PHOSPHORUS
PHOSPHORUS
CASRN: 7723-14-0
http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~AAAcoaWVv:1
Human Health Effects:
Human Toxicity Excerpts:
SYMPTOMATOLOGY: A. ACUTE
POISONING, TYPICALLY IN 3 STAGES. 1. FIRST STAGE ... A. SKIN CONTACT PRODUCES
PAINFUL PENETRATING 2ND & 3RD DEGREE BURNS, WHICH HEAL SLOWLY. THESE LESIONS
REPRESENT BOTH CHEMICAL & THERMAL DAMAGE. B. INGESTION PRODUCES A SENSATION
OF WARMTH OR A BURNING PAIN IN THE THROAT & ABDOMEN, WITH INTENSE THIRST. C.
NAUSEA, VOMITING, DIARRHEA, SEVERE ABDOMINAL PAIN. A GARLIC ODOR FROM BREATH
& EXCRETA IS HIGHLY SUGGESTIVE OF PHOSPHORUS POISONING ... . LUMINESCENT
VOMITUS & FECES ARE ESSENTIALLY DIAGNOSTIC OF PHOSPHORUS. D. SHOCK MAY BE
SEVERE ENOUGH TO CAUSE DEATH IN 24 TO 48 HR. 2. SECOND STAGE ... SYMPTOM-FREE
PERIOD OF SEVERAL DAYS ... PATIENT SEEMS TO BE RECOVERING.
THIRD STAGE ... A. NAUSEA,
PROTRACTED VOMITING, DIARRHEA; MASSIVE HEMATEMESIS MAY OCCUR. B. LIVER
TENDERNESS & ENLARGEMENT, JAUNDICE, PRURITUS. C. HEMORRHAGES INTO SKIN,
MUCOUS MEMBRANES, & VISCERA, DUE TO INJURY OF BLOOD VESSELS & INHIBITION
OF BLOOD CLOTTING ... D. RENAL DAMAGE, ... OLIGURIA, HEMATURIA, CASTS,
ALBUMINURIA, ... ANURIA. E. CARDIOVASCULAR COLLAPSE ... LATE IN THE COURSE OF
POISONING. F. CENTRAL NERVOUS INVOLVEMENT RESULTING IN CONVULSIONS, DELIRIUM,
& COMA. IF PATIENT SURVIVES, CEREBRAL SYMPTOMS MAY PERSIST FOR A LONG TIME.
G. DEATH OCCURS USUALLY IN 4-8 DAYS ... IRREVERSIBLE SHOCK, HEPATIC FAILURE,
CENTRAL NERVOUS SYSTEM DAMAGE, ... HEMATEMESIS, OR RENAL INSUFFICIENCY MAY BE
PROXIMAL CAUSE OF DEATH.
CHRONIC POISONING (FROM
INGESTION OR INHALATION) IS CHARACTERIZED BY BONY NECROSIS, ESP OF MANDIBLE,
SPONTANEOUS FRACTURES, ANEMIA, WT LOSS.
WHITE PHOSPHORUS FUMES ...
CAUSE SEVERE OCULAR IRRITATION WITH BLEPHAROSPASM, PHOTOPHOBIA, &
LACRIMATION. PARTICLES ... ARE CAUSTIC & SERIOUSLY DAMAGING IN CONTACT WITH
TISSUES. ... CORNEA WERE RENDERED OPAQUE, BUT INTERSTITIAL VASCULARIZATION &
EPISCLERITIS DEVELOPED. EPISODES OF INFLAMMATION RECURRED FOR MANY YR, BUT GOOD
VISION WAS MAINTAINED.
WHITE: ... SYSTEMIC PHOSPHORUS
POISONING ... CAN LEAD TO LOSS OF ONE OR BOTH EYES FROM NECROTIC &
DESTRUCTIVE PROCESS IN MAXILLA EXTENDING INTO ORBIT, CAUSING DESTRUCTION OF
ORBIT & GLOBE.
"RED" PHOSPHORUS IS
NON-VOLATILE, INSOL, UNABSORBABLE, & THUS NON-TOXIC WHEN INGESTED, UNLESS IT
IS CONTAMINATED WITH TRACES OF YELLOW PHOSPHORUS ... GENERAL PROTOPLASMIC POISON
WHOSE TOXICITY IS ENHANCED WHEN ... DISSOLVED IN SOLVENTS SUCH AS ALCOHOL OR
DIGESTIBLE FATS & OILS LIKE CASTOR OIL.
ACUTE POISONING EARLY IN THIS
CENTURY WAS CAUSED BY INGESTION OF MATCH TIPS, FIREWORKS & QUACK NOSTRUMS.
THERE IS NO SCIENTIFIC BASIS FOR ITS MEDICINAL USE, & LEGISLATION TOGETHER
WITH INTERNATIONAL TRADE AGREEMENTS HAS LARGELY ELIMINATED IT FROM ABOVE
SOURCES.
Elemental yellow phosphorus
causes second- and third-degree burns on skin contact and may cause systemic
symptoms from absorption. The compound is highly toxic. The acute fatal dose in
adults is 15 to 100 mg (1 mg/kg), although survival has occurred after an
ingestion exceeding 1 g. The fatality rate varies between 20% and 50%, and the
prognosis is good if the patient survives for 6 days.
The human lethal oral dose of
phosphorus (white) is about 1 mg/kg body weight, and as little as 0.2 mg/kg may
produce adverse effects. Acute oral phosphorus intoxication generally has two
stages. In the initial phase gastrointestinal effects predominate and may
include nausea, vomiting, and belching. The onset may be within 30 min after
ingestion. Death from cardiovascular collapse can occur in about 12 hr. A period
of regression and apparent recovery lasting about 2 days may occur. The second
stage is characterized by the return of the gastrointestinal distress plus signs
of hepatic, renal, and cardiovascular problems, for example, jaundice, pitting
edema, oliguria, high pulse rate, and low blood pressure. In either phase,
smoking, luminescence, and a garlic odor of the vomitus and feces are
characteristic but not diagnostic. The most common pathological findings in
deaths have been fatty degeneration of the liver and kidneys.
A dose of 15 mg of phosphorus
can cause severe poisonings in humans and as little as 50 mg may be fatal.
Shortly after ingestion phosphorus produces severe gastrointestinal irritation,
and if a sufficient dose in ingested, hemorrhage and cardiovascular failure may
prove fatal within 24 hours. The vomitus after phosphorus ingestion is
luminescent and has a characteristic garlic odor. If the patient survives the
initial gastrointestinal irritation phase, secondary systemic poisoning due to
liver necrosis may ensue. Severe acute yellow atrophy of the liver is one
delayed sequela that may ultimately prove fatal.
White phosphorus is extremely
poisonous and can cause "phossy jaw", a disease ... caused by
phosphorus fumes that are inhaled or absorbed through cavities in the teeth and
that then attack and destroy bones, particularly the jaw bone. Phossy jaw is
usually fatal ... .
The most important
manifestation of chronic phosphorus poisoning is osteomyelitis of the jaw bones
("phossy jaw"), most frequently of the mandible and less often of the
maxilla, which commonly begins as a dental disturbance. If the tooth is
extracted, in the subsequent course of the condition, the pressure of a purulent
discharge and failure of the tooth socket to heal normally will generally make
the dentist suspicious of a severe underlying condition in the bone. In that
case, he will allow the infected bone to separate and then remove it surgically,
trying to conserve as much as possible of the natural bone outline to avoid
facial disfigurement. /Phosphorus/
The mortality rate for acute
phosphorus poisoning is approximately 25% for victims who had early symptoms of
nausea and vomiting, nearly 50% when both gastrointestinal and CNS symptoms were
present, and almost 75% when the first manifestation of poisoning was
restlessness, irritability, drowsiness, stupor, or coma. This difference in
survival rates most likely reflect the interval between time of ingestion and
treatment. The toxic dose is 15 mg, and as little as 50 mg may be lethal.
Skin, Eye and Respiratory Irritations:
Yellow: ... Fumes are
irritating to the respiratory tract and cause severe ocular irritation. ...
Red: Irritates eyes.
Medical Surveillance:
Indicators of occupational
exposure to phosphorus include depressed erythrocyte concn, elevated monocyte
concn and elevated phospholipid concn in blood.
... Employment medical
examination should include X-ray studies of the teeth and jaw, and good
dentition should be required for placement. Routine dental examination should be
made monthly if exposure is high or prolonged.
Probable Routes of Human Exposure:
Occupational exposure involves
acetyl cellulose makers, bronze alloy makers, munitions workers, smoke bomb and
incendiary makers, pesticide rat poison worker, fertilizer makers,
electroluminescent-coating makers, and semiconductor workers. /Phosphorus/
Minimum Fatal Dose Level:
The toxic dose is 15 mg, and
as little as 50 mg may be lethal.
Antidote and Emergency Treatment:
A case report of phosphorus
poisoning in an 18 month old male, treated with large multiple doses of
activated charcoal, is presented. The child ingested 65 mg yellow phosphorus in
a rodenticide paste. Within 90 min, ipecac-induced emesis, gastric lavage, and
30 g oral activated charcoal had been completed. Charcoal was continued at a
dose of 10 g every 4 hr for 24 hr. Clinical and laboratory data remained normal.
First aid can be given by
standard treatment. After ingestion of white phosphorus a 0.1 M solution of
copper sulfate should be given orally until vomiting occurs. Other treatments
are the same as in the case of collapse and acidosis. Burned areas of body
should be washed with a 5% solution of copper sulfate, followed by usual burn
therapy.
Basic treatment: Establish a
patent airway. Suction if necessary. Watch for signs of respiratory
insufficiency and assist ventilations if necessary. Administer oxygen by
nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if
necessary ... . Monitor for shock and treat if necessary ... . Anticipate
seizures and treat if necessary ... . For eye contamination, flush the eyes
immediately with water. Irrigate each eye continuously with normal saline during
transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5
mL/kg up to 200 mL of water for dilution if the patent can swallow, has a strong
gag reflex, and does not drool. Administer activated charcoal ... . If product
was ingested, protect yourself from contact with vomits as it may cause burns.
/Phosphorus and Related compounds/
Advanced treatment: Consider
orotracheal or nasotracheal intubation for airway control in the patient who is
unconscious or in respiratory arrest. Positive-pressure ventilation techniques
with a bag-valve-mask device may be beneficial. Monitor cardiac rhythm and treat
arrhythmias as necessary ... . Start an IV of D5W TKO /SRP: "To keep
open", minimal flow rate/. Use lactated Ringer's if signs of hypovolemia
are present. Watch for signs of fluid overload. Consider drug therapy for
pulmonary edema ... . For hypotension with signs of hypovolemia, administer
fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with
diazepam (Valium) ... . Monitor for signs of hypoglycemia (decreased LOC,
tachycardia, pallor, dilated pupils, diaphoresis, and/or dextrose stick or
glucometer readings below 50 mg/dL) and administer 50% dextrose if necessary.
Draw blood sample before administration ... . Use proparacaine hydrochloride to
assist eye irrigation ... . /Phosphorus and Related compounds/
Animal Toxicity Studies:
Evidence for Carcinogenicity:
CLASSIFICATION: D; not
classifiable as to human carcinogenicity. BASIS FOR CLASSIFICATION: Based on no
data in humans or animals. HUMAN CARCINOGENICITY DATA: None. ANIMAL
CARCINOGENICITY DATA: None.
Non-Human Toxicity Excerpts:
RED: ... INJECTED SMALL AMT OF
AQ SUSPENSION OF RED PHOSPHORUS INTO CORNEAS OF BOTH EYES OF RABBIT, & INTO
ANTERIOR CHAMBER IN ONE EYE. ... IRIS DEVELOPED NUMEROUS FINE ABNORMAL VESSELS.
... IN EYE IN WHICH THE RED PHOSPHORUS HAD BEEN INJECTED INTO ANTERIOR CHAMBER
GROSS HYPOPYON DEVELOPED & VESSELS OF IRIS ... BECAME CONSPICUOUSLY DILATED.
WHITE: /AFTER INGESTION/ ...
INTENSE ABDOMINAL PAIN & PROFUSE VOMITING IN ANIMALS CAPABLE OF IT. VOMITUS
MAY BE LUMINOUS IN DARK & ... POSSIBLE TO DETECT THE CHARACTERISTIC
GARLIC-LIKE ODOR ... ABDOMINAL PAIN & VOMITING THEN RECUR, TOGETHER WITH
JAUNDICE & NERVOUS SIGNS. ... DELIRIUM & CONVULSIONS, & EVENTUALLY
COMA & DEATH ...
... INFLAMMATION OF MUCOUS
MEMBRANES OF STOMACH & INTESTINES, FATTY DEGENERATION & INFILTRATION OF
PARENCHYMATOUS ORGANS, PARTICULARLY LIVER, OF MUSCLES & ENDOTHELIUM OF BLOOD
VESSELS, & EXTRAVASATION OF BLOOD INTO SUBCUTANEOUS TISSUE, SKIN &
MUSCLES.
... RATS INJECTED
SUBCUTANEOUSLY WITH 0.05 MG/KG OF YELLOW PHOSPHORUS/DAY DEVELOPED BONE CHANGES
AFTER ADMINISTRATION OF 50 MG. ... INCR MORTALITY RESULTED FROM DOSAGE OF 0.8
MG/KG/DAY. ... SUBCUTANEOUS INJECTION OF 0.2-0.4 MG/KG/DAY IN DOGS CAUSED
DELAYED DEATHS WITHIN A FEW DAYS.
INHALATION OF PHOSPHORUS VAPOR
BY RABBITS FOR 30 MIN DAILY @ 150-160 MG/CU M LED TO DECR HEMOGLOBIN &
ERYTHROCYTE COUNTS.
HALF THE CRUSTACEAN POPULATION
DIED AFTER 4.5 DAYS EXPOSURE TO WATER CONTAINING 20 MG PHOSPHORUS/L. ELEMENTAL
PHOSPHORUS @ 5-15 MG/L WATER DISRUPTED FEEDING, REPRODUCTION, & BODY COLOR
AMONG DAPHNIA MAGNA STRAUS POPULATIONS.
Rabbits and rats were exposed
to single doses of smoke from pyrotechnic mixtures containing red phosphorus.
The survivors were observed for up to 14 days. Most of the histological changes
observed were found in the respiratory tract, including abnormalities in the
larynx and trachea, alveolitis and, in a few cases, frank pneumonia.
A system was developed which
could continuously produce quantities of fresh phosphorus aerosol for several
hours for inhalation exposure studies. In a preliminary range-finding study,
Sprague-Dawley rats were exposed to red phosphorus derived-aerosol entailing
four one-hr (3.2, 4.3, 5.3 or 8.5 mg/l) exposures and one 4-hr (1.5 mg/l)
exposure. Rats died on days 1, 2, 6, 8, 9, 10 or 11 after exposure, suggesting
both acute and delayed effects. At the lower doses, the laryngeal region
appeared to be the most consistent target area with laryngeal and epiglottal
ulcerations and edema. Pulmonary congestion, edema and hemorrhage were more
pronounced only in the higher dose groups.
Mice and rats were exposed to
the smoke produced by ignition of a red phosphorus pyrotechnic composition, 1
hr/dy, 5 dy/week, at two different dose levels, together with controls. The mice
received 180 exposures, while the rats received 200 exposures. Guinea pigs also
underwent 200 exposures at the lower concentration, but all animals exposed at
the higher concentration died during or immediately after the first dose. Growth
of the test groups of mice and rats was depressed during the exposure period.
Organ specific toxicity appeared not to be present in rats and was generally
confined to the respiratory tract of the mice and the guinea pigs. A
significantly higher proportion of the test group mouse lung showed aggregates
of macrophages containing granules than was present in the control group. Severe
congestion was observed in practically all the lung from the decedent high-dose
group guinea pigs.
Rabbits and guinea pigs were
not killed by a dosage of 0.66 mg/kg/day but they developed a cirrhosis-like
condition.
INHALATION OF MORE THAN 20 PPM
PHOSPHORUS VAPORS BY RATS (7 HR/DAY, 5 DAYS/WK) RESULTED IN SEVERE RESPIRATORY
IRRITATION AND IN A HIGH MORTALITY RATE PRIMARILY DUE TO PULMONARY EDEMA AND
BRONCHOPNEUMONIA.
Non-Human Toxicity Values:
LD50 Rat oral 3030 ug/kg
LD50 Mouse oral 4820 ug/kg
TSCA Test Submissions:
In a one-generation
reproduction study, male and female Sprague Dawley rats (15 males and 30
females/group) were orally exposed by gavage to elemental yellow phosphorus in
corn oil vehicle at dose levels of 0, 0.005, 0.015 or 0.075 mg/kg/day for 80
days prior to mating (2 females/male), and continued throughout mating,
gestation and lactation periods. Due to low fertility in the first litter, the
study was extended to 2 litters and dosing continued throughout the entire
study. All pups were sacrificed at weaning and parental animals were sacrificed
after weaning of the F1b litter. There were significant differences between
treated and control animals in the following: decreased F0 male body weights
(high-dose group, after 15 weeks of the study). There were no significant
differences between treated and control animals in the following: parental
mortality, food consumption, fertility indices, mean length of gestation,
numbers of viable pups and pup survival, pup body weights, and gross or
microscopic examinations at necropsy.
Metabolism/Pharmacokinetics:
Metabolism/Metabolites:
SOME PHOSPORUS IS THOUGHT TO
BE SLOWLY OXIDIZED TO HARMLESS ACIDS, WHICH ARE GRADUALLY EXCRETED BY KIDNEYS.
In the body, phosphorus is
converted to phosphates.
... It appears that it is
metabolized to hypophosphoric acid via oxidation.
Absorption, Distribution & Excretion:
PHOSPHORUS (WHITE-YELLOW) CAN
BE ABSORBED THROUGH SKIN, BY INGESTION, & THROUGH RESP TRACT ... .
PHOSPHORUS IS EXCRETED CHIEFLY IN URINE IN COMBINED FORMS, SUCH AS PHOSPHATES.
... IN PHOSPHORUS POISONING, INSIGNIFICANT AMT OF PHOSPHORUS MAY BE EXCRETED IN
EXHALED BREATH ... IN SWEAT. ELEMENTAL PHOSPHORUS MAY BE FOUND IN BREATH, BLOOD,
& FECES, BUT NOT IN URINE.
Elemental yellow phosphorus is
well absorbed from the skin and gastrointestinal tract; phosphine toxicity
results from inhalation. The lung and gut excrete yellow phosphorus, but little
elimination occurs via the kidneys. Red phosphorus is practically unabsorbable.
Net phosphorus absorption may
occur in the small intestine in some species but is primarily a function of the
colon in horses.
Urinary excretion, the chief
mode of elimination, is largely an organic and inorganic phosphate.
Unreacted elementary
phosphorus may be demonstrated in the tissues of people who die several days
after ingesting phosphorus but not in those who die after longer periods.
If there is a decrease in
vitamin D or its activity, calcium and phosphorus absorption will be reduced.
Interactions:
... LIQ PETROLATUM IS SAID TO
RETARD ABSORPTION & DECR PHOSPHORUS TOXICITY.
It has been demonstrated that
intragastric admin of cysteine hydrochloride in a dose of 50 mg/kg and sodium
sulfate in a dose of 25 mg/kg with reference to sulfate ion reduced the
circulatory disturbances, dystrophic and sclerotic changes in the rat liver
caused by intragastric admin of yellow phosphorus at a dose of 1 mg/kg. Admin of
the drugs interfered with the development of liver cirrhosis, stimulated
regeneration, and raised the adaptive abilities of hepatocytes. Cysteine
protected hepatocyte mitochondria from phosphorus and activated their function.
Pharmacology:
Interactions:
... LIQ PETROLATUM IS SAID TO
RETARD ABSORPTION & DECR PHOSPHORUS TOXICITY.
It has been demonstrated that
intragastric admin of cysteine hydrochloride in a dose of 50 mg/kg and sodium
sulfate in a dose of 25 mg/kg with reference to sulfate ion reduced the
circulatory disturbances, dystrophic and sclerotic changes in the rat liver
caused by intragastric admin of yellow phosphorus at a dose of 1 mg/kg. Admin of
the drugs interfered with the development of liver cirrhosis, stimulated
regeneration, and raised the adaptive abilities of hepatocytes. Cysteine
protected hepatocyte mitochondria from phosphorus and activated their function.
Minimum Fatal Dose Level:
The toxic dose is 15 mg, and
as little as 50 mg may be lethal.
Environmental Fate & Exposure:
Probable Routes of Human Exposure:
Occupational exposure involves
acetyl cellulose makers, bronze alloy makers, munitions workers, smoke bomb and
incendiary makers, pesticide rat poison worker, fertilizer makers,
electroluminescent-coating makers, and semiconductor workers. /Phosphorus/
Natural Pollution Sources:
ABUNDANCE IN EARTH'S CRUST:
APPROX 0.12%. DOES NOT OCCUR FREE IN NATURE; FOUND IN FORM OF PHOSPHATES IN
MINERALS CHLORAPATITE ... FLUORAPATITE ... VIVIANITE, WAVELLITE &
"PHOSPHATE ROCK" OR PHOSPHORITE; OCCURS IN SMALL QUANTITIES IN GRANITE
ROCKS; OCCURS IN ALL FERTILE SOIL; AN ESSENTIAL CONSTITUENT OF PROTOPLASM,
NERVOUS TISSUE & BONES.
ELEMENTAL PHOSPHORUS HAS BEEN
REPORTED AS SUCH IN A METEORITE.
Environmental Bioconcentration:
A comprehensive examination of
metal levels at various trophic levels within an undisturbed Precambrian Shield
lake ecosystem was made. Concn of 21 naturally occurring elements including
phosphorus were measured in sediments, clams, fish, birds, and mammals. Mercury
was the only element to exhibit biomagnification.
Macronutrient and trace metal
content was determined in reindeer lichens (Cladonia cladina) from 23 bogs; C
arbuscula was sampled from 20 localities, C stellaris (C alpestris) from 12 and
C mitis from 2. Calculated on the basis of the total atmospheric fallout in the
region, the annual retention percentages in the Cladonis carpets were 124% for
phosphorus. Apparently there is a significant active uptake of phosphorus; it is
chiefly accumulated in the living top part.
Effluent Concentrations:
From 23 American cities
phosphorus concn in sewage sludge, determined by emission spectrometry, ranged
from 0.27 to 3.2% dry wt.
Plant Concentrations:
The elemental composition of a
group of airborne and settled grain dusts is reported. Concn of phosphorus were
less than 1% in barley, corn, Durum wheat, flax, and spring wheat dusts, while
oats and selected other grain dusts contained approximately 4000 and 2800 ppm,
respectively.
Environmental Standards & Regulations:
FIFRA Requirements:
As the federal pesticide law
FIFRA directs, EPA is conducting a comprehensive review of older pesticides to
consider their health and environmental effects and make decisions about their
future use. Under this pesticide reregistration program, EPA examines health and
safety data for pesticide active ingredients initially registered before
November 1, 1984, and determines whether they are eligible for reregistration.
In addition, all pesticides must meet the new safety standard of the Food
Quality Protection Act of 1996. Pesticides for which EPA had not issued
Registration Standards prior to the effective date of FIFRA, as amended in 1988,
were divided into three lists based upon their potential for human exposure and
other factors, with List B containing pesticides of greater concern and List D
pesticides of less concern. Phosphorus is found on List C. Case No: 3111; Case
Status: No products containing the pesticide are actively registered ... The
case /is characterized/ as "cancelled." Under FIFRA, pesticide
producers may voluntarily cancel their registered products. EPA also may cancel
pesticide registrations if registrants fail to pay required fees or make/meet
certain reregistration commitments, or if EPA reaches findings of unreasonable
adverse effects.; Active ingredient (AI): phosphorus; AI Status: The active
ingredient is no longer contained in any registered pesticide products ...
"cancelled."
TSCA Requirements:
Pursuant to section 8(d) of
TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section
8(d) model rule requires manufacturers, importers, and processors of listed
chemical substances and mixtures to submit to EPA copies and lists of
unpublished health and safety studies. Phosphorus is included on this list.
Section 8(a) of TSCA requires
manufacturers of this chemical substance to report preliminary assessment
information concerned with production, use, and exposure to EPA as cited in the
preamble in 51 FR 41329. /White phosphorus/
CERCLA Reportable Quantities:
Persons in charge of vessels
or facilities are required to notify the National Response Center (NRC)
immediately, when there is a release of this designated hazardous substance, in
an amount equal to or greater than its reportable quantity of 1 lb or 0.454 kg.
The toll free number of the NRC is (800) 424-8802; In the Washington D.C.
metropolitan area (202) 426-2675. The rule for determining when notification is
required is stated in 40 CFR 302.4 (section IV. D.3.b).
Persons in charge of vessels
or facilities are required to notify the National Response Center (NRC)
immediately, when there is a release of this designated hazardous substance, in
an amount equal to or greater than its reportable quantity of 1 lb or 0.454 kg.
The toll free number of the NRC is (800) 424-8802; In the Washington D.C.
metropolitan area (202) 426-2675. The rule for determining when notification is
required is stated in 40 CFR 302.4 (section IV. D.3.b).
Releases of CERCLA hazardous
substances are subject to the release reporting requirement of CERCLA section
103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part
355. Phosphorus is an extremely hazardous substance (EHS) subject to reporting
requirements when stored in amounts in excess of its threshold planning quantity
(TPQ) of 100 lbs.
RCRA Requirements:
D003; A solid waste containing
white and yellow phosphorus may become characterized as a hazardous waste when
subjected to testing for reactivity as stipulated in 40 CFR 261.23, and if so
characterized, must be managed as a hazardous waste.
Atmospheric Standards:
Listed as a hazardous air
pollutant (HAP) generally known or suspected to cause serious health problems.
The Clean Air Act, as amended in 1990, directs EPA to set standards requiring
major sources to sharply reduce routine emissions of toxic pollutants. EPA is
required to establish and phase in specific performance based standards for all
air emission sources that emit one or more of the listed pollutants. Phosphorus
is included on this list.
Clean Water Act Requirements:
Designated as a hazardous
substance under section 311(b)(2)(A) of the Federal Water Pollution Control Act
and further regulated by the Clean Water Act Amendments of 1977 and 1978. These
regulations apply to discharges of this substance.
Federal Drinking Water Guidelines:
EPA 0.1 ug/l /White
phosphorous/
Chemical/Physical Properties:
Molecular Formula:
P
Molecular Weight:
123.90 (P4 with atomic weight
of P = 30.97376)
Color/Form:
Exists in three main
allotropic forms: white, black, and red. The same liquid is obtained from all
forms on melting.
Colorless or white,
transparent, crystalline solid; waxy appearance; darkens on exposure to light.
Sometimes called yellow phosphorus; color due to impurities. Two allotropic
modifications: alpha-form exists at room temperature; cubic crystals containing
P4 molecules; beta-form hexagonal crystals.
Yellow /allotropic form/:
White to yellow, soft, waxy solid.
BLACK /ALLOTROPIC FORM/:
POLYMORPHIC, ORTHORHOMBIC CRYSTALLINE FORM, AMORPHOUS FORM.
VIOLET /ALLOTROPIC FORM/:
VIOLET MONOCLINIC
RED /ALLOTROPIC FORM/: RED TO
VIOLET POWDER; POLYMORPHISM.
Odor:
Garlic-like
Acrid
Boiling Point:
280 deg C
Melting Point:
44.1 deg C
Critical Temperature & Pressure:
Critical temperature: 994 K
Density/Specific Gravity:
1.83 (alpha-form); 1.88 (beta
form)
Heat of Vaporization:
49.8X10+6 J/kg-mol
Solubilities:
BLACK: INSOL IN CARBON
DISULFIDE, CONCN SULFURIC ACID; WHITE: SOL IN AMMONIA, ALKALI, TOLUENE; VIOLET:
INSOL IN ORG SOLVENTS; RED: SOL IN ABS ALC, VERY SLIGHTLY SOL IN COLD, INSOL IN
HOT WATER, IN CARBON DISULFIDE, ETHER, AMMONIA.
In water: one part/300,000
parts; in absolute alcohol: one g/400 ml; in absolute ether: one g/102 ml; in
CHCl3: one g/40 ml; in benzene: one g/35 ml; in CS2: one g/0.8 ml. Solubility in
oils: one gram phosphorus dissolves in 80 ml olive oil, 60 ml oil of turpentine,
about 100 ml almond oil.
0.33 mg/100 g water at 15 deg
C; 2.7 g/100 g benzene at 15 deg C; 89.8 g/100 g carbon disulfide at 10 deg C
Spectral Properties:
WHITE: INDEX OF REFRACTION:
2.144
Vapor Density:
RED: 4.77; WHITE: 4.42 (AIR=
1)
Vapor Pressure:
O.026 mm Hg at 20 deg C
Viscosity:
1.69 cP at 50 deg C (liquid)
Other Chemical/Physical Properties:
WHITE /ALLOTROPIC FORM/:
COLORLESS OR WHITE, TRANSPARENT, CRYSTALLINE SOLID; WAXY APPEARANCE.
Beta-form of white phosphorus
prepared by conversion of alpha-form at -79.6 deg C.
Upon heating, alpha white
phosphorus first melts, then either vaporizes or converts to amorphous red
phosphorus. The conversion proceeds slowly in 1-2 days at temperatures slightly
below the 280 deg C boiling point.
Volatile; sublimes in vacuo at
ordinary temp when exposed to light. When exposed to air in the dark, emits a
greenish light and gives off white fumes. Ignites at about 30 deg in moist air;
the ignition temp is higher when the air is dry.
Combines directly with the
halogens to form tri- or pentahalides; combines with sulfur to form sulfides.
Reacts with several metals to form phosphides. Yields orthophosphoric acid when
treated with nitric acid. Reacts with alkali hydroxides with formation of
phosphine and sodium hypophosphite. Incompatibilities: Sulfur, iodine, oil of
turpentine, potassium chlorate.
Polymorphic. Orthorhombic
crystalline forms: table in air; resembles graphite in texture; specific gravity
2.691. Does not catch fire spontaneously. Insoluble in organic solvents.
Amorphous form prepared at lower pressures. At higher pressure the orthorhombic
form undergoes reversible transition to a rhombohedral structure, specific
gravity 3.56, and a cubic structure, specific gravity 3.83. /Black phosphorus/
Polymorphous. Red to violet
powder. The properties of red phosphorus are intermediate between those of the
white and black forms. Sublimes at 416 deg C, triple point 589.5 deg C under
43.1 atm pressure. Specific gravity 2.34. Insoluble in organic solvents. Soluble
in phosphorus tribromide. Less active than the white form; reacts only at high
temperature. Yields the white modification when distilled at 290 deg C. Catches
fire when heated in air to about 260 deg C and burns with formation of the
pentoxide. Burns when heated in an atmosphere of chlorine. /Red phosphorus/
Produced from the white
modification under high pressures. /Black phosphorus/
Phosphorus atoms exist as
symmetrical, tetrahedral P4 molecules in the liquid phase and in the vapor phase
below 800 deg C; molecules dissociate to P2 above 800 deg C.
Atomic number 15; valences 3,
5. One naturally occurring isotope: 31P; artificial, radioactive isotopes:
28-30; 32-34. Does not occur free in nature.
Vapor pressure: 0.181 mm Hg at
melting point (44.1 deg C)
White phosphorus burns rapidly
in air to form phosphoric oxide.
White: garlic-like /odor/
Heat of fusion: 2.5X10+6
J/kg-mol
Density = 1.74 g/cu cm at 50
deg C (liquid)
Phosphorus vapor exists as P4
molecules until dissociation to P2 begins at 800 deg C. Essentially all the
vapor is P2 at 1500 deg C, but further dissociation to monatomic P is less that
0.1% at that temperature.
Chemical Safety & Handling:
DOT Emergency Guidelines:
Fire or explosion: Extremely
flammable; will ignite itself if exposed to air. Burns rapidly, releasing dense,
white, irritating fumes. Substance may be transported in a molten form. May
re-ignite after fire is extinguished. /Phosphorus, white, dry or under water or
in solution; Phosphorus, white, molten; Phoshporus, yellow, dry or under water
or in solution/
Health: Fire will produce
irritating, corrosive and/or toxic gases. TOXIC; ingestion of substance or
inhalation of decomposition products will cause severe injury or death. Contact
with substance may cause severe burns to skin and eyes. Some effects may be
experienced due to skin absorption. Runoff from fire control may be corrosive
and/or toxic and cause pollution. /Phosphorus, white, dry or under water or in
solution; Phosphorus, white, molten; Phoshporus, yellow, dry or under water or
in solution/
Public safety: ... Isolate
spill or leak area immediately for at least 100 to 150 meters (330 to 490 feet)
in all directions. Stay upwind. Keep unauthorized personnel away. Keep out of
low areas. /Phosphorus, white, dry or under water or in solution; Phosphorus,
white, molten; Phoshporus, yellow, dry or under water or in solution/
Protective clothing: Wear
positive pressure self-contained breathing apparatus (SCBA). Wear chemical
protective clothing which is specifically recommended by the manufacturer.
Structural firefighters' protective clothing is recommended for fire situations
only; it is not effective in spill situations. /Phosphorus, white, dry or under
water or in solution; Phosphorus, white, molten; Phoshporus, yellow, dry or
under water or in solution/
Evacuation: Spill: Consider
initial downwind evacuation for at least 300 meters (1000 feet). Fire: If tank,
rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile)
in all directions; also, consider initial evacuation for 800 meters (1/2 mile)
in all directions. /Phosphorus, white, dry or under water or in solution;
Phosphorus, white, molten; Phoshporus, yellow, dry or under water or in
solution/
Fire: Small fires: Water
spray, wet sand or wet earth. Large fires: Water spray or fog. Do not scatter
spilled material with high pressure water streams. Move containers from fire
area if you can do it without risk. Fire involving tanks or car/trailer loads:
Fight fire from maximum distance or use unmanned hose holders or monitor
nozzles. Cool containers with flooding quantities of water until well after fire
is out. Withdraw immediately in case of rising sound from venting safety devices
or discoloration of tank. ALWAYS stay away from the ends of tanks. /Phosphorus,
white, dry or under water or in solution; Phosphorus, white, molten; Phoshporus,
yellow, dry or under water or in solution/
Spill or leak: Fully
encapsulating, vapor protective clothing should be worn for spills and leaks
with no fire. ELIMINATE all ignition sources (no smoking, flares, sparks or
flames in immediate area). Do not touch or walk through spilled material. Do not
touch damaged containers or spilled material unless wearing appropriate
protective clothing. Stop leak if you can do it without risk. Small spills:
Cover with water, sand or earth. Shovel into metal container and keep material
under water. Large spills: Dike for later disposal and cover with wet sand or
earth. Prevent entry into waterways, sewers, basements or confined areas.
/Phosphorus, white, dry or under water or in solution; Phosphorus, white,
molten; Phoshporus, yellow, dry or under water or in solution/
First aid: Move victim to
fresh air. Call emergency medical care. Apply artificial respiration if victim
is not breathing. Administer oxygen if breathing is difficult. In case of
contact with substance, keep exposed skin areas immersed in water or covered
with wet bandages until medical attention is received. Removal of solidified
molten material from skin requires medical assistance. Remove and isolate
contaminated clothing and shoes at the site and place in metal container filled
with water. Fire hazard if allowed to dry. Effects of exposure (inhalation,
ingestion or skin contact) to substance may be delayed. Keep victim warm and
quiet. Ensure that medical personnel are aware of the material(s) involved, and
take precautions to protect themselves. /Phosphorus, white, dry or under water
or in solution; Phosphorus, white, molten; Phoshporus, yellow, dry or under
water or in solution/
Skin, Eye and Respiratory Irritations:
Yellow: ... Fumes are
irritating to the respiratory tract and cause severe ocular irritation. ...
Red: Irritates eyes.
Fire Potential:
WHITE: IGNITES @ APPROX 30 DEG
C IN AIR; IGNITION TEMP IS HIGHER WHEN AIR IS DRY. BLACK: DOES NOT CATCH FIRE
SPONTANEOUSLY. RED: CATCHES FIRE WHEN HEATED IN AIR TO APPROX 260 DEG C &
BURNS WITH FORMATION OF THE PENTOXIDE. BURNS WHEN HEATED IN ATMOSPHERE OF
CHLORINE.
NFPA Hazard Classification:
Health: 1. 1= Materials that,
on exposure, would cause irritation, but only minor residual injury, including
those requiring the use of an approved air-purifying respirator. These materials
are only slightly hazardous to health and only breathing protection is needed.
/Phosphorus, amorphous/
Flammability: 1. 1= This
degree includes materials that must be preheated before ignition will occur,
such as Class IIIB combustible liquids and solids and semi-solids whose flash
point exceeds 200 deg F (93.4 deg C), as well as most ordinary combustible
materials. Water may cause frothing if it sinks below the surface of the burning
liquid and turns to steam. However, a water fog that is gently applied to the
surface of the liquid will cause a frothing which will extinguish the fire.
/Phosphorus, amorphous/
Reactivity: 1. 1= This degree
includes materials that are normally stable, but may become unstable at elevated
temperatures and pressures and materials that will react with water with some
release of energy, but not violently. Fires involving these materials should be
approached with caution. /Phosphorus, amorphous/
Health: 4. 4= Materials that,
on very short exposure, could cause death or major residual injury, including
those that are too dangerous to be approached without specialized protective
equipment. A few whiffs of the vapor or gas could cause death, or contact with
the vapor or liquid may be fatal, if it penetrates the fire fighter's normal
protective gear. The normal full protective clothing and breathing apparatus
available to the typical fire fighter will not provide adequate protection
against inhalation or skin contact with these materials. /Phosphorus, white,
molten/
Flammability: 4. 4= This
degree includes flammable gases, pyrophoric liquids, and Class IA flammable
liquids. The preferred method of fire attack is to stop the flow of material or
to protect exposures while allowing the fire to burn itself out. /Phosphorus,
white, molten/
Reactivity: 2. 2= This degree
includes materials that, are normally unstable and readily undergo violent
chemical change, but are not capable of detonation. This includes materials that
can undergo chemical change with rapid release of energy at normal temperatures
and pressures and materials that can undergo violent chemical changes at
elevated temperatures and pressures. This also includes materials that may react
violently with water or which may form potentially explosive mixtures with
water. In advanced or massive fires, fire fighting should be done from a safe
distance or a protected location. /Phosphorus, white, molten/
Autoignition Temperature:
Red: 260 deg C; White: 30 deg
C
Fire Fighting Procedures:
Flood with water to control
flames, then smother with wet sand, clay, ground limestone. Approach fire from
upwind to avoid hazardous vapors and toxic decomposition products. Where access
to the area is strictly controlled, it may be best to allow the release to burn
itself out. Fire situations may require evacuation. Fight fire from protected
location or maximum possible distance. /Phosphorus, white, molten/
Flood with water to control
flames, then smother with wet sand, clay, ground limestone. Approach fire from
upwind to avoid hazardous vapors and toxic decomposition products. /Phosphorus,
amorphous/
Toxic Combustion Products:
Red: Burning yields toxic
oxides of phosphorus.
Yellow: Toxic gases and vapors
such as phosphoric acid fumes are released.
Firefighting Hazards:
White phosphorus may be
present as a contaminant or formed in fire situations. Fumes from phosphorus
fires are highly irritating to lungs, skin, eyes. /Phosphorus, amorphous/
Fumes from phosphorus fires
are highly irritating to lungs, skin, eyes. /Phosphorus, white, molten/
Hazardous Reactivities & Incompatibilities:
Red: Avoid uncontrolled
contact with oxidizing agents ... or with strong alkaline hydroxides. Can react
violently with oxidizing agent in presence of air & moisture, liberating
phosphorus acids & toxic, spontaneously flammable phosphine gas.
Air, oxidizers (including
elemental sulfur & strong caustics), halogens [Note: Ignites spontaneously
in moist air].
CAUTION: AVOID CONTACT WITH
POTASSIUM CHLORATE, POTASSIUM PERMANGANATE, PEROXIDES & OTHER OXIDIZING
AGENTS; EXPLOSIONS MAY RESULT ON CONTACT OR FRICTION.
Phosphorus boiled with
alkaline hydroxides yields mixed phosphines which may ignite spontaneously in
air.
A mixture of white (or yellow)
phosphorus and ammonium nitrate can be exploded by percussion.
White or red phosphorus and
boron triiodide react with incandescence.
A combination of finely
divided phosphorus with finely divided bromates (also chlorates or iodates) of
barium, calcium, magnesium, potassium, sodium, or zinc will explode with heat,
percussion, and sometimes, light friction.
Phsophorus reacts vigorously
below 250 deg C with any of the following materials: cesium, lithium, potassium,
rubidium, sodium, sulfur.
Cesium acetylene carbide
becomes incandescent when warmed in contact with phosphorus.
Phosphorus sprinkled with
animal charcoal ignites at 15.5 deg C in the open air.
Phosphorus burns spontaneously
in gaseous chlorine. Phosphorus (white or yellow) burns in chlorine gas with a
pale green light. Red phosphorus reacts with chlorine at ordinary temperatures.
Finely divided red phosphorus ignites spontaneously in chlorine at ordinary
temperatures. The reaction of phosphorus and chlorine, fluorine, or bromine is
highly exothermic. All can explode in contact with white phosphorus. The
reaction of white phosphorus and liquid chlorine is explosive.
Yellow phosphorus reacts
feebly with chlorosulfonic acid if cold. At temperatures from 25 deg to 30 deg
C, the reaction begins vigorously (with evolution of hydrogen chloride and
sulfur dioxide) and ends with an explosion. With red phosphorus a higher
temperature is necessary to start the reaction.
When lead dioxide and red
phosphorus are ground the mass ignites; with yellow phosphorus, there is an
explosion.
A student was injured by an
explosion when he attempted to mix these two chemicals /magnesium perchlorate
and phosphorus/ in the laboratory.
A mixture of mercuric oxide
and phosphorus explodes when struck with a hammer and when boiled with water and
phosphorus. A mixture of mercurous nitrate and phosphorus explodes violently
when struck with a hammer.
Phosphorus ignites the vapor
of nitric acid and burns with an intense white light.
Phosphorus and oxygen or
iodine undergo a vigorous reaction at room temperature.
If a drop of solution of
phosphorus in carbon disulfide is placed on powdered potassium chlorate, an
explosion occurs as the solvent evaporates.
When phosphorus is boiled with
a solution of sodium or potassium hydroxide, phosphine gas is evolved which is
spontaneously flammable.
If red or white phosphorus is
mixed with potassium iodate and moistened with a few drops of water, the mixture
reacts violently, sometimes explosively.
Crystals of potassium
permanganate explode vigorously when ground with phosphorus.
Red phosphorus reacts in the
cold with selenium oxychloride evolving light and heat; white phosphorus reacts
explosively.
A mixture of silver nitrate
and phosphorus explodes violently when struck with a hammer. When amorphous
phosphorus is ground with silver oxide, the mixture ignites.
Red phosphorus and sodium
chlorite react in aqueous suspension in a strongly exothermic manner. The
reaction can have a sudden, almost explosive stage.
Phosphorus and sodium peroxide
react with flame or explosion.
When a mixture of sulfur and
yellow phosphorus is warmed, the two elements unite in all proportions with
vivid combustion and powerful explosions.
Yellow phosphorus ignites
after exposure to the vapor of sulfur trioxide. A piece of phosphorus dropped
into liquid sulfur trioxide reduces the latter with violence. When the pieces of
phosphorus are large, the heat raises the temperature of the phosphorus
sufficiently to cause ignition.
Yellow phosphorus ignites when
placed in boiling concentrated sulfuric acid.
Phosphorus and zirconium react
with incandescence when heated in a vacuum.
The mixture /vanadium
oxytrichloride and phosphorus/ produces an explosive reaction below 100 deg C
with more than small amounts.
Dangerous explosion hazard by
chemical reaction with ... Antimony pentafluoride, Barium bromate, Beryllium,
... Calcium bromate, Magnesium bromate, Potassium bromate, Sodium bromate, Zinc
bromate, Bromine, ... Bromine trifluoride, BrN3,... Cesium, CsHC2, Cs3N, ...
Chlorite, (Cl2 + heptane), ClO, Chlorine trifluoride, Chlorate ... CrO3,
Cr(OCl)2, copper, NCl, Iodine monobromide, Iodine monochloride, Iodine
pentafluoride, Iron, Lanthanum, ... Li2C2, Li6CS, magnesium perchlorate,
manganese, ...Neodymium, nickel, nitrates, NBr, Nitrogen dioxide, Nitrogen
bromide, Nitrogen chloride, NOF, FNO2, oxygen, performic acid, Platinum, ...
K3N, ... K2O2, ... RbHC2, Se2Cl2, ... SeOF2, SeF4, Na2C2, Na2O2, ... Thorium,
peroxyformic acid, ... halogen azides, hexalithium disilicide.
Hazardous Decomposition:
When heated to decomp ...
emits toxic fumes of /phosphorus oxides/.
Immediately Dangerous to Life or Health:
5 mg/cu m
Protective Equipment & Clothing:
Red: Dust mask; gloves of
rubber vinyl; chemical safety glasses; rubber shoes.
Yellow: ... Use
flame-retardant clothing, gloves, face shields (eight-inch minimum), and any
other appropriate protective clothing to prevent any possibility of skin contact
... . Use dust and splash-proof safety goggles .... Any clothing which becomes
contaminated ... should be removed immediately ... .
Respiratory protection
(supplied-air respirator with full facepiece or self-contained breathing
apparatus) should be available where these compounds are manufactured or used
and should be worn in case of emergency and overexposure. /Phosphorus compounds/
Wear appropriate personal
protective clothing to prevent skin contact. [Note: Flame retardant personal
protective equipment should be provided.]
Wear appropriate eye
protection to prevent eye contact.
Eyewash fountains should be
provided in areas where there is any possibility that workers could be exposed
to the substance; this is irrespective of the recommendation involving the
wearing of eye protection.
Facilities for quickly
drenching the body should be provided within the immediate work area for
emergency use where there is a possibility of exposure. [Note: It is intended
that these facilities should provide a sufficient quantity or flow of water to
quickly remove the substance from any body areas likely to be exposed. The
actual determination of what constitutes an adequate quick drench facility
depends on the specific circumstances. In certain instances, a deluge shower
should be readily available, whereas in others, the availability of water from a
sink or hose could be considered adequate.]
Recommendations for respirator
selection. Max concn for use: 1 mg/cu m. Respirator Class(es): Any supplied-air
respirator.
Recommendations for respirator
selection. Max concn for use: 2.5 mg/cu m. Respirator Class(es): Any
supplied-air respirator operated in a continuous flow mode. Eye protection
needed.
Recommendations for respirator
selection. Max concn for use: 5 mg/cu m. Respirator Class(es): Any
self-contained breathing apparatus with a full facepiece. Any supplied-air
respirator with a full facepiece.
Recommendations for respirator
selection. Condition: Emergency or planned entry into unknown concn or IDLH
conditions: Respirator Class(es): Any self-contained breathing apparatus that
has a full facepiece and is operated in a pressure-demand or other
positive-pressure mode. Any supplied-air respirator that has a full facepiece
and is operated in a pressure-demand or other positive-pressure mode in
combination with an auxiliary self-contained breathing apparatus operated in
pressure-demand or other positive-pressure mode.
Recommendations for respirator
selection. Condition: Escape from suddenly occurring respiratory hazards:
Respirator Class(es): Any appropriate escape-type, self-contained breathing
apparatus.
Preventive Measures:
Contact lenses should not be
worn when working with this chemical.
SRP: The scientific literature
for the use of contact lenses in industry is conflicting. The benefit or
detrimental effects of wearing contact lenses depend not only upon the
substance, but also on factors including the form of the substance,
characteristics and duration of the exposure, the uses of other eye protection
equipment, and the hygiene of the lenses. However, there may be individual
substances whose irritating or corrosive properties are such that the wearing of
contact lenses would be harmful to the eye. In those specific cases, contact
lenses should not be worn. In any event, the usual eye protection equipment
should be worn even when contact lenses are in place.
WHITE: CAUTION: HANDLE WITH
FORCEPS.
SRP: Contaminated protective
clothing should be segregated in such a manner so that there is no direct
personal contact by personnel who handle, dispose, or clean the clothing.
Quality assurance to ascertain the completeness of the cleaning procedures
should be implemented before the decontaminated protective clothing is returned
for reuse by the workers. Contaminated clothing should not be taken home at end
of shift, but should remain at employee's place of work for cleaning.
The worker should immediately
wash the skin when it becomes contaminated.
Work clothing that becomes wet
or significantly contaminated should be removed and replaced.
Workers whose clothing may
have become contaminated should change into uncontaminated clothing before
leaving the work premises.
Stability/Shelf Life:
BLACK: STABLE IN AIR.
WHITE: DARKENS ON EXPOSURE TO
LIGHT
Yellow: Gives off acrid fumes
on exposure to air
Shipment Methods and Regulations:
No person may /transport,/
offer or accept a hazardous material for transportation in commerce unless that
person is registered in conformance ... and the hazardous material is properly
classed, described, packaged, marked, labeled, and in condition for shipment as
required or authorized by ... /the hazardous materials regulations (49 CFR
171-177)./
The International Air
Transport Association (IATA) Dangerous Goods Regulations are published by the
IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and
constitute a manual of industry carrier regulations to be followed by all IATA
Member airlines when transporting hazardous materials.
The International Maritime
Dangerous Goods Code lays down basic principles for transporting hazardous
chemicals. Detailed recommendations for individual substances and a number of
recommendations for good practice are included in the classes dealing with such
substances. A general index of technical names has also been compiled. This
index should always be consulted when attempting to locate the appropriate
procedures to be used when shipping any substance or article.
Storage Conditions:
Separate from air, oxidizing
materials, combustibles. Always keep container closed, with material under water
or inert gas. /Phosphorus, white, molten/
Store in a cool, dry,
well-ventilated location. Separate from oxidizing materials. Always keep
container closed. /Phosphorus, amorphous/
Cleanup Methods:
Immediately douse the spill
with water & cover with wet sand or dirt.
Disposal Methods:
Generators of waste (equal to
or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste
number D003, must conform with USEPA regulations in storage, transportation,
treatment and disposal of waste.
Phosphorus (white or yellow)
is a waste chemical stream constituent which may be subjected to ultimate
disposal by controlled incineration.
Yellow: After solidification
& covering with sand or dirt, may be disposed of in a secured sanitary
landfill.
Cover with wet sand, shovel
into bucket and remove to safe, open, isolated area where the phosphorus can be
burnt off under supervision after drying out. Small spillages of phosphorus can
be burnt off in a fume cupboard. Recommendable methods: Incineration & open
burning. Not recommendable method: Landfill. Peer-review: Spontaneously
flammable if dry. Mix with wet earth, allow to dry, ignite at a remote place.
(Peer-review conclusions of an IRPTC expert consultation (May 1985))
White and yellow phosphorus is
a waste chemical stream constituent which may be subjected to ultimate disposal
by controlled incineration. Controlled incineration followed by alkaline
scrubbing and particulate removal equipment.
Occupational Exposure Standards:
OSHA Standards:
Permissible Exposure Limit:
Table Z-1 8-hr Time Weighted Avg: 0.1 mg/cu m.
Threshold Limit Values:
8 hr Time Weighted Avg (TWA):
0.1 mg/cu m. /Phosphorus (yellow)/
Excursion Limit
Recommendation: Excursions in worker exposure levels may exceed three times the
TLV-TWA for no more than a total of 30 min during a work day, and under no
circumstances should they exceed five times the TLV-TWA, provided that the
TLV-TWA is not exceeded. /Phosphorus (yellow)/
NIOSH Recommendations:
Recommended Exposure Limit: 10
Hr Time-Weighted Avg: 0.1 mg/cu m.
Immediately Dangerous to Life or Health:
5 mg/cu m
Other Occupational Permissible Levels:
Australia: 0.1 mg/cu m (1990);
Federal Republic of Germany: 0.1 mg/cu m (total dust), short-term level 0.2
mg/cu m, 5 min, 8 times per shift (1991); United Kingdom: 0.1 mg/cu m, 10 min
STEL 0.3 mg/cu m (1991).
Manufacturing/Use Information:
Major Uses:
The active ingredient is no
longer contained in any registered pesticide products ... "cancelled."
WHITE PHOSPHORUS HAS BEEN USED
AS INSECTICIDE IN PASTES MADE BY GRINDING YELLOW PHOSPHORUS IN PRESENCE OF WATER
& MIXING WITH FLOUR. PHOSPHORUS PASTE WAS USED TO CONTROL AMERICAN
COCKROACH, ALSO AS RAT POISON.
Most (85%) of the elemental
phosphorus is converted to phosphoric acid which is used directly or converted
to phosphate compound. Final applications include home laundry and automatic
dishwasher detergents, industrial and institutional cleaners, food and
beverages, metal cleaning and treatment, potable water and wastewater treatment,
antifreeze and electronics. The remaining elemental phosphorus (15%) is used in
P4-dependent applications which require the element as a direct reactant (P2S5,
PCl3, POCl3, P2O5, and hypophosphite with smaller amounts leading to PH3, red
phosphorus, phosphonates and other derivatives. Final applications include flame
retardants, lubricant additives, insecticides, herbicides, water treatment,
cleaning compounds, plasticizers, and semiconductors.
Striking surfaces for matches,
fireworks, flame retardants in polymers, semiconductors, and PH3. /Red
phosphorus/
Manufacture of rat poisons;
for smoke screens, gas analysis. /White phosphorus/
Pyrotechnics; manufacture of
safety matches; in organic synthesis; manufacture of phosphoric acid, phosphine,
phosphoric anhydride, phosphorus pentachloride, phosphorus trichloride;
manufacture of fertilizers, pesticides, incendiary shells, smoke bombs, tracer
bullets. /Red phosphorus/
Manufacturers:
FMC Corporation, Chemical
Products Group, Alkali Chemicals Division, Phosphorus Chemicals Division, Hq,
200 East Randolph Drive, Chicago, IL 60601 (312) 861-6000. Production site:
Pocatello, ID 83201
Monsanto Company, Chemical
Group, Hq, 800 North Lindbergh Boulevard, St. Louis, MO 63167, (314) 694-1000.
Production sites: Soda Springs, ID 83276
Methods of Manufacturing:
White phosphorus: Produced in
an electric furnace from phosphate rock, sand, and coke. The phosphorus vapor is
driven off and condensed under water. By reaction of phosphate rock with
sulfuric acid, the resulting calcium sulfate being removed by filtration and the
phosphoric acid concentrated by evaporation (wet process).
Red phosphorus is produced by
heating white crystalline phosphorus to about 400 deg C under an atmosphere of
an oxygen-free inert gas, such as nitrogen or argon.
General Manufacturing Information:
Aqueous solns of red
phosphorus are used to remove nitrogen dioxide from flue gases.
Elemental phosphorus is
produced and marketed in the alpha-form, of white or yellow phosphorus, the
tetrahedral P4 allotrope. A small amount of red phosphorus, P, is produced by
conversion from white phosphorus. The black modification prepared under high
pressure does not have commercial importance.
Commercial product is
generally somewhat yellow owing to the presence of small amounts of the red
phosphorus allotrope. It may also be slightly gray in color because of
incomplete separation of coke dusts and other impurities generated in the
manufacturing process.
A biochemical, histochemical,
and pathomorphological study indicates that the sulfate ion has protective
effects against phosphorus-induced intoxication in rats.
Formulations/Preparations:
Technical 99.9%; electronic
grade 99.9999%
WHITE OR YELLOW IS THE
SIGNIFICANT COMMERCIAL FORM OF ELEMENTAL PHOSPHORUS WITH A 99.8% MINIMUM PURITY.
Impurities:
Typical manufacturers'
analysis for a straw yellow product: arsenic, 30-250 ppm; toluene insolubles,
0.01 - 0.05 wt %; oils (hydrocarbons), 30-100 ppm as carbon.
Consumption Patterns:
77% IS USED IN THE PRODUCTION
OF PHOSPHORIC ACID; 2% IS USED TO PRODUCE PHOSPHORUS TRICHLORIDE (FOR ORGANIC
PHOSPHATES, PLASTICIZERS, GASOLINE & OIL ADDITIVES, FLOTATION AGENTS, FLAME
RETARDANTS, & INSECTICIDES); 2% TO PRODUCE PHOSPHORUS PENTASULFIDE (FOR
PHOSPHATE PESTICIDES, LUBRICATING OIL ADDITIVES, & FLOTATION AGENTS); 19% IN
MISC APPLICATIONS (1968)
END USE PATTERN DERIVATIVE:
PHOSPHORIC ACID, 85%; PHOSPHORUS PENTASULFIDE, 5%; PHOSPHORUS TRICHLORIDE, 5%;
MISC, 5% (1984-ESTIMATE)
CHEMICAL PROFILE: Phosphorus.
Thermal phosphoric acid, 82%; (sodium phosphates, 70%; direct phosphoric acid
sales, 20%; calcium ammonium and potassium phosphates, 10%); direct reaction
chemical production, including phosphorus trichloride, pentasulfide and
pentoxide, 12%; exports, 6%.
CHEMICAL PROFILE: Phosphorus.
Demand: 1987: 340,000 tons; 1988: 330,000 tons; 1992 /projected/: 310,000 tons
(Includes exports; in addition, between 4,000 and 5,000 tons were imported in
1987, mostly from Canada).
Thermal phosphoric acid, 85%
(sodium phosphates, 55%; direct phosphoric acid sales, 25%; calcium, ammonium
and potassium phosphates, 20%); direct reaction chemical production, including
phosphorus trichloride, pentasulfide and pentoxide, 15%.
U. S. Production:
(1968) 5.52X10+11 G ELEMENTAL
PHOSPHORUS
(1975) 4.09X10+11 G
(1984) 3.50X10+11 g
(1989) 365,000 tons
/Elemental, white (yellow), and red/
Production capacity estimate
as of 4/1/97 (P4 basis): 257 thousand short tons.
1993: 350,000 tons (includes
demand for elemental phosphorus and purified wet-acid on a phosphorus-equivalent
basis, as well as exports of roughly 20,000 annual tons, but not of imports of
5,000 to 10,000 tons per year)
U. S. Imports:
(1968) 3.80X10+8 G ELEMENTAL
PHOSPHORUS
(1975) 9.08X10+8 G
(1984) 2.12X10+9 G.
1993: 5,000 to 10,000 tons
(elemental phosphorus and purified wet-acid on a phosphorus-equivalent basis)
U. S. Exports:
(1968) 1.55X10+10 G EXPORTED
TO MEXICO
(1975) 3.27X10+10 G
(1984) 1.49X10+10 G.
1993: roughly 20,000 tons
(elemental phosphorus and purified wet- acid on a phosphorus-equivalent basis)
Laboratory Methods:
Analytic Laboratory Methods:
NIOSH Method S 334: Analyte:
Phosphorus (yellow); Matrix: Air; Procedure: Gas chromatography /Flame
photometric detection; Range: 0.056 - 0.244 mg/ cu m; Precision (CVT): 0.090.
NIOSH Method 257: Analyte:
Phosphorus (white); Matrix: Air; Procedure: Gas chromatography; Range: 0.01 to
1.00 mg/cu m in a 20 liter sample of air; Precision: 0.06 at 0.1 mg/cu m.
NIOSH Method 242: Analyte:
Phosphorus (yellow, white); Matrix: Air; Procedure: Flame photometric gas
chromatography; Range: 0.005 - 5.0 mg/cu m; Precision: 0.033 relative standard
deviation (analytical).
Air samples containing
phosphorus are analyzed using Inductively Coupled Argon Plasma - Atomic Emission
Spectroscopy at a wavelength of 214.9. An ashing step with concentrated nitric
acid/concentrated perchloric acid (4:1 v/v) is necessary. This method has an
instrumental detection limit of 22 ng/ml, a sensitivity of 0.17, and a precision
of 0.056 at 1000 ug/filter. /Phosphorus/
NIOSH Method 7300.
Determination of Elements by Inductively Coupled Argon Plasma - Atomic Emission
Spectroscopy (ICP-AES). Air. Detection limit not reported.
NIOSH Method 7905.
Determination of Phosphorus by Gas Chromatography using Phosphorus Flame
Photometric Detection. Air. Detection limit 0.050 ug/cu m.
Photometric method is used for
determination of soluble, dissolved, and insoluble phosphorus in water.
/Phosphorus/
AOAC Method 973.55. Phosphorus
in water. Photometric method. Detection limit not reported. /Total Phosphorus/
AOAC Method 973.56. Phosphorus
in water. Automated method. Detection limit not reported. /Total Phosphorus/
Phosphorus was determined by a
continuous flow method using fluorescence quenching of Rhodamine 6G with
molybdophosphate. /Phosphorus/
Phosphorus and organic carbon
was simultaneously determined in wastewater using flame ionization and
photometric detectors. /Phosphorus/
Phosphorus was determined in
natural waters by direct current plasma atomic emission spectrometry.
/Phosphorus/
Proton-induced x-ray emission
analysis constitutes a method for trace element analysis characterized by
multielement capability, detection limits in the low ppm-range, and size
resolution approximating a millimicron. /Phosphorus/
Microamounts of phosphorus in
wastewater were determined by high-speed liquid chromatography. /Phosphorus/
EPA EMSLC Method 200.7.
Inductively Coupled Plasma-Atomic Emission Spectrometric Method for Trace
Element Analysis of Water and Wastes. Method detection limit 60 ug/l. /Total
phosphorus/
EPA EAD Method 1620. Metals by
Inductively Coupled Plasma Atomic Emission Spectroscopy and Atomic Absorption
Spectroscopy. Water, soil, sediment, sludge samples. Lowest threshhold limit 1.0
mg/l. /Total Phosphorus/
EPA EMSL Method 365.
Phosphorous Determination by Colorimetry. Drinking, surface and saline waters
and domestic and industrial wastes. Concentration range 0.01 to 20.0 mg P/L.
Detection limit not reported.
EPA OSW Method 7580. White
Phosphorus (P4) by Solvent Extraction and Gas Chromatography. Soil, sediment,
and water samples. Sensitivity 0.010 ug/l.
Sampling Procedures:
NIOSH Method 257: Analyte:
Phosphorus (white); Matrix: Air; Procedure: Sorption on Tenax-GC, elution with
xylene; Flow rate: 50 to 200 ml/min.; Sample size: 20 l. Analysis should be
performed within 24 hours.
NIOSH Method S 344: Analyte:
Phosphorus (yellow); Matrix: Air; Procedure: Collection on Tenax-GC, extraction
with xylene; Flow rate: 0.2 l per minute for 60 minutes; Sample size: 12 l.
NIOSH Method 242: Analyte:
Phosphorus (yellow, white); Matrix: Air; Procedure: Filter/impinger (xylene);
Flow rate: 0.5 to 1.0 lpm; Sample size: 24-96 liters. The minimum volume of air
sampled will allow the measurement of at least 1/10 times the TLV, 0.01 mg/cu m.
Special References:
Special Reports:
Stula RT et al; Airborne
Emission Control Technology for the Elemental Phosphorus Industry; NTIS Report
Order No PB84-156421, 412 pp (1984). A report on airborne emission control
technology for the elemental phosphorus industry.
MARTIN EE; DEVELOPMENT
DOCUMENT FOR EFFLUENT LIMITATIONS GUIDELINES AND NEW SOURCE PERFORMANCE
STANDARDS FOR PHOSPHORUS DERIVED CHEMICALS SEGMENT OF THE PHOSPHATE
MANUFACTURING POINT SOURCE CATEGORY; US NTIS, PB REP: 158 PAGES (1974) ISS
241018. A STUDY WAS MADE OF THE PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY
FOR THE PURPOSE OF DEVELOPING EFFLUENT LIMITATIONS GUIDELINES, FEDERAL STANDARDS
OF PERFORMANCE, AND PRETREATMENT STANDARDS FOR THE INDUSTRY. EFFLUENT
LIMITATIONS GUIDELINES WERE DEVELOPED, DEFINING THE DEGREE OF EFFLUENT REDUCTION
ATTAINABLE THROUGH THE APPLICATION OF THE BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE AND THE BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE.
THE STANDARDS OF PERFORMANCE FOR NEW SOURCES WERE ALSO DEFINED. PROCESSES,
WASTES, AND COSTS ARE ALSO DISCUSSED.
WHO; Diseases Caused by
Phosphorus and Its Toxic Compounds; Early Detection of Occupational Diseases pg
53-62 (1986). Review of diseases and health related effects resulting from
exposure to phosphorus or phosphorus cmpd.
Synonyms and Identifiers:
Synonyms:
BLACK PHOSPHORUS
**PEER REVIEWED**
BONIDE BLUE DEATH RAT KILLER
**PEER REVIEWED**
Exolit LPKN
**PEER REVIEWED**
Exolit VPK-n 361
**PEER REVIEWED**
FOSFORO BIANCO (ITALIAN)
**PEER REVIEWED**
GELBER PHOSPHOR (GERMAN)
**PEER REVIEWED**
PHOSPHORE BLANC (FRENCH)
**PEER REVIEWED**
Phosphorous (white)
**PEER REVIEWED**
PHOSPHORUS-31
**PEER REVIEWED**
Phosphorus (red)
**PEER REVIEWED**
Phosphorus, white, molten
(dry)
**PEER REVIEWED**
RAT-NIP
**PEER REVIEWED**
RED PHOSPHORUS
**PEER REVIEWED**
TETRAFOSFOR (DUTCH)
**PEER REVIEWED**
TETRAPHOSPHOR (GERMAN)
**PEER REVIEWED**
VIOLET PHOSPHORUS
**PEER REVIEWED**
WEISS PHOSPHOR (GERMAN)
**PEER REVIEWED**
WHITE PHOSPHORUS
**PEER REVIEWED**
YELLOW PHOSPHORUS
**PEER REVIEWED**
Formulations/Preparations:
Technical 99.9%; electronic
grade 99.9999%
WHITE OR YELLOW IS THE
SIGNIFICANT COMMERCIAL FORM OF ELEMENTAL PHOSPHORUS WITH A 99.8% MINIMUM PURITY.
Shipping Name/ Number DOT/UN/NA/IMO:
UN 2447; Phosphorus, white,
molten
UN 1381; Phosphorus, white or
yellow, dry or in water, in solution or under water
UN 1338; Phosphorus,
amorphous, red.
IMO 4.2; Phosphorus, white,
molten; Phosphorus, white or yellow, dry or in water, in solution or under water
IMO 4.1; Phosphorus,
amorphous, red.
Standard Transportation Number:
49 167 25; Phosphorus,
amorphous, red (crude, red & yellow mixed)
49 161 42; Phosphorus,
amorphous, red
49 161 41; Phosphorus, white
or yellow, in water
49 161 40; Phosphorus, white
or yellow, dry
EPA Hazardous Waste Number:
D003; A waste containing white
and yellow phosphorus may (or may not) be characterized a hazardous waste
following testing for the reactivity characteristics as prescribed by the
Resource Conservation and Recovery Act (RCRA) regulations.
RTECS Number:
NIOSH/TH3500000
Administrative Information:
Hazardous Substances Databank
Number: 1169
Last Revision Date: 20020722
Last Review Date: Reviewed by SRP on 1/31/1999