
smoke, ingestion of food, and dermal contact with vapors and other products
containing hydrazine(SRC).
Evidence for Carcinogenicity:
Evaluation: There is inadequate evidence in humans for the carcinogenicity of
hydrazine. There is sufficient evidence in experimental animals for the
carcinogenicity of hydrazine. Overall evaluation: Hydrazine is possibly
carcinogenic to humans (Group 2B).
CLASSIFICATION: B2; probable human carcinogen. BASIS FOR CLASSIFICATION: Tumors
have been induced in mice, rats and hamsters following oral, inhalation or
intraperitoneal administration of hydrazine and hydrazine sulfate. Hydrazine is
mutagenic in numerous assays. HUMAN CARCINOGENICITY DATA: Inadequate. ANIMAL
CARCINOGENICITY DATA: Sufficient.
A3; Confirmed animal carcinogen with unknon relevance to humans.
Drug Warnings:
...The presence of this compound in inadequately purified or aged medicinal
drugs can expose a section of the human population to hydrazine. Two drugs that
exemplify this exposure risk are isoniazid and hydralazine. Hydrazine can also
be formed during the metabolism of these drugs. Recently, hydrazine was detected
in the plasma of 8 healthy male volunteers taking isoniazid for 2 weeks and in
the plasma of 8 out of 14 hypertensive patients treated with, among others,
hydralazine. After 2 weeks of dosing with isoniazid, the average level of
acid-labile hydrazine in men of a slow acetylator phenotype was 2.7 times higher
than in men of a rapid acetylator phenotype.
Probable Routes of Human Exposure:
THE SMOKE FROM A BLENDED US CIGARETTE CONTAINED 31.5 NG HYDRAZINE.
An industrial hygiene assessment of the extent of exposure to hydrazine
compounds was carried out due to the growing number of such compounds shown to
be animal carcinogens in laboratory studies. The report summarizes production
and uses of hydrazine compounds, the toxic effects of such compounds, relevant
exposure standards, sampling and analytical methods relevant to exposure
assessment, and observations made during surveys conducted at eight facilities
in the United States where these compounds were either prepared or used. The
sites visited for the survey were of four basic types: those which used
hydrazine compounds as propellants, those which manufactured the compounds,
those which used hydrazine as an aircraft emergency power unit fuel, or sites
where hydrazine was used in boiler water treatment. Personal exposures measured
were generally within the range from below the limit of detection to 1.0 ppm as
an 8 hour time weighted average. The OSHA permissible exposure limits for the
hydrazine compounds of interest ranged from 0.5 to 5 ppm. The number of workers
exposed was found to be low. Large scale propellant and emergency jet power unit
usage was relatively new, and the manufacturing methods had not been used until
recently. /Data indicated/ that the accumulated person years of exposure are
relatively low; it is unlikely that suitable cohorts exist for retrospective
exposure studies.
NIOSH (NOES Survey 1981-1983) has statistically estimated that 59,147 workers
(2,840 of these are female) are potentially exposed to hydrazine in the US(1).
About 2000 Finnish employees were exposed to hydrazine between the years
1980-1989(2). Occupational exposure may be through inhalation and dermal contact
with this compound at workplaces where hydrazine is produced or used(SRC). The
general population will be exposed to hydrazine via inhalation of cigarette
smoke, ingestion of food, and dermal contact with vapors and other products
containing hydrazine(SRC).
Skin, Eye and Respiratory Irritations:
Vapors are very irritating to the mucous membranes, nose, throat, and upper
respiratory tract.
All of the above is
directly from http://toxnet.nlm.nih.gov/