-------
PROFILE REPORTS ON
Barium Compounds
Barium Carbonate (52). Barium Chloride (53), Barium Cyanide (469)
Barium Nitrate (471), Barium Sulfide (472)
1. GENERAL
Introduction
Barium compounds exhibit a close relationship to the compounds of the
other alkaline earth metals, calcium and strontium. Barium behaves
generally as a bivalent element, as do the other.alkaline earth metals.
The solubilities of barium salts are typical of the alkaline earth group.
The halides and nitrate are quite soluble, whereas the carbonate and
sulfate are insoluble. With the exception of barium sulfate, the salts
dissolve partially in carbonic acid and completely in hydrochloric or
nitric acid. The sulfate is extremely insoluble and is useful for the
determination of the barium ion.
Precipitated oarium carbonate is the most important of the
manufactured pure barium chemicals. In production tonnage it is second
to the principal mineral, barite. The production of barium carbonate has
decreased considerably in the last few years. In 1969, there were 114,000
tons of barium carbonate produced in the United States. In 1970 the
production of barium carbonate declined to 61,083 tons. In that same year
the production of all other barium compounds totaled 57,000 tons. Of'that
total it is estimated that there were less than 10,000 Ibs of barium cyanide
produced. Individual production figures for the other barium compounds
discussed in this Profile Report are not available.
Manufacture
All major barium salts in the United States are produced from the
chemical grade of barite (BaS04). Since barite is highly insoluble, the
starting point of the barium-plant process is the reduction of barite to
227
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soluble barium sulfide or black ash. This is then converted to the various
barium compounds.
Barium Carbonate. Black ash is dissolved in water and its clear solu-
tion is the usual raw material for barium carbonate manufacture. There are
two basic methods of manufacture which differ mainly in the way the carbonate
ion is introduced.
BaS + Na2C03 - &»- BaC03 + Na2$ (1)
BaS + C02 + H20 - ®-BaC03 + H2S (2)
The product from the straight-gassing process (equation 2) is more impure
than the soda ash product (equation 1). Large scale commercial facilities
for the manufacture of barium carbonate include the following :
Barium and Chemicals Incorporated, Painesville, Ohio
Chemical Products Corporation, Cartersville, Georgia
FMC Corporation, Modesto, California
Sherwin-Williams 'Company, Coffeyville, Kansas.
Barium Chloride. Barium chloride is produced by treating a barium
sulfide solution with hydrochloric acid:
BaS + 2HC1 - B»- Bad + H$
Barium Cyanide. Barium cyanide (Ba(CN)2) is prepared by reaction of
hydrogen cyanide on barium hydroxide suspended in petroleum ether. The
di hydrate is formed and then dried carefully under vacuum to yield a pro-
duct of 95 percent purity. Barium cyanide is produced by Phillips Brothers
Chemicals, Incorporated, New York.
Barium Nitrate. Barium nitrate is made by the interaction of a suspen
sion of barium carbonate in a mother liquor with nitric acid, followed by
crystallization after filtration. "Another method is to dissolve sodium
nitrate in a saturated solution of barium chloride, with subsequent perci-
pitation of barium nitrate. The precipitate is centrifuged, washed and
228
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dried. Barium nitrate is produced by Barium and Chemicals, Incorporated,
Painsville, Ohio.
Barium Sulfide. Black ash is produced by reducing ground barite with
coal at high temperatures. The reaction is:
BaS04 + 2C ——»- BaS + 2C02
Barium sulfide is also produced by Barium and Chemicals, Incorporated,
Painsville, Ohio.
Uses
The principal application areas of the five barium compounds have been
summarized by Miner (Table 1).
Sources and Types of Barium Wastes
The sources of barium wastes may include the following: (1) barium
compound manufacturers, and (2) commercial and industrial processes including
those from paper manufacturing pi ants» ceramic and enamel manufacturing plants,
etc.
In general, barium wastes can be classified as either diluted or con-
centrated wastes. Diluted barium wastes include those generated in the
waste waters of manufacturers and uses of barium chemicals. Concentrated
barium wastes include any unused or contaminated barium compounds that require
disposal or recovery.
Physical and Chemical Properties
The physical and chemical properties of the five barium compounds are
included in the attached worksheets.
229
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TABLE I0646
APPLICATION AREAS OF BARIUM COMPOUNDS
Compound
Uses
Barium Carbonate, BaCO.
Barium Chloride, Bad.
Barium Cyanide, Ba(CN)2
Barium Nitrate, Ba(N03)2
Barium Sulfide, BaS
As rat poison; in ceramics, enamels; .
in manufacture of paper, barium salts,
optical glasses; in case-hardening
steels.
In manufacturing of blanc fixe
(precipitated BaSO.); as mordant for
acid dyes; in weighting and dyeing
textile fabrics; as boiler compounds
for softening water; as purifying agent
in brines; in manufacture of barium
colors and of chlorine and sodium
hydroxide; as flux for magnesium alloys,
in case hardened steels.
In electroplating processes.
In manufacture of Ba02; as pyrotechnic
for green fire; as green signal lights;
in the. vacuum tube industry.
As raw material for other barium
compounds.
230
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2, TOXICOLOGY
Soluble barium compounds are highly toxic when ingested, while
insoluble compounds, such as barium sulfate9 are generally nontoxic.
Inhaled barium compounds cause a benign pneumoconiosis, called baritosis.
Ingestion of soluble barium compounds results in strong stimulation of
the muscles, including the heart; irritation of the intestinal tract;
and irritation of the central nervous system.
The symptoms of barium poisoning are severe abdominal pain with
vomiting, dyspnoea, rapid pulse, paralysis of the right arm and leg, and
eventually cyanosis and death. The usual result of exposure to the sulfide
and carbonate is irritation of the eyes, nose and throat, and of the skin,
producing dermatitis.
The five barium compounds included in this Profile Report are all
highly toxic and exhibit similar toxicity symptoms. With barium cyanide,
however, the toxic effects of both elements of the compound must be
considered (refer to Profile Report on Cyanides).
The relative oral L.DCQ values to the rat are 50-200 mg/kg for barium
carbonate and 355-533 mg/kg for barium chloride. The estimated oral
LDgQ values for man are 55 mg/kg for barium carbonate and 80 mg/kg for
barium chloride. The American Conference of Governmental Industrial
Hygienists (1971) recommended a Threshold Limit Value (TLV) in air of
0.5 mg/M for all soluble barium compounds. For cyanides (Ba(CN)p) the
TLV in air is 5.0 mg/M3. °225 The U.S. Public Health Service established
the permissible criteria for barium in public water supplies as 1.0 ppm.
This agency also recommends that the concentration of cyanides be kept
1752
below .01 ppm for both fish and people.
3. OTHER HAZARDS
Barium nitrate is an oxidizing material. In contact with easily
oxidizable substances it may react rapidly enough to cause ignition,
231
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violent combustion, or explosion. It increases the flammability of any
combustible substance.
The fire hazard of barium sulfide by spontaneous chemical reaction
is moderate; air, moisture or acid fumes may cause it to ignite. Barium
sulfide may react violently and explosively on contact with powerful
oxidizers.0766
Other than the toxic effects, barium carbonate, barium chloride and
barium cyanide present no further hazardous problems.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, Transportation
Care should be exercised in handling barium compounds because of
their high toxicity. The use of rubber gloves is advisable. Any material
which comes in contact with the skin should be immediately removed with
plenty of soap and water.
Barium nitrate should be stored in an area where it will be separated
from combustible, organic or other readily oxidizable materials. Avoid
storage on wood floors. Any spilled nitrate should be immediately removed
and disposed of. All of the barium compounds discussed in this report
should be stored away from foodstuffs, feeds, or any other material intended
for consumption by humans or animals.
Adequate procedures for the transportation of barium cyanide and
0278
barium nitrate have been established by the Department of Transportation.
Label requirements, as well as the maximum quantities permitted to be
shipped in one outside container, are also specified.
232
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Disposal/Reuse
Disposal or reuse of waste barium compound streams must take into
account the toxic nature of these materials. The discharged barium compounds
must be treated by the methods described in Section 5 or diluted to a concen-
tration of 1 ppm (.01 ppm for Ba(CN)2).
The safe disposal of barium compounds is defined in terms of the recom-
mended provisional limits:
Contaminant in Air
Barium Carbonate
Barium Chloride
Barium Cyanide
Barium Nitrate
Barium Sulfide
Provisional Limits
.005 mg/M3
.005 mg/M3
.005 mg/M3
.005 mg/M3
.005 mg/M3
Basis for
Recommendation
.01 TLV
.01 TLV
.01 TLV
.01 TLV
.01 TLV
Contaminant in Water
and Soil
Barium Carbonate
Barium Chloride
Barium Nitrate
Barium Sulfide
Barium Cyanide
Provisional Limits
1 mg/1
1 mg/1
1 mg/1
1 mg/1
.01 mg/1
Basis for
Recommendation
U. S. Public Health
Service recommendation
for public drinking water.
It should be noted that the recommended provisional limit for the barium
compounds (except barium cyanide) in water are less than that of .01 of the
TLm for fish.
1752
The provisional limit of barium cyanide in public drinking
water (.01 mg/1) is also a safe level for fish. It was found that trout
could survive a cyanide concentration of .02 mg/1 for more than 27 days.
1752
233
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Waste
Option No. 1 - Precipitation. By far the most widespread method used
for removing barium from industrial waters is precipitation with sulfate
ion (usually sulfuric acid) in settling ponds. The precipitate formed,
BaSO^, is only slightly soluble in water and the resulting effluent from
the pond contains about 2 ppm of barium. This effluent would then be di-
luted with an equal amount of water to meet the permissible criteria for
barium in public water supplies (1.0 ppm). Precipitation and settling is
normally a slow procedure and with high effluent flow it is normally nec-
essary to have settling ponds or lagoons in which to allow the slow coag-
ulation process to occur, the clear effluent removed and the precipitate
dried. Since barium sulfate is important in the barium industry (see
section on Manufacturing) it can be economically recycled. This method can
be used for both concentrated and dilute barium wastes. In the case of
barium cyanide wastes, the cyanide must be removed first before precipitating
the barium with sulfuric acid. The primary method of removing cyanide is to
oxidize it to C02 and N2 with an alkaline chlorine solution. Other methods
for removing cyanide include ion exchange, electro-oxidation, and reaction
with aldehydes (refer to Profile Report on cyanides for additional informa-
tion). Barium could also be precipitated by chromate ion to form barium
chromate. This is a workable method but is not normally economically feas-
ible unless a market as pigments for the precipitate is available.
Option No. 2 - Ion Exchange. Ion exchange can be used to remove
barium from dilute aqueous waste streams. Barium will behave much like
calcium and magnesium and can be removed from an aqueous waste stream by
either a sulfonic acid type cation exchange resin or a carboxylic weak acid
1795
type resin, depending upon the pH of the stream. An ion exchange unit
cannot usually handle an influent concentration load above 1500 ppm. An
advantage of ion exchange is that due to the coricentrative effects it is
possible to apply this process in recycling barium materials or in concen-
trating wastes for transport to centralized disposal. The major difficulty
in ion exchange operation is the critical dependence on flow rate. The ion
234
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exchange system is designed to operate with a particular efficiency at a
certain set flow. Should this flow be exceeded for even short periods of
time, the efficiency for absorbing the barium ion decreases drastically
causing the effluent to exceed the permissible limit.
Option No. 3 - Reverse Osmosis. The effectiveness of reverse osmosis
1812
to remove barium from water has been investigated by Sourirajan. Follow-
ing passage of a barium waste stream through a porous cellulose acetate mem-
brane, it was found that the barium concentration was reduced from 34.35
g/liter to 7.35 g/liter. It is conceivable that "R.O." is applicable to
dilute barium salt solutions as well, but no data is available to support
this assertion. With an effluent concentration of 7.35 g/liter, the "R.O."
unit would have to be used in conjunction with some other process (ion ex-
change for example) to produce an effluent with a permissible concentration
of barium.
Option No. 4 - Adsorption on Activated Carbon. Activated carbon has
1813
been shown to remove barium from acetate solutions by Kuzin et al.
Although the laboratory investigation was principally directed towards the
separation of uranium from other metallic compounds; it was found in the
same study that activated carbon possessed a sorption capacity for soluble
barium compounds of 0.7 mg/g carbon, thus demonstrating the feasibility of
activated carbon adsorption as a near future process for removing soluble
barium compounds from water.
The processes mentioned above deal exclusively with barium wastes in
the conventional aqueous form. If, however, the barium wastes are present
in the particulate form in a gas stream, the usual methods for removal of
particulates, such as bag filters, electrostatic precipitation, and wet
scrubbers should prevent their escape to the atmosphere.
The best method for disposing of both dilute and concentrated aqueous
barium wastes is precipitation with sulfate ion. The technique is efficient
and adequate for large scale removal of barium.
235
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The other processes discussed (ion exchange, reverse osmosis, and
adsorption on activated carbon) will result in reduced amounts of waste
barium but are not applicable as primary treatment methods. These pro-
cesses should function mainly as a secondary treatment of the effluent
from a barium precipitative facility.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Considering the provisions for the recycle and recovery of waste barium
by the producers, it is felt that waste streams containing barium compounds
do not warrant National Disposal Site treatment. The precipitation method
for the removal of barium from waste streams is inexpensive enough for even
the small barium manufacturers and users to operate.
In summary, the recovery and/or disposal of barium wastes can be cur-
rently handled adequately at the industrial site level and this mode should
be continued.
236
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7. REFERENCES
0096. National Fire Protection Agency. Fire protection guide on
hazardous materials, 3d ed. 1969. 950 p.
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards, p 35-40,
Aug. 1971.
0278. Code of Federal Regulations. Title 49--transportation, parts 71
to 90. (Revised as of January ls 1967). Washington, U.S.
Government Printing Office, 1967. 794 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. April 1, 1968.
Washington, Federal Water Pollution Control Administration.
234 p.
0646. Miner, S. Air pollution aspects of barium and its compounds.
Technical Report, Litton Systems, Inc., Sept. 1969. 69 p.
0766. Sax, N.I. Dangerous properties of industrial materials. 2d ed.,
New York. Reinhold Publishing Corp. 1957. 1,467 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers. 1963-1971.
1506. Barium carbonate. Jji Chemical profiles. New York, Schnell
Publishing Company, 1967.
1752. Public Health Service. Drinking Water Standards, 1962. U.S.
Department of Health, Education and Welfare, 1962. 61 p.
1794. Personal communication. B. Blank, Sherwin Williams Co., to
D. Dal Porto, TRW Systems, June 2, 1972. Barium waste stream
treatment.
1795. Personal communication. C. T. Dickert, Rohm & Haas to D. Dal Porto,
TRW Systems, May 16, 1972. Ion exchange applications- to barium
waste treatment.
1812. Sourirajan, S. Separation of some inorganic salts in aqueous
solution by flow, under pressure through porous cellulose,
acetate membranes. Industrial and Engineering Chemistry
Fundamentals, 3(3):286-210, Aug. 1964.
1813. Kuzin, A., V. P. TaushkanoV, B. M. Leonov, and Y. A. Boganch.
Sorption of metals by SKT activated carbon from acetate solutions.
Journal of Applied Chemistry of the U.S.S.R. 39(2): 325-328,
Feb. 1966.
1814. Personal communication, Olsen, U.S. Tariff Commission to D. Dal
Porto, TRW Systems, May 18, 1972. Production data on barium compounds.
237
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Barium Carbonate(52)
Structural Formula
IUC Name
Common Names
BaCO
3
Molecular Wt. T97.37 Melting Pt. 1740 @ 90 atm Boiling Pt. Decomposes
Density (Condensed) 4.43 @ Density (gas}_ 9
Vapor Pressure (recommended 55 C and 20 C)
(a § @
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 0.0022g/10Qg @ 18 C Hot Water 0.0065 g/lOQg & IQOCEthanol insoluble
Others:
Acid, Base Properties ••
Highly Reactive with
Compatible with_
Shipped in Bags, barrels and kegs
ICC Classification Coast Guard Classification
r . White powder
Comments
References (1) 0766.
238
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HAZARDOUS WASTES PROPERTIES
b&RKSHEET
H. M. Name Bar1um Chloride (53)
IUC Name
Coimton Names
Structural Formula
Bad.
Molecular Wt.
208.27
Melting Pt.
92S c
Density (Condensed) 3'856 g 24 c Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Boiling Pt. 1560 C
§
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water 37.5g/100g @ 26 C
Others:
Hot Water 59 g/TQOg B inn r Ethanol
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in Bags, barrels and kegs
ICC Classification
Comments
Coast Guard Classification
References (1) 0766.
239
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Barium Cyanide (469)
Structural Formula
IUC Name
Common Names
Ba(CN)
2
Molecular Wt. 189.40 Melting Pt. Slowly decomposp": Boiling Pt.
Density (Condensed) @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper.
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water 1 gm/1.5ml Hot Water . Ethanol i gm/?nmi
Others:
Acid, Base Properties_
Highly Reactive with_
Compatible with
Shipped in Bags, barrels and kegs
ICC Classification Coast Guard Classification
Comments
240
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Barium Nitrate (471)
IUC Name
Common Names
Structural Formula
Ba(N03)2
Molecular Wt.
261.38
Melting Pt. 592 c
Density (Condensed) 3.24 @ 23_ _C Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
Boiling Pt. Decomposes
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
Solubility
Cold Water 8.7g/100cc
Others:
Hot Mater 34.2g/100cc
Ethanol Insoluble
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped in Bags, barrels, kegs, casks, drums
ICC Classification
Coast Guard Classification
Comments In contact with easily oxidizable substances it may react rapidly enough to cause
ignition, violent combustion or explosion.
References (1)0766.
0096.
241
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Barium Sulfide (472)
IUC Name
Common Names
Structural Formula
BaS
169.43
Molecular Wt.
Density (Condensed) 4.25
1200 C
_ Melting Pt. _
@ 1£ _C Density (gas)
Boiling Pt.
Vapor Pressure (recommended 55 C and 20 C)
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X)
Solubility
Cold Water Soluble
Others:
Lower
Upper_
Upper_
Hot Water
Soluble
Ethanol Insoluble
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped jn Ba9s, barrels, kegs
ICC Classification Coast Guard Classification
Comm t ^a^ reac^ violently and explosively on contact with powerful oxidizers.
242
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PROFILE REPORTS
Beryllium Powder (59), Beryllium Carbonate (473),
Beryllium Chloride (474), Beryllium Hydroxide (475),
Beryllium Oxide (476), and Beryllium Selenate (477)
1. GENERAL
Production
There are two beryllium producers in the United States: the Brush
Beryllium Company, Elmore, Ohio °394 and KBI Industries (formerly
Kawecki-Berylco or the Beryllium Corporation of America), Reading,
Pennsylvania.0599 Production amounts to 50 to 75 tons/year (as beryl-
lium metal) divided approximately equally between the two companies.°^58
Each of the two producers has his own methods of winning the metal
from its principal ore, beryl, 3BeO.Al203.6Si02- The processes are dis-
cussed extensively in the literature. ^33,1417 y^y ^g^ involve the
production of Be(OH)2 as an intermediate step with a 90 percent extraction
efficiency (as beryllium metal), followed by calcining to BeO, conversion
to BeF2, and reduction by Mg to beryllium metal. The metal is then pul-
verized, sintered, and sawed or ground into desired shapes and parts. If
the popular Be-Cu alloys are desired (2-4 percent beryllium, remainder Cu),
the BeO is reduced with carbon in the presence of copper.1677
The French produce Beryllium directly by the electrolysis of Bed2.
but this process is regarded as uneconomical in the United StatesJ433-1720
Overall efficiency in going from beryl ore to sintered beryllium parts
is about 63 percent.0458 Because the metal is so valuable (about $60/lb)
every effort is made to recycle dross continuously at every step. Both
Brush and KBI actively seek their customers' scrap material, which they
0394
purchase for $10 to 20/lb contained beryllium and recycle. This recycled
243
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scrap accounts for approximately 6 percent of the total annual production.
The final waste and slag contains less than 1 percent beryllium as insoluble
0394
oxide and is stored currently on the refinery property.
Uses
It is anticipated that prices will remain strong at $60/lb contained
beryllium, so uses will remain limited to fairly exotic applications. Be-
Cu alloys have gained some popularity for applications where high electrical
conductivity is required together with high strength. These alloys account
for approximately half of all the beryllium used today. Another third is
used as metal in various applications involving the nuclear and aerospace
industries, almost exclusively in projects funded by the Federal Government.
While most beryllium metal is used for structural and machine parts, it is
also being considered as an additive in powder form to increase the thrust
of rocket engines. ' The amount used in this way is not known.
The high cost of beryllium is due to a number of factors which are not
likely to change in the foreseeable future: (1) the lack of mineral re-
sources, (2) the complexity of its extractive metallurgy, (3) the complexity
of its' fabrication technology, and (4) its toxicity.
0599 1720
Neither the beryllium producers ' nor a sampling of principal
1722 1723 1724
users ' ' report any significant sale or use of beryllium carbon-
ate, beryllium chloride, beryllium hydroxide, or beryllium selenate, although
the hydroxide is an intermediate in the production of metal and oxide. No
special problems are associated with this use as an intermediate.
Sources and Types of Beryllium Wastes
Since the beryllium users can practically resell all beryllium scrap
to the producer at $10 to $20/lb contained beryllium, there is very little
scrap material which is actually disposed of as waste. Most of the
beryllium wastes are in the form of solid parti.culates or in a dilute aqueous
solution (scrubber liquor), and are generated as a result of the attempts to
control the emission of beryllium dusts, fumes, and mists. The sources of
these beryllium wastes include beryllium extraction plants and beryllium
244
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users such as machine shops, foundries, ceramic plants, and propellent
plants.
2. TOXICOLOGY
Health and Safety Standards
Health and safety standards for beryllium workers and the general public
have evolved over a period of 30 years, ever since the first positive
diagnoses of beryl!iosis were made. Currently, the Environmental Protection
Agency is formalizing national emission standards, which are based on
conditions already observed by all AEC contractors. ' Almost
all beryllium producers, fabricators, and users already comply with these
standards, and "little economic impact on the industry" will result from
their implementation. An excerpt from the proposed standards is quoted
here:1678
"The proposed beryllium standards are designed to protect the
public from 30-day average atmospheric concentrations of
beryllium greater than 0.01 microgram per cubic meter (ug/m ).
Experience over more than 20 years has shown this to be a safe
level of exposure. For short-term, periodic exposures, the safe
3
level has been determined to be 25 ug/m for a maximum of 30
minutes. This periodic exposure limit is the basis for the
standard pertaining to rocket-motor firings.
"The proposed beryllium emission standards for extraction plants,
machine shops, foundries, ceramic plants, propel!ant plants, and
incinerators designed or modified for disposal of these substances
allow the operator to demonstrate compliance with either 1 or 2
below:
1. No more than 10 grams of beryllium emitted per 24-hour day.
2. No emission that will cause atmospheric concentrations of
beryllium to exceed an average of 0.01 microgram per cubic
meter of air for 30 days.
245
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"The beryllium emission standards given below are being proposed
for rocket-motor test facilities:
1. No emissions that will cause atmospheric concentrations of
beryllium to exceed 75 microgram-mlnutes per cubic meter
of air within the limit of 10 to 60 minutes.
2. No more than 10 grams of beryllium will be emitted per 24-
hour day when rockets are fired into a tank and the exhausts
are gradually released."
Epidemiology
Although annual beryllium consumption in the 20-year period 1948-1968
increased 500 percent, there have been no new cases except those currently
in incubation. '' Principal means of exposure include the
burning of coal. Coal contains 1 to 3 ppm beryllium with peak values of 31 ppm
having been reported. Approximately 500 million tons are burned annually.
To date, there is no evidence that anyone has ever contracted berylliosls
from handling beryl ore. There are 812 registered victims in the
United States, of which 60 are classified as "neighborhood victims", i.e.,
they had the misfortune to live near a beryllium plant, but never worked
with the material directly. However, they may have come in contact with
workers wearing contaminated clothing, etc.
The clinical manifestations of berylliosis are well documented. '
0276,1676,0641,1433,etc. Jn addnion to tne manifestations attributable to
all beryllium compounds, beryllium chloride, beryllium selenate, and other
soluble salts produce dermatitis on contact with the skin. Although
many berylliosis victims have contracted cancer, positive statistical
correlation is lacking. There is increasing circumstantial evidence for
246
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possible carcinogenic properties for beryllium in humans, since lung tumors
have been successfully induced in monkeys and rats and sarcomas have been
induced in rabbits. The 1971 Toxic Substances Annual List reports
that 0.1 mg/M have produced toxic effects in man by inhalation. Reported
50th percentile lethal doses (LD50) for beryllium compounds are:
Beryllium Carbonate: 150 mg/kg in the guinea pig injected
intraperitoneally
Beryllium Chloride: 86 mg/kg in the rat administered orally
Beryllium Hydroxide: 0.35-2.5 mg/kg in the rat injected
intravenously, depending on the
crystalline form of the hydroxide.
Recent laboratory studies1720'1721'1725'1744 in which rats and rabbits
were injected intratrachea!ly with BeO of respirable particle size (1 to
5y) indicate that there is a definite inverse correlation beween the toxicity
of the BeO and the temperature at which it is calcined. Beryllium oxide
calcined at 500 C produced severe pneumonitis and the eventual development
of adenocarcinomas. The pathological changes associated with, the intra-
tracheal injection of BeO calcined at 1100 C were qualitatively similar,
but quantitatively less severe. In contrast, BeO calcined at 1600 C was
"almost inert" and produced "minimal" pathologies. Beryllium oxide obtained
from rocket firings produced symptoms characteristic of the 1600 C-calcined
material.
There is no preferential uptake or concentration of beryllium or
beryllium compounds from the environment by any animals or plants, includ-
ing humans.0615'0641'0276'1127
3. OTHER HAZARDS
Finely divided beryllium metal may explode to form beryllium oxide* an
exceptionally stable compound. All other beryllium compounds react non-
violently with varieties of gases, liquids, and solids to eventually form
the ultimately stable beryllium oxide.
247
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4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling, Storage, and Transportation
Procedures for the handling, storage, and transportation of beryllium
waste are well-documented.0039'1678'0278 Sintered beryllium ingots or fabri-
cated parts and hot-pressed beryllium oxide shapes require no special shipping
or packaging precautions. A label is usually attached to indicate that fumes
or dust of this material may be toxic if inhaled.
Beryllium metal powder has a weight limitation of 25 Ib net per metal
container, when shipped under Department of Transportation regulations.
It is classified as a Class B poison, and must be so labeled. No regula-
tions exist for beryllium compounds as such, but the 25 Ib rule is generally
followed on the theory that controlled ventilation (such as a common
laboratory hood) will be available for 25 Ib quantities, but may not be
available for larger quantities.
Disposal and Reuse
Since the beryllium producers eagerly purchase all available scrap at
$10 to $20/1b containing beryllium, all users capture as much waste as possible
0394 0460
for resale to the producers. ' There is therefore ,very little scrap
material which is actually disposed of as waste.
The means of collection and control of dust, fume, and mist have been
summarized in new regulations being promulgated by the Environmental Protec-
tion Agency. 75'1678 Standard collection techniques such as scrubbers,
packed towers, cyclones, and fabric-filter units are currently in use on an
industry-wide basis to bring essentially everyone within the new target
emission concentration of OiOl yg/m . Scrubber liquors, etc. are disposed
of adequately with other liquid wastes.0275'0460'0461'1678
248
-------
Recommended provisional limits for beryllium and beryllium compounds
in the environment are as follows:
Basis of
Contaminant and Environment Provisional Limits Recommendation
Beryllium and beryllium 0.0001 mg/M EPA proposed
compounds in air standard
Beryllium and beryllium 1 ppm (mg/1) Drinking water
compounds in water standards
and soil
For the disposal of beryllium and beryllium compounds, an alternate
emission standard of no more than 10 gm of beryllium per 24-hour day for
each beryllium producing or beryllium using plant has also been proposed
by EPA, and operators have the option of complying with this standard instead
of the recommended provisional limits. For rocket-motor test facilities,
special beryllium emission standards have been proposed by EPA and these
are: (1) no more than 75 yg-min/M within the limit of 10 to 60 min; or
(2) no more than 10 gm per 24-hour day, provided the exhausts are trapped
and gradually released.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Recycling to Primary Producers
This is most desirable from the standpoints of users, producers, and
environmentalists. Beryllium and beryllium compounds are difficult to pro-
duce and the primary producers repurchase all available material at $10 to
$20/lb contained beryllium. ' This situation is expected to continue
indefinitely.0458
Option No. 2 - Burial
Liquid, solid, or particulate waste which is too dilute to recycle is
buried on private property or in public landfills. Often waste is first
burned to produce the insoluble, chemically inert oxide. This is easily
and safely done, providing the exhaust gases are scrubbed to remove any
249
-------
0394
particulates. These procedures were verified with KBI Industries,
two other large beryllium users, ' and the County of Los Angeles,
California, which operates several landfills which receive liquid
coolant wastes containing beryllium. All independently agreed with this
analysis.
Since there have been no new reported cases of berylliosis in 20 years
and demand is expected to remain static for the indefinite future, it may
be concluded that practices are adequate at present and for the foreseeable
future.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Since there have been no new reported cases of beryl!iosis contracted
within the past 20 years and essentially all producers and users already
comply with the proposed Environmental Protection Agency standards, it may
be concluded that beryllium and beryllium compounds are under adequate
control as hazardous wastes.
The continued high demand for scrap at $10 to $20/lb contained beryllium
makes its recovery extremely attractive for all users. Recovery systems
currently in operation keep ambient concentrations below the required 0.01
3
yg/m . The small amount that does not get recovered is disposed of by
burial, or dumping0461.0039,1678,0398,0460 at nQ great expen$e Qr danger>
Recent clinical and laboratory studies1720'1725'1721'1744 indicate that any
beryllium waste can be rendered virtually innocuous by heating to form the
oxide and then firing at 1600 C for 16 hr. The resulting material produces the
mild symptoms generally associated with dusts of clays, iron oxides, etc.
While it is not known how much beryllium is released to the environment
by the burning of coal, investigations in urban and rural areas show a
negligible uptake by humans, animals,, or plants. 64'»0615>
In summary, the recovery and/or disposal of beryllium wastes is
currently handled very adequately at the industrial site level and this
mode should be continued.
250
-------
7. REFERENCES
0039. National Safety Council. Beryllium. National Safety Council Data
Sheet 562, 1965.
0275. Environmental Protection Agency. National emission standards for
hazardous air pollutants, proposed standards for asbestos,
beryllium, and mercury. Federal Register, v. 36, No. 235,
Dec. 7, 1971. p. 23,239-23,256.
0276. Stokinger, H. E., ed. Beryllium: its industrial hygiene aspects.
American Industrial Hygiene Association for the Division of
Technical Information, U. S. Atomic Energy Commission, Academic
Press, New York, 1966. 394 p..
0278. Code of Federal Regulations, Department of Transportation. Title 49,
Parts 71-90. Washington, Superintendent of Documents, U. S.
Government Printing Office, 1967. 794 p.
0394. Personal communication. KBI, to M. Appel, TRW Systems, Jan. 12, 1972.
0398. Personal communication. Dr. M. E. Remley, Atomics International, to
M. Appel, TRW Systems, Jan. 12, 1972.
0458. Bureau of Mines. Mineral facts and problems. 1965 ed. Bulletin 630,
1,117 p.
0459. Personal communication. Brush Beryllium Company, to M. Appel, TRW
Systems, Jan. 21, 1972.
0460. Personal communication. North American Rockwell, to M. Appel, TRW
Systems, Jan. 21, 1972.
0461. Personal communication. County Sanitation Department, Industrial
Wastes Section, to M. Appel, TRW Systems, Jan. 21, 1972.
0599. Personal communication. P. Wilson, Brush Beryllium Company, to
M. Appel, TRW Systems, Feb. 7, 1972.
0615. Schroeder, H. A. Metals in the environment. Environment, 13(8):
18-24, Oct. 1971.
0641. Durocher, N. L. Air pollution aspects of beryllium and its compounds.
Technical Report PB-188-078. Bethesda, Maryland, Litton Systems,
Inc., Sept. 1969. 92 p.
1127. Meechan, W. R., and L. E. Smythe. Occurrence of beryllium as a trace
element in environmental materials. Environmental Science and
Technology, 1(10):839-844, Oct. 1967.
251
-------
REFERENCES (CONTINUED)
1312. Christensen, H. E. Toxic substances; annual list 1971. Rockville,
Maryland, U. S. Department of Health, Education, and Welfare,
Health Services and Mental Health Administration, National
Institute for Occupational Safety and Health, 1971, 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1668. Robinson, J. M., G. I. Gruber, W. D. Lusk, and M. J. Santy. Engineering
and cost effectiveness study of fluoride emissions control, v. 1.
McLean, Virginia, Resources Research Inc., Jan. 1972. 560 p.
1675. Cholak, J. Toxicity of beryllium. ASD-TR-62-7-665. Illinois,
Apr. 1972. 69 p.
1676. Zielinski, J. F. Nature and incidence of beryllium associated diseases.
Brush Beryllium Company, Nov. 1962. 16 p.
1677. Beryllium-hazardous air pollutant. Environmental Science Technology,
5(7):584-585, July 1971.
1678. Environmental Protection Agency. Background information—proposed
national emission standards for hazardous air pollutants—asbestos,
Be, Hg. Research Triangle Park, North Carolina, Dec. 1971.
1719-. Personal communication. Dr. C. R. Sharp, NAPCA, to M. Appel, TRW
Systems, Feb. 11, 1972.
1720. Personal communication. J. P. Butler, KBI Industries, Inc., to
M. Appel, TRW Systems, May 11, 1972.
1721. Personal communication. H. C. Spencer, DOW Chemical Company, to
M. Appel, TRW Systems, May 15, 1972.
1722. Personal communication. Dr. M. E. Remley, Atomics International, to
M. Appel, TRW Systems, May 13, 1972.
1723. Personal communication. G. Port, NAR, Los Angeles Division, to
M. Appel, TRW Systems, May 13, 1972.
1724. Personal communication. H. Weiss, NAR, Rocketdyne, to M. Appel,
TRW Systems, May 13, 1972.
1725. Spencer, H. C., R. H. Hook, et al. Toxicological studies on beryllium
oxides and beryllium-containing exhaust products. AMRL-TR-68-148.
Wright Patterson Air Force Base, Ohio, Aerospace Medical Research
Laboratory, Dec. 1968.
1744. Personal communication. Dr. L. Scheel, National Institute for
Occupational Safety and Health, to M. Appel, TRW Systems, May 22, 1972.
252
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Beryllium Ponder (59)
Common Names Beryllium Powder
Be
Molecular Wt. 9-013
Melting Pt. ^82 C
Density (Condensed) 1 .85 g/cc @ _ 4^ J| _ Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Boiling Pt. 2970 C
9
Flash Point mnn F
Autoigm'tion Temp. N.A.
Flammability Limits in Air (wt %) Lower Moderate
Explosive Limits in Air (wt. %) Lower Slight
Upper_
Upper
Solubility
Cold Water
0
Hot Water Slightly
Ethanol
0?
Others: Dilute acid, base
Acid, Base Properties Slightly basic
Highly Reactive with H2S04' HC1 • Ailing water to evolve H?
Compatible with other metals, oxides, air
Shipped in •
ICC Classification Meta1 P°wder» Poison B. 200 1ttoast. 6uard classification metal powder,
Conrnents c°de °f Federal Regulations (Transportation). Sec. 73-363-73-365 poison B
253
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name :
Structural Formula
IUC Name Beryllium Carbonate (474)
Common Names Basic Beryl!ium Carbonate
BeC03 + Be(OH)2
Molecular Wt. 112.05 Melting Pt. Boiling Pt.
Density (Condensed) @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
Flash Point N'A' Autoigr.ition Temp.N'A'
Flammability Limits in Air (wt %) Lower N.A. Upper_
Explosive Limits in Air (wt. %) Lower N.A. Upper_
Solubility
Cold Water °_ Hot Water Palates EthanQl 0?_
Others: Acids, bases
Acid, Base Properties Basic
Highly Reactive with Dissociates easily in acids
Compatible with Oxides
Shipped in_
ICC Classification Poison B,Poison label, 200 IbsCoast Guard Classification
Conine"tr Highly un^tahlp, pa^iiy rnpyoft'"1 to BpOtOH)-^ by heatin
Code of Federal Regulatinns (Transportation), Spr 7^ ?
254
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name Beryllium Chloride (475)
Common Names Beryllium Chloride
Structural Formula
Bed.
79.93
Molecular Wt.
Density (Condensed) 1.899
Melting Pt. 399 C
25_ _C Density (gas)_
Boiling Pt. 483 C
Vapor Pressure (recommended 55 C and 20 0
1 mm @ 291 C(sublimes)
Flash Point
N.A.
Autoignition Temp .N.A.
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Lower_
Lower
N.A.
N.A.
Upper_
Upper_
very soluble
Solubility
Cold Water
Others: Ether. Benzene. Pyridine
Acid, Base Properties Basic
Hot Water dissociates
Ethanol very soluble
Highly Reactive with Dissociates readily in aqueous solution
Compatible with insoluble in acetone. NH-,
Shipped in
ICC Classification Poison B. Poison Label 200'tbast Guard Classification
Comments Code of Federal Regulations (Transportation). Sec. 73.363-73.365
255
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Beryllium Hydrnxidp (47b)
Common Names Beryllium Hydroxide
Be(OH)2
Molecular Wt. 43-04 Melting Pt. 138 C (decomposes) Boiling Pt.
Density (Condensed) 1.909 @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
Flash Point N.A. Autoignition Temp .M. A.
Flammability Limits in Air (wt %) Lower N-A- Upper_
Explosive Limits in Air (wt. %) Lower N.A. Upper_
Solubility
Cold Water slightly Hot Water slightly Ethanol Q?
Others: Acids. Bases, (NH4)gCQ3
Acid, Base Properties Basic
Highly Reactive with Acid
Compatible with Bases, metals other than alkali metals
Shipped in
ICC Classification Poison B. Poison Label, 200 Ibfoast Guard Classification
Comments rw»rnmn«\goc ;»+ ita r »n p^n A u n
L-vu,,rUm ou D.-U u <-u uau nu
Code of Federal Regulations (Transportation). Sec. 73.363-73.365
256
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
!l. M. Name
n i,- r. -j lAn\ Structural Formula
Beryllium Oxide I4")
IUC Name
Common Names BromellHe, Beryllium Oxide
BeO
Molecular Wt. 25.0 __ Melting Pt. 2530 + 30 C Boiling Pt. 3900 C
Density (Condensed) 3.025 (? __ Density (gas) _ & ___
Vapor Pressure (recommended 55 C and 20 0
Flash Point N.A. _ Autoignition Temp. N. A.
Flammability Limits in Air (wt %) Lower _ N.A. _ Upper
Explosive Limits in Air (wt. %) Lower N.A. _ Upper
Solubility
Cold Water Insoluble Hot Water Insolube Ethanol Insoluble
Others: Cone. H2S04. Fused KOH
Acid, Base Properties Slightly Basic .
Highly Reactive with Very unreactive. extremely stable
Compatible with Metals. Oxides. Air. Water
Shipped in_
ICC Classification Pnisnn p Poisnn Label 200 lbsCoast Guard Classification
nnnd mafprial^ pY*T>pg>rt''^S . ¥pry toy*C
Of Fpdpral BoQiilatinnt (Trangpnrtatinn) , <:cr ?T Jf.Tt.Ti
257
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Beryllium Selenate(478)
Common Names Beryllium Selenate
BeSe04-4H20
Molecular Wt. 224.04 _ Melting Pt. -2H?0 9 100 C ; '4 Wj 1310n°g
Density (Condensed) 2.03 @ 20 _c _ Density (gas) _ &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point _ Autoignition Temp.
Flamniability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %} Lower Upper_
Solubility
Cold Water Very soluble Hot Water ygry soluble Ethanol
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in
ICC Classification Poison B. Poison Label. 200 Ibfoast Guard Classification
Comments Code of Federal Regulations (Transportation). Sec. 73.363-73.305
258
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PROFILE REPORT
Boric Acid (60)
1. GENERAL
Introduction
Boric acid is a white crystalline solid belonging to the triclinic
system. Its solubility in water is low at room temperature but is greatly
increased by heating.
Boric acid reacts with various pyridine bases to form soft, white,
crystalline solids, reported to be nonhygroscopic and, with the exception
of the piperidine-boric acid compound, completely hydrolyzed by dissolution
in water.1433
In 1969, there were 138,969 tons of boric acid produced in the
United States.1751
Manufacture
Boric acid is usually manufactured from borax or from colemanite.
Granulated borax or a hot saturated solution of borax from the borax
refining plant is charged into a reaction vessel. Sulfuric or hydrochloric
acid, concentrated or dilute, is added until the solution is acidic. The
solution is then cooled to the proper temperature, and boric acid crystals
are removed by filtration. If sulfuric acid is used, the mother liquor is
cooled further to recover sodium sulfate decahydrate. The crude boric acid
may be refined by one or more crystallizations from water to yield purified
boric acid.
When boric acid is made from colemanite, the colemanite is ground to
a very fine powder and added in proportions to dilute the mother liquor
and sulfuric acid at about 90 C. To prevent coating the unreacted colemanite
particles with the precipitated gypsum, the slurry is stirred vigorously.
259
-------
The excess acid is neutralized with lime, the iron is oxidized with
permanganate, and the solution is decolorized with activated carbon and
1433
filtered. The solution is cooled to crystallize the boric acid.
Large scale commercial facilities for the manufacture of boric acid
include the following:
U. S. Borax and Chemical Corporation; Des Plaines, Illinois
Ashland Chemical Company; Kansas City, Missouri
Baker Chemical Company; Charlotte, North Carolina
Uses
Boric acid has a wide variety of industrial uses. It is used in salt
glazing in ceramics and in making glazes and ceramic colors. It is a
raw material in making chemicals such as boron trifluoride, fluoborates,
i>orides, and boron carbide. It is used in making boron alloys and
ferroboron, which may be used for hardening steel. It is used in washing
fruit to inhibit mold. It is used in cosmetics, dye stabilizers,
solutions for electroplating nickel, electrolytes for electrolytic condensers,
enamels, flameproofing, welding and brazing fluxes, hardening steel by
heat treatment, fiber glass, optical glass, borosilicate glass, leather
finishing, deliming hides and skins, latex base paints, photography, sand
casting magnesium alloys, laundry starch and textile finishing, sizing,
and scouring compositions.
Boric acid is used in many pharmaceutical preparations as a nonirritant,
mildly antiseptic solution or in protective ointments for inflammations of
the skin and mucous membranes and minor cuts and injuries.
A weak solution of boric acid has for years been a standard household
remedy for washing the eyes. Boric acid is also used in hair rinses and
hand lotions.1433
260
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Physical and Chemical Properties
The physical and chemical properties of boric acid are included in
the attached worksheet.
2. TOXICOLOGY
Boron compounds,with the exception of hydrides are not highly toxic
and therefore are not considered to be an industrial poison. Fatal poisoning
of children has been caused in some instances by the accidental substitution
of boric acid for powdered milk. The medical literature reveals many in-
stances of accidental poisoning due to boric acid, oral ingestion of borates
or boric acid, and presumably absorption of boric acid from wounds and burns.
The fatal dose of orally ingested boric acid for an adult is somewhat more
than 15 or 20 grams and for an infact 5 to 6 grams.
Boron is one of a group of elements, such as lead, manganese and
arsenic, which effects the central nervous system. It is cumulative poison
and since its antiseptic value is weak, other more active and less harmful
therapeutic agents should be employed for medicinal use. Boron poisoning
causes depression of the circulation, persistent vomiting and diarrhea,
followed by profound shock and coma. The temperature is subnormal and a
scaletina from rash may cover the entire body. Boric acid intoxication
can come about from absorbing toxic quantities from ointments applied to
burned areas or wounds involving loss or damage to such areas of skin, but
it is not absorbed from intact skin. When a 5 percent acid solution is used
to irrigate body cavities most of the boric acid is absorbed by the tissues.
Repeated doses can produce pathological changes in the central nervous
system and kidneys.0766
The oral LD5Q value to the rat is 3.5 g/kg for boric acid. The boron
equivalent of this is .60 g/kg.
Rainbow trout were unaffected in a 30-minute test in 0.2 percent boric
acid (350 ppm boron); in 2 percent boric acid .the trout appeared distressed,
261
-------
but were alive after 30 minutes; after one-half hour exposure to a slurry of
solid boric acid (8%), they recovered if placed in running water. The LD5Q
to 15-month old rainbow trout is 339 ppm boron for 48 hours. Safe limits
are listed as 30 ppm for bass and 33 ppm for bluegill.2358
Boron is an essential element to plant growth but is toxic to many
plants at levels as low as 1 mg/liter. The Public Health Service has
established a limit of 1 mg/liter which provides a good factor of safety
physiologically and also considers the domestic use of water for home
gardening.
3. OTHER HAZARDS
Other than the toxic effects, boric acid presents no further problems.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
coat.
Workers handling boric acid should wear rubber gloves and a laboratory
0095
Boric acid should be stored in containers away from any material
intended for consumption by humans or animals.
Adequate procedures for the transportation of boric acid have been
0278
established by the Department of Transportation. Label requirements,
as well as the maximum quantities permitted to be shipped in one outside
container, are also specified.
262
-------
Disposal/Reuse
United States Borax and Chemical Corporation will accept contaminated
and degraded boric acid for reprocessing as long as there is a significant
OO
amount of the material to be reprocessed and it is in concentrated form.
U. S. Borax has a plant that manufacturers boric acid in Wilmington,
California. The effluent from the plant contains about 3,000 ppm of boron
and has been discharged directly into the ocean for many years. Although
U. S. Borax plans to discontinue this practice shortly, it is claimed that
the marine life around the discharge point has not been affected.
The acceptable criteria for the release of boric acid into the environment
are defined in terms of the following provisional limits:
Contaminant and Basis for
Environment Provisional Limits Recommendation
Boric acid in air 0.1 mg/M3 0.01 TLV for B203
Boric acid in water 1 ppm (itig/1) as B Drinking water
and soil standard
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Coagulation and Filtration.
U.S. Borax and Chemical Corporation indicates that boric acid
may be removed from aqueous waste streams by reacting the material with
appropriate quantities of lime. Lime will react with boric acid to deposit
calcium borates which can be filtered from solution. This will not remove
all of the borate, however, as calcium borates are soluble in water to the
extent of about 0.2 percent BgOg (620 ppm boron). The removal of this
residual amount will require more elaborate treatment methods such as
ion exchange or adsorption with selected clays. The borates contained
in the calcium borate sludge formed in this process are not easily
263
-------
recoverable, and are usually sent to Class 1 sanitary landfill areas
for disposal.2346
Option No. 2 - Ion Exchange
Rohm and Haas offers a boron specific ion exchange resin (Amberlite
XE 243) which will remove boron from solution to extremely low levels
(below 1 nig/liter). Since ion exchange systems operate best with dilute
solutions, this process could be used in conjunction with coagulation and
filtration (discussed above) to produce an effluent with an acceptable
concentration of boron. The major drawback affiliated with the use of
the Rohm and Haas resin is the high operating costs involved.
Option No. 3 - Adsorption with Clays.
Selected clays might be used for the removal of borate in low
concentrations. This process could be used in conjunction with coagulation
and filtration to further reduce the boron concentration. Clays, however,
are not specific and a large volume would be required per unit of liquor
passing the clay body.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Considering the relatively low toxicity of boric acid, and the
provisions for the disposal of the major portion of waste boric acid
by the producers, it is felt that boric acid does not warrant National
Disposal Site treatment. The problem of small amounts of residual waste
boric acid being discharged in the plant effluent is currently being
solved by the manufacturers because of the stringent environmental
regulations recently imposed. U.S. Borax, for example, wilt soon connect
with a new industrial sewer line that will take the combined effluents
of the industries in the area to a secondary treatment plant before
discharge to the ocean.
In summary, the disposal of waste boric acid can be handled
adequately at the industrial site level and this mode should be continued.
264
-------
7. REFERENCES
0095. Laboratory waste disposal manual. Manufacturing Chemists
Association. (Revised as of May 1970). Washington, 1970.
175 p.
0278. Code of Federal Regulations. Title 49—transportation parts 71
to 90. (Revised as of Jan. 1, 1967). Washington, U. S.
Government Printing Office, 1967. 794 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. Washington,
Federal Water Pollution Control Administration. Apr. 1, 1968. 234 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. v. 2. New
York, Interscience publishers. 1966. 899 p.
1670. Chemical Week. 1972 Buyers guide issue, part 2. 109 (17):618,
Oct. 1971.
2346. Personal communication. Grover Collins, U. S. Borax and Chemical
Corporation to D. Dal Porto, TRW Systems, Sept. 25, 1972.
Boric acid waste treatment.
2358. Sprague, R. W. The ecological significance of boron. Los Angeles,
U. S. Borax and Chemical Corp., 1972. 58 p.
265
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. H. Name Boric Acid (60)
Structural Formula
IUC Name
Common Names Boric Acid
H3B03
(1)
Molecular Wt. 61.84 * ' Melting Pt.185 C (decomposes) Boiling Pt..1 1/2 HgO
Density (Condensed) 1.435(1) » 15 C ^ Density (gas) » ~^° C
Vapor Pressure (recommended 55 C and 20 Q)
Flash Point ._ Autoignition Temp.
Flamiability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water 6.35 g/100 a:*1) Hot Mater 27.6 g/100 CC (]) Ethanol.
Others: glycerine 28 g/100 CC; methyl alcohol 20.20 g/100 CC^)
Acid, Base Properties .
Highly Reactive with
Compatible with
Shipped in_
ICC Classification Coast Guard Classification
Commen ts '
References (1) 0766
266
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PROFILE REPORT
Boron Trlfluoride (63)
1. GENERAL
Boron trifluoride is a colorless gas which fumes in moist air and has
a pungent suffocating odor. It is nonflammable and does not support
combustion. It is normally packaged in cylinders as a nonliquified gas
at pressures of 2,000 psig at 70 F. It is very soluble in water with
decomposition (forming fluoboric and boric acids) and is heavier than
air.1301 I
worksheet.
air. Physical/chemical properties are summarized in the attached
Boron trifluoride is used extensively, industrially, as a catalyst
in isomerization, alkylation, polymerization, esterification and con-
densation reactions. Boron trifluoride is also used in gas brazing. Its
other uses are as a filling gas for neutron counters and in the preparation
of diborane. 1301
Boron trifluoride is manufactured commercially by adding borax to
hydrofluoric acid to yield water and Na20'(BF3)., or by treating boric
acid with ammonium fluoride to yield water, ammonia and the compound
(NH^JpO*(BF-J^. The boron trifluoride complex is transferred to a
generator and is treated with cold fuming sulfuric acid. The reaction
mass is slowly heated and the generation of boron trifluoride is controlled
by regulating the temperature.
267
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2. TOXICOLOGY
Human Toxicity
Boron tri fluoride is very irritating to the respiratory tract. Exposure
of the skin and eyes, and breathing of boron tri fluoride should be avoided.
The American Conference of Governmental Industrial Hygiem'sts in 1971 recom-
•J
mended a Threshold Limit Value (TLV) in air of 2 mg/M . No medical:
evidence of chronic effects has been found among workmen who have frequently
been exposed to small amounts for periods up to 7 years. In tests on mice,
a concentration of 15 ppm for 30 days produced dental fluorosis. The inha-
lation lethal concentration (LC) for rats is 750 ppm. At high concentra-
tions boron trifluoride causes burm &n the skin similar to, but not as
penetrating as those from hydrogen fluoride.
Toxicity Toward Plant Life
If allowed to escape, boron trifluoride will kill plant life in the;
nearby area. Trace amounts of boron trifluoride escaping from a reactor can
be detected by the white fumes produced. In Los Angeles, the Los'Angeles Air
Pollution Control District makes frequent inspections of any users-plant.
3. OTHER HAZARDS
Boron trifluoride is nonflammable and does not support combustion.
BF3 hydrolyzes in contact with water, forming fluoboric and boric acids.
The boric acid is extremely corrosive to iron, steel, and aluminum.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Boron trifluoride is packaged and shipped, in steel cylinders
under Department of Transportation and Coast Guard regulations as a
nonflammable, compressed gas, taking a Green Label. The filled
cylinders have an internal pressure of 2,000 psig at 70 F. Boron
268
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trifluoride cylinders should be handled with all of the precautions ^used
with cylinders of high pressure compressed gases. The cylinders should
be protected against impact, assigned a definite dry cool well-ventilated
fire-resistant area for storage, and shielded from direct sunlight, the
extremes of weather, and temperatures above 125 F. In addition, due to
the reactivity of BF3 with water, amines, alcohol, ether and other compounds,
traps or check valves should be used in the piping system to prevent
suckback of liquid into the cylinder.
Personnel handling the BF3 should wear chemical safety goggles and
rubber gloves, and should be provided with a gas mask for acid gases,
or have an independent air/oxygen supply mask available. Dry boron
triffuoride can be handled in steel, stainless steel, copper,nickel,
monel, brass and aluminum and the more noble metals up to 200 C. At
low pressures and for temperatures up to 200 C Pyrex glass can be used.
Copper is recommended as the metal for handling the moist gas. Saran
tubing, hard rubber, Teflon, polyethylene, Pyrex glass and pure polyvinyl
chloride are not attacked at temperatures up to 80 C.
Disposal/Reuse
A definition of acceptable criteria for the disposal of boron
trifluoride must also take into account acceptable criteria for the
release or treatment of compounds formed during treatment of boron
trifluoride. Compounds formed and their disposition are as follows:
Compounds Formed Disposition
Calcium Fluoride Insoluble, place in landfill
Boric Acid See Profile Report on boric
acid (60)
Safe disposal of BF3 is defined in terms of the recommended provisional
limits in the atmosphere, water and soil. These are:
269
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Contaminant in Provisional Limit Basis for Recommendation
Air
Boron trifluoride 0.03 mg/M3 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Boron trifluoride 0.15 mg/1 Stokinger and Woodward
hydrolysis products Method
5. EVALUATION OF PRESENT MANAGEMENT PRACTICES
The manufacturers of boron trifluoride do not normally discharge
waste streams because the preparation is carried out in a closed system.
Boron trifluoride is usually recovered after its use as a Lewis acid
1415
catalyst in organic reactions by distillation, by chemical reaction,
or by combinations of the two methods. When amines or ammonia are used
to strip BF3 from spent catalyst, NH3'BF3 or RNH2'BF3 are formed; the boron
trifluoride is liberated from the complexes by treatment with sulfuric
acid. The amine or ammonia complexes can also be reacted with compounds
that form more stable complexes than the boron trifluoride complex, thus
liberating boron trifluoride. Selective solvents are sometimes used to
extract the spent boron trifluoride catalyst from the reaction media.
If a fluoride salt is added to the spent catalyst, a precipitate,
BFo'MF is formed which upon heating liberates boron trifluoride. The
regenerated BF3 from these processes is recycled for reuse.
The method currently employed to dispose of excess or contaminated
boron trifluoride, is to discharge the gaseous BF3 into a water spray.
The reaction first gives a precipitate of boric acid and then a solution
of fluoboric acid:
BF3 + 3H20 •* B(OH)3 + 3HF
BF3 + HF•* HBF4
270
-------
The fluoboric acid is treated with lime or limestone, and decomposes to
calcium fluoride and boric acid. The calcium fluoride produced is
either sent to a land fill, or lagooned. The boric acid produced is
discharged to sewer; it can be handled as discussed in the Profile
Report on boric acid (60).
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is expected that boron trifluoride will either be recovered for
reuse or destroyed by the satisfactory procedure discussed above. It is
our conclusion that boron trifluoride is not a candidate waste stream
constituent for National Disposal Sites.
271
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7. REFERENCES
1160. Durrant, P. J., and B. Durrani. Introduction to advanced inorganic
chemistry. 2d ed. New York, John Wiley and Sons, 1970. 1,249 p.
1301. Matheson gas data book. 4th ed. East Rutherford, New Jersey,
Matheson Co. Inc., 1966. 500 p.
1304. Personal communication. Mr. Stanfield, Allied Chemical Corporation,
to J. R. Denson, TRW Systems, Mar. 16, 1972.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
supplement. New York, Wiley-Interscience Publishers, 1963-1971.
272
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
i
H. M. Name Boron Trifluoride (63)
Structural Formula
IUC Name Boron Tri fluoride
Common Names
BF
3
Molecular Wt. 67-82 Melting Pt. -127.1C Boiling pt. -100-4 C
Density (Condensed) 1.57 0-100.4 C Density (gas) 3.077 @ Q c
Vapor Pressure (recommended £5 C and 20 0
139.7 Torr 9 -120.5 C 760 Torr 9 -1QQ.4 C 10 atmos. $ -54.4
Flash Point Autoignition Temp._
Flammability Limits in Air (vrt X) Lower Upper_
Explosive Limits in Air {wt. *> Lower Upper_
Solubility
Cold Mater' 369.4g/10Qq fe 6 C Hot Water Ethanol Forms Complex
Others: 1.94g/100g HoS04; soluble in most organic liquids such as saturated hydrocarbons
Acid, Base Properties Lewfs acid
Highly Reactive with HNOj 9 20 C; decomposes in aqueous bases
Compatible with Copper, iron, stainless steel, chromium, mercury
Shipped in SteeT cylinders under pressure. 1500-1800 psi
cylinders are either 6 or 62 Ib. BF, - in tube trailers 12,000-13,000 Ib.
ICC Classification Nonflammable coup, gas Coast ward Classification Nonflammable comp.
Consents.
Green label gas Green Label
Critical temp - 12.25
Critical Pressure - 12.25 C
References (1) 7301
273
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PROFILE REPORT
Bromic Acid (64)
1. GENERAL
Bromic acid is a colorless or slightly yellow liquid that turns yellow
on exposure to air. It is unstable except in dilute solutions and is
almost never sold as bromic acid. Bromic acid is used as an oxidizing
agent in the preparation of dyes, organic compounds, and Pharmaceuticals
and in the oxidation of mercaptan groups to disulfide groups in wool and
hair treatment. When required, it is usually prepared for immediate use
by adding sulfuric acid to barium or sodium bromate and the bromic acid
recovered as an aqueous solution by subsequent distillation and absorption
in water.
Potassium and sodium bromate, because of their use as "neutralizers"
in home permanent cold wave kits, are the major bromate wastes. They are
generally discharged as dilute solutions, directly to municipal or other
local sewer systems.
The limited physical/chemical properties reported for bromic acid
are summarized on the attached worksheet.
2. TOXICOLOGY
Bromic acid is not highly toxic, but because it is a strong oxidizing
agent it causes severe irritation of the skin, eyes and upper respiratory
tract.
Potassium and sodium bromate are the most common sources for bromate
ingestion. The mean lethal dosage for bromate has not been established;
rabbits succumbed to an oral dosage of 0.5 gm/Kg of NaBrO.,, while about
14.2 gm has been the cause of death in a 19 month old child.2376
275
-------
Upon heating or standing bromic acid decomposes with liberation of bromine
and oxygen. The toxicity of bromine then becomes the controlling factor
(See Profile Report on Bromine £65]). Bromine has a Threshold Limit Value
(TLV) of 0.7 mg/M3.
3. OTHER HAZARDS
Bromic acid produces a fire hazard on contact with organic matter. It
1138
will corrode most metals other than silver, platinum, and tantalum.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Bromic acid is handled in the same manner as any aqueous solution of
a strong acid which is also a strong oxidizing agent. Contact with reducing.
substances is permitted only under controlled conditions. Solutions of HBrO^ .
should be stored in glass or Teflon, protected from sunlight and extremes
of temperatures.
Though bromic acid is almost never shipped it may be shipped under
Department of Transportation regulations for a corrosive liquid with a
White Label, in properly protected glass containers.
Bromic acid, because of its instability, will probably decompose to
bromine and bromides on release to the environment. Safe disposal of bromic
acid is defined, therefore, in terms of the recommended and provisional
limits for bromine in the atmosphere and in water and soil. These recommended
provisional limits are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Bromine 0.007 mg/M3 0.01 TLV
Contaminant in Water Provisional Limit Basis for
and Soil r_ Recommenda ti on
Bromine 0.035 mg/L Drinking Water
Studies
276
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Reduction and Discharge
Small packaged lots of bromic acid may be decomposed by the addition of
reducing materials such as sodium thiosulfate, bisulfites or ferrous salts.
This method is recommended by the Manufacturing Chemists Association, but
procedures for recovery of the bromides produced are not provided. Instead,
when reduction is complete, the treatment solution is neutralized with soda
ash, and the solution is washed down the drain with a large excess of water.
This process is satisfactory for small quantities of bromic acid, but the
process is not recommended for larger quantities because valuable bromides
will be lost.
Option No. 2 - Reduction and Recovery as Bromide
Bromic acid, like bromine, is recovered from a dilute solution or
waste stream by passing an aqueous solution over iron turnings to produce
the so-called ferrosoferric bromide. This is decomposed by sodium carbonate,
the excess carbon dioxide boiled off and the sodium bromide crystallized
and sold.1138
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Bromic acid is not a candidate waste stream constituent for National
Disposal Sites because it is not stable, and therefore, requires treatment
at the site where the waste originates. Option No. 2 is the process re-
commended for treatment of wastes containing bromic acid. This process
is simple and can be performed by any plant using bromic acid.
277
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7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. v. 35. Occupational Hazards, Aug. 1971.
p. 35-40.
1138. Jolles, Z. E. Bromine and its compounds. New York, Academic Press,
1966. 640 p.
1305. Personal communication. Mr. Sharp, Dow Chemical Company, to
J. R. Denson, TRW Systems, March 16, 1972. Bromine, hydrogen
bromide and bromic acid disposal.
1416. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
2376. Gleason, M. W., R. E. Gosselin, H. C. Hodge, and R. P. Smith.
Clinical Toxicology of Commercial Products 3rd ed. Baltimore,
Williams and Wilkins Company, 1969. 1,428 p.
278
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Bromlc acid (64)
IUC Name Bromic acid
Common Names
Structural Formula
HBrO,
Molecular Wt. 128.92
(1)
Melting Pt.
(1)
Boiling Pt. decomposes 100C
Density (Condensed) 3.188 g/cc @ 20 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water completely miscible Hot Water
Others:
Acid, Base Properties strong acid ; strong oxidizing agent
Ethanol
Highly Reactive with Reducing substances; bases; most metals
Compatible with Glass
Shipped in Not usually shipped
ICC Classification Corrosive liquid
Comments White Label
Coast Guard Classification corrosive liquid
White Label
References (1) 1416
279
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PROFILE REPORT
Bromine (65)
1. GENERAL
Bromine is a member of the halogen family and is a brown-red, fuming,
heavy and highly corrosive liquid. It is the only non-metallic element
liquid at room temperature. Bromine is manufactured in the United States
principally at the Ethyl Dow plant at Freeport, Texas, built during the sec-
ond World War. Other production is from the Michigan brines. About 90
percent of the domestic output is used in the manufacture of ethylene di-
bromide, an anti-knock fluid, used in conjunction with tetra-ethyl lead in
gasoline. This demand is subject to change as lead is phased out of gasoline.
In the United States the chief raw material for bromine manufacture is
sea water in which bromine occurs in concentrations of 60 to 70 ppm. It is
also manufactured from natural brines. Sea water or brine is acidulated
with dilute sulfuric acid to a pH of 3, and chlorinated.
The chlorinated sea water (or brine) is stripped of bromine by air
blowing, and returned to the ocean (or re-injected via a deep well). The
moist bromine-containing air from the stripping tower, contaminated with
a small amount of vaporized chlorine, is reacted with less than stoichio-
metric quantities of sulfur dioxide and water in an absorption tower to
form a solution of bromine in mixed hydrobromic, hydrochloric and sulfuric
acids. The mixed solution is reacted with an excess of'chlorine and the
liberated bromine is steam-stripped from the solution, condensed as liquid,
and purified by distillation. Any excess chlorine is recycled, as is the
residual sulfuric and hydrochloric acid solution. This manufacturing
process creates as waste streams only the sea water or brine from which
1138
the bromine was removed.
281
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The physical/chemical properties for bromine are summarized in the
attached worksheet.
2. TOXICOLOGY
Human Toxidty
Liquid bromine rapidly attacks the skin and other tissues, producing
irritation and burns which heal slowly. Even very low concentrations of
the vapor are highly irritating to the respiratory tract. The chronic
effects of inhalation of bromine vapors include reduced red cell and
hemoglobin content of the blood. The leucocyte count may increase, some-
times up to fourfold.1138
The good warning properties of bromine (its pungent, irritating nature
and dark brown color) help in preventing dangerous exposure of humans to
the vapor. Concentrations as low as 0.3 ppm cause irritation of the eyes.
A concentration of 7 ppm of bromine in the air is thought to cause fatal
illness in man after exposure of half an hour to one hour. The TLV for
bromine, the highest concentration considered safe for 8 hours continuous
11 ^8
exposure, is 1 ppm.
Other Toxicity
Bromine reacts rapidly, at ambient temperatures in an aqueous media,
with many substances known to be constituents of living matter. With
unsaturated aliphatic acids, dibromides and bromohydrins are formed;
aromatic aminoacids such as tyrosine undergo ring substitution; amino
groups form bromamine derivatives; and thiols are oxidized to sulphinic
and sulfonic acids and disulfides. Specific toxic action is illustrated
by the rapid germicidal effect of trace concentrations, 0.1 ppm of bromine
or less, on the activity of various enzymes. Bromine is more effective
than chlorine in killing bacterial spores, yeasts, molds and algae.
Bromines toxicity to microorganisms has been put to good use, but like
282
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chlorine the concentration level must be controlled to avoid damage to
plants and fish. In swimming pools concentrations of 9 ppm bromine can be
1138
reached without irritation to the eyes to swimmers.
3. OTHER HAZARDS
Bromine may produce a fire on contact with organic matter such as
sawdust. Moist bromine reacts with most metals with lead being attacked
only slowly. Dry bromine can be contained by monel.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Storage, Handling, and Transportation
Drums for bromine storage are made of monel or of lead-lined steel.
Only very dry bromine can be stored in monel. Glass or glass lined con-
tainers are also used.
The chemical reactivity of elemental bromine with living matter presents
a serious hazard in handling. Prolonged exposure to even very low concen-
trations of the vapor must be avoided. Effective safety devices which should
be at hand when bromine is handled are: water safety showers and eye-wash
fountains, safety face shields and rubber gloves. Annydrous ammonia in
cylinders can be used to knock down bromine fumes. Liquid spills can be
decontaminated with saturated alkaline thiosulfate solution or a lime slurry.
Bromine is classified by the Department of Transportation (DOT) as a
corrosive liquid requiring a White Label. Due to the high cost of packing
and insurance, bromine is seldom transported overseas. Only small quantities
compared to the total production are shipped. Most of bromine produced is
consumed in the integrated chemical plants where it is manufactured. Drums
(monel or lead lined) with a capacity up to 225 Ib are in use for shipping
I I OQ
bromine; tank cars with a capacity up to 50 tons are used for bulk
shipment.
283
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Disposal/Reuse
Because the value of bromine is great, little is disposed of. The
recommended provisional limits for bromine in the atmosphere and in water
and soil are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Bromine 0.007 mg/M3 0.01 TLV
Contaminant in Basis for
Hater and Soil Provisional Limit Recommendation
Bromine 0.035 mg/1 Stokinger and
Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Bromine is a valuable commodity and is seldom disposed of as a waste.
If disposal of contaminated bromine or bromine solution is required, the
bromine or bromine solution is returned to the manufacturer for recovery.
The manufacturer will in most cases buy the bromine. If bromine vapor
is in a process waste stream, it can be condensed easily. If the bromine
is in an aqueous waste stream that is too dilute for shipment, concentra-
tion is required. Concentration is accomplished in the same manner used
to recover bromine from sea water, i.e., chlorine is used to oxidize any
bromide to bromine and the solution is air stripped of the bromine, which
is subsequently trapped in an ice cooled condenser. The impure bromine can
be used or returned to the manufacturer.
An alternate recovery process is to pass an aqueous waste stream con-
taining bromine over iron turnings to produce so called ferroso-ferric
bromide. This is decomposed by sodium carbonate, the excess carbon dioxide
1138
boiled off and the sodium bromide crystallized and sold.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
With the exception of the return of contaminated bromine or bromine
compounds to the manufacturer for purification, bromine waste streams can
284
-------
be best handled at the site where they originate. Designated sites (at
the primary bromine producers) should be identified for the economic
recovery of bromine from waste streams from .the few sources not equipped
with recovery systems.
285
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7. REFERENCES.,
1138. JolTes,, Z. E. Bromine and its compounds. New. York, Academic Press,
1966, 940. p.
1305. Personal' communication. M. Sharp, Dow Chemical Company,, to J. R.
Denson, TRW Systems, Mar. 16, 1972.
286
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Bromine
Structural Formula
IUC Nams Bromine
Common Names
Molecular Wt. 79.909 _ Melting Pt. -7.3 C Boiling Pt. 52.2 C
Density (Condensed) 3.119 g 25 C^ Density (gas) 3.5 _ (3 _ 20_ C
Vapor Pressure (recommended 55 C and 20 0
2 atm g 78.8 C 3 atm 9 110.3 C 10 atm p 139.8
Flash Point - Autoignition Temp. -
Flammability Limits in Air (wt %) Lower -_ Upper_
Explosive Limits in Air (wt. X) Lower - Upper_
Solubility
Cold Water 3.41 g/lOOg at 20 C Hot Water 3.33 q/IOOg at 40 C Ethanol freely soluble
Others: freely in chloroform, CS2, CCl^ H)
Acid, Base Properties
Highly Reactive with Alkali hydroxides, arsenites and other oxidizable materials'"'
Compatible with
Shipped in 1 and 6.5 Ib bottle, 10 gal drums, tank cars, trucks
ICC Classification corrosive liquid <1 qt^2^ coast Guard Classification *h1te label1
white
Comments
References (1) 1492
(2) 0766
287
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PROFILE REPORT
Chlorosulfonic Acid (112)
1. GENERAL
Chlorosulfonic acid is an important item of commerce, tank-car
quantities being used as an intermediate in the production of synthetic
detergents, drugs, ion exchange resins, and dyestuffs. It has also
been used as a smoke-forming agent in warfare. Chlorosulfonic acid may
be considered as a mono acid chloride of sulfonic acid, since one
chlorine atom has replaced one hydroxyl group. It is a clear, colorless,
mobile liquid which decomposes slightly when distilled. It reacts with
water with explosive violence and fumes strongly in moist air to form a
persistent, irritating aerosol of sulfuric and hydrochloric acids. It
also reacts with almost all organic materials; in some cases with
charring.
Chlorosulfonic acid is a strong acid containing a relatively weak
sulfurchlorine bond. It is a powerful sulfating and sulfonating agent,
a fairly strong dehydrating agent, and a specialized chlorinating agent.
In most of its applications it is used to form sulfates, sulfonates and
sulfonyl chlorides with such organic compounds as hydrocarbons, alcohols,
phenols and amines. Many salts and esters of Chlorosulfonic acid are
known, but most of them are relatively unstable or hydrolyze readily in
moist air.
Manufacture of Chlorosulfonic acid is accomplished by the direct
union of sulfur trioxide with dry hydrogen chloride gas. The sulfur
trioxide may be in the form of 100 percent liquid or gas, as obtained
from boiling oleum, or may be present as a dilute gaseous mixture obtained
directly from a contact sulfuric acid plant. The reaction of sulfur
trioxide and hydrogen chloride takes place spontaneously with evolution
1433
of a large quantity of heat. The chemical/physical properties for
Chlorosulfonic acid are given in the attached worksheet.
289
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2. TOXICOLOGY
Chlorosulfonic acid will cause severe acid burns on contact of the
liquid with the skin or mucose, and the vapor is very irritating to the
eyes, lungs, and mucous membranes. It can cause acute toxic effects in
either the liquid or vapor state. Inhalation of concentrated vapor may
cause loss of consciousness with serious damage to lung tissue. Upon
ingestion, it will burn and destroy the mucose of the mouth, esophagus
and stomach to a serious degree. Contact of the liquid with the eyes can
cause permanent destruction of the tissues involved. Even in the vapor
state it causes conjunctivitis. Chlorosulfonic acid does not have a
Threshold Limit Valve (TLV) established by the American Conference of
Governmental Industrial Hygienist (ACGIH) but the TLV of 5 ppm for
hydrochloric acid should be considered the maximum level of exposure for
0095
an 8-hr work day of a 40-hr work week.
3. OTHER HAZARDS
Chlorosulfonic acid is corrosive, functioning both as a strong acid
and as a dehydrating and charring agent. It has an appreciable vapor
pressure and through the action of moisture in air (or water) is
decomposed to hydrochloric acid and sulfuric acid. Good ventilation
should be provided, and goggles, gloves, protective clothing, and face
shields should always be worn when handling this material.
The acid itself is not flammable, but may cause ignition by contact
with combustible materials. The flammable and explosive gas, hydrogen,
is slowly generated by action of the acid on moist metals.
4. .DEFINITION OF ADEQUATE WASTE MANAGEMENT
When working with Chlorosulfonic acid waste or spills, in addition
to the protective devices indicated above, a self-contained breathing
apparatus should be employed. For small quantities work can be performed
in a fume hood, and a laboratory coat, goggles and gloves should be worn.
Spills of small quantities should be covered with excess sodium
290
-------
bicarbonate and the mixture diluted with a large quantity of water.
Spills of larger quantities should very carefully be diluted with a large
quantity of water and neutralized with lime.
Chlorosulfonic acid is shipped in bottles, 170-lb carboys, 1,600-lb
stainless steel drums and 8,000-gal tank cars. It is shipped under
Department of Transportation regulations as a corrosive liquid requiring
a White Label.1416
The safe disposal of chlorosulfonic acid is defined in terms of the
recommended provisional limits 1n the atmosphere and in water and soil
environments. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limits Basis for Recommendation
3
Chlorosulfonic Acid .01 mg/M Limit for hLSO.
Contaminant in
Water and Soil Provisional Limits Basis for Recommendation
H2S04 (hydrolysis .05 ppm Limit for H2SO.
product of chloro-
sulfonic acid in
water)
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The method of disposal of packaged lots of chlorosulfonic acid
recommended by the Manufacturing Chemists Association is satisfactory
if the effluent from the disposal process is within the limits for pH,
chloride ion» and sulfate ion.
In this procedure chlorosulfonic acid is decomposed by pouring small
quantities from behind a shield onto a dry layer of sodium bicarbonate.
After mixing thoroughly, the sodium bicarbonate, while being stirred, is
sprayed with 6M ammonium hydroxide. Then the sodium bicarbonate is covered
with a layer of crushed ice; and while continuing stirring, the sodium
bicarbonate mixture is again sprayed with 6M ammonium hydroxide. When
evolution of ammonium chloride (which must be trapped and disposed of) has
291
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partially subsided, the sodium bicarbonate solution is neutralized with
hydrochloric acid. Following dilution to the concentration permitted for
effluents (see Section 4), the treated solution is discharged into a stream
or storm sewer.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that the great majority of chlorosulfonic waste
will continue to be best handled at the source of the waste generated.
Because the process requires little special equipment and, when performed
properly, no new very toxic materials are created, chlorosulfonic acid
does not appear to be a candidate waste stream constituent for a National
Disposal Site.
292
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7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal
manual. 2d ed. Washington, 1969. 176 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22v. and
Supplement. New York, Wiley-Interscience Publishers, 1963-1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p..
0536. Federal Water Pollution Control Administration. Water quality
criteria, Washington, 1968. 234 p.
1416. Ross, A. and E. Ross. Condensed chemical distionary. 6th ed.
New York, Reinhold Publishing Corporation, 1966. 1,256 p.
293
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Chlorosulfonic Add
IUC Name Chlorosulfonic Acid
Common Names Sulfuric Chlorohydrin
Structural Formula
C1S03H
Molecular Wt. 11.653
Density (Condensed) 1.766
Melting Pt. -80C
18 _C Density (gas)_
Boi.ling Pt. 151.DC
Vapor Pressure (recommended 55 C and 20 C)
1 torr at 32 C
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. 3!) Lower_
Upper_
Upper_
Solubility
Cold Water_
Others:
reacts
Hot Water reacts violently Ethanol reacts
Acid, Base Properties
contact with water forms hydrochloric or sulfuric acid.
Highly Reactive with Most organic materials; water
Compatible with_
Shipped jn Carboys. 1600 pound drums. 8.000 gallon tank cars
ICC Classification corrosive liquid Coast Guard Classification corrosive liquid
Comments Extremely caustic, corrosive and toxic liquid.
References (1) 1416
294
-------
PROFILE REPORT
Chrome (113)
1. GENERAL
Introduction
Chromium is a metallic element with properties resembling iron
occurring mainly in chrome/iron ore (FeO • Cr203). It is a very
infusible, hard, gray metal which is incorporated in the manufacture of
stainless steel and other corrosion resistant alloys. Chrome is exten-
sively used as a plating on other metal surfaces to give a hard, corrosion
resistant, beautiful surface and also finds wide use as a catalyst.
The ferro chromium alloys are made by silicon reduction of chromite
ores in a two-stage process. Initially a high silicone ferro chromium is
produced in a submerged arc furnace. Then this product is treated in an
open arc type furnace with a synthetic slag containing Cr203> To
produce chromium metal either electrolytically or by the reduction of
chromium compounds, a chemical treatment is necessary to remove the iron
and other impurities from the starting materials. Reduction methods start
with chromium oxide Cr20o which has been obtained from chromite ore via
sodium bichromate. Commercial chromium metal is produced by reducing
Cr^Oo with aluminum, although silicon and carbon are sometimes also used
as reducing materials. The aluminum reaction is performed in a refractory
lined vessel which contains the exothermic, self-sustaining reaction.
Chromium metal can also be produced by the electrowinning of chromium from
1433
either chrome alum or chromic acid electrolytes. As far as can be
determined by a review of the literature, no significant amounts of chrom-
ium metal appear as wastes from the production processes.
In 1968 approximately 300,000 short tons of chromium were consumed in
chromium ferro allloys and chromium metal in the United States. The
greatest proportion was used in various ferro chromium alloys. This rep-
1975
resents 60 to 70 percent of the chromium ore processed in the United States.
295
-------
Occurrence as a Waste Product
Chromium, either as a ferro alloy, stainless steel, metallic catalyst
or plate, is relatively valuable and normally is not disposed of without
reuse. Stainless steel and other alloys have considerable value as scrap
metal and these are normally recycled. Chromium plate on scrap metal,
such as that coming from scrapped automobiles, normally is recycled, not
necessarily for the chrome plate but for the scrap steel. The chrome is
believed to be melted down without any prior removal of the chrome plate.
The occurrence of ferro chrome alloys and chrome plated metal as recycled
scrap is widespread in the United States. At the present time the amount
of chrome metal that is actually Tost in junk yards and trash dumps is
not known.
2. TOXICOLOGY
Zero valent chromium, as the pure metal or alloy, is considered to be
1492
essentially nontoxic to plants and animals.
3. OTHER HAZARDS
The dust of chromium metal is considered a moderate fire hazard.
Chromium metal does not exhibit any other hazards.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Chromium does not require special handling when it occurs as a waste
in alloys or as a decorative plate on other metal surfaces. The industries
that use large amounts of chrome and chrome alloy materials should have a
program by which the various types of chrome containing scrap materials
are collected and segregated for recycling. No safety precautions are
required for the handling of the scrap materials except those which would
normally be used for the handling of other common scrap metals. For chrome
dust particles, the recommended provisional limit is:
Contaminant in Air Provisional Limit Basis for Recommendation
Chrome 0.01 mg/M3 0.01 TLV
296
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The only feasible waste management option for chrome metal and chrome
metal alloys is that of recycling scrap for use in new products. There is
a considerable market for this type of scrap material and it is believed
that all major industries who work with these metals have a program by
which the scrap is segregated and saved for sale to a scrap dealer.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Waste chromium metal and chrome alloys are not candidate waste stream
constituents for national disposal. They are essentially non-toxic to both
plant and animal life. Additionally, they are very corrosion resistant
and do not weather to produce harmful corrosion products. Waste chrome
metals and their alloys have inherent value and scrap recovery and recycle
1975
programs are widespread in the industry.
297
-------
7. REFERENCES
0766. Sax, N. I., Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed., 22 v. and
suppl. New York, Interscience Publishers Inc. 1963-1971.
1492. The Merck Index of Chemicals and Drugs. 7th ed. Rahway, New Jersey,
Merck and Company, Inc., 1960. 1,634 p.
1570. Weast, R.C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Chemical Rubber Company, 1969, 2,100 p.
1975. Bureau of Mines. Mineral facts and problems. Bulletin 650.
Washington, Department of the Interior, 1970. 1,291 p.
298
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name
Chrome (113)
Structural Formula
Common Names
Cr
(1)
Molecular Wt.
C1
Density (Condensed) 7.20(1J @ 28
Melting Pt. 1890C
l\
J
Boiling Pt. 2482
(1)
Density (gas) N/A @
Vapor Pressure (recommended 55 C and 20 G)
1 mm
1616C
(2)
Flash Point N/A
Autoignition Temp.
Flammability Limits in Air (wt X) Loner N/A
Explosive Limits in Air (wt. X) Lower N/A
(1)
Upper_
Upper_
N/A
N/A
Solubility
Cold Water insoluble
Hot Water insoluble
(1)
Ethanol
Others : sol in dil
HC1
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
Comments Moderate fire hazard in dust fornr '
Coast Guard Classification
References (1) 1570
(2) 0766
299
-------
PROFILE REPORT
Cobalt Nitrate (116). Ferrous Sulfate (198).
Stannous Chloride (409), Cobalt Chloride (489)
1. GENERAL
Introduction
The inorganic chemicals in this Profile Report are grouped together
because they can be handled by similar disposal processes. Concentrated
aqueous solutions of the salts constitute a hazard or nuisance.
Manufacture and Uses
Cobalt Nitrate. Cobalt nitrate, or cobaltous nitrate, Co(N03)2, is a
red crystalline material which is deliquescent in moist air. Cobaltous
nitrate is prepared by the action of nitric acid on cobalt hydroxide
1492
followed by purification through recrystallization. It is used in:
(1) sympathetic inks;
(2) cobalt pigments; 4
(3) preparation of cobalt catalysts;
(4) additives to soils and animal feeds;
(5) additives to vitamin preparations;
(6) hair dyes;
(7) decorations on porcelain.
Ferrous Sulfate. Ferrous sulfate, FeS04'7H20, crystals or granules
are green, and are often brownish-yellow in color from oxidation and
efflorescence. The sources of commercial ferrous sulfate are:
301
-------
(1) by-product production (from the pickling of steel and from
many other chemical operations);
(2) direct reaction between dilute sulfuric acid and iron;
(3) oxidation of pyrites in air, followed by leaching and treatment
with scrap iron;
(4) by-product production from ilmenite.
The uses for ferrous sulfate include:0955' 1492> 1662
(1) water purification;
(2) source for other iron salts and oxides;
(3) fertilizer;
(4) feed additive;
(5) writing inks;
(6) pigments;
(7) medicine;
(8) deodorizer;
(9) metallurgy;
(10) aluminum etching;
(11) wood preservative compositions.
Stannous Chloride. Stannous chloride, SnCU. is a white crystalline
mass that absorbs oxygen from the air to form the insoluble oxychloride.
1492
It is prepared by dissolving tin in hydrochloric acid. SnClp is used:
(1) as a reducing agent in the manufacture of chemicals and dyes;
(2) in tin galvanizing;
(3) as a reagent in analytical chemistry;
(4) as a stain remover;
(5) in anti sludging agents for lubricating oils;
(6) as a chemical preservative.
Cobalt Chloride. Cobalt chloride or cobaltous chloride,
is prepared by recrystallization of the crude material obtained by reacting
1492
hydrochloric acid with cobalt oxide. It is used:
302
-------
(1) as an absorbent for ammonia;
(2) in gas masks;
(3) in electroplating;
(4) in sympathetic inks;
(5) in hygrometers;
(6) in catalysts;
(7) in barometers;
(8) as a flux for magnesium refining;
(9) as a trace element in feeds and in vitamin B,2 preparation.
Physical/Chemical Properties
The physical/chemical properties for the compounds covered by this
Profile Report are summarized on the attached worksheets.
2. TOXICOLOGY
Stannous chloride is considered relatively nontoxic. Ferrous sulfate,
although used as a diet supplement, has caused death when excessive
OOTC
quantities were ingested. Lowest lethal dose was 0.5 gm. The cobalt
salts have LD50's which range from 100 to 400 mg/Kg for mouse and rabbit.
With the exception of FeSOy,, which has a Threshold Limit Value (TLV)
o 0025
of 1 mg/M as Fe, the American Conference of Governmental Industrial
Hygienists has not established TLV's for any of the compounds listed in
this report.
303
-------
3. OTHER HAZARDS
Cobaltous nitrate is an oxidizing material which, in contact with
organic or other readily oxidizable substances,may cause a violent reaction
or combustion. Ferrous sulfate in aqueous solution witiHg^drrode iron and
most steels.149 The iron, cobalt, and tin salts liste^aJlflhydrolyze to
produce acid solutions. wmci <•
i
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
As discussed in Section 3, cobaltous material is an oxidizing material
and must be handled and stored as such. It is classified by the Department
of Transportation (DOT) and the U.S. Coast Guard as an oxidizing material
that requires a Yellow Label. Ferrous sulfate etches iron and aluminum;
316 stainless steel is relatively unaffected by FeSO^, and is used in con-
tact with aqueous solutions. Other than protection from moisture there are
no additional handling, storage or transportation requirements for the
compounds included in this Profile Report.
Disposal/Reuse
The inorganic chemicals discussed in this report can be reprocessed
for reuse if both quality and quantity of the waste discharged are con-
sistent with economic recovery. If disposal is required,, the acceptable
criteria for the release of these compounds into the environment is defined
in terms of the following provisional limits:
304
-------
Contaminant in Air
Cobalt nitrate
Ferrous sulfate
Stannous chloride
Cobalt chloride
Provisional Limit
0.001 mg/M3 as Co
0.01 mg/M3 as Fe
3
0.02 mg/M as Sn
0.001 mg/M3 as Co
Basis for
Recommendation
0.01 TLV for Co
0.01 TLV for Fe
0.01 TLV for Sn
0.01 TLV for Co
Contaminant in Water
and Soil
Cobalt nitrate
Ferrous sulfate
Stannous chloride
Cobalt chrloride
Provisional Limit
0.05 ppm as Co
0.03 ppm as Fe
0.05 ppm as Sn
0.05 ppm as Co
Basis for
Recommendation
Chronic toxicity
drinking water
standards
Drinking water
standard
Chronic toxicity
drinking water
standards
Chronic toxicity
drinking water
standards
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The Manufacturing Chemists Association has recommended disposal of
packaged lots of the materials in this report as follows. The salts are
dissolved in a large excess of water, and treated with a slight excess of
soda ash which precipitates the cobalt, ferric and tin ions. When the
sulfate ion is present, slaked lime is also added to reduce the sulfate
ion concentration. After standing 24 hours, the supernatant liquid is
decanted into another container and neutralized with hydrochloric acid,
and the liquid is diluted further before discharge into a sewer or stream.
The sludge is added to a landfill.
305
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Based on the discussion of disposal in Section 5, it may be concluded
that after preliminary treatment with soda ash (and lime when sulfate ions
are present) the treated waste streams containing the materials discussed
in this report can be discharged into municipal sewers or streams. Because
waste treatment can be handled adequately locally, these compounds do not
merit consideration as candidate waste stream constituents for national
disposal.
306
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, 35:35-40, Aug. 1971.
0776. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation, 1957. 1,467 p.
0955. Sittig, Marshall. Inorganic chemical and metallurgical process
encyclopedia. Park Ridge, New Jersey, Noyes Development
Corporation, 1968. 883 p.
1492. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, Chemical Rubber Company, 1966. 1,500 p.
1662. Shreve, R. N. Chemical process industries. 2d ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
2376. Gleason, M. N., R. C. Gosselin, H. C. Hodge, and R. P. Smith.
Clinical toxicity of commercial products. 3d ed. Baltimore,
Maryland, The Williams and Wilkins Company, 1969.
307
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Cobalt Nitrate (116)
IUC Name Cobaltous Nitrate
Common Names
Structural Formula
Co(N03)2 • 6H20
Molecular Wt. 291.05
(1)
Melting Pt. <100 C
(1)
Boiling Pt. -3H00. 55
Density (Condensed) 1 .87g/cc @ _ 20 r' Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 138.8g/100 ml at 0
Others:
Hot Water very soluble
^1
Ethanol100 ml at 12 C
0).
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped jn Glass bottles, wooden barrels^ '
ICC Classification oxidizing material'
Cotnmen ts
Coast Guard Classification oxidizing material'
References (1) 1570
(2) 1492
308
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Ferrous Sulfate (198)
IUC Name
Common Names Copperas, Iron SuTfate
Structural Formula
FeS04 • 7H20
Molecular Wt. 278-01 Melting Pt. 64 C. -6H?0
Density (Condensed)! .898q/cc @ 20 C Density (gas)
Boiling Pt. 300 C. -7H90
Vapor Pressure (recommended 55 C and 20 Q
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 15.65g/100 ml
Others:
(1)
(1)
Hot Water 48.6g/100 ml at 50 C Ethahol Insoluble
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in Bottles, bags, barrels, bulk
ICC Classification None
Comments
(2)
Coast Guard Classification None
(2)
References (1) 1570
(2) 1492
309
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Stannous Chloride (409)
IUC Name Stannous Chloride
Common Names Tin Chloride
Structural Formula
SnCl.
Molecular Wt. 189.
Density (Condensed) 3.393g/cclT^d 245
Vapor Pressure (recommended 55 C and 20 0
Melting Pt. 264.0 C
(1)
Density (gas)
Boiling Pt. 623 C(1)
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper
Solubility
iDinty ^j
Cold Water 83.9g/TOO-ml at 10 C^ Hot Water 269.8g/100 ml at 15 CEthanol soluble^1*
Others :
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in bottles, drums^ '
ICC Classification none
Comments
(2)
Coast Guard Classification none
(2)
References (1) 1570
(2) 1492
310
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Cobalt chloride (489)
IUC Name Cobaltous chloride
Common Names
Structural Formula
CoCI.
Molecular Wt.129.85
(1)
Density (Condensed) 3.356g/cc (8 30 C
Melting Pt. subl.
(1)
(1)
Boiling
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water 45g/100 ml at 7 C
(1)
Hot Water105g/100 ml at 96 C(1)£thanol 54.4g/100 ml(l)
Others: acetone 8.6g/100 ml*'}
Acid, Base Properties
Highly Reactive with
Compatible with
t2T
Shipped in Bottles, tins, drums
ICC Classification_None
Comments
(2)
Coast Guard Classification None
(2)
References (1) 1570
(2) 1492
311
-------
PROFILE REPORTS ON THE COPPER SALTS
Copper Nitrated21), Copper Sul fated 22)
1. GENERAL
The subject copper compounds, copper II nitrate, copper I sulfate,
and copper II sulfate, are moderately poisonous materials. It is believed
that only the copper II compounds, (cupric nitrate and cupric sulfate)
occur as waste materials to any significant extent.
Industries, besides producers, which utilize these materials in
various forms include metal plating, metal pickling, and circuit board
etching. Normally waste streams that contain these compounds do not exist
as pure solutions, but rather are contaminated with other inorganic and
organic material. There are cases, however, in which copper sulfate wastes
occur as reasonably pure materials. Copper sulfate wastes from pickling
have the. greatest volume of all sources by far and are fairly pure. Copper
nitrate does find uses in electroless plating, but waste volumes from this
source are relatively low.
Commercial grade copper sulfate is produced by the action of sulfuric
acid on copper ores and scrap copper. The copper sulfate which is formed
in the solution is transferred to settling tanks where foreign material is
removed. The product solution is then filtered, evaporated, recrystallized,
and finally dried. The mother liquor from evaporation/recrystallization is
returned to the evaporator, creating no liquid waste other than spills.
The sludge that is obtained from settling and filtration is dumped. The
process is 99 percent efficient which indicates that waste output is
approximately 1 percent of the total production. Production figures
for 1963 are estimated at 40,000 tons. Thus, 400 tons per year of waste
copper sulfate from production is the current estimate.
313
-------
There is a significant portion of copper and copper alloy pickling
11 in
industry where the acid used for copper pickling is still being dumped.
Included in this waste is an anhydrous copper sulfate sludge which can
and should be easily recovered. The actual pickling tanks are rarely
dumped since the copper sulfate concentration increases, with use, until
saturation and it precipitates out of solution. Additions of sulfuric
acid replace precipitated sulfate to "sharpen up" the baths for renewed
HP! r
efficiency."*1
The manufacture of printed circuit boards creates large amounts of
copper wastes. Commonly used etchants include ferric chloride, chromic
acid/sulfuric acid, a family of alkaline solutions, cupric chloride and
ammonium persulfate., The use of ammonium persulfate materials is decreasing
in large shops due to material costs and waste treatment difficulties. The
presence of the ammonium ion in spent solutions complicates the normal
waste treatment process of precipitation by pH adjustment. When the waste
solution is made alkaline, free ammonia is liberated. The ammonia, a
noxious air pollutant, also complexes the copper in solution thereby
preventing precipitation. Industrial Filters Corp. claims that
additions of ferric chloride to isolated concentrates of this problem
solution will break the complexes. The use of hexavalent chrome is also
discouraged because of the additional chemical reduction step required
in the treatment process, as discussed in the Profile Report on the
chromates (21,22,etc.).
The large shops.which are close to suppliers often have their spent
solutions picked up by the supplier or have in-plant precipitation and
flocculation equipment. The small or remote printed circuit board shop
must rely on tank truck pick-up, private scavengers, or diluted sewer
dumping. In addition, the small shop is more likely to use the chrome/
sulfuric and ammonium persulfate etchants, because they have general, all
around capability. However, these are the two wastes which are the most
difficult to treat. The industry was characterized as having no big
problem with bulk disposal of spent solutions. Their real difficulties
lie with dragout and rinse waters, which can contain 20 to 100 ppm
copper.2156'2352 This rinse effluent must be reduced to levels compatible
314
-------
with waste water treatment plants. A large firm was noted as having an
poco
effluent output of 12,000 gal. per hour.
There are additional printed circuit board copper wastes from the
electroless plating used to apply the first layer of copper on the bare
composite board. Ammonium and ethylenediaminetetracetic acid (EDTA) complexed
copper again present the difficult waste treatment problem in dragout
2352
described above. Small shops tend to make up these solutions, use them
until they are nearly depleted, and then dump them. The larger shops can
afford the analysis of the solutions and make additions required to maintain
them.2349'2350
Metal plating is another significant contributor of copper sulfate
and nitrate wastes. The primary source is dragout as the actual plating baths
can be maintained indefinitely. Estimates of generated wastes range from
0.1 to 5 percent of the total copper used depending on equipment, stream
segregation, shape of the plated part, etc. ' Booz-Allen indicates
that "finishing effluents from fabricated metal parts" can contain 6 to
300 ppm Cu.1623
Copper sulfate has enjoyed wide use as a fungicide (applied directly)
but this has more or less been replaced by the Bordeaux Mixture (CuSO^
and CaCOHjp make a flocculent copper hydroxide-calcium sulfate complex).
Copper sulfate is also used in fungicides for treating wood. These uses
result in small amounts of waste material in containers and preparation
equipment. Consumption in agriculture has been as high as 50 percent of
the total production.
Copper nitrate is a difficult compound to profile because most of
the production and consumption is on a captive basis where it is made and
consumed entirely within a company. Captive production is primarily for
catalyst manufacture. Commercial copper nitrate is also sought as a raw
.material for catalyst manufacture.2348 Most of the remainder appears to
be used in metal finishing as discussed earlier. Copper nitrate is used
in the preparation of a wide variety of chemicals and catalysts, many of
which are made at one plant. The types and uses of these catalysts are
highly proprietary and little information is available. The assumption
315
-------
is made that waste dissolved copper nitrate occurs in highly mixed,
diverse waste streams-.
2. TOXICOLOGY
The compounds of copper exhibit a general toxicity which is less
severe than some of the other heavy metals. Sax describes them as being
moderately toxic and says that they may cause both irreversible and
reversible damage not generally severe enough to cause death and injury.
However, it is also specifically stated that the ingestion of a large
quantity of copper sulfate has caused vomiting, gastric pain, dizziness,
exhaustion, convulsions, shock, and coma which can finally lead to death.
As little as 27 grams have caused death while others have recovered after
ingestions of up to 120 grams. Symptoms of nervous system, kidney, and
liver damage have also been reported. Copper nitrate is not mentioned as
having toxicological properties different from those exhibited by the
whole class of copper compounds. The sulfate and nitrate anions, are not
considered to be toxic insofar as the toxic properties of compounds
containing these anions are normally attributed to that of the cation with
which they are bound.
The-U.S. Public Health Service indicates that copper in small amounts is
generally regarded as nontoxic and is in fact considered essential for
human metabolism. In 1942 the maximum permissible concentration of copper
in drinking water was raised from 0.2 mg/1 to 3.0 mg/1. However, since
it does contribute to ,an undesirable taste, the U.S. Public Health Service has
1752
recommended a maximum concentration of 1.0 mg/1. The critical
concentration for fish has been established at 0.15 to 0.18 ppm.
Copper sulfate has also been used extensively as a fungicide and
its general toxicity towards plants is significant. It has also been
established that high concentrations of copper in waste streams will
seriously impair the microorganisms that are employed in secondary water
treatment processes. For this reason, large scale dumping of dissolved
copper in the municipal sewer lines is discouraged by sewage treatment
authorities.
316
-------
3. OTHER HAZARDS
No flammable explosive, or other hazard has been found to exist for
these compounds.
4, DEFINITION OF ADEQUATE WASTE MANAGEMENT
Since it is apparent that waste copper compounds can create serious
problems with plant and animal life in sewer systems and open waterways,
it is necessary to define waste management techniques which will minimize
these hazards. Plants and processes must be designed so that no untreated
wastes reach open waterways or contaminate the surroundings. Each firm
should have the facilities to treat and recover copper from waste streams
and temporarily hold any treatment products for ultimate disposal. If a
firm is permitted to discharge to municipal sewer systems, suitable
holding or pretreatment tanks are required on the plant premises.
Handling, Storage, and Transportation
Dried waste materials containing copper sulfate or copper nitrate can
be packed, stored, and otherwise handled as if one were handling the pure
compound. Barrels, drums, bags, boxes, and bottles can all be used
to store and ship these materials. Protective clothing such as aprons,
gloves, and eyewear should be worn to prevent contact with these wastes.
All Department of Transportation (DOT) regulations should be followed when
shipping or otherwise handling these compounds.
All personnel and supervisory staff who work with these materials
should be carefully educated as to the precautions that must be taken to
prevent hazardous exposure.
317
-------
Disposal/Reuse
The U.S. Public Health Service recommends a maximum copper level of
1752
1.0 mg/1 (ppm) in drinking water. The proper levels of copper waste
discharge to municipal sewage systems or cooperative industrial waste
treatment would of course vary with such parameters as waste water volume,
efficiency of the plant, etc. For the safe disposal of copper nitrate and
copper sulfate, the acceptable criteria for their release into the environ-
ment are defined in terms of the following recommended provisional limits:
Contaminant in Air Provisional Limit Basis for Recommendation
Copper ni-trate 0.01 mg/M3 as Cu 0.01 TLV for Cu
Copper sulfate 0.01 mg/M as Cu 0.01 TLV for Cu
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
Copper nitrate 1 ppm (mg/1) as Cu Drinking water standard
Copper sulfate 1 ppm (mg/1) as Cu Drinking water standard
Copper sulfate and copper nitrate both have inherent value when present
as concentrates in wastes. Very large amounts of copper sulfate are produced
from the numerous copper and copper alloy pickling processes that are
carried out in the nation. Waste copper nitrate normally occurs in dilute
solutions and is not as likely a candidate for recovery and reuse as
copper sulfate. The same is true with any dilute copper waste solutions.
However, with increased utilization of solution concentrating equipment,
along with waste stream segregation, some dilute copper solutions are
being economically recovered. The various means by which solutions can
be concentrated and waste copper compounds recovered are discussed later.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
There are two basic waste management practices which involve copper
sulfate and copper nitrate. The first method, product recovery, is used
318
-------
primarily in industries where the waste can be kept pure through segregation
and concentration. The other basic waste management option is that of
destructive precipitation. This involves either pH adjustment or discharge
to sewers.
Option No. 1 '- Recovery of Copper Process Byproducts
Since copper sulfate has inherent value as a chemical commodity
(80 to 90 cents per pound for purified grades) it is advantageous for the
metal finisher to attempt recovery if it is economically feasible. There
are several approaches by which valuable copper or copper compounds can
be recovered.
As previously described with copper pickling, copper oxide removal
continues until the pickling bath becomes saturated with copper sulfate
and it settles out of the pickling solution. This nearly pure copper
sulfate can be mechanically removed from the tanks, packaged and sent to
a commercial reclaiming firm.
There are also in-plant processes for recovering copper metal from
pickling solutions. An example of an integrated recovery and waste
treatment system is described by Lancy and Pinner who have installed an
electrolytic copper removal unit through which is pumped the sulfuric acid
pickling solutions. Copper metal is electrolytically plated out thereby
regenerating the sulfuric acid to be returned to the pickling tanks. The
1119
system is said to be simple to operate and can be easily automated.
Copper sulfate and copper nitrate waste solutions that are generated
by the metal plating processes are nearly always dilute solutions (less
than 500 ppm copper). Any type of copper recovery process for these
dilute solutions will likely require some type of solution concentrating
equipment. The addition of this type of equipment is costly, but if the
value of chemicals being lost from large volume shops is larger than the
cost of installing and operating recovery equipment, then such an approach
is justified. The types of process which might be considered for
319
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concentrating a dilute but pure waste stream include reverse osmosis, ion
exchange, dialysis, and multiple effect 'evaporators. The solutions can be
concentrated to a point where electrolytic or other copper recovery can be
carried out. Alternatively, the concentrates can be returned to plating
baths, etc. or sent to a reclaiming firm.
Option No. 2 - Precipitation by pH Adjustment
Precipitation is most suitable for dilute mixed streams where copper
will not be recovered for reuse. Soda ash, caustic or other alkaline
chemicals can be added to copper bearing solutions to adjust the pH to
about 9.5. This precipitates copper as an insoluble hydroxide gel along
with the precipitates of other heavy metals which might be present in a
mixed solution. Alum or other suitable floccuating agents can also be
used to speed up settling, and clarification of the effluent. The treated
effluent has characteristic heavy metal levels of 0 to 5 ppm. The alkaline
effluent is neutralized before sewering and the resultant sludge is almost
always landfilled. This procedure can be carried out in either batch or
continuous processes. Turn key equipment systems are available for
performing the precipitation on an automated or semi-automated basis.
There are two major disadvantages for using this procedure. The first
is the problem of handling and disposing of the highly hydrated metal
hydroxide sludges. It is not unusual for these sludges to contain upwards
of 75 to 80 percent water by volume. Precipitation and settling is normally
slow and it is necessary to have settling ponds in which to allow the
coagulation process .to occur. The second major disadvantage of precipitation
methods is that no feasible process has yet been developed for the
recovery of chemical or metal credits from this type of precipitated waste.
The sludge often contains many other organic and inorganic materials which
are present in the waste stream before treatment and these hinder effective
purification and recovery. These mixed sludges can serve no useful purpose
and can only be ultimately disposed. The method is adequate when the pH
is made high enough to leave only low ppm traces of pollutants in the
effluent. The ultimate disposal of the sludges is discussed later.
320
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Option No. 3 - Dilute Discharge to Municipal Sewers
Much of the major metal finishing industry is located in highly
industrial and large metropolitan areas. Significant amounts of copper
waste solutions generated in pickling, plating and other related industries
are being discharged to existing municipal sewage treatment. '
The only pretreatment which is customarily given metal finishing wastes
before discharge into municipal sewers is neutralization. If the material
being discharged is of a considerable quantity, or if the discharge
point is close to the sewage treatment plant, it is necessary to closely
monitor the discharge to ensure that there will be no undesirable ill
effects on the sewage stream.
When discharged to sewers, most of the copper ion will precipitate
when it reacts with the sulfides that are found in normal domestic streams.
This precipitation occurs in transit to the waste treatment plant and
the solids are removed at the primary screening and settling facilities
or after secondary biological treatment processes. This method of
disposal is considerably widespread and may be considered environmentally
acceptable only if the waste water treatment plants receiving these
discharges can efficiently deal with the waste loads. In spite of the
increased emphasis on recovery and recycling of wastes with value, the
trend for using municipal sewers for industrial discharge is actually
increasing.
Ultimate Disposal of Sludges from Options 2 and 3
Three ultimate disposal options for these sludges are: (1) landfill,
(2) incineration, and (3) ocean disposal. Landfill is believed to be, by
far, the most prevalent final disposal procedure but the problem of
potential contamination of surrounding land or water tables, due to the
leaching of poisonous materials from the sludge, must be considered.
Incineration reduces the sludge to an ash residue which can be more
easily handled for ultimate disposal but at the same time could also lead
321
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to the formation of poisonous, soluble metal oxides. Incineration also
requires additional equipment and a combustible fuel source as well as
equipment for air pollution control. Ocean disposal is currently being
practiced to a considerable degree by municipal waste treatment plants
located near the coast where the primary and secondary sludges can be either
pumped or barged out to submarine disposal areas. This disposal approach
has been the subject of much recent debate and it is likely that it will
not long remain one of the significant sludge disposal options.
Summary of Available Waste Management Options
i
Recovery Waste copper is a valuable commodity and
can be easily recovered.
Precipitation by Best method for dilute streams, mixed
pH adjustment streams, or other cases where recovery
is not practical.
Dilute discharge to Adequate for dilute streams or mixtures
municipal sewers only if treatment facilities can
' operate to meet local discharge
•i standards.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The installation of waste treating equipment specifically for copper
sulfate and copper-nitrate is not recommended for National Disposal Sites
for the following .reasons: (1) the inherent value of copper and its
compounds has led-a large proportion of the firms handling these materials
to install the various types of copper recovery equipment; and (2) the
transport of huge volumes of non-recyclable dilute solutions is simply
too expensive. Industry will continue to treat the dilute wastes by
destructive precipitation, or discharge to municipal sewers.
As stated in other Profile Reports, it is very likely that a general
facility for pH adjustment and precipitation will be required to handle
the waste streams generated within the site itself. This same facility
could also be used to treat various heavy metal wastes which might
occasionally be sent to the site. These would include waste mixtures
containing chromium, zinc, nickel, lead, mercury, copper and other metals.
322
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7. REFERENCES
0225. Threshold limit values for 1971. Occupational Hazards, Aug. 1971,
p. 35-41. -
0766. Sax, N. I., Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1119. Ceresa, M., L. E. Lancy. Metal finishing waste disposal. Metal
Finishing (3 parts) 66(4): 56-62; 66(5): 60-65; 66(6) :112-118;
Apr., May, June 1968
1121. Lancy, L. E., R. Pinner. Waste treatment and metal recovery in
copper and copper alloy pickling plant. Metallurgia 73(437)119-122;
Mar. 1966
1501. Faith, W. L., D. B. Keyes, and R. L. Clark. Industrial chemicals. 3d
New York, John Wiley and Sons, Inc., 1965. 824 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Chemical Rubber Company, 1969. 2,100 p.
1752. Public health drinking water standards. U. S. Department of Health
Education and Welfare, Public Health Service Publication No. 956,
Environmental Control Administration, Rockville, Maryland 1962.
2156. Graham, A. K., ed. Electroplating engineering handbook, 2d ed.,
New York, Reinhold Publishing Corp., 1962. 774 p.
2347. Personal communication. Fred Stewart, Lancy Labs, to J. F. Clausen,
TRW Systems, Sept. 15, 1972.
2348. Personal communication. W. Witzleben, Allied Chemical Co.,
to J. F. Clausen, TRW Systems, Sept. 28, 1972.
2349. Personal communication. Simon Gary, Scientific Control Labs, to
J. F. Clausen, TRW Systems, Sept. 26, 1972.
2350. Personal communication. Don Hutchinson, Harshaw Chemical Co., to
J. F. Clausen, TRW Systems, Sept. 26, 1972.
2352. Personal communication. Frank Gorman, Cinch-Graphik Inc., to
J. F. Clausen, TRW Systems, Sept. 29, 1972.
323
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. in. Name Copper sulfate (122)
Structural Formula
IUC Name Copper II sulfate pentahydrate
Conmon Names Blue Vitriol, Chalcanthite' ' CaSO. • 5H?0
Molecular Wt. 249.68(1) Melting Pt. -4HoO at 110C(1* Boiling Pt. -5HJ3 at 150 C
Density (Condensed) 2.284 @ --_ Density (gas) P
Vapor Pressure (recommended 55 C and 20 0
@ e @
Flash Point Autoignition
Flammability Limits in Air (wt %) Lower none Upper none
Explosive Limits in Air (wt. %) Lower none Upper none
y m 100 c*1*
Cold Water 31.6g/100 cc at 0 C" Hot Hater 203.3 g/100cc at Ethanol insoluble
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in Barrels, drums, boxes, bags, bottles
(2)
ICC Classification N° label reguiredv Coast Guard Classification,
Commen ts
References (1) 1570
(2) 0766
324
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H. M. Name Copper ni
IUC Name Copper II
HAZARDOUS WASTES PROPERTIES
WORKSHEET
(121)
tri hydrate
Structural Formula
Common Names
Cu(N0)
3'2 '
Molecular Wt. 241.60^ Melting Pt. 114.5 C
Oensity (Condensed) 2-3? 9/cc @ 25 C( ' Density (gas)
Vapor Pressure (recommended 55 C and 20 Q)
& 9
(1)
-HNO, at 1?0 .
Boiling Pt. J 1/0 C
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Solubility
Lower
Upper_
Upper_
(1) 100 g/100 cc
Cold Water 137.8 g/100 cc at 0 C^Aot Water 1270 g/lOOcc at IQo'cEthanol *' it~U5
Others: very soluble in liquid NH
3
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
(2) 0766
325
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
•). ;•!. Name Co'P'P'er Nitrate (121)
HJi Name Copper II Nitrate, hexahydrate
Structural Formula
Common '<(iiiu:s
Cu(N03)2 • 6H20
Molecular Wt. 295.64'
(1)
Melting Pt.-3H20 at 26.4
Density (Condensed) 2.074 g/ccv' '@ N/A Density (gas)
Boiling Pt. N/A
Vapor Pressure (recommended 55 C and 20 C)
Dash Co int.
Autoignition Temp.
Flammabi I i ty Limits in Air (wt %} Lower_
Limits in Air (wt. %) Lower
Solubili ty /^ \
Cold Water ?43.7 g/100 cc at 6 C Hot Water infinite
Othe rs:
Acid, Base Properties
Upper
Upper_
(1)
Ethanol soluble
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
326
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PROFILE REPORT
v^
Hydrazine (212)
1. GENERAL
Hydrazine is a clear, oily, water-white liquid with an odor
similar to that of ammonia. It is a strong reducing agent, weakly
alkaline and very hygroscopic. It will react with carbon dioxide and
oxygen in air. Exposure of hydrazine to air on a large surface (as
on rags) may result in spontaneous ignition from the heat evolved
by its oxidation with atmospheric oxygen. With water it forms the
diamide hydrate, H2NNH2 . H20.1300
Hydrazine is formed by reacting equimolar quantities of sodium
hypochlorite and ammonia in an alkaline solution to give chloroamine
(NHpCl). This reacts at elevated temperature with ammonia to give
hydrazine:
NH3 + NaOCl •+ NaOH + NH2C1
NH3 + NH2C1 + NaOH + N2H4 + NaCl + H20
A side reaction occurs which leads to the decomposition of
hydrazine:
2NH2C1 + N2H4 -* N2 + 2NH4C1
This side reaction is catalyzed by dissolved chloride. Gelatin, glue,
amino acids or simple peptides are added to complex the chlorides.
Hydrazine is recovered from aqueous solution by distilling water until
the still bottoms approach the composition of hydrazine hydrate. The
hydrate is either treated with sodium hydroxide at a temperature
above the boiling point of hydrazine and the hydrazine distilled and
collected, or treated with aniline which is used to effect removal of
the water by azeotropic distillation.
Hydrazine is used in jet and rocket fuels, intermediates for
327
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agricultural chemicals, antioxidants, textile chemicals, explosives,
photographic developers, blowing agents, scavengers for chlorine in
hydrogen chloride, corrosion inhibitors and scavengers for oxygen.
The chemical and physical properties for hydrazine are summarized
in the attached worksheet.
2. TOXICOLOGY
Hydrazine is a strong irritant and may damage the eyes and cause
respiratory tract irritation. If spilled on the skin or eyes, liquid
hydrazine can cause severe local damage or burns and can cause derma-
titis. It can penetrate the skin. If inhaled, the vapor causes local
(irritation of eye and respiratory tract) and systemic effects. For
long exposure, systemic effects involve the central nervous system.
On exposure to higher concentrations, convulsions and possibly death
follow. Repeated exposures may cause toxic damage to the liver and
1300 1993
kidney, as well as anemia. '
The exposure limits recommended are as follows:
Threshold limit (ACGIH) -1.0 ppm (1.3 mg/m3)
Emergency exposure limits -
10 min - 30 ppm (39 mg/m3)
30 min - 20 ppm (26 mg/m )
o
60 mih - 10 ppm (13 mg/m )
3. OTHER HAZARDS
Hydrazine is flammable over a broad range of concentrations: 4.7
to 100 percent. It is hypergolic with some oxidants, such as hydrogen
peroxide, nitrogen tetroxide, fluorine, halogen fluorides, and nitric
acid. A film of hydrazine in contact with metal oxides, such as those
of iron, copper, lead, manganese and molybdenum, may ignite owing to
the heat of chemical reaction. Hydrazine vapors in a closed system may
explode when exposed to air. In the presence of finely-divided or
other high surface area forms of some metal or metal oxides, hydrazine
dissociates into nitrogen, hydrogen and ammonia.
328
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Adequate procedures for the safe handling, transportation and storage
of hydrazine are described in two publications,1300'1993 and in the military
specification for hydrazine, MIL-P-2705.1995 Hydrazine is classified by
Department of Transportation (DOT) as a corrosive liquid and is shipped
under a White Label. Under DOT specifications hydrazine may be shipped in
1-gal. glass bottles packed in cans, in metal barrels or drums of 304 or
347 stainless steel, or in tank cars of 304L, 347 stainless steel,
aluminum 103A AL-W, or aluminum 111A100-W-6.
Hydrazine as a waste will generally be encountered as excess material,
as contaminated material from spills, or in aqueous streams from chemical
process industries. Because of the hazards involved (unpredictable
decomposition), hydrazine is usually not recovered in a concentrated form
from contaminated or dilute systems. In ponds or holding tanks dilute
hydrazine is decomposed by the air and bacteria into nitrogen, hydrogen,
water and ammonia. In a concentrated form, hydrazine is destroyed by
burning. .
The safe disposal of hydrazine is defined in terms of £he recommended
provisional limits in the atmosphere, water and soil. These recommended
provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
Hydrazine 0.01 ppm 0.01 TLV
Contaminant in Water
and Soil Provisional Limit Basjs for Recommendation
Hydrazine 1.0 ppm Quantity will rapidly
oxidize to near-zero
concentration
329
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Hydrazine is generally destroyed by oxidation to water and nitrogen.
In dilute solution, dissolved oxygen, catalysis, or bacterial action con-
vert hydrazine to nitrogen, hydrogen, ammonia and water. Therefore, there
are no problems in dealing with the products from waste treatment. Current
disposal practices for hydrazine are briefly described in the following
paragraphs together with recommendations as to adequacy.
Option No. 1 - Open Pit Burning
Hydrazine poured into an open lined pit is burned to nitrogen and
water. The transfer of the hydrazine and the ignition must be accomplished
by a remote means. For drum quantities of hydrazine this method is
generally acceptable although since excessive NO might be generated
X
another option would be preferred.
Option No. 2 - Incineration
The Air Force has a minimum of ten trailer-mounted incinerators capable
of incinerating up to 6 GPM of hydrazine in a variety of mixtures with water
(from 100 percent hydrazine to 100 percent water). The effluents from the
19Q4
units is limited to 0.03 Ibs/min NO when incinerating hydrazine. These
/\
units are acceptable for disposing of large quantities of hydrazine.
Option No. 3 - Catalytic Decomposition
One of the applications for hydrazine is its use as a monoprope11 ant.
When hydrazine is passed over a support (usually aluminum oxide) coated with
certain metals or metal oxides, it is decomposed into nitrogen, hydrogen and
ammonia. The details of catalyst composition are usually found in the
classified literature. In most cases the catalyst is expensive, but TRW
Systems has preliminary data on a low cost catalyst that should be further
investigated.
330
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Option No. 4 - Diluting with Water and Holding
If hydrazine is diluted with water, e.g., after spills, and placed in
open lined ponds or holding tanks, the hydrazine is decomposed to water,
nitrogen, and ammonia by air oxidation and bacterial action. For small
quantities of hydrazine in aqueous solution this method is acceptable if
adequate space is available.
Option No. 5 - Chemical Treatment
Small quantities and dilute solutions are collected in open containers
and treated with oxidizing compounds such as 10 percent hydrogen peroxide or
calcium hypochlorite. The oxidizing agents should be applied slowly until
in excess. This method is not recommended except for small quantities
because considerable heat is liberated during decomposition.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Hydrazine does not appear to be a candidate waste stream constituent
for National Disposal Sites. It is anticipated that packaged hydrazine
and hydrazine in aqueous waste streams will continue to be treated at the
source of waste generation. The major products of combustion or decomposi-
tion are the elements, water, or ammonia which do not present a secondary
disposal problem.
331
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7. REFERENCES
1300. JANAF Hazards Working Group. Chemical rocket/propel 1 ant hazards,
Volume III, liquid propellent handling, storage and transportation.
CPIA Publication No. 194, May 1970.
1157. Astle, J. Industrial organic nitrogen compounds. American Chemical
Society Monograph, New York, Reinhold Publishing Co., 1961.
1433. Kirk-Othmer Encyclopedia of chemical technology. 2d ed. New York,
Interscience Publishers, 1963.
1662. Shreve, R.N. The chemical process industries. McGraw-Hill series
in chemical engineering, 2d ed. New York, 1956. 1,004 p.
1993. U. S. Air Force Medical Service. The handling and storage of
liquid propel 1 ants. Department of the Air Force, Air Force
Manual No. 160-39, Apr. 1, 1964.
1995. U. S. Air Force. Military specification, propellant, hydrazine.
MIL-P-26536C. Edwards Air Force Base, May 23, 1969.
1994. Coen Company. Liquid wastes. Chemical Engineering, 78 (14): 43,
June 21, 1971, Advertisement.
332
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrezine (212)
Structural Formula
IUC Name Hydrazine_
_ ,. Di ami n e
Common Names
Molecular Wt. 32.05 Melting Pt. 1.5 Boiling Pt.113.5
Density (Condensed) 1.008 g cc @ 20 C Density (gas) 1.1 § _0 C
Vapor Pressure (recommended 55 C and 20 C)
0.07 psia @ 40 F 0.36psia g 80 F 2.9psia & 160 F
Flash Point 52. c Autoignition Temp.270__ c
Flammability Limits in Air (wt %) Lower 4.7% Upper 100% at 100 C
Explosive Limits in Air ,(wt. %) Lower Upper
Solubility
Cold Water Miscible Hot Water Miscible Ethanol Miscible
Others: acetone - miscible
Acid, Base Properties NPHA + H90 _ N9H/ + OH" K = 8.5 x TO'7
Highly Reactive with Acids, metal oxides
Compatible with Stainless steel, aluminum
Shipped in Bottles, drums, tank cars
White Label
ICC Classification Corrosive Liquid.Hhite Label coast Guard Classification Corrosive Liquid
Comments
Kofertnces (1) 1300
333
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-1
3. Recipient's Accession No.
4. Tiiie and subtitle Recornmenc|ec| Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume XII, Indus-
trial and Municipal Disposal Candidate Waste Stream. Constituent
Profile Reports - Inorganic Compounds __
5- Report Date
Issuing date - Aug. 1973
6.
7. Author(s) R. S. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
6. I. Gruber, M. J. Santy, and C. C. Shin
8- Performing Organization Rept.
No.
21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089 .
12. Sponsoring Organization Name and Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
Volume XII of 16 volumes.
16. Abstracts
This volume contains summary information and evaluation of waste management methods in
the form of Profile Reports for inorganic compounds. These Profile Reports were pre-
pared for either a particular hazardous waste stream constituent or a group of related
constituents. Each Profile Report contains a discussion of the general characteristics
of the waste stream constituents, their toxicology and other associated hazards, the
definition of adequate management for the waste material, an evaluation of the current
waste management practices with regard to their adequacy, and recommendation as to the
most appropriate processing methods available and whether the waste material should be
considered as a candidate for National Disposal, Industrial Disposal, or Municipal
Disposal.
17. Key Words and Document Analysis. 17a.
Hazardous Wastes
Alkali and Ammonium Fluorides
Aluminum Compounds
Phosphates
Inorganic Compounds
Industrial Disposal Candidate
Municipal Disposal Candidate
Oxides
Ammonium Compounds
Sodium Compounds
Carbonates
17b. Identifiers/Open-Ended Terms
Descriptors
Hydroxides
Sulfur Compounds
Potassium Compounds
Beryllium Compounds
Sulfates
Cobalt Compounds
Barium Compounds
Antimony Compounds
Nitrates
Arsenic
Hydrazine
Acids
Magnesium Compounds
17c. COSATl Field/Group Qgp.
18. Availability Statement
Release to public.
- 334 -
19.. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCl-ASSIFIKD
21. No. of Pages
340
22. Price
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