EPA-670/2-73-053-m
August 1973
Environmental Protection Technology Series
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY OR
DISPOSAL OF HAZARDOUS WASTE
Volume Xlli Inorganic Compounds
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
-------
EPA-670/2-73-053-m
August 1973
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY
OR DISPOSAL OF HAZARDOUS WASTE
Volume XIII. Industrial and Municipal Disposal
Candidate Waste Stream Constituent Profile Reports
Inorganic Compounds
(Continued)
By
R. S. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
G. I. Gruber, M. J. Santy, and C. C. Shih
TRW Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-03-0089
Program Element No. 1D2311
Project Officers
Norbert B. Schomaker
Henry Johnson
Solid and Hazardous Waste Research Laboratory
National Environmental Research Center
Cincinnati, Ohio 45268
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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REVIEW NOTICE
The Solid Waste Research Laboratory of the National Environmental
Research Center - Cincinnati, U.S. Environmental Protection Agency has
reviewed this report and approved its publication. Approval does not
signify that the contents necessarily reflect the views and policies of
this Laboratory or of the U.S. Environmental Protection Agency, nor does
mention of trade names of commercial products constitute endorsement or
recommendation for use.
The text of this report is reproduced by the National Environmental
Research Center - Cincinnati in the form received from the Grantee; new
preliminary pages and new page numbers have been supplied.
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FOREWORD
Man and his environment must be protected from the adverse
effects of pesticides, radiation, noise and other forms of pollu-
tion, and the unwise management of solid waste. Efforts to protect
the environment require a focus that recognizes the interplay between
the components of our physical environment—air, water, and land.
The National Environmental Research Centers provide this multidisci-
plinary focus through programs engaged in:
• studies on the effects of environmental
contaminants on man and the biosphere, and
• a search for ways to prevent contamination
and to recycle valuable resources.
Under Section 212 of Public Law 91-512, the Resource Recovery
Act of 1970, the U.S. Environmental Protection Agency is charged
with preparing a comprehensive report and plan for the creation of
a system of National Disposal Sites for the storage and disposal of
hazardous wastes. The overall program is being directed jointly by
the Solid and Hazardous Waste Research Laboratory, Office of Research
and Development, National Environmental Research Center, Cincinnati,
and the Office of Solid Waste Management Programs, Office of Hazard-
ous Materials Control. Section 212 mandates, in part, that recom-
mended methods of reduction, neutralization, recovery, or disposal
of the materials be determined. This determination effort has been
completed and prepared into this 16-volume study. The 16 volumes
consist of profile reports summarizing the definition of adequate
waste management and evaluation of waste management practices for
over 500 hazardous materials. In addition to summarizing the defini-
tion and evaluation efforts, these reports als.o serve to designate a
material as a candidate for a National Disposal Site, if the material
meets criteria based on quantity, degree of hazard, and difficulty of
disposal. Those materials which are hazardous but not designated as
candidates for National Disposal Sites, are then designated as candi-
dates for the industrial or municipal disposal sites.
A. W. Breidenbach, Ph.D., Director
National Environmental Research Center
Cincinnati, Ohio
m
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TABLE OF CONTENTS
VOLUME XIII
INDUSTRIAL AND MUNICIPAL DISPOSAL CANDIDATE
/
WASTE STREAM CONSTITUENT PROFILE REPORTS
Inorganic Compounds (Continued)
Page
Domestic Bauxite Mud (232), Foreign Bauxite Mud (283) 1
Chlorates with Red Phosphorus (516) 5
TRIVALENT CHROMIUM SALTS - Chromic Fluoride (485), Chromic
Sulfate (486), Chromium Cyanide (487) 13
Copper (275), Lead and Zinc (276) Mill Tailings 29
Slag I (SIC 3331) Copper Smelting (371), Slag II (SIC 3332)
Lead Smelting (372) 41
Hydrazoic Acid (528) 45
Hydrobromic Acid (Hydrogen Bromide) (213) 51
Hydrocyanic Acid (215), Hydrogen Cyanide (218) 57
Hydrogen Sulfide (221) 65
Lead (233) . . . 79
LEAD COMPOUNDS - Lead Acetate (234), Lead Carbonate (237), Lead
Chlorite (238), Lead Nitrate (240), Lead Nitrite (241) 87
Lead Oxides (242) 103
Manganese (499) 115
Manganese Chloride (501), Manganese Sulfate (252) 129
Nickel Ammonium Sulfate (290), Nickel Chloride (294), Nickel
Nitrate (296), Nickel Sulfate (298) . 137
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TABLE OF CONTENTS (CONTINUED)
ANTIMONY, ARSENIC, AND SELENIUM COMPOUNDS OF NICKEL - Nickel
Antimonide (291), Nickel Arsenide (292), Nickel Selenide (297) ... 153
Phosphorus, White or Yellow (332) 163
HALOGENATED PHOSPHORUS COMPOUNDS, PHOSPHORUS CHLORIDES - Phosphorus
Oxychloride (333), Phosphorus Pentachloride (334), Phosphorus
Trichloride (336) 171
Phosphorus Pentasulfide (335) 187
Potassium Permanganate (349) 195
Potassium Peroxide (350), Sodium Monoxide (508), Sodium
Peroxide (400) 201
Selenium (367) 211
Sodium Acid Sulfite (380), Sodium Nitrite (397), Sodium
Sulfite (405) 221
Sodium Alloy (374), Sodium-Potassium Alloy (402) 229
Sodium Azide (378) 237
Sodium Chlorate (385) . 243
Sodium Iodide (395) 253
Sodium Silicates (403) 259
Strontium (410) 265
Taconite Tailings (419) 269
Thallium (430), Thallium Sulfate (431) 275
ZINC COMPOUNDS - Zinc Chloride (456), Zinc Nitrate (459), Zinc
Permanganate (461), Zinc Peroxide (462), Zinc Sulfide (463) .... 285
vi
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PROFILE REPORT
Domestic Bauxite Mud (282) and Foreign Bauxite Mud (283)
1. GENERAL
Bauxite is a heterogeneous material composed principally of the
aluminum oxide minerals, gibbsite [A! (OH),], a tri hydrate [AlgOvSHpO],
and the monohydrates , backmite [AIO(OH)], and diaspore [HAIO^]. Major
impurities in the bauxite ores are iron oxides, aluminum silicates, and
titanium oxides.1975'2492
Bauxite is normally refined by the Bayer process. This process
involves leaching the bauxite with caustic at elevated temperatures and
pressures, followed by the separation of the resulting sodium aluminate
solution and the selective precipitation of alumina
The residue, or tailings from this process is commonly called "red
mud." In the case of some ores, the tailings, "red mud", are further
treated to extract the aluminum silicates and the residuals from this
process are known as "brown mud."
The alumina is further treated by electrolysis in a molten bath of
cryolite [SNaF-AlF^] to produce primary aluminum.
The primary bauxite ores of concern are Jamaican, Surinam and
Arkansas. "Jamaican ore is a mixture of both tri hydrate and monohydrate
materials, and this type contains about 50% AlpO-, 1 to 2 percent silica,
and 20 to 30 percent ion oxide. The Surinam type is mainly the trihydrate
gibbsite usually containing 50 percent or more Al90o, 2 to 15 percent
1975
silica, and 5 to 15 percent iron oxide." The Arkansas ores are lower
in iron oxides and higher in aluminum silicates since they were formed
-------
from the weathering of nepheline syenite.
The concentrate from the processing of the ores is in all cases
alumina for further processing to primary aluminum.
Tailings from the process have chemical compositions as delineated
below:0146
Bauxite
Source
Jamaica
Surinam
Arkansas
Residue
Type
Red Mud
Red Mud
Brown Mud
Composition-Percent
A1203
20
20
9
Fe2-4
47
25
8
Ti02
6
10
3+
Si02
--
--
17
Na20
4
10
5
CaO
5
6
40
These tailings are all quite fine, indeed one Jamaican red mud sample
had an average grain size between 0.5 and 2.0 microns with some agglomer-
ated particles to 10 microns. The Jamaican tailings are normally floccu-
lated by the addition of starch and dewatered by settling in thickeners,
even so the final residue has a solids content of only 20 percent. The
other tailings, though filterable, are also quite fine.
The major areas of production of alumina plant wastes are the lower
Mississippi River, on the gulf coast, and in Arkansas. Some 7 million
tons of tailings are generated annually in these areas.
2. TOXICOLOGY
Bauxite tailings constitute a negligible toxicological hazard.
3. OTHER HAZARDS
Although not presenting a toxicological problem, bauxite tailings
constitute an environmental problem on the basis of two major elements:
(1) the sheer volume of the refuse materials; (2) the dust problems
encountered because of the fineness of the tailings when they are finally
dewatered.
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Bauxite tailings are presently disposed of by collection in tailings
ponds (see Profile Report on Copper, Lead and Zinc tailings) or by direct
discharge into the Mississippi River.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Of the two disposal methods described in Section 4 of this report,
only that of ponding is judged to be an acceptable method. The discharge
to tailings into large potable water sources has not been proven an acceptable
method of disposal and should be curtailed until the environmental effects of
this practice are determined.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Because of the negligible toxicological effect, bauxite tailings are
not considered candidates for National Disposal Sites.
The United States Bureau of Mines has done considerable work in
extracting mineral values from the "red mud" residues. However, the major
volume of material will remain to constitute an environmental hazard. In
addition to the recommendations for research and development to alleviate
the environmental effects contained in the Profile Report on Copper (275),
Lead and Zinc (276), the development of more effective flocculants would
be most useful in providing a viable alternative to dumping tailings into
the Mississippi River.
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REFERENCES
0146. U.S. Bureau of Mines. Utilization of red mud residues from alumina
production. Report of Investigations No. 7454. Nov. 1970. 32 p.
1975. U.S. Bureau of Mines. Mineral facts and problems. Bulletin No. 650,
1970.
2492. Smith, 0. C. Identification and qualitative chemical analysis of
minerals. New York, D. Van Nostrand Company, Inc., 1946.
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PROFILE REPORT
Chlorates with Red Phosphorus (516)
1. GENERAL
Potassium chlorate is a very powerful oxidizing agent which in
admixture with combustible materials forms a number of powerful explosives.
Red phosphorus, a reducing material, is used in- some of these explosive
compositions. Mixtures used in toy pistol caps and toy torpedoes contain
both potassium chlorate and red phosphorus. Two examples of these mixtures
are as follows: (1) 67 parts potassium chlorate, 27 parts red phosphorus,
3 parts sulfur, and 3 parts calcium carbonate bound with an unspecified
amount of "gum water", and (2) 61 parts potassium chlorate, 4 parts red
phosphorus, 21 parts black antimony sulfide, 2 parts calcium carbonate, and
12 parts animal glue.2169
The physical/chemical properties for potassium chlorate and red
phosphorus are summarized on the attached worksheets.
2. TOXICOLOGY
Potassium chlorate, like sodium chlorate (see Profile Report on Sodium
Chlorate [385]) is not highly toxic, but ingestion or excessive inhalation
of dust should be avoided. Prolonged exposure to chlorate dust may cause
2123
skin irritation to the mucous membrane of the eyes, nose and throat.
Red phosphorus is considered relatively non-poisonous and is much less
reactive than white phosphorus. The other components of these mixtures
are generally considered non-poisonous.
3. OTHER HAZARDS
Potassium chlorate and red phosphorus mixtures, when confined, are
sensitive to electrical discharge, heat, friction, and impact. They
undergo detonation when subjected to a very mild electrical, mechanical
-------
or thermal shock from a spark, flame or percussion. These mixtures
cannot be stored under water prior to use because potassium chlorate is
soluble and wi-11 be extracted from the mixture.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Relatively small quantities of cap and torpedo mixtures are manufactured.
They are not shipped prior to formulation into the end products. The sensi-
tivity of these mixtures requires that excess and scrap material from fire-
works charging operations be stored underwater until destroyed by burning.
Caps are described as "toy caps" and are shipped according to Department of
Transportation (DOT) regulations for Explosives, Class C,2170 if the indi-
vidual caps each contain less than 0.25 grains of the explosive mixture.
"Torpedoes, cap" are commonly packed in sawdust in pasteboard cartons and
are described as special fireworks. They are shipped as Explosives, Class
poop
B if they contain less than 1/2 grain of KC103 - P mixture, or less
than 4 grains of KC103, Sb2$3 and P mixture.
The safe disposal of potassium chlorate-phosphorus mixtures is defined
in terms of the recommended provisional limits in the atmosphere and in
water and soil environments. These recommended provisional limits are as
follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Phosphorus, red 0.001 mg/M3* 0.01 TLV*
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Phosphorus, red 0.005 mg/1* Stokinger & Woodward Method
*Estimated from data for white phosphorus
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Detonator Destruction Furnace
The approved method referenced in the Ordnance Safety Manual for the
destruction of detonators and primers may be used for torpedoes containing
chlorate-phosphorus mixtures. In this method the components are fed to
the combustion chamber of a specially designed detonator destruction
furnace by means of a channel chute and a special conveying device.
Scrubbers are employed to remove toxic fumes and dusts such as NO , P^O-in,
HC1, S02, and metal oxides.
Option No. 2 - Burning Pit Detonation
Torpedoes and caps in large quantities are detonated by burning in
pits by applying heat from a fire. The devices are placed on top of a
flammable substance such as straw and the flammable substance is ignited
by means of a squib. Other explosives must be kept behind a barricade
with overhead protection during destruction operations and located at a
distance that assures safety. Personnel should be similarly shielded. '
This destruction process is not satisfactory because individual components
may not detonate and will constitute a personnel hazard during clean-up and
because NOX, metal oxides, P/iO-ms S02 and hydrogen chloride will be liberated
during the destruction process on an uncontrolled basis.
Option No. 3 - Controlled Incineration
(Municipal and Plant Incinerators)
Potassium chlorate mixtures» toy torpedoes and toy caps which have
been properly marked to permit due precautions in handling can be destroyed
safely by burning in municipal or plant incinerator systems equipped with
scrubbing and mist removal systems. The incinerators should be fed by
automatic conveyor devices, and the scrubber effluent should be neutralized
and processed in a standard secondary treatment sewage system before
discharge. This technique is recommended for disposal of the mixtures and
devices.
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Plants manufacturing torpedoes and caps which contain potassium
chlorate and red phosphorus mixtures have facilities for the disposal of
such mixtures. Devices which are not processed for disposal at such
manufacturing facilities are not candidates for National Disposal Sites.
The process to be employed for disposal should be Option No. 3, as
recommended in Section 5. Surplus, scrap or obsolete materials should be
handled by experienced plant personnel or other qualified ordnance
demolition personnel.
8
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21485-6013-RU-OO
7. REFERENCES
1416. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed.
New York, Reinhold Publishing Corporation, 1961. 1,256 p.
1141. Department of the Army and the Air Force. Military explosives,
TM-1910. Washington, Apr. 1955. 336 p.
2123. Manufacturing Chemists' Association. Chemical safety data sheet SD-42,
Washington, 1952. 1 p.
2169. Tedoroff, G. J. Encyclopedia of explosives and related items, v. 1.
Picatinny Arsenal, 1960. 692 p.
2170. Ordnance Corps, Department of the Army. Ordnance safety manual,
ORDM7-224. Washington, 1951.
2382. Association of American Railroads, Bureau of Explosives. B. E.
Pamphlet 7. General information relating to explosives and
other dangerous articles. Washington, 1972. 87 p.
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H..H. Name Phosphorus, red (516)
IUC Name
Common Names
Structural Formula
Molecular Wt. 124.08
(1)
Melting Pt.
Density (Condensed)j.34 g/cc @ 20
Boiling Pt..
Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
0
Flash Point
Autoignition Temp. 260 C
Flammability Limits in Air (wt *} Lower Upper_
Upper_
Explosive Limits in Air (wt. %)
Solubility ^'
Cold Water Insoluble
Others:
Lower
Hot Water Insoluble
Ethanol Insoluble
Insoluble all solvents
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in
ICC Classification flammable so1idv
Comments :
inflammable solid
Coast Guard Classification yellow label
References (1) 1415
10
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Potassium Chlorate
IUC Name
Potassium Chlorate
Structural Formula
Common Names
KC10,
Molecular Wt. 122.55
(1)
Melting Pt. 368 C
Density (Condensed) 2.337 g/cc (j> 20 C nDensity (gas)_
Vapor Pressure (recommended 55 C and 20 0
(1)
decomposes'''
Boiling Pt. 400 C
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower
Solubility (')
Cold Water Soluble
Others:
Hot Water Soluble
Upper_
Upper_
Ethanol Slightly soluble
Acid, Base Properties_
Highly Reactive with reducing substances^ '
Compatible with_
Shipped in_
ICC Classification oxidizing material (1)
Commen ts
oxTdvzTngTrr
Coast Guard Classification material
References (1) 1416
11
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PROFILE REPORTS ON
THE TRIVALENT CHROMIUM SALTS
Chromic Fluoride (485), Chromic Sulfate (486).
Chromium Cyanide (487)
1 . GENERAL
The salts of trivalent chromium, Cr III, are moderately poisonous
materials. Of the three compounds in this Profile Report, only two have any
commercial significance. They are chromic fluoride, CrF3, and chromic
sulfate, Cr2(S04)3. Chromium cyanide is not believed to exist at all; a
fact to be detailed later. Chromic fluoride was found to have some uses
in the textile industry as part of the dyeing operation. Chromic sulfate
is extensively used in the leather tanning and finishing industry in a
modified, basic form.
Chromic Sulfate
Normal chromic sulfate, Cr2(S04)3 is of no commercial importance, but
the so-called basic chromic sulfates are produced in large amounts for use
in the leather tanning industry, and are incorporated in various proprietary
chrome tan mixtures. These basic chromic sulfate tanning solutions -can
either be made commercially and supplied to the tanning industry or be
prepared directly in the tanning vats. The normal preparation process is
the reduction of a sodium di chroma te solution with either an organic
material (Equation No. 1) or sulfur dioxide (Equation No. 2).2055 The
organic reduction using crude molasses, corn sugar, and sometimes even
sawdust is the older and more widely used method. Sulfur dioxide, when
used, plays the dual role of reducing agent and, upon oxidation, of
furnishing the required sulfate. If sugar is used,sulfuric acid must be
added.
8Na2Cr20? + 24H2S04 + C^H^O^ +16Cr(OH)S04 + 8Na2S04 + 27H20 + 12C02 (1)
Na2Cr207 + 3S02 + H20 -> 2Cr(OH)S04 + Na2S04 (2)
13
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The actual composition of the product is much more complicated than that
indicated by the formulas shown. The chromic sulfate produced by these
reactions is described as one-third basic since, stoichiometrically, only
two-thirds as much sulfate is combined with the chromium as in the normal
sulfate. A whole range of basicities is available to the tanning industry
for different types of tanning. The production of basic chromic sulfate
is performed on a batch basiss and if prepared at the tannery, the hides
are added to the same vat in which the reduction took place. No purification
of the commercial product is performed before it is spray dried and packed.
It is believed that the manufacture of basic chrome sulfate results in no
significant amounts of contaminated waste solids or liquids.
The actual chrome tanning of the hides however does create very large
amounts of chromic sulfate wastes in aqueous solution resulting from the
tanning and subsequent washing of the hides. Hide tanning, by definition,
essentially consists of removing organic matter from the hides,thus
preserving them. This organic matter, if allowed to build up in the chrome
tanning solutions would interfere with the tanni'ng process. Therefore
the solutions are normally dumped after being used once or possibly twice.
There are incomplete details on some tanneries that are renewing their
chrome tanning solutions with more concentrated chromic sulfate rather than
dumping the spent tanning solutions. They claim that some chromium tanning
solutions are being reused as many as 15 times without detrimental effects.
This situation is currently the exception and not the rule.
An additionals proposed chrome sulfate conservation technique is to
precipitate chromium hydroxide from the chrome tanning solutions, filter
it,and then redissolve it with sulfuric acid. This technique can remove
some of the organic water and allow reuse but most tanners consider the
process to be economically impractical and the greater proportion of the
tanneries are only using their tanning solutions once.
Very little waste stream segregation is performed in the tanning
industry and the 2 to 12 ppm trivalent chrome concentration in the diverse
mixture of brines, fat, acids, and large amounts of rinse water
constitute a fairly typical waste stream. The majority of tanneries
-------
are located in or near large metropolitan areas to permit the utilization
of municipal or joint water treatment facilities. The cities are
always the meat packing centers, i.e., Chicago, Milwaukee, or Los Angeles.
It is estimated that 80 percent of the tanning wastes are being discharged
to sewers for treatment by municipal waste water treatment plants. The
remaining 20 percent are being treated in onsite plants for solids and
BOD reduction before discharge to sewers or waterways. The quantity of
trivalent chromium in inadequately treated tannery effluents discharged
to open waterways, if any, was not determined because of the obvious
difficulties in obtaining such sensitive information, but it is expected
that future tightening of discharge limits will result in no discharge
from tanneries into open waterways.
Chromic Fluoride
Chromic fluoride is used in the textile industry as a dyeing aid and
mordant. Other trivalent chrome compounds can be used in its place. The
constantly changing processes in the textile industry as well as the free
substitution of different chemicals for process applications makes it
difficult to determine exactly how much chromic fluoride is being used,
?OR^ ?f)R4 ?DRR
but it is believed that its consumption is very small/UOJ^UD^"iu:)0
The completely anhydrous chromic fluoride is insoluble and is not
used in the textile trade. Two hydrated compounds are commercially
available. They are CrF3 • 4H,,0 and the more soluble CrF3 • 9H 0. These
compounds and their basic, complex compounds are used as mordants for
wool, in aftertreating oxidation sensitive direct cotton dyes, and with
special mordant acid dyes in the printing of worsted woolen. It has also
been stated that chromic fluoride imparts some moth-proofing qualities.2055
When used, chromic fluoride is contained in vats and is exhaustively
deposited on the textile that is either dipped or run through continuously.
A significant portion of solution is lost by transfer to subsequent
rinsing and post treatment tanks.
15
-------
The chrome wastes from textile mills are characteristically mixtures of
the effluents from many different processes and contain 1 to 100 ppm tri- .
valent chromium. Most of the Southern mills have some sort of on-site
water treatment facilities whereby chromium and other heavy metal wastes are
removed by precipitation through pH adjustment techniques. An official
of the American Association of Textile Chemists and Colorists indicated
that virtually all of the Southern mills have responded to the needs for
some water treatment. They either operate their own on-site water treatment
facilities or are cooperating with a neighboring city for joint municipal
treatment. The Northern textile millss benefiting from the greater
availability of water, are characterized as normally sewering their
trivalent chromium wastes and diluting it as required for municipal
treatment.1480
Chromium Cyanide
No references to chromium cyanide could be found in the literature
except for a brief discussion of chrome cyanide compoundy by Udy.
Chromous cyanide and chromic cyanide are products of reactions under
exacting conditions between KCN and CrCl2 or CrCl3 respectively. They
decompose quickly in air and often undergo a variety of additional reactions
in solution. No uses were identified by Udy or in any of the literature
investigated in preparing for this Profile Report. A maker or supplier of
chromium cyanides could not be found and no process or industry could be
identified which might produce chromium cyanides as a waste from any process.
The presence of chromic cyanide was described by one source as a highly
unlikely occurrence since cyanides can only exist in an alkaline media
1981
which would ordinarily precipitate trivalent chromium. No physical
properties were found in any of the standard works that are consulted in
these studies and identified in other Profile Reports.
-------
2. TOXICOLOGY
Trivalent chromium compounds are said to be less toxic than
the hexavalent chromium compounds. Eczema-like skin conditions from
trivalent chromium contact have been reported. The toxicology
literature discusses the hexavalent compounds in considerable detail but
the available literature does not distinctly describe the hazardous
properties of the trivalent compounds by themselves. The Threshold Limit
D??*!
Value (TLV) for trivalent chrome compounds is 0.5 mg per cubic meter.
Internally, chrome salts act as an irritant causing tissue corrosion in
the gastrointestinal tract. Complaints of a bad taste in the mouth,
vomiting and bloody stools are often noted. In addition, the central
nervous system is often involved and dilated pupils, coma, collapse» slow
• 207R
respirations, shock and death sometimes occur.
When drinking water contains fluoride in relatively low concentrations,
it will help prevent dental caries. No ill effects will result from these
small amounts of fluoride. Excessive fluoride which is ingested by
drinking water with high fluoride content or ingesting other fluoride
contaminated materials will produce an objectionable dental fluorosis
accompanied by an embrittlement of bones. The fluorosis in bones can have
a crippling effect when 20 or more milligrams of fluoride from all sources
is consumed per day for 20 or more years. Death will occur when 2.2 to 4.5
1752
grams of fluoride is consumed in a single dose.
Other Hazards
No other flammability or explosive hazards have been found to exist
for these compounds.
17
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The toxicity of the trivalent chrome compounds necessitates the use
of careful precautions when storing, handling,, transporting, disposing,
or reusing these materials. Dried, waste chromic sulfate can be packed in
multi-wall moisture resistant paper bags and in fiber drums. Chromic
fluoride is shipped by Allied Chemical in 100- and 300-1b steel drums
and it is believed that these are also adequate for the transportation of
1980
chromic fluoride wastes. The International Air Transport Association
(IATA) classifies solid chromic fluoride as "other restricted articles";
Class B; no label is required. Chromic fluoride solutions are classified
by the IATA as corrosive liquids, requiring a White Label. These materials
should be stored in areas separate from food stuffs. The use of outer
protective clothing, rubber gloves, and dust controlling breathing equipment
is recorpended for personnel handling open containers of this material to
prevent the possibility of burns and skin lesions.
All personnel and supervisory staff that deal with these types of
compounds should be well instructed in the precautions that must be
undertaken to prevent hazardous exposure to these materials. These same
precautions are, of course, applicable to any procedures or waste management
techniques designed to reprocess, repurify, or reconcentrate these materials
for reuse in the future.
Disposal/Reuse
Chromic sulfate and chromic fluoride do not occur in concentrated
waste forms so that the chromium values could be more readily recovered.
For the safe disposal of the trivalent chromium compounds, the
acceptable criteria for their release into the environment are defined
in terms of the following recommended provisional limits:
-------
Contaminant Basis for
In Air Provisional Limit Recommendation
Chromic sulfate
0.005 mg/M3 as Cr 0.01 TLV
Chromic fluoride 0.005 mg/M3 as Cr 0.01 TLV
Chromic cyanide 0.005 mg/M3 as Cr 0.01 TLV
Contaminant Basis for
In Water and Soil Provisional Limit Recommendation
Chromic sulfate 0.05 ppm (mg/1) as Cr Drinking water standard
Chromic fluoride 0.05 ppm (mg/1) as Cr Drinking water standard
Chromic cyanide 0.01 ppm (mg/1) as CN Drinking water standard
Option No. 1 - Precipitation by pH Adjustment
Soda ash or other alkaline chemicals are added to trivalent chrome or
other heavy metal solutions to adjust the pH to about 9.5;thereby
precipitating the insoluble heavy metal hydroxide gels. Aluminum sulfate
(alum) or other suitable flocculating agents are also often used to aid in
precipitation, settling of the gels and clarification of the effluent.
Slaked lime must also be added to precipitate insoluble calcium fluoride,
a reaction which requires at least 24 hours. The effluent is neutralized
before sewering and the resultant sludge is landfilled. The procedure
can be carried out in either batch or continuous processes. Complete
equipment systems are available for performing the precipitation on an
automated or semi automated basis. The biggest drawback of this procedure
is the removal and disposal 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 a slow procedure and
with a high volume of effluent it is normally necessary to have settling
ponds or lagoons in which to allow the slow coagulation process to function.
The clear effluent can be removed and the residual sludge dried. No
feasible economic process has yet been developed for the reclamation of
valuable metals or other credits from this type of sludge since it often
contains other organic and inorganic materials which hinders effective
purification and recovery.
19
-------
Three ultimate disposal options for these sludges are:(l) 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. It is
therefore recommended that California Class 1 type landfill be utilized for
these wastes. 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 to the formation of poisonous soluble metal oxides. Incineration of
course 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.
These three sludge disposal options are discussed in greater detail in
the Profile Reports on the chromate (ammonium chromate [21]) and
dichromate (potassium dichromate [345]) salts.
Option No. 2 - Dilute Chrome Discharge to Municipal Sewers
The textile and leather tanning industries, the areas of nearly all
the consumption of the subject hazardous materials, can both be
characterized as relying mainly on municipal sewage treatment systems
to handle the greatest proportion of their waste products in dilute
effluents.1601'0087'1988'1"0'1"1
When discharged to sewers, most trivalent chrome will be precipitated
in the sewers by sulfides found in the normal types of domestic and industrial
sewage. Precipitation of chromic sulfide occurs in transit to the waste
treatment plant and these solids are removed by the primary sedimentation
and screening facilities of the water treatment plant.
-------
It is currently feasible to treat tannery wastes including the chrome
content in adequately designed and operated municipal waste water treatment
plants where screening, flotation, and neutralization or precipitation are
necessary pretreatments. This option is environmentally acceptable only
when it is possible to construct adequate facilities in step with the
demand on them.
To summarize, precipitation by pH adjustment is an adequate waste
management method for trivalent chromium wastes; diluted discharge to
municipal sewers can be considered adequate if municipal treatment
facilities can efficiently remove the waste trivalent chromium. Whether
the trivalent chromium is handled in a pH adjustment process or is
precipitated as a result of sewering, the end result is a sludge of
metal hydroxides or sewage solids containing precipitated chromium
compounds. As discussed previously, the ultimate disposal of solids
from public and private waste treatment still remains a difficult and
critical problem. Again, it is recommended that Class 1 type landfill be
utilized where significant levels of toxic metals are present in the sludges.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is recommended that processes for treating concentrated metal wastes
be included in the design of National Disposal Sites but not necessarily for
the compounds discussed in the Profile Report. The waste handling character-
istics of the tanning and textile industries that create these waste materials
are such that no waste stream segregation is being performed to capture these
materials in concentrated form for transport to a National Disposal Site.
In addition, the procedures currently being used either in the on-site
industrial treatment plants and the municipal water treatment plants can be
designed to adequately manage the chromic sulfate and chromic fluoride waste
discharges as they are believed to currently exist. The facility that is
recommended for a National Disposal Site should be used for various metal-
containing, concentrated wastes which could occasionally need treatment.
These would Include other Cr compounds, Pb, Hg, Cu, and others.
21
-------
It is, of course, necessary for those with authority in private and
municipal waste water treatment to keep pace with the demands that these
waste chromium compounds and other waste materials place upon the waste
treatment plants. It is also reiterated that the greatest problem facing
the current types of waste treatment previously discussed is that of
disposing the solids and sludge material from the various and private
municipal treatment plants.
-------
7. REFERENCES
0087. Cost of clean water, v. 3. Industrial Waste Profiles No. 7, Leather
Tanning and Finishing. Washington, Federal Water Pollution
Control Administration, 1967. 59 p.
0095. Laboratory waste disposal manual. Manufacturing Chemists
Association, 1970. 176 p.
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.
1480. Personal communication. T. Alspaugh, Cone Mills, to J. F. Clausen,
TRW Systems, Mar. 17, 1972.
1492. The Merck Index of chemicals and drugs. 7th ed. v. 11. New York,
Interscience Publishers, 1966. 899 p.
1601. The textile industry and the environment. American Association of
Textile Chemists and Colorists Symposium, Atlanta, Mar. 31-Apr. 1, 1971.
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. 61 p.
1980. Personal communication. R. Jackson, Allied Chemical Corp., to
J. F. Clausen, TRW Systems, June 13, 1972.
1981. Personal communication. D. Hutchison, Harshaw Chemical Co., to
J. F. Clausen, TRW Systems, May 30, 1972.
1989. Personal communication. W. Roddy, American Leather Chemists
Association, to J. F. Clausen, TRW Systems, Mar. 28, 1972.
1990. Personal communication. C. Lafferty, Sierra Pine Tanning Co., to
J. F. Clausen, TRW Systems, Mar. 28, 1972.
1991. Personal communication. Plant Manager, Los Angeles Tanning Co.,
to J. F. Clausen, TRW Systems, Mar. 28, 1972.
2028. Gonzales, T. H., M. Vance, M. Helpern, and C. J. Umberger. Legal
medicine, pathology and toxicology. New York,
Appleton-Century-Crafts, Inc., 1954. 1,349 p.
2053. Personal communication. C. Cook, Burlington Mills, to J. F. Clausen,
TRW Systems, June 19, 1972.
-------
REFERENCES - CONTINUED
2054. Personal communication. R. Stone, American Association of Textile
Chemists and Colon'sts, to J. F. Clausen, TRW Systems,
June 19, 1972.
2055. Udy, M. J. Chromium chemistry of chromium and its compounds, v. 1.
New York, Reinhold Publishing Corporation, 1956. 433 p.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Chromic f lunririp (485)
structure
IUC Name
Common Names Chromium tHflunrirfp CrFj
J
1 Formula
0)
Molecular Wt. 108.990) Melting Pt. 1000 C(1) Boiling Pt. sublimes05
Density (Condensed) 3.8°' 9 Density (gas) &
(1100-1200 )
Vapor Pressure (recommended 55 C and 20 0
@ 9 9
Flash Point Autolgnition Temp.
Flamnability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water insoluble" Hot Water Ethanol insoluble
Others: slightly
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Chromic Sulfate(486)
IUC Name . :
Common Names Chromium Sulfate, Wool Mordant
Structural Formula
Cr2(S04)
Molecular Wt.
392.18
(1)
Melting Pt.
Density (Condensed) 3.012'^
Density (gas)_
Boiling Pt._
9
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 Mater Both soluble and 1nso1ulfr10't Water
Ethanol slightly soluble
Others:
Acid, Base Properties_
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
*
Coast Guard Classification
Some chromir ^alts p«1«:t in tun fnrmt. a cnlnhln and an
Comments,
Basic chromic sulfates existing varying mixtures and no one set of physical data Is
representative of the class of compounds.
mnH
-------
HAZARDOUS WASTES. PROPERTIES
WORKSHEET
H. M. Name Chromium Cyanide (487)
Structural Formula
IUC Name
Common Names
Cr(CN) or Cr(CN)
3
Molecular Wt. Melting Pt. Boiling Pt._
Density (Condensed)_ @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
G> 0 . «
Flash Point Autolgnition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Hot Water Ethanol_
Others:
Acid, Base Properties •
Highly Reactive with Decomposes in air.
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification
Coiments CrCl3 + 3KCN Cr(CN)3 (a green blue precipitate in excess KCN)^
CrCl, + 2KCN Cr(CN), (a white precipitate) "*
References (1) 2055
-------
PROFILE REPORT
Copper (275). Lead & Zinc (276) Mill Tailings
1. GENERAL
Processing
The mill tailings environmental problems stemming from the production
of copper, lead and zinc have been grouped in this Profile Report since
the major ores (all sulphides) of these materials are concentrated in a
similar manner. Though vast quantities of finely ground wastes are pro-
duced, they are in themselves innocuous and it is only the leachate of
contained minerals or the small quantities of flotation reagents which
are contained which could constitute hazards.
Typically, the processes involved in the production of a concentrate
of the mineral of interest and the attendant waste product (tailings) for
copper, lead, zinc follow this pattern:
(1) Crushing
(2) Gravity Separation (Lead and Zinc)
(3) Grinding
(4) Flotation Separation
Crushing. Crushing2486 is predominantly 3-stage, comprising almost
universally a jaw or gyratory crusher as the primary stage, a cone crusher
as the secondary machine, and rolls or short-head cone crushers as the
third stage. Oversize material from each stage of crushing is normally
separated by grizzlies or screens and recirculated.
Gravity Separation. "The coarsely disseminated ores of lead, lead-
silver, and lead-zinc, with gangue of average specific gravity (2.6 to 2.8)
yield important quantities of high-grade lead concentrate by gravity con-
centration on jigs and/or tables."
Grinding. The crushed ore is then ground to an average size sufficient
to liberate the ore mineral from the gangue (35 to 48 mesh or as fine as
necessary to free the minerals). As in the crushing stage, oversize
material is recirculated. In order to obtain the required recoveries a
-------
large amount of the material must of necessity be ground much finer than
the average.
9 AQ£
Flotation. Taggart's Handbook of Mineral Dressing describes
flotation as a method of concentrating minerals in a relatively finely
divided state. It is essentially a method of gravity concentration in
water in which the effective specific gravity of the ore minerals is sub-
stantially decreased by causing air bubbles to attach to particles of the
particular mineral of interest whereupon they float on the separating
medium while the unaffected minerals (tailings) sink.
After grinding, the steps in froth flotation are: (1) dilution to a
pulp consistency of 15 to 35 percent solids; (2) addition to the pulp of
small quantities of conditioning agents, (burned lime or sulphuric acid
for pH adjustment-1 to 4 Ibs/ton, sodium cyanide, etc. .2 to 2 Ibs/ton of
ore), which prepare the mineral surfaces; (3) addition of a collector re-
agent which has the function of coating the mineral to be floated with a
water repel 1 ant film (xanthates are commonly used for Cu, Pb and Zn-0.04
to 0.2 Ibs/ton of ore); (4) addition of a frothing agent which imparts per-
sistence to bubbles when they reach the surface (pine oils, eucalyptus oil,
alcohols, etc. --0.4 to 0.1 Ibs/ton of ore); (5) aeration by agitation or
by air injection of a combination of the two; (6) separation of the mineral
bearing froth from the liquid pulp containing the residual pulp.
Ores and Concentrates
Copper. As described in Taggart's Handbook of Mineral Dressing
the primary sulfide economic minerals of copper are bornite [Cu5 Fe S.],
Chalcocite [Cu^S], Chalcopyrite [Cu Fe S«], or native copper [Cu]. Copper
is found in practically every type of ore deposit and associated, in one
place or another, with practically every metallic and rock-forming mineral.
The largest and best known deposits are the sulfide-vein deposits of
Montana, the native-copper deposits of the Lake Superior region, and the
"oxidized" and "porphyry" deposits of the southwestern United States. At
Butte, Montana, the ore-bearing veins occur in granite, the chief copper
-------
minerals are chalcocite, enargite [Cu^ (As, Sb) S.], bornite, and chalcopy-
rite, and the principal associated vein minerals are quartz and pyrite.
In the Lake Superior region the native copper, associated with native silver,
occurs as part of the cementing matter in a conglomerate, as a cavity
filling in lava beds, and in veins cutting both igneous and sedimentary
rocks. The usual gangue minerals are calcite and zeolites. The "oxidized"
deposits of the southwest carry amounts of the oxidized copper minerals,
malachite, azurite, and cuprite, and directly below or closely associated
with these, bonanzas of massive secondary chalcocite. Both classes of
minerals are derived from the primary copper sulphides, largely chalcopy-
rite and cupriferous pyrite, which are found unaltered in greater depths.
The deposits occur in limestone or at limestone-porphyry contacts. The
"porphyry coppers" are mineralized zones in granitic porphyries and schists.
The principal copper mineral is chalcocite, which occurs as grains and
veinlets in the country rock. Pyrite, chalcopyrite, and magnetite are the
principal metallic associates; quartz and the rock-forming silicates form
the nomentallic gangue.
Copper ores may contain native copper (one mine operating in the
United States) or either of the three sulphides, chalcocite, bornite or
chalcopyrite, as the principal value-bearing constituent; in which case
a given weight of copper-bearing mineral will carry respectively 100, 80,
56, or 35 parts of copper per 100 parts of pure concentrate, with a corres-
ponding limitation on the highest possible grade of concentrate that can
be made.
Most of the U.S. production (over 90%)1975 is presently derived from
five western states. Most of the remainder comes from Michigan and
Tennessee. Fifteen of the leading mines are located in Arizona, which
produces more than 50 percent of the U.S. production. Arizona produces
approximately 100 million tons of copper mill tailings per year. Utah
ranks second with over 30 million tons of tailings per year. Mines and
concentration plants in Michigan, Montana, Nevada, New Mexico and Tennessee
make up the remainder. .
31
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Since most of the large disseminated ore bodies which are the pri-
mary source of present production range from 015 to 1.0 percent copper,
the tremendous amounts of material which must be processed to produce
concentrates approaching the theoretical limits required for the produc-
tion of 1,205,000 tons of copper can easily be seen. Some typical analy-
ses of copper tailings are shown in Table 1. ^
Lead & Zinc. "Occasionally one of these metals2486 is found in
economic quantities in an ore in which the other is lacking or is but a
minor constituent; such occurrence is, however, so rare that the localities
can almost be counted on the fingers of one hand, e.g., lead in southeastern
Missouri, Leadville, Colorado, and Tintic, Utah, and zinc at Mascot,
Tennessee, Franklin Furnace, New Jersey, and southwestern Wisconsin. The
usual ores contain galena [PbS], and sphalerite [ZnS]; many carry important
amounts of silver; minor amounts of copper are not uncommon and are usually
accompanied by minor quantities of gold; pyrite and pyrrhotite are common
associates; carbonates and quartz are the most usual rock-forming gangue
minerals, but other gangue associates are legion.
The economic minerals of lead are galena [PbS], cerussite [PbCO-J,
anglesite [PbS043, and pyromophite iSPb^PO^'Pb C12]. Galena ores
comprise t&e great majority. There are three general classes; (1)
those containing lead alone as an economic metal; (2) lead-zinc ores;
(3) lead-silver ores.
Calcite, dolomite, and pyrite are the common gangue minerals of the first
two classes, quartz of the third class.
The economic minerals of zinc are sphalerite, smithsonite, [ZnCO],
calamine [ZnSi03'Zn (OH)2J, franklinite [Zn Fe2 04], wiHenrite, and zincite.
These are several distinct types of ores. Argentiferous and auriferous
zinc sulphides with or without some lead, copper, and iron sulphides in
quartzose gangue are typical of the Rocky Mountain deposits. Sphalerite
alone or with galena and, usually, with some pyrite in limestone are typi-
cal of the Mississippi Valley deposits."
32
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0169
TABLE I
CHEMICAL ANALYSES OF COPPER TAILINGS
Location Si02 A1203 Na20 K20 MgO CaO Cu Fe Ni S C02 Ti02
Magna, Utah 70.8 12.0 1.0 5.1 3.9 1.7 0.10 2.7 0.0020.95 0.23 0.35
Hayden, Arizona 81.33 8.50 0.4 4.0 0.86 0.14 0.115 3.75 .5
San Manuel, Arizona 67.2 13.3 1.5 6.0 1.5 1.28 0.06 2.4 — 1.00 — 0.8
-------
Primary lead-zinc production, mostly from the state of Missouri,
amounts to over 5.5 million tons per year, which leaves a residue of over
5 million tons per year of tailings. Tennessee represents the primary
source of zinc in the United States with over 20 percent of the national
production. Again, the production of 5.5 million tons of ore leads to a
residue of over 5 million tons of tailings.
Though an average analysis for all lead mining operations, consider-
ing the varying geology of the areas of production, would not be meaning-
ful, analyses typical of Missouri lead mines are shown below:
Old "Lead Belt" - 52% CaC«3, 40% MgC03
Joplin District - Predominantly Silica
New "Lead Belt" - 52% CaC03, 40% MgC03
Plus Trace Impurities from Flotation and
Residual Lead and Zinc
A fairly typical analysis of tailings from zinc mines in Tennessee
is shown as follows:
Chemical Analysis
SiO,
R2°3
ZnS
9.80 1.45 0.18
Lime eouivalent = 95.55
CaCO
MgCO,
36.35
Screen Analysis
Screen Size
+20
+35
+65
+100
+150
+200
-200
Total
Wt % on Screen
0.4
8.0
22.4
11.0
10.8
6.0
41.4
100.0
34
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2. TOXICOLOGY
Copper, lead and zinc tailings constitute a negligible toxicological
hazard.
3. OTHER HAZARDS
The tailings, although not presenting a toxicological problem,
constitute an environmental problem on the basis of three major elements:
(1) the sheer volume of the refuse materials; (2) the dust problems en-
countered because of the fineness of tailings; (3) the production of
acidic, iron containing leachates which may also contain small quantities
of flotation reagents.
As an example of the types of leachates which may be produced, mine
drainage (similar to the leachate produced from the tailings dumps) from
a lead-zinc mine in southeast Kansas contained 1,000 ppm of iron at a pH
of 2.65.2485
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Present methods of waste management have evolved around the entrap-
ment of the tailings in ponds and the subsequent stabilization of the
dried tailings. As described in the Dames and Moore Engineering Bulletin
No. 34, tailing ponds are developed by two basic methods:
"1) Building Retaining Dams. For this system, earth dams are con-
structed for retaining the tailings to the planned height. After the dams
are completed, the tailings are deposited behind the dams in essentially
the same manner as would be used to fill a water reservoir. Such dams
are usually designed and constructed to water retention standards."
"2) Build With Tailings. Another system consists of building the
dams by using the tailings themselves. A small starter dike is constructed
with imported materials on the downstream side of the pond after that, the
remaining perimeter embankments are constructed by controlling the hydrau-
35
-------
lie deposition of the tailings. Such control usually involved adjustments
in the decant system of the pond and the use of a limited amount of imported
fill. In developing ponds by this system, the various factors influencing
water handling and embankment construction must be considered during the
entire life of the tailings pond."
"The first system—involving the initial construction of earthen
retaining dikes--usually results in a high initial investment but low
operating costs. The second system—building with tailings—results in
a low initial investment, but requires continuing attention during the
operation of the facility. Most installations evolve into a combination
of the two systems, particularly since the continuous desposition of tail-
ings often requires a larger storage capacity than that available behind
the initially constructed retaining dam."
Stabilization of tailings is presently being attempted by one, or
combinations of the following methods:
1) Coatings. Some dried tailings areas have been covered with
asphaltic or clay coatings to prevent the problems of blowing dust.
2) Chemica1 Stabi1i zati on. "Chemical stabilization involves
reacting mineral wastes with a reagent to form a water- and air-resistant
crust or layer. Many reagents have been tested on different tailings.
These studies indicated that cement, lime, sodium silicate with FeSCL and
CaCl2 additives, oxidized pyrite or pyrrhotite, various lignin sulfonates,
redwood bark extracts, amines, dicalcium silicate, bituminous base products,
elastomeric polymers, sulfonated petroleum products, and resinous adhesives
were effective stabilizers for most types of tailing wastes."
3) Vegetative Stabilization. Vegetative stabilization consists of
providing a vegetative cover that renews itself and provides a suitable
habitat for the enroachment of native plant species. This is normally
accomplished by planting a mixture of seeds and seedlings native to the
area of interest.
-------
Though vegetative stabilization is the most ecologically satisfac-
tory method of stabilization, it is complicated by the fact that most
tailings are: (1) deficient in certain plant nutrients; (2) unfavor-
able for plant growth due to textural and structural properties which
adversely influence soil aeration and moisture; (3) include unconsolidated
sands which, when windblown, tend to sandblast or bury young plants; (4)
are light in color and reflect solar radiation to the darker surfaces of
plants thus intensifying physiological stresses; (5) contain salts and
heavy metal phytotoxicants that adversely affect plant growth."
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The disposal of tailings in ponds and subsequent stabilization by
the methods described in Section 4 of this report are judged to be
adequate methods of disposal.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is apparent that copper, lead and zinc tailings are not
"hazardous" materials in a toxicological sense, though they are a large
environmental problem, and consequently they are not candidates for
National Disposal Sites.
However, it is readily apparent that much must be accomplished to
make existing and future tailings ecologically acceptable. In the reduc-
tion of the environmental problems associated with tailings disposal, the
following elements should be considered for research and development as
well as the agronomical efforts required for the development of effective
vegetative cover at each site. (1) A very inexpensive method of agglom-
erating tailings is required, both to improve the aeration characteristics
of the soil and to improve its tilth; (2) less expensive means of chemi-
cally stabilizing tailings while vegetative stabilization is developing
would be most useful; (3) one reference speaks of the advantages of
adding sewage sludge to "improve the structure and add organic matter."
Many municipalities are in difficult straits in their efforts to dispose
37
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of sewage sludge in a non-polluting manner. The development of an inte-
grated system of sludge disposal and tailings stabilization could be most
beneficial in many cases in aiding both mining companies and municipalities
in solving their environmental problems.
38
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7. REFERENCES
0136. U.S. Bureau of Mines—R.I. 7261, Chemical vegetative stabili-
zation of a Nevada copper porphyry mi 11-tailing, 1969
0169. ITT Research Institute for the U.S. Bureau of Mines, Contract
No. G6027, Techno-economic analysis of mining & milling
wastes, 1969
1975. U.S. Bureau of Mines, Mineral facts & problems. Bulletin No.
650, 1970
2484. Dames & Moore, The planning of tailings ponds. Engineering
Bulletin No. 34. Dames & Moore, Los Angeles
2485. State Geological Survey of Kansas, Treatment of mine water
as a factor in the mineral production in southeastern
Kansas, 1961.
2486. A. F. Taggart, Handbook of mineral dressing. John Wiley &
Sons, Inc., 1945
39
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PROFILE REPORT
Slag I (SIC 3331) Copper Smelting (371)
and Slag II (SIC 3332) Lead Smelting (372)
1. GENERAL
Introduction
Copper is extracted from ore concentrates by smelting in a
reverberatory furnace. The materials may be prepared by drying or
roasting or they may be charged directly into the furnace.
The molten charge in the furnace separates into layers of matte and
slag. Slag is removed at this point while the molten matte is transferred
to converters where silica flux is added and air blown through. Iron
sulfide is oxidi2ed and the iron is removed as a silicate slag, while
the copper sulfide is converted to blister copper for further refining.
Lead sulfides are converted to oxides of lead and sulfur in the
preliminary sintering step. The oxidized material is then reduced in
the blast furnace to form impure metal and slag. To form the slag the
materials used are limestone, silica, and small amounts of scrap iron.
These are added in the amounts required to form a free running slag.
Composition
Copper. The two molten products of the reverberatory furnace generally
have the following range of values (in percent):
Component Matte Slag
Copper 25-50 0.4-0.7
Iron , 29-35 34 -40
Silica 0.8-1.0 35 -40
Sulfur 22-29 1.0-1.5
41
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Lead. The slag is removed from the blast furnace separately and
is conveyed to a fuming furnace for recovery of lead and zinc. As it
goes to the fuming furnace the slag contains 10 to 20 percent zinc,
one to two percent lead, the remainder is mainly siliceous and contains
iron- and calcium.
Minor Constituents in Nonferrous Smelting. "Ores and concentrates
of copper, zinc, and lead have varying amounts of minor constituents that
sometimes require the use of special processing methods to recover them
or to overcome or avoid the problems they could cause. There is not
only considerable variation in the constituents from one smelter to
another, but also from time to time in particular smelters. These
constituents include chlorine compounds in lead smelters, fluorine in
copper, zinc, and lead smelters, and arsenic in most ores of the
western United States. Cadmium is commonly associated with zinc, and
the quantities are large enough so that most plants recover it. Mercury
is found in some zinc ores and has been recovered in some instances.
Bismuth, selenium and tellurium are often present in ores of most
nonferrous metals.
Volatile constituents such as arsenic get into the gases and usually
deposit in the flue system. One copper smelter has recovered and purified
2943
arsenic for sale as a byproduct."
2. TOXICOLOGY
The leachates from slag dumps may present toxicological hazards
depending upon the minor constituent metals contained in the slag of
interest. The toxicological hazard and the recommended methods of
treatment are discussed in the Profile Reports covering the metals
of interest. Detailed chemical analysis of slags and leachates from
each operation would be required to make a judgement since the feed
ore and byproduct recovery are so variable.
-------
3. OTHER PROBLEMS
Slags constitute an environmental problem mainly because of the large
volume of material produced and the large amount of acreage utilized for
their deposit.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Slag is generally dumped in the most economical, available area.
Some efforts have been made to utilize slags as aggregates in concrete,
for road metal etc., but the economic limits for the transportation of
these low value products only allows them to be used in the area of
the smelters.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Current disposal methods, as presented in Section 4 above are
judged to be acceptable methods of slag disposal.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Because of their volume and their low toxicological impact, slags are
not candidates for National Disposal Sites. To alleviate their environ-
mental impact research efforts should be encouraged which will: 1) provide
economical extraction of all metal values and 2) improve their accepta-
bility to State Highway Departments and others for use as aggregate and
other building products.
43
-------
7. REFERENCE
2493. McKee, Arthur G. and Company. Systems study for control of
emissions primary nonferrous smelting industry, v. 1. Final
Report under contract QH 86-65-86. San Francisco, Arthur
McGee and Company, Western Knapp Engineering Division.
June 1969.
44
-------
PROFILE REPORT
Hydrazoic Acid (528)
1. GENERAL
Hydrazoic acid is a colorless liquid, of sharp, irritating odor with
a boiling point of about 37 C. It is highly poisonous with a toxicity
about equal to that of hydrogen cyanide. Liquid liydrazoic acid is very
dangerous to handle owing to the ease with which it explodes.
Hydrazoic acid is a weak acid. It reacts with zinc, iron, magnesium,
and aluminum to form azides with evolution of hydrogen. A small amount of
ammonia is also produced, due to the reduction of hydrazoic acid. Hydrazoic
acid also reacts with copper, silver and mercury to form azides without loss
of hydrogen. A considerable amount of hydrazoic acid is reduced to ammonia
of hydrazine and free nitrogen in these systems. Hydrazoic acid, like nitric
acid, oxidizes hydrogen sulfide to form sulfur:
HN3 + H£S -> S + N2 + NH3
When mixed with hydrochloric acid it forms a solution resembling nitro-
hydrochloric acid in its properties and is capable of dissolving noble metals.
There are two methods for the manufacture of hydrazoic acid or its salts.
One is based on the action of nitrous acid on hydrazine:
N2H4 + HN02 -»• HN3 + 2H20
An excess of nitrous acid decomposes hydrazoic acid in accordance with the
equation as follows:
HN3 + HN02 -»• N2 + N20 + H20
45
-------
This is a quantitative reaction and is used to destroy waste azides.
Nitrous esters may be employed for the manufacture of hydrazoic acid,
e.g., ethyl nitrate in the presence of sodium hydroxide.
NaOH
With this reaction sodium azide is formed instead of hydrazoic acid. The
second method of manufacture is based on the action of nitrous oxide on
sodium amide.1662'2171
Hydrazoic acid is not normally sold or shipped even in laboratory
1411
quantities. In the laboratory, sodium azide is reacted with sulfuric
2171
acid and the resultant hydrazoic acid purified by distillation.
The physical/chemical properties of hydrazoic acid are summarized in
the attached worksheet.
2. TOXICOLOGY
Vapors of hydrazoic acid irritate the respiratory tract, particularly
the nasal mucosa, and its aqueous solution burns the skin. Hydrazoic acid
interferes with the oxidation-reduction processes in the human body causing
injury to kidneys and spleen. Headache, weakness, and unsteadiness have
also been reported following continued industrial exposure. The chief
physiological effect of azides is a marked lowering of the blood pressure
with an accompanying rise in heart beat and an increase in respiration rate.
Concentrations in air within the range 0.5 to 7.0 mg/M3 evoke marked symptoms
of intoxication. The toxic effect may be delayed; symptoms appearing the
2171
day following exposure. A Threshold Limit Value (TLV) for hydrazoic acid
has not been established by the American Conference of Government Industrial
Hygienists.0225
46
-------
3. OTHER HAZARDS
Liquid hydrazoic acid explodes on heating to 100 C in a tube. An
explosion may also occur on rapid cooling or on handling the liquid under
vacuum or in passing compressed oxygen into a vessel containing liquid
hydrazoic acid. In dilute aqueous solution hydrazoic acid is stable and not
liable to decompose even on long boiling. However, a 17 percent aqueous
solution of hydrazoic acid can detonate. Gaseous hydrazoic acid is liable
to non-explosive decomposition above 250 C. At 33 C its half-life is
12 min. Hydrazoic acid decomposes when exposed to ultraviolet light.
The heavy metal azides are used as primary explosives, and are extremely
sensitive to mechanical, electrical or thermal shock. For this reason, extreme
caution should be employed in handling HN3 which has been in contact with
heavy metals. The acid should be handled in all-glass equipment.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Hydrazoic acid in aqueous solution dissolves iron, zinc and copper
with formation of the azide, nitrogen and ammonia, but glass equipment is
satisfactory for handling hydrazoic acid. When required as acid rather
than as one. of its salts, the hydrazoic acid is usually prepared at the
pi 71
location where it is to be used. No commercial source for hydrazoic
acid exists, and there are no regulations permitting its shipment.
The safe disposal of hydrazoic acid is defined in terms of the recom-
mended provisional limits in the atmosphere and in water and soil. These
recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
Hydrazoic acid 0.005 mg/M 0.01 of minimum level that
produces symptoms of in
intoxication.2''^
47
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Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
Hydrazoic acid 0.025 mg/1 Stokinger and Woodward
Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Hydrazoic acid as a waste will not be encountered in large quantities
and a satisfactory method for its destruction exists. An excess of nitrous
acid decomposes hydrazoic acid in accordance with the following equation:
HN3 + HN02 -»• N2 + N20 + HgO
This reaction is accomplished by diluting the hydrazoic acid with 500 times
its weight of water, slowly adding 12 times its weight of a 25 percent
solution of sodium nitrite, agitating, and then slowly adding 14 times its
weight of a 36 percent solution of nitric acid or glacial acetic acid.
A red color produced on addition of ferric chloride solution indicates
azide to be present; more time or additional reagents are required to effect
complete destruction of azide. ' After pH adjustment to 6.0 to 9.0,
the reacted solution is diluted to a nitrite and nitrate concentration of
less than 450 ppm, a typical maximum allowable concentration in an effluent
being discharged to a storm sewer or stream.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The difficulty encountered in shipping hydrazoic acid and the limited
quantity used indicates that it is not a likely candidate waste stream
constituent for a National Disposal Site. The treatment facilities that
will be available at a National Disposal Site will permit easy treatment
of hydrazoic acid, if ever required. The only facilities required are
for diluting, addition of chemicals, and mixing.
-------
7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limits for 1971. Occupational Hazards, Aug. 1971. p. 35-40.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of Interior. Apr. 1, 1968. Washington,
Federal Water Pollution Control Administration. 234 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1147. Department of the Army and the Air Force. Military explosives.
TM9-1910, Washington, Apr. 1955. 336 p.
1411. Chemical Week. 1972 Buyers Guide Issue. 109(14) :275, Oct. 27, 1972.
1662. Shreve, R. N. The chemical process industries. 2d ed. McGraw-Hill
Book Company, Inc., New York. 1956. 1,004 p.
2169. Fedoroff, B. T. Encyclopedia of explosive and related items, v. 1.
Picatinny Arsenal, U. S. Army, 1960. 692 p.
2171. Urbanski, T. Chemistry and technology of explosives, VIII. Warszawa,
Polish Scientific Publishers, 1967. Translated by Jurecki, Marian,
New York, Pergamon Press. 714 p.
49
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
ri. H. Name Hydrazoic Acid (528)
Structural Formula
IUC Name Hydrazoic Acid
Common Names Azoimide
NH
3
Molecular Wt. 3'°3 Melting Pt. '8° C Boiling Pt. 37 C
Density (Condensed) @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flamiability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 2-14 ml/100 ml Hot Water 0.85 ml/100 ml Ethanol 6.925 yn/100 ml
Others:
Acid, Base Properties Weak arid. Y. = ? a v in'5
Highly Reactive with reducing agents, iron, zinc, copper
Compatible with hydrocarbons, glass
Shipped in not normally shipped
ICC Classification Coast Guard Classification_
Comments :
References (1) 1415
-------
PROFILE REPORT
Hydrobromic Acid (Hydrogen Bromide) (213)
1. GENERAL
Hydrogen bromide is a colorless, very irritating, corrosive gas at
atmospheric temperature and pressure. As a liquid, it has a yellow color.
In cylinders, hydrogen bromide is a liquified gas at 70 F with a vapor
pressure of about 320 psig. HBr is very soluble in water; hydrobromic
acid is sold commercially as a 47 to 49 percent solution of HBr in water.
Hydrogen bromide adds to olefins and acetylenes, and is used as a catalyst
in a variety of organic -reactions. Hydrobromic acid is used for the
preparation of numerous inorganic bromides.
Hydrogen bromide is obtained as a by-product of the substitution
bromination of organic compounds. The physical/chemical properties
of hydrogen bromide are summarized in the attached worksheet.
2. TOXICOLOGY
Hydrogen bromide, like hydrogen chloride, is a toxic gas. It is
severely irritating to the upper respiratory tract and corrosive to the
eyes, skin and mucous membranes. The recommended maximum allowable
concentration for an 8-hr exposure is the 5 ppm Threshold Limit Value (TLV),
Because of its irritation to the upper respiratory tract, hydrogen
bromide provides adequate warning for prompt voluntary withdrawal from
contaminated atmospheres.
n
Contact of the eyes with hydrogen bromide gas rapidly causes severe
irritation of the eyes, and eyelids. Hydrogen bromide has a corrosive
action upon the skin and mucous membranes. It will cause severe burns.
51
-------
When hydrobromic acid in a waste stream is neutralized with sodium
hydroxide or carbonate, the stream will contain sodium bromide. Since
bromide ion is intermediate in abundance between chloride and fluoride
in natural waters, the presence of small additional concentrations of
bromide over that already present should present no problem. The total
amount of bromine in the earth is estimated at 10 tons of which about
half is thought to be contained in living organisms. Sea water contains
50 to 65 ppm of bromide. The presence of some bromide is necessary for
plant and mammal metabolism. Limits for bromide concentration in
streams and lakes have not been established, but waste streams that do
not cause an elevation of the bromide content of natural streams and
lakes above 50 ppm should generally be acceptable. Evidence that small
quantities of bromide do not affect humans is demonstrated by the fact
that as much as 0.45 g of sodium bromide administered daily to tuber-
culomeningitic patients increased the blood bromide level to 5 to 10
times normal. This level was maintained for several months without any
serious side effects.
3. OTHER HAZARDS
Hydrogen bromide is resistant to oxidation. The dry gas is essentially
non-reactive with commonly used structural metals under normal conditions
(room temperature and one atmosphere of pressure). In the presence of
moisture, hydrogen bromide will corrode most metals other than silver,
platinum, and tantalum.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
r
Adequate procedures for the safe handling, transportation and storage
of hydrogen bromide are provided by Matheson Company, Inc. Their
Gas Data book provides recommended procedures for equipment design, leak
tests, first aid, employee safety, and material specifications. The
handling of aqueous solutions of hydrogen bromide (hydrobromic acid)
is similar to that of any strong acid.
-------
Hydrogen bromide is classified by Department of Transportation (DOT)
as a nonflammable gas and is shipped in cylinders under a Green Label.
Hydrobromic acid (HBr solution in water) is shipped in glass bottles and
carboys as a corrosive liquid under a White Label.
Disposal Reuse
Hydrogen bromide as gas, as solute in organic solvents, and as hydro-
bromic acid in water solution is not normally discharged as a waste, but
is recovered because of its economic value.
In those instances in which discharge is necessary, the safe disposal
of hydrogen bromide is defined in terms of the recommended provisional
limits in the atmosphere and in water and soil environments. These pro-
visional limits are as follows: . ,
Basis for
Contaminant in Air . Provisional Limit Recommendation
HBr 0.03 ppm 0.01 TLV
Contaminant in Basis
Water and Soil Provisional Limit Recommendation
HBr 0.50 ppm Stokinger and
Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
In most industrial processes where hydrogen bromide or hydrobromic
acid are evolved as by-products, the recovery of hydrogen bromide is
essential for the commercial viability of the process. Impure hydrogen
bromide or hydrobromic acid usually can be sold to bromine and hydrogen
bromide manufacturers. Hydrobromic acid is often converted to bromine
by the chlorination process (see Profile Report on Bromine [65]).
Hydrogen bromide gas is purified by cooling to -60 C to freeze out
any moisture and most of the solvent vapors present. The partially
purified hydrogen bromide is then solidified with liquid air or nitrogen.
Fractionation permits the recovery of pure hydrogen bromide. The methods
53
-------
described briefly above are in commercial use and are satisfactory for
recovery of HBr.
!v 6. APPLICABILITY TO NATIONAL DISPOSAL SITES
With the exception of the return to the manufacturers of contaminated
hydrobromic acid (hydrogen bromide) or hydrobromic acid converted to impure
bromine, hydrobromic acid (hydrogen bromide) waste streams can be best
handled at the site where they are created by regeneration of purified
hydrogen bromide or preparation of bromine. Designated sites (located at
Br2 or HBr manufacturers) should be identified for processing and
purification of impure hydrogen bromide or bromine for resale.
54
-------
7. REFERENCES
1140. Jones, Z. E. Bromine and its compounds. New York, Academic Press,
1966. p. 164
1301. Matheson Company, Inc. Matheson gas data book. 4th ed. East
Rutherford, New Jersey, 1966. 500 p.
1305. Personal communication. M. Sharps Dow Chemical Company, to J. R.
Denson, TRW Systems, Mar. 16, 1972.
55
-------
* HAZARDOUS WASTES PROPERTIES
WORKSHEET
i
H. M. Name Hydrogen Bromide (213)
,, itructura
IUC Name hydrogen Bromide
! Common Names Anhydrous hydrobromic acid HBr
1
I Formula •
i
1
Molecular Wt. 80.92 Melting Pt. -87 C Boiling Pt. -67 C j
' Density (Condensed) 2.16 g/ml . @ -67 C Density (gas) 3.64 g/L @
o c (STP) :
\ Vapor Pressure (recommended 55 C and 20 C) }
J 320 psig @ 70 F 114 psig @ OF Crit. Temp. @ 91 C1
'• Flash Point Autoignition Temp. I
; Flammability Limits in Air (wt %) Lower NA Upper
NA
; Explosive Limits in Air (wt. %) Lower NA Upper NA
i Solubility
Cold Water 70 g/lOOg Hot Water - Ethanol - "<
^ Others: Acetic acid @ 11 C - 41% (w/w) j
I Acid, Base Properties Apparent dissociation in 0.1 N soln. at 20°C = 93%
'• Highly Reactive with all bases ;
I • ',
' Compatible with most metals when dry. In presence of moisture, compatible with Ni , Au, Ta, \
- and stainless steel.
* Shipped in steel cylinders, as liquified gas
; ICC Classification White label, non-flammable Coast Guard ClassificationNon-flammable gas, '
Comments
i Constant boiling mixture with water, 47%, has b.p. of 126 C
green label [
'
' *
References (1) 1140
0
1
56
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PROFILE REPORT
Hydrocyanic Acid (215) and Hydrogen Cyanide (218)
1. GENERAL
Hydrogen cyanide (also known as hydrocyanic acid) is a water-white
liquid at temperatures below 26.5 C. It has a faint odor of bitter almonds.
Hydrogen cyanide is miscible in all proportions with water and alcohol, and
in aqueous solution is weakly acidic; dissociation constant at 18 C is 1.3 x
_q
10 . When not stabilized, hydrogen cyanide polymerizes spontaneously with
explosive violence. Hydrogen cyanide is manufactured commercially by six
different processes: (1) by treating a cyar'de, usually sodium or calcium,
with dilute sulfuric acid; (2) by catalytically reacting ammonia and air with
methane or natural gas; (3) by recovery from coke oven gases; (4) decomposition
of formamide; (5) from ammonia and hydrocarbons by electrofluid reaction
in the presence of a platinum-rhodium catalyst; and (6) by pyrolytic decom-
position of residues from beet-sugar molasses. The principal uses of hydrogen
cyanide are in the manufacture of acrylonitrile, acrylates, adiponitrile,
1433
cyanide salts, dyes, fumigants, chelates, rubbers, and plastics.
The physical/chemical properties for hydrogen cyanide are summarized
in the attached worksheet.
2. TOXICOLOGY
Human Toxicity
Hydrogen cyanide and the cyanides are true protoplasmic poisons,
combining in the tissues with the enzymes associated with cellular oxidation.
They thereby render the oxygen unavailable to the tissues, and cause death
through asphyxia. The suspension of tissue oxidation lasts only while the
cyanide is present; upon its removal, normal function is restored provided
death has not already occurred. Hydrogen cyanide does not combine easily
57
-------
with hemoglobin but does combine easily with methemoglobin to form cyanmethe-
moglobin. Exposure to concentrations of 100 to 200 ppm for periods of 30 to
60 min can cause death. The Threshold Limit Value (TLV), American Conference
of Governmental Industrial Hygienists (AC6IH) recommended, is 10 ppm in air (11
mg per cubic meter). Hydrocyanic acid can be absorbed through the skin.0536
Other Toxicity
Cyanides, either as hydrogen cyanide or its salts, are important
industrial chemicals, and because of their solubility in water are often
'found in industrial aqueous waste streams. At low pH values, cyanide, as
hydrocyanic acid, is especially toxic. Cyanide ion is, for the most part,
unaffected by the basic water treatment plant. Many lower animals and fish
are able to convert cyanide to thiocyanate ion, which does not inhibit respiratory
enzyme activity. Hence, a permissible criterion has been recommended of
0.20 mg/1 for waste discharged into streams, and a desirable criterion of
complete absence from public waters was recommended by the Federal Water
Pollution Control Administration (FWPCA) Water Quality Committee.
3. OTHER HAZARDS
When hydrogen cyanide is exposed to heat, flame or oxidizing chemicals,
a fire or explosion may occur. Under certain conditions, particularly contact
with alkaline materials, hydrogen cyanide can polymerize or decompose
explosively. The compressed gas is commonly stabilized by addition of
acids.1416
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Liquid hydrogen cyanide is subject to the Department of Transportation
(DOT) regulations for the transportation of explosives and other dangerous
articles. It is defined a Class "A" poison. The commercial product usually
contains 96 percent to 98 percent hydrogen cyanide with the balance water and
small quantities of free mineral acids (about 0.05 percent) for stabilizing
purposes.
S&
\J>(J
-------
When hydrogen cyanide is stored in bulk, steel storage tanks are used
that should be kept cool and protected from mechanical injury. Routine
inspection for stability (liquid colorless) should be carried out. Before
filling with hydrogen cyanide, containers should be cleaned and treated to
remove alkaline contaminants.
Hydrogen cyanide is packed for interstate shipment in metal cylinders,
which must have not more than 125-lb water capacity and must be charged
with not more than 0.6 Ib of liquid for 1-lb water capacity of the cylinder.
Before shipment, the cylinder must be tested to insure against leakage.
This is done by passing a'piece of paper treated with sodium picrate over the
closure to test for escape of hydrogen cyanide. The cylinder must carry a
"Poison Gas" label. Shipment may be made by freight but is not accepted by
1433
Railway Express.
Disposal/Reuse
Hydrogen cyanide appears in both aqueous and gaseous waste streams from
hydrogen cyanide manufacturing plants, acidified cyanide salt (plating shops,
metal treating plants, etc.), organic chemical and plastic manufacturing,
and fumigating operations. In addition, coal coking and degassification
plants and oil refining operations produce hydrogen cyanide as one of the
byproducts. Complete removal of hydrogen cyanide from the effluent is
difficult. HCN passes into waste water in the course of the wet scrubbing
processes used to remove the HgS, NHg and phenol contaminants. Alkaline
scrubbing usually converts most of the hydrogen cyanide to the alkaline
cyanide salt. Hydrogen and the residual unstripped hydrogen cyanide,
though sometimes vented, are usually sent to a furnace where they are used
1963
as a fuel. Provisional limits for public exposure resulting from the
disposal of hydrogen cyanide have been defined in this study. These
recommended provisional limits are as follows:
59
-------
Contaminant in Provisional Limit Basis for Recommendation
Air
HCN 0.11 mg/M3 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
HCN 0.01 mg/1 as CN Drinking Water Standard
The quantities and locations of wastes containing HCN are too diverse
to summarize, since HCN is normally discharged as a very dilute solution.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Hydrogen cyanide in aqueous streams is easily destroyed by first
adjusting the pH to the 10 to 11 range and adding chlorine or hypochlorite
which converts the cyanide to cyanate. Then the pH is adjusted to the
8 to 9 range and further oxidizing agent converts the cyanate to carbon
dioxide and ammonia. Other methods though not often used are available and
are discussed in the combined Profile Report for the cyanide salts. In an
alternate equally acceptable method, hydrogen cyanide is removed from aqueous
solution by passing air through the solution. The venting of this air
containing hydrogen cyanide is not recommended, but instead the contaminated
air must be passed through an alkaline scrubber.
The destruction of hydrogen cyanide is usually accomplished by inciner-
ation which produces only carbon dioxide and nitrogen along with possibly some
NO that can be stripped from the incinerator effluent with an alkaline
1 *ifi?
scrubber, or reduced over a catalyst.
Air containing hydrogen cyanide, either as an effluent from a storage
tank, process, or from stripping of an aqueous solution, is absorbed by
passing the air through a sodium or potassium hydroxide scrubber which
produces the cyanide salt. The salts obtained in this manner are recovered
upon evaporation of the water.
-------
The disposal processes described are equally acceptable. The selection
of disposal processes are governed by the economics of destruction/recovery.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Hydrogen cyanide does not appear to be a candidate waste stream
constituent for National Disposal Sites. It is anticipated that aqueous a
and gaseous waste streams containing hydrogen cyanide will continue to be
treated at the source of the waste generation.
-------
7. REFERENCES
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. Apr. 1 „ 1968.
Washington, Federal Water Pollution Control Administrations 234 p.
1416 Ross, A. and E. Ross. The condensed chemical dictionary. 6th ed. New
York, Reinhold Publishing Corporation, 1966. 7,450 p.
1433. Kirk-Othmer. encyclopedia of chemical technology. 2d ed. 22v.and
suppl. New York. Uiley-Interscience Publishers, 1966. 969 p.
1562. Graham, A. K. Electroplating engineering handbook. 2d ed. Westwood,
New York, Metals and Plastics Publications Inc., 1962. 774 p.
1963. Kaumert, P. Hydrogen cyanide recovery. U. S. Patent 3,096,156.
May 1963.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrogen Cyanide (218)
Structural Formula
IUC Name Hydrogen Cyanide
Common Names Hydrocyanic Acid, Prussic Acid
HCN
Molecular Wt. 27.03 Melting Pt. -13.2 C Boiling Pt. 25.7 C
Density (Condensed) n fis« @_2Q_ £ Density (gas) n.QfiQ & 31 c
Vapor Pressure (recommended 55 C and 20 C)
360 torr & 7 C 658.7 torr@ 21.9 C @
Flash Point p 'p Autoignition Temp._
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water miscible Hot Water miscible Ethanol miscible
Others:_ ether-mi scible
Acid, Base Properties Acid, weak
Highly Reactive with must be stabilized with acids, reacts with bases
Compatible with most meta1s
Shipped in metal cylinders, 125-lb water capacity
ICC Classification Class "A" Poison Coast Guard Classification Class "A" Poison
Comments Critical temperature 183.5 C
References (1) 1433
63
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PROFILE REPORT
Hydrogen Sulfide (221)
1. GENERAL
Hydrogen sulfide is a toxic, flammable gas with a pungent odor,
which appears in a number of chemical industry waste streams (in
particular in refinery and natural gas processing waste streams).
Approximately 1 million tons per year of elemental sulfur are recovered
from hydrogen sulfide waste streams in the refinery industry alone. At
least an equal amount of waste hydrogen sulfide is burned and vented to
the atmosphere as sulfur dioxide. A detailed discussion on the fate of
hydrogen sulfide in refinery operations is presented. Physical/
chemical properties are summarized in the attached worksheet.
2. TOXICOLOGY
Human Toxicity
Hydrogen sulfide is a highly toxic gas which is extremely dangerous
in very low concentrations. The Threshold Limit Value (TLV) for hydrogen
sulfide is 10 ppm as defined by the American Conference of Governmental
Industrial Hygienists (ACGIH). This represents the condition to which
nearly all workers may be repeatedly exposed, day after day, without
adverse effect. H^S is both an irritant and an asphyxiant and may be
characterized by its repugnant odor of "rotten eggs." The toxic hazard
is aggravated because unprotected exposure to nontoxic levels of hydrogen
sulfide results in temporary olfactory fatigue limiting the capability to
detect dangerous levels. Human toxic effect as a function of time and
concentration is outlined (Table 1).
-------
TABLE 1
ACUTE EFFECTS OF HYDROGEN SULFIDE GAS0743
Concentration (ppm)
0.13
10.0
50-100
200-300
500-700
900
1000
Time
Sniff
8 hours
1 hour
1 hour
1/2 hour
Minutes
Minutes
Effect
Odor detectable
Threshold limit
Mucous membrane
Mucous membrane
(severe)
Coma
May be fatal
Fatal
irritation
irritation
-------
The acute effects of hydrogen sulfide inhalation represent the most
serious threat in handling. Although it is not a cumulative poison,
severe exposure may result in brain damage from oxygen deficiency if
breathing is not.rapidly regained. Permanent olfactory damage (loss of
sense of smell) may result from extended exposure at less than lethal
levels.
Exposures in the 700 to 1,000 ppm range may be fatal in 30 minutes.
Very high concentrations will be instantly fatal.
Toxicity Towards Aquatic Life
The toxicity of inorganic sulfides (primarily H^S) to fish increases
as the pH value is lowered. However, inorganic sulfides have proved fatal
to sensitive fish, such as trout, at concentrations between 0.5 and 1.0
mg/1 even in neutral and somewhat alkaline solution. Sulfides impart
an unpleasant tase and odor to drinking water at concentrations as low as
0.2 mg/1.0091
3. OTHER HAZARDS
Hydrogen sulfide is an extremely flammable gas. It burns in air to
form sulfur dioxide and water with the liberation of heat. In
concentrations of 4.3 to 46 percent HpS by volume in air it explodes upon
ignition. A mixture of (2) volumes of hydrogen sulfide and (3) of oxygen
explodes violently upon ignition. The autoignition temperature of
hydrogen sulfide is 500 F. This very low autoignition temperature
indicates the relative ease with which hydrogen sulfide/air mixtures can
be inadvertently ignited. Open flames, hot surfaces, and sparks will
ignite combustible or explosive H^S/air mixtures. Because of the
extremely high vapor pressure of liquid hydrogen sulfide, contact with
the skin will result in severe frostbite.
67
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4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling, Storage, and Transportation
Adequate procedures for the safe handling, storage, and transportation
of concentrated hydrogen sulfide wastes are described in detail by Stauffer
Chemical Company, and the Manufacturing Chemists Association.
These documents provide recommended procedures for building design, equip-
ment design, ventilation, air analysis, electrical equipment design,
employee safety, design of shipping and storage containers, federal
classification and regulations, tank and equipment cleaning and repairs,
emergency rescue, first aid, and material specifications.
^S is classified by the Department of Transportation (DOT) as a
Flammable Compressed Gas with a maximum permitted filling density of
62.5 percent in cylinders (Spec. 3A480, 3AA480, 3B480, 4A480, 4B480,
26-480, 3E1800) and 68 percent in tank cars (105A-600W). All federal
labeling, loading, and handling regulations must be followed.
Disposal/Reuse
A definition of acceptable criteria for the disposal of hydrogen
sulfide must also take into account acceptable criteria for the release
of sulfur dioxide to the environment since current practice in hydrogen
sulfide disposal usually involves processing the hydrogen sulfide to
sulfur and/or sulfur dioxide. The acceptable criteria for the release of
HpS and S02 into the environment are defined in terms of the following
recommended provisional limits:
Contaminant in Air Provisional Limit Basis for Recommendation
Hydrogen sulfide 0.1 ppm (0.15 mg/m ) 0.01 TLV
Sulfur dioxide 0.05 ppm (0.13 mg/m3) 0.01 TLV
Contaminant in Water
and Soil Provisional Limit Basis for Recommendation
Hydrogen sulfide 0.75 ppm (mg/1) Stokinger and Woodward Method
Sulfur dioxide 0.65 ppm (mg/1) Stokinger and Woodward Method
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Figure 1 summarizes HpS disposal options for both sour (HpS
containing) gas streams and sour water streams. Current practice as well
as processing options which are currently in pilot plant or demonstration
plant stages of development are included. Typical or expected effluent
concentrations of S02 and H2S are indicated (Figure 1) for each of the
processing options. The processing options are very briefly described in
the following paragraphs together with recommendations as to adequacy.
Detailed discussions of the major processing options are presented in the
referenced waste treatment process reports.
Sour Gas Disposal Processes
Sour gas waste streams which provide the input feed to HpS disposal
processes may contain in addition to HpS, hydrocarbons, carbon monoxide,
carbon dioxide, nitrogen, and ammonia, and traces of other sulfur
compounds and phenols.
Option No.l - Incineration or Combustion in Heaters and Boilers.
Current practice in some installations involves direct combustion of the
HpS in the sour gas waste stream and venting of the residual SOp gas
directly to the atmosphere. This procedure is only adequate if the
concentration of HpS in the sour gas stream is very low and the throughput
is small. In order to be adequate under current regulations the final
effluent concentration of SOp in the stack must be less than 500 ppm and
no more than 200 Ib/hr of SOp must issue from a single stack.
Option No.2 - Removal of HpS from Sour Process Streams by Amine
Scrubbing.0539>Q36° Scrubbing solutions of monoethanolamine or
diethanolamine in aqueous solution are very effective in removing H2$
from sour gas streams and this practice is used extensively in the
refinery industry. HpS can be removed from a gas stream by amine
scrubbing down to a concentration level of a few parts per million.
Regeneration of the rich amine solutions yields a stream of concentrated
-------
FLUE GASES PLUS
ANY RESIDUAL SO,
STACK
(T) Sweet Gas (4-16 ppm H2$ typical)
/ ^
\
^
s«,,r r« WINE SCRUBBER p- .
Sour Gas AND Concentrated F,!;AUS
(7)"" STRIPPER
(H2S Waste Stream)
Sour §2) SOUR
Water • STRIP
^ (Swee
Ulate
<7 mg
/Typi
VRefi
WATER
TREATMENT
PLANT
HgS
^
>ER
t
r
/liter
cal
nery St
/^
W 1 1
A,J
Liquid S
°2
\
^ .TRW
fa\ <; inn
7\lCJ UNIT
«.=
ream |
Liquid S
1
u.
© 15.000-30,000
ppm H-S + SOg Typical
(?) IFP 2000- 4COO
.a* rmilRRFB nnm H <> + "^fl tvni i
\
Liquid S
BEAVON <4-UO ppm
* SCRUBBER u c a. en
Liquid S ' ^
ClT) IFP SMALL
— — ^— HO *;ri7iinnrn RTflunN
* SCRUBBER
L1(^uidS LiqJidS
<50 ppm S02 1n Vent Gas Effluent '
J
1
INCINERATION
OR COMBUSTION
IN HEATERS
AND BOILERS
- ,, i
:al
200 .
ppm HgS + SOp
T
0.1 mg/liter S"
Typical Effluent
From Biological
Water Treatment
Process
-AIR
Figure 1. H2S waste treatment process (Option tree).
-------
HoS (50-100 percent typical) which must either be recycled for reuse
within the plant or further processed on a pollution-free basis to sulfur.
Amine scrubbing units are considered to be adequate for removing all but
the last few ppm of HpS from process gas streams. It is normal to convert
the residual few ppm of HpS to SOo by combustion prior to venting the
stream gas to the atmosphere.
Options No.3 and No.5 - Glaus Process for Conversion of a Concentrated
(YOCO
HpS Stream to Elemental Sulfur. Claus process units are universally
used in refineries and natural gas processing plants to convert a
concentrated stream of HpS (from regeneration of amine scrubbing solutions
and from sour water stripping units) into high purity elemental sulfur
which is sold as a product. Unfortunately, existing Claus systems are not
adequate from a pollution viewpoint without modification in that they
convert on the average only about 93 percent of the incoming HpS stream
into elemental sulfur. The remaining sulfur exits the process as a high
concentration stream of HpS + SOp which is usually combusted to yield a
final effluent of 15,000 to 30,000 ppm of S02 which is vented to the
atmosphere. As a result of this deficiency in the basic Claus process,
several modifications (or "hang-on" units) have been developed to further
treat the effluent from a standard Claus Unit to produce additional
sulfur and less sulfur oxide pollutants.
Option No. 6 - Claus-IFP Process for Conversion of a Concentrated
H^S Stream to Elemental Sulfur. This process results in further
treatment of the effluent from a standard Claus unit to yield more
elemental sulfur and a final vented effluent concentration of SOp of
200 to 400 ppm. The effluent SOp concentration from this process is
still too high to be considered adequate.
Option No.7 - Claus-Beavon Process for Conversion of a Concentrated
HpS Stream to Elemental Sulfur. The Beavon unit operates on the
effluent gas from a Claus plant and results in additional conversion of
HpS + S09 to sulfur and a final vented effluent which is reported to
0367
contain less than 200 ppm SOp. The Beavon system has been operated
71
-------
at the large pilot plant scale but has not yet been introduced on a
commercial scale. If it performs as reported, the Claus-Beavon process
is adequate for converting a concentrated HpS stream to sulfur.
Option No.8 - Claus-IFP-Beavon Process for Conversion of a
Concentrated FLS Stream to Elemental Sulfur. This combination of a Claus,
IFF, and small Beavon unit results in slightly lower capital and operating
costs than the Claus-Beavon system. However, this sequence of unit
operations has not yet been demonstrated. In principle it should have
about the same operating characteristics as the Claus-Beavon system and
hence should be adequate for treating concentrated waste H~S streams.
Option No. 4 - TRW S-100 Process for Conversion of H0S Streams to
t '"""
Elemental Sulfur. Recently, TRW conceived a new process (designated S-100)
for converting HpS wastes to elemental sulfur. The great advantage of the
TRW process over the current Claus system is that the TRW process S-100 is
extremely efficient in recovering the sulfur and emits an exceedingly small
quantity of sulfur compounds to the atmosphere. This new process has been
investigated in bench and pilot-plant studies but has not as yet been
demonstrated as a complete system on a commercial scale. The S-100 process
shows promise of being a lower cost method of converting HpS to sulfur on
essentially a pollution-free basis as indicated below. S-100 processing
details are presented in TRW's "Proposal for Demonstration of the TRW
S-100 Process.
"0742
Process
S-100
Claus
Claus + IFP
Claus + Beavon
Claus + IFP + Beavon
Capital Cost
$ Million
1.2
0.9
1.2
2.1
2.0
Effluent Purity
ppm SQo
<50
15,000 - 30,000
2,000 - 4,000
<250
<250
Lbs of S02 Emitted
to the Atmosphere
Per Lb of H2S Fed
to the Process
<2 x 10"5
5 x 10"2 to 2 x 10"1
9 x 10"3 to 2 x 10"2
<1 x 10"3
-------
Sour Hater Disposal Process
In addition to waste gas stream containing HpS, hydrogen sulfide may
also appear as a dissolved gas in waste water streams (sour water streams)
which are sent to municipal or industrial waste-water treatment plants.
Option No. 9 - Sour Water Stream is Sent Directly to Water Treatment
Plant Without Pretreatment. This option is only adequate when the
concentration of H2$ in the waste water is relatively low and the
magnitude of the sour water stream is fairly small. Since biological
treatment processes, such as activated sludge or aerated lagoon systems,
only have a sulfide removal efficiency of 90 to 99 percent, the
influent streams should contain no more than 1-10 mg/1 of sulfide in
order to insure that the effluent from a biological water treatment
plant contains less than the recommended maximum of 0.1 mg/1 of dissolved
hydrogen sulfide. In addition, high concentrations of sulfides must be
reduced in sour waters before biological treatment as they are toxic to
the microorganisms present in the biological treatment units.
Option No.10 - Sour Water Stream is Processed in a Stripping Unit
Prior to Discharge into the General Waste Water System for Biological
Treatment. For sour water streams containing high concentrations of
dissolved H9S, the sour water can be stripped of H9S with steam or flue
0091
gas in a packed or pi ate-type column. Hydrogen sulfide gas released
from the waste water can be recovered as sulfur by one of the waste gas
processing options discussed previously. The bottoms from the column
have a low enough sulfide concentration to adequately permit discharge
into the general waste water system for biological treatment. Sour
water stripping units can be expected to achieve HpS removal efficiencies
of 85 to 99 percent.0091
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that systems to handle the great majority of the
hydrogen sulfide waste streams generated in the chemical process industries
will continue to be located at the source of H~S waste generation rather
-------
than at National Disposal Sites in view of the economics involved.
However, some capacity to process hLS waste to sulfur on a pollution-
free basis is required at National Disposal Sites to handle the
following kinds of requirements:
(1) Occasional tank-cars or other smaller lots of extremely
hazardous liquid hydrogen sulfide which for one reason
or another are required to be disposed of in a safe,
pollution-free manner.
(2) Secondary sour gas or sour water streams generated
within the National Disposal Site as the result of
processing other sulfur containing wastes.
(3.) Regeneration of amine (H?S) scrubbing solutions from
refinery operations if the National Disposal Site is
located within reasonable pipeline distance from the
refineries.
It is suggested that the following kinds of unit operations will be re-
quired at National Disposal Sites:
(1) HpS Scrubbing and Stripping Units
Ethanolamine scrubbing units are used in many refineries
and are recommended for National Disposal sites for ini-
tial removal of H2S from sour gas streams. The rich amine
solutions are regenerated by heating and a concentrated
stream of H£S passes out of the stripping tower and is
sent to the sulfur recovery plant.
(2) Sour Water Stripping Unit
A pi ate-type or packed column for initially stripping
H2$ from sour waste waters with steam or flue gas will
be required at National Disposal sites. The concentra-
ted HpS gas is sent to the sulfur recovery plant.
(3) Sulfur Recovery Plant
Sulfur recovery from concentrated HgS streams must be
performed on essentially a pollution free basis. The
following processes are considered to be adequate:
74
-------
Process Order of Preference Remarks
Claus-Beavon First Choice Demonstrated technol-
ogy; adequate sulfur
recovery
TRW S-100 Second Choice Looks better on paper
but not yet demonstra-
ted
Claus-IFP-Beavon Third Choice Never been operated as
a single plant so that
projections of lower cost
have not yet been demon-
strated
75
-------
7. REFERENCES
0091. The cost of clean water. ln_ Industrial waste profiles, v. 3. No. 5,
petroleum refining. Publication No. I.W.P.-5. Washington, Federal
Water Pollution Control Administration, 1968. 199 p.
0359. Ballard, D. How to operate an amine plant. Hydrocarbon Processing,
45(4):137-144.
0360. MEA process to be considered first. Oil and Gas Journal, v. 65,
No. 34. Aug. 21, 1967.
0362. Kwong, S. S. Cost estimate for a 100 LT/D Claus plant. Unpublished
data (TRW IOC 4742.6.71-473, July 28, 1971).
0363. Land, J. S. Beavon economics. Unpublished data (TRW IOC 4742.6.71-
451, July 29, 1971).
0367. Beavor, D. K., and W. K. King. Prevention of air pollution by sulfur
plants. Paper presented at the Canadian Natural Gas Processing
Association, Sept. 18, 1970. 13 p.
0742. Proposal for demonstration of the TRW S-100 process. Proposal No.
2173.000. TRW Systems Group, Feb. 18, 1972.
0743. Stauffer Chemical Company. Safe handling of liquid hydrogen sulfides.
Product Report. Los Angeles. 24 p.
0744. Manufacturing Chemists Association. Properties and essential infor-
mation for safe handling and use of hydrogen sulfide. Chemical
Safety Data Sheet SD-26. Feb. 1968. 14 p.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name HYDROGEN SULFIDE (221)
IUC Name
HYDROGEN SULFIDE
Structural Formula
Common Names SOUR GAS
Molecular Wt. 34-°8 _ Melting Pt. -82. 9° C Boiling Pt. -76.4 C (760
Density (Condensed) ,790 313" @ 60 F _ Density (gas) 34 g/liter @ _ 0 C and 1 atflr
~~ — ^~ -"^ - -i ... . — — ' ~ -~ _ . . . —
Vapor Pressure (recommended 55 C and 20 0
300 psia @ • 75 F 80 psia €>
Flash Point
Autoignition Temp. 260
Flammability Limits in Air (wt %) Lower 4.3% _
Explosive Limits in Air (wt. %)
400 psia @
Lower 4.3%
Upper
Upper
46%
46%
Solubility
Cold Water_
Others:
0 C
186 air/liter H,0 40 C
Ulll / I I UCI M£V W V» IOU UN / I I ICI \\n\J TU l»
1 atm HS pressure Hot Mater 1 atn HoS pressure Ethanol
I Acid, Base Properties
Weak Acid
100
[Highly Reactive with Strong oxidizers, nitric acid, attacks many metals forming sulfides,
extremely flammable
[Compatible with 316 stainless steel, superalloys, some low carbon steels-do not use copper
or brass tubing or fittings
Shipped in Specially designed tank trailers and tank cars ^ '
irr n •*• *-
ICC Classification
- T
-------
PROFILE REPORT
Lead (233)
1. GENERAL
Lead is a soft, heavy, bluish-gray metal. Its surface oxidizes
readily, and is then very resistant to corrosion. It is soluble in nitric
acid and in many organic acids, but not in dilute sulfuric or hydrochloric
acid, and is one of the most stable metals. Lead and its compounds are
cumulative poisons and should not be used in contact with foods. It is used
for containers and tank linings for many corrosive liquids, such as sulfuric
acid. Lead as the metal and as the dioxide is used in large quantities in
storage batteries. The metal and its alloys are used in solders, type
metal, bearings, pipe, cable covering, plumbing, ammunition, and in the
manufacture of tetraethyl- and tetramethyl lead. It is also used as a
sound absorber and as a radiation shield.
Lead ores are usually sulfides (galena, PbS), oxides, or carbonates.
By means of complicated flotation, leaching, and smelting processes, lead is
recovered from its ores. Lead not recovered will generally end up in slag
piles.1433
The chemical/physical properties of lead are summarized in the attached
worksheet.
2. TOXICOLOGY
Lead is present in the individual's normal environment. The daily intake
of lead in the food and beverage of American adults is about 0.3 mg. The
human body is capable of eliminating this amount daily. However, if more
lead is taken into the system than is eliminated, a condition exists which
is referred to as "chronic lead poisoning."
79
-------
Initially, the symptons of lead intoxication usually take the form of
weakness, pains in the joints, severe constipations and colic-like pains.
Exposure over longer periods of time will frequently intensify the pains in
the joints and the weakness of the muscles. Acute attacks of colic will
develop0766
Lead may enter the human system through inhalation., ingestion, or skin
contact. Industrially, inhalation of dust9 mist, or fumes is the chief
metifod by which lead and its inorganic compounds may enter the body. In
practice, the amount of lead or its inorganic compounds in the work
atmosphere should not exceed an average of 0.2 mg of lead per cubic meter
for an 8-hr working day of a 40-hr work week., Threshold Limit Value (TLV).
Ingestion is not an important form of lead exposure in the present-day
industrial establishment when care is taken to avoid its contact with
food. Direct skin contact is of negligible importance in connection
with inorganic lead compounds. However, in the case of organic lead
compounds, skin contact can be a real hazard.
The toxicity of lefd and its inorganic compounds varies with several
factors of a chemical and physical nature. The most important considerations
are the form in which the lead is present, the particle size, and the length
of exposure time. The fineness of the lead-containing particles is of great
importance. Particles above 10y are frequently not absorbed in the lungs at
all and are screened out by the nasal mucosa and hairs. It is generally
only particles below 5p that are retained to any extent, and retention is at
a maximum below ly. Plants handling lead must, therefore, take care to
avoid creating fine lead particles; or if produced, personnel must be
protected from fine dusts.
3. OTHER HAZARDS
Lead does not usually present any special hazards other than those
associated with its toxicology.
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Lead is insoluble in water and therefore, its use in pipes and as a
joint dope is harmless with most water supplies. Some waters do dissolve
lead from plumbing, but the reasons are not known. Naturally soft waters
which are slightly acid and low in mineral content are the most corrosive
and should not be used with lead plumbing. When lead compounds are used in
ceramic glazes, lead is solubilized and extracted by the organic acids
present in food and the use of lead compounds in glazes is therefore a
serious hazard. A maximum level with respect to extractable lead in ceramic
glazes is 7 mg per milliliter, released after extracting a piece of
dinnerware for 24 hours at room temperature in a 4 percent acetic acid
solution. Atmospheric lead contamination by discharge from (1) primary
and secondary lead smelters, (2) combustion of coal and fuel, (3) incineration,
and (4) combustion of gasoline containing lead antiknock additives is a
serious health problem.
Lead is usually shipped as pigs or in fabricated form. There are no
special regulations governing the transportation of lead.
The safe disposal of lead is defined in terms of the recommended
provisional limits in the atmosphere, and in water and soil. These
recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis of Recommendation
Lead 0.0015 mg/M3 0.01 TLV
Contaminant in ©
Water and Soil Provisional Limit Basis of Recommendation
Lead 0.05 ppm Drinking Water Standard
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Recent estimates indicate that 42 percent of all lead is reclaimed with
the remainder continuing in use or lost in dumps or to the environment in an
uncontrolled manner. The chief sources of reclaimed scrap include automobile
storage batteries, cable sheathing, plumbing pipes, sheets, solder0 joint
caulking, type metal, freight car bearings, loaded brass and bronzes, spent
ammunition, discarded ballast, foil, and blast furnace matte. Reclamation
and processing of scrap are less costly sources of lead metal than mining
and smelting primary lead, and replaces primary lead production to the
extent available. Processes for reclaiming lead from scrap or blast furnace
matte are briefly discussed in the following paragraphs together with
recommendations as to adequacy.
Current Processes
Option No. 1 - Melting into Ingots. If scrap lead is pure, it is melted
1699
and cast into ingots for sale and shipment. The off-gas from furnaces
used to melt lead is cooled by air dilution and then filtered by a cloth
bag dust collector used in conjunction with other dust collecting equipment
such as a cyclone. ' The particulate matter is then returned to
the furnace. When the scrap is pure or nearly pure lead, this is obviously
the recovery method of choice.
Option No. 2 - Recovery in Lead Blast Furnace. Blast furnaces used for
smelting lead ore are also used for the secondary recovery of lead from such
sources as battery plates. In a blast furnace^ scrap lead to be recovered
along with a mixture of roasted and part unroasted ore is charged to the
furnace with irqn oxide, silica and carbon. Upon heating, the copper present
collects in the iron sulfide matte (which also contains 0 to 18 percent
lead) while other metals remain in the lead. In refinement of the crude
blast furnace lead, the more electropositive impurities are removed by air
oxidation from frequent stirring of the molten lead over a several hour
period. The impurities, when oxidized, rise to the surface and are skimmed
off. Off-gas from smelting plants is cooled by air dilution and then
-------
filtered by a cloth bag dust collector used in conjunction with other dust
collecting equipment such as a cyclone. ' The particulate matter is
then returned to the smelter. If the lead contains appreciable quantities
1 oofi
of bismuth, the lead is purified electrolytically. These custom
smelting plants provide the most efficient and economical means for the
recovery of lead. For efficient operation, a smelting plant requires a
continuous supply of raw materials which can best be supplied with a
mixture of primary and secondary lead. Also, a smelting plant requires a
large capital expenditure which can only be justified by a large continuous
operation. The use of smelters is recommended because more than 80 percent
1 ope
of the secondary lead is recovered by this means.
Option No. 3 - Recovery from Blast Furnace Matte. A process developed
by the Bureau of Mines at the College Park Metallurgic Research Center
0128
recovers lead and copper from lead matte. In this process, all the
sulfides are first oxidized to sulfates by roasting, so that subsequent
water leaching of the roasted products will extract the copper and other
water-soluble salts. The copper is recovered from solution by cementing
with iron powder. The water-insoluble residue is treated with a saturated
brine solution to dissolve lead as a lead chloride complex while the
associated sulfate ion is rendered insoluble by formation of calcium sulfate
upon treatment with lime. The dissolved lead is then precipitated as
3 PbO • PbCl2 by the addition of more lime. An alternate method that does
not require roasting involves oxidation by the bacterium Ferrobacillus
ferrooxidans in dilute sulfuric acid solution or by air oxidation of a
dilute sulfuric acid leach. The lead and copper sulfates are recovered as
described above. The lead oxide is reduced by treatment at high temperature
with carbon or carbon monoxide.
Option No. 4 _- Assignment to Land Fills. Because lead is insoluble in
water and not attacked by most inorganic acids or bases, lead in small
quantities is often disposed of in landfills. Though this disposal
method is satisfactory under most conditions, it is not recommended because
lead is lost to future use. In addition, under certain conditions, lead is
solubilized as either the chloride or the sulfate, which are both slightly
soluble in water.
83
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Lead present in most waste forms or lead alloys can best be recovered
by returning the lead-containing wastes to blast furnaces designed for
processing primary lead. Numerous companies purchase or salvage scrap lead
1 326
which is then sold to primary lead processors. Therefore, processes for
the recovery of lead are not a candidate for National Disposal Sites.
-------
7. REFERENCES
0095. Manufacturing Chemists Association, Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0128. Corrick, J.D. and J.A. Button Oxidation of lead blast furnace matte
by Ferrobacillus ferrooxidans in a dilute acid solution. Report
prepared by the Bureau of Mines, Report RI-7126, College Park. 1968.
19 p.
0635. Athanassiadis, Y.C. Air pollution aspects of zinc and its compounds.
Report prepared by Litton Systems Inc., Technical Report PH 2268-25,
Bethesda, 1969. 90 p.
0673. Bureau of Mines, Control of sulfur dioxide emissions in copper, lead,
and zinc smelting. Information Circular 8527. Washington. 62 p.
0766. Sax, N.I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation. 1968. 1,251 p.
1326. Callaway, H.M. Lead, a material survey. Report prepared by the Bureau
of Mines, PB 192 858, Washington. 1953. 203 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
supplement. New York, Wiley-Interscience Publishers, 1963-1971.
1699. Engel, R.E., D.I. Hammer, R.J.M. Horton, N.M. Land, and L.A. Plumber,
Environmental lead and public health. Report prepared by Environmental
Protection Agency, Air Pollution Control Office, Publication number
AP-90. Research Triangle Park. 1971. 34 p.
85
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Lead (233)
IUC Name Lead
Structural Formula
Common Names Plumbum
Pb
Molecular Wt.
207.21
Melting Pt. 327'43 C
Density (Condensed) 11.3437q/cc@ 20 C Density (gas)
Vapor Pressure (recommended 55 C and 20 Q)
1.0 torr @ 987 C 10 torr @ 1167 C
Boiling Pt. 174° c
100 torr @ 1417
Flash Point
Autoignltlon Temp.,
Flammability Limits In Air (wt %) Lower_
Explosive Limits in Air (wt. 3») Lcwer_
Upper_
Upper
Solubility
Cold Water insoluble
Others:
Hot Water Insoluble
Ethanol insoluble
soluble-nitric acid, most organic acids
Acid, Base Properties
Highly Reactive with most organic adds in presence of oxygen.
Compatible with most inorganic acids and bases except nitric acid.
Shipped in pigs
ICC Classification_
Comments
none
Coast Guard Classification none
References (1) 1433
86
-------
PROFILE REPORT ON LEAD COMPOUNDS
Lead Acetate (234). Lead Carbonate (237)
Lead Chlorite (238). Lead Nitrate (240). Lead Nitrite (241)
1. GENERAL
Introduction
In spite of its position in Group IVA of the periodic table, the
usual valence of lead in its compounds is +2 instead of +4. In many
properties the bivalent lead compounds resemble those of some of the
alkaline earth elements such as barium and strontium. They also show
a remarkable tendency toward forming basic salts of both anhydrous and
hydrated types. Lead forms a soluble acetate, nitrate, nitrite, a
slightly soluble chlorite, and an insoluble carbonate.
Among the five lead salts covered in this report, the chlorite and
nitrite are not known to have any significant commercial and industrial
consumption as reflected by the fact that no producer or distributor of
these two compounds in the United States is listed in the major references
of chemical suppliers. '' Consequently, the emphasis of this
Profile Report will be placed on the acetate, carbonate, and nitrate.
However, any pertinent information for the chlorite and nitrite are
included wherever they were available.
Lead Acetate
Lead acetate, Pb^pHgOpJo'S^O, is also known as plumbous acetate or
sugar of lead. It is a colorless monoclinic crystal or white granules or
149?
powder. It is poisonous. It is manufactured by dissolving litharge
2272
(PbO) in hot dilute aqueous acetic acid solution. On cooling, large
crystals are formed and can be separated by filtration. Its uses are:
87
-------
(1) manufacture of other lead salts as basic lead carbonate and
lead chromate;
(2) as a mordant in dyes;
(3) as a drier in paints;
(4) lead-coating of metals;
(5) as an analytical reagent;
(6) as an astringent on unbroken skin and mucous membranes;
(7) as an astringent and sedative on bruises and superficial
inflammatory conditions for animals;
(8) formerly used internally as an astringent for diarrhea and
in form of rectal suppositories for hemorroids.
Lead Carbonate
Normal lead carbonate, PbCC^, occurs naturally as the mineral cerussite.
It is a white to grayish ore found in conjunction with other lead minerals,
being formed by the action of carbonated water on galena (lead sulfide) or
its oxidation products. In the pure state, it is a colorless crystal or
rhombic form. It is practically insoluble in water. It has a limited use
in the paint and ceramic industries. More important commercially, and
manufacturered in larger tonnage, however9 is the basic lead carbonate,
2PbC03'Pb(OH)2, also known as the white lead.1433 It is a heavy, white
powder, insoluble in water and alcohol.
White lead is formed when various basic salts of lead are treated with
2273
C02. Commercially, metallic lead or litharge, PbO, is used. COo gas
is passed through an aqueous solution of litharge in the presence of a small
quantity of acetic acid. A series of chemical reactions is believed to take
ppyr
place as follows. First,.litharge is hydrolyzed to form lead hydroxide
which reacts with acetic acid to form normal (or neutral) lead acetate. The
latter dissolves additional lead hydroxide to yield basic lead acetate.
Finally, C02 reacts with basic lead acetate to yield basic lead carbonate
and reproduce normal lead acetate. The basic lead carbonate formed is
precipitated and separated from the solution by filtration. The filtrate
is recycled to digest more litharge. So, the acetic acid plays the role
'88
-------
of catalytic agent in the cycle with normal lead acetate acting as a solvent
for lead hydroxide.
White lead has been one of major pigments in making white paint.
However, due to its poisoning effect, particularly to small children, its
use in house paint is an environmental issue and its future is somewhat
uncertain. Basic lead carbonate is also used in cements, in making putty
14Q2
and lead carbonate paper, and in the processing of parchment.
Lead Nitrate
Lead nitrate, Pb(NO^)«, forms colorless cubic or monoclinic columnar
1492
crystals. It is highly soluble in water and poisonous. It is
manufactured by reacting litharge (PbO) or metallic lead, or lead carbonate
2274 1492
with nitric acid. Its uses are:
(1) manufacture of matches and special explosives;
(2) as a mordant in dyeing and printing on textiles;
(3) manufacture of other lead salts;
(4) as a mordant for staining mother-of-pearl, horn;
(5) as an oxidizer in dyes industry;
(6) as sensitizer in photography;
(7) process engraving;
(8) as a chemical reagent;
(9) formerly, as an astringent and antiseptic for
external use.
Other Lead Compounds
Very little information is available regarding the properties,
manufacturing methods, and uses for lead chlorite and nitrite. Pertinent
data available are presented as follows:0766'1433'1492
Lead chlorite, PbCClOp)?* is a yellow crystal of monoclinic form.
It is slightly soluble in water. Upon heating to 126 C, it explodes.
Hence, it causes a severe explosion hazard when exposed to heat. Lead
nitrite, 3PbO-N203-H20, is a light yellow powder or crystal. It is
89
-------
a powerful oxidizing agent, thus a potential fire and explosion hazard,
however, the details of such hazards are unknown. It is also listed
as poisonous. Large amounts taken by mouth may produce nausea,
vomiting, cyanosis, collapse and coma.
Sources and Types of Wastes
The only significant wastes containing the lead compounds under con-
sideration in this report have been found to come from the following
sources: (1) paint manufacturers; (2) printing ink manufacturers; and
(3) paint residue left in old containers.
In the manufacture of solvent-based paints, sludges are generated
from both the washing system and the solvent recovery stills. The combined
solvent-based paint sludge is characterized by the following composition:
4.5 percent inorganic pigment (excluding titanium dioxide), 8.5 percent
titanium dioxide, 14.5 percent pigment extenders, 25.0 percent binders and
47.5 percent organic solvents. It is estimated that a total of 49,700 Ib
of lead carbonate are lost through 37 million Ib of solvent-based paint
sludges every year.*
Lead pigments are still used by some manufacturers in the production
of certain types of printing inks and wastes are generated as a result of
the operations to clean up the ball mills, mixing tanks, and other equip-
ments. The typical liquid waste may contain 300 to 1000 ppm of lead
(mostly as lead carbonate) mixed with varying amounts of other metals in
organic solvents and water washes. It is estimated that a total of
21,000 Ib of lead are lost through 2.1 million Ib of liquid wastes per year.'
The lead carbonate containing paint residues left in containers nor-
mally discarded in municipal dumps constitute another source of lead car-
bonate wastes. It is estimated that a total of 344,000 Ib of lead carbonate
are lost as paint residues every year.*
** The basis for these estimates are discussed in detail in the
appendix volume on Waste Forms and Quantities.
-------
Physical and Chemical Properties
The physical and chemical properties of five lead salts are given in
the attached worksheets.
2. TOXICOLOGY
All of the lead compounds are sufficiently soluble in digestive juices
T A *5 *5
to be considered toxic. In general, lead poisoning may be caused by
(1) inhalation of dusts, fumes or vapors; (2) ingestion of lead compounds;
and (3) absorption through the skin. However, there is no evidence that
inorganic lead compounds can be absorbed through the skin in sufficient
1433
quantities to produce lead intoxication.
Lead is a cumulative poison. Increasing amounts of lead could
build up in the body and eventually a point is reached where symptoms
and disability occur. The symptoms of lead poisoning may be classified
according to their clinical picture as: (1) aliminetary; (2) neuromotor;
and (3) encephalic.
The alimentary type occurs most frequently. It is characterized by
abdominal discomfort or pain. Other complaints are constipation and/or
diarrhea, loss of appetite, metallic taste, nausea and vomiting, lassitude,
insomnia, joint and muscular pains, irritability, headache and dizziness.
In the neuromuscular type, the chief complaint is weakness, frequently of
the extensor muscles of the wrist and hand, unilateral or bilateral.
Gastroenteric symptoms are usually present, but not as severe as in the
alimentary type of poisoning. Lead encephalopathy 1s the most severe but
the rar.est manifestation of lead poisoning. It may be caused by rapid
and heavy lead absorption. Lead encephalopathy begins abruptly, and is
characterized by signs of cerebral and meningeal involvement. There is
usually stupor, progressing to coma9 with or without convulsion, and
often terminates in death.
91
-------
For treatment of lead poisoning, it has been found that the chelating
agent, calcium ethylenediaminetetracetate (CaEDTA), and related compounds
are highly efficacious in removing absorbed lead from the tissues of the
body. CaEDTA is effective only when administered intravenously.
Of the various lead compounds, the carbonate, monoxide, and sulfates
are considered to be more toxic than metallic lead or other lead compounds.
The Threshold Limit Value (TLV) for lead in air recommended by the
American Conference of Governmental Industrial Hygienists, 1971, is 0.15
3 1 "?1 ?
mg/M . The lethal doses reported for the lead compounds are given below:
(1) Lead acetate:
iv LD5Q 120 mg/kg, rat
ip LD5Q 150 mg/kg, rat
(2) Lead carbonate (neutral):
ip LDCA 124 mg/kg, guinea pig
Lead carbonate (basic):
MLD, orally 1.0 g/kg, guinea pig
(3) Lead nitrate
ip LDCA 270 mg/kg, rat
(4) Lead chlorite and Nitrite: No data
The U.S. Public Health Service has established the limits and ranges
of lead concentrations in public water affecting human health as follows:
(1) Physiologically safe:
Lifetime 0.05 mg/1
Short period, a few 2-4 mg/1
weeks
(2) Harmful range:
Borderline 2-4 mg/1 for 3 months
Toxic 8-10mg/l for several weeks
-------
Lethal Unknown, but probably more than
15 mg/1 for several weeks
Lead in soft water is highly toxic to certain fish; 0.1 rag/1 is toxic to
small sticklebacks, larger fish are somewhat less susceptible to lead
poisoning.
For lead nitrate, there is an additional toxic effect. Serious and
occasionally fatal poisonings in infants have occurred following ingestion
of well waters shown to contain nitrate (NO^). This has occurred with
sufficient frequency and widespread geographic area to require an assigned
limit to the concentration of nitrate in drinking water. The limit recommended
by the U.S. Public Health Service is 10 mg nitrate nitrogen (or 45 mg nitrate)
1752
per liter of water.
3. OTHER HAZARDS
Lead nitrate is a powerful oxidizing agent. Fire hazard is moderate.
It may also explode when shocked, exposed to heat or flame or by spontaneous
chemical reaction.
Lead nitrite is also a powerful oxidizing agent. However, little is
known about its details on fire and explosion hazards.
Lead chlorite causes a severe explosion hazard when exposed to heat.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
\
Because of the hazard of lead poisoning, special care must be
exercised in the handling, storage and transportation of all lead compounds.
In storage, they should be kept in the original containers supplied by the
manufacturers and away from feed and food products. Powerful oxidizing
agents, such as lead nitrate and lead nitrite, should be kept away from
materials which are either flammable or susceptible to oxidation easily.
To prevent explosion caused by spontaneous chemical reaction, the nitrate,
nitrite, and chlorite should be stored in cool and we11-ventilated areas.
93
-------
In handling the lead compounds, the most important thing is to avoid
breathing any lead-containing dusts, fumes, or vapors. Therefore, the use
of respiratory protective devices is recommended. In shipping, lead acetate
is labeled as Class B poison and lead nitrate, as oxidizing material. They
must be shipped in accordance with the U. S. Department of Transportation
(DOT) or IATA regulations.
Disposal/Reuse^
Contaminated lead compound wastes could be reprocessed. The main
consideration is the economic feasibility. For the safe disposal of these
compounds, the acceptable criteria for their release into the environment
are defined in terms of the following recommended provisional limits:
Contaminant in Air
Lead Acetate
Lead Carbonate
Lead Chlorite
Lead Nitrate
Lead Nitrite
Contaminant in Water
Lead Acetate
Lead Carbonate
Lead Chlorite
Lead Nitrate
Lead Nitrite
Provisional Limit
0.0015 mg/M3 as Pb
0.0015 mg/M3 as Pb
0.0015 mg/M3 as Pb
0.0015 mg/M3 as Pb
0.0015 mg/M3 as Pb
Provisional Limit
0.05 ppm (mg/1) as Pb
0.05 ppm (mg/1) as Pb
0.05 ppm (mg/1) as Pb
0.05 ppm (mg/1) as Pb
0.05 ppm (mg/1) as Pb
Basis.for
Recommendation
.01 TLV
.01 TLV
.01 TLV
.01 TLV
.01 TLV
Basis for
Recommendation
Drinking Water
Standard
Drinking Water
Standard
Drinking Water
Standard
Drinking Water
Standard
Drinking Water
Standard
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Waste
Option No. 1 - Sulfide Precipitation. Three of the lead compounds in
this report, the acetate, nitrate, and nitrite are very soluble. Even for
the less soluble lead chlorite, removal of lead from an aqueous waste stream
by simple filtration is no longer satisfactory. The filtrate still contains
too high a lead concentration. Therefore, it is necessary to convert them
into an insoluble compound. The general practice is to convert the soluble
2272
lead salts into the insoluble lead sulfide using hydrogen sulfide.
The lead sulfide precipitate is removed by filtration. For current indus-
2273
trial practice, the filtrate stream is discharged to a settling pond.
Periodically, the deposit from the pond is removed and sent to a smelter
for recovery of the lead content. The effluent from the pond can be safely
discharged.
Option No. 2 - Carbonate Precipitation. Soluble lead salts can also
be removed from aqueous waste streams as insoluble lead carbonate by the
addition of ammonium carbonate. Since lead carbonate is scarcely soluble
in water, it can be economically removed from water by simple filtration.
For example, at 20 C, only 0.11 mg of normal lead carbonate dissolves in
one liter of water. This is equivalent to 0.085 mg Pb/1 and is not far
above the recommended provisional limit of 0.05 mg Pb/1 in water. The
filtrate can be further treated as described in Option No. 1.
Concentrated Waste
Option No. 1 - Conversion to Sulfide. Contaminated solid wastes of lead
compounds are generally treated with concentrated nitric acid to form the
nitrate which is then converted to lead sulfide by hydrogen sulfide.
The insoluble lead sulfide is removed by filtration and sent to a smelter
to recover its lead content. The filtrate may be treated as described
previously.
95
-------
Option No. 2 - Landfill. Disposal of soluble lead compounds such as
the acetate, nitrate and nitrite by landfill technique is generally unac-
ceptable. Even the slightly soluble lead chlorite should not be disposed
of by landfill. However, lead carbonate is practically insoluble in water
and, in fact9 occurs naturally as the mineral cerussite. Similiarily,
lead sulfide is also insoluble in water and occurs naturally as the mineral
galena. Therefore, disposal of these two lead compounds by the landfill
technique in California Class I type disposal sites might be considered
adequate.
In summary, soluble lead wastes in aqueous waste streams can be
treated adequately by precipitation as the sulfide or as the carbonate.
For lead containing solid wastes, conversion to either the sulfide or the
carbonate and followed by either lead recovery in smelters or disposal in
California Class I type landfills are considered adequate methods of
management.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Since lead is toxic in nature and has inherent value as a raw material,
it is a common practice for the lead compound manufacturers and users to
recycle the waste streams and to recover the waste product. Furthermore,
the precipitation methods for the removal of lead from spent aqueous re-
action solutions is effective and inexpensive enough for all lead compound
manufacturers or users to operate. The lead carbonate and lead sulfide
sludge deposits from the settling ponds can be sent to smelters for the
recovery of the lead value or can be adequately disposed of in California
Class I type landfills. It is concluded that the disposal of lead wastes
I
can be handled adequately at the industrial site level and does not warrant
consideration for treatment at the National Disposal Site.
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual
(revised May, 1970). Washington, Manufacturing Chemists Association,
1970. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed. .
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971. Washington,
U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1492. The Merck Index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
1571. Schnell Publishing Company, Inc. 1971-72 OPD Chemical buyers
directory. 59th ed., New York, 1971. 1,584 p.
1670. Chemical Week. 1972 Buyers guide issue, part 2. 109(17):618,
Oct. 1971.
1752. Public Health Service. Drinking water standards, 1962. Washington,
U.S. Department of Health, Education, and Welfare, 1969.
1790. Chem Sources, 1970 ed. Flemington, New Jersey, Directories Publishing
Company, 1969.
2272. Personal communication. George Brown, Mallinckrodt Chemical Works, to
S. S. Kwong, TRW Systems, Aug. 22, 1972.
2273. Personal communication. William C. Spaingenburg, Hammond Lead
Products, Inc. to S. S. Kwong, TRW Systems, Aug. 21, 1972.
2274. Personal communication. Crompon Chemetron Corporation, to S. S. Kwong,
TRW Systems, Aug. 21, 1972.
2275. Mellor, J. W. A comprehensive treatise on inorganic and theoretical
chemistry, v. 7. New York, John Wiley & Sons, Inc. 1963.
97
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead Acetate (234)
IUC Name
Common Names
Structural Formula
Molecular Wt. 379.34^ Melting Pt. 75 C
Density (Condensed) ^.55 @
Pb(C2H30 )2'3H20
(1)
decomposes
Boiling Pt. 9 200 C
Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
(3
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water 45-61 9/^00 cc @ 15 C Hot Water 200 g/100 cc @ 100'C Ethanol insoluble
Others: soluble in
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification_
Commen ts
Coast Guard Classification
References (1) 1570
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead Carbonate, basic (237)
IUC Name
Common Names
Structural Formula
2PbC03 • Pb(OH)2
Molecular Wt. . 775.6?
Density (Condensed) 6.14
decomposes @
Melting Pt. 400 C Boiling Pt.
Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
0
Flash Point
Autolgnition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Solubility
Cold Water insoluble
Hot Water insoluble
Upper_
Upper_
Ethanol insoluble
Others: soluble in HN03
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in
ICC Classification_
Comments
Coast Guard Classification
References (1) 1570
99
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Lead Chlorite (238)
Structural Formula
IUC Name
Common Names
Pb(C102),
explodes @
Molecular Wt. 342-09 Melting Pt. 126 C Boiling Pt.
Density (Condensed)_ @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
@ &
Flash Point Autoignition Temp._
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 0.095 g/IOQ cc @ 20 C Hot Water Q.42 g/lQQ cr a inn (Ethanol
Others: soluble in KOH
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification
Comments _____
References (1) 1570
100
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead Nitrate <240>
Structural Formula
IUC Name
Common Names
Pb(NOj
32
decomposes @
Molecular Wt. 331.20 Melting Pt. 470 C Boiling Pt..
Density (Condensed) 4.53 @ - Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
8.77 @ 22 C
Cold Water 37.65 g/100 cc @ 0 C Hot Water 127 g/100 @ 100 C Ethanoljn 43% alcohol
Others: soluble in alkali.NH3
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in
ICC Classification • Coast Guard Classification_
Comments . —
References (1) 1570
101
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
.H. H. Name Lead Nitrite (241)
IUC Name
Common Names
Structural Formula
Molecular Wt. 763.60
Melting Pt.
Boiling Pt._
Density (Condensed)
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 very soluble
Hot Water
Ethanoi
Others; soluble in dil HN03
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification_
Commen ts
Coast Guard Classification
References (1) 1570
-------
PROFILE REPORT
Lead Oxides (242)
1. GENERAL
Introduction
Lead forms a number of oxides. There are the monoxide (PbO), the
dioxide (Pb02), the sesquioxide (Pb203), the tetroxide (Pb304), and the
suboxide (PbgO). They are all insoluble in water. With the exception of
the monoxide, they decompose upon heating to elevated temperatures and
therefore possess no true melting point. Absorbed into the body, they
.cause the well-known lead poisoning. Since only the monoxide and the
tetroxide are of industrial importance, the discussion in this report will
be focused upon these two oxides.
Lead Monoxide1433
Lead monoxide, PbO, also called plumbous oxide, exists in two
polymorphic forms; the tetragonal reddish crystal, «-PbO or litharge, and
the orthorhombic yellow crystal, 3-PbO or massicot. Commercially, litharge
and tetraethyl lead are the two most important lead compounds. The lead
monoxide is produced in large tonnage by many different processes to suit
specific applications. Four major manufacturing processes based on furnace
techniques are in use.
(1) Metallic lead is partially oxidized and milled to a powder
• • (called 'the black oxide in trade) which is charged into a
reverberatory furnace at about 600 C to complete the
oxidation to yield the ordinary "chemical" litharge.
(2) Pig lead is oxidized and stirred in a reverberatory furnace
or rotary kiln directly to form the lead monoxide.
103
-------
(3) Molten lead is run into a cupelling furnace held at about
1,000 C and molten litharge is produced.
(4) Molten lead at about 500 C is atomized into a flame where
it burns vigorously to yield "sublimed" or "fumed" litharge.
In all cases the product must be cooled quickly to below 300 C to avoid the
formation of red lead, Pb^. In 19659 about 105,000 tons of litharge
were produced in the United States. Its main uses are:
(1) in the preparation of storage battery plates (for this purpose,
the partially oxidized powder, the black oxide, is more widely
used than the fully oxidized product);
(2) in the ceramics industry for the manufacture of certain glasses,
glazes, and vitreous enamels, and as a flux for painting of
porcelain and glass;
(3) as an activator in rubber compounding;
(4) as a raw material for producing other lead compounds;
(5) in oil refining to convert the mercaptans to less evil-smelling
disulfides;
(6) as a drier in varnishes;
(7) as a yellow pigment.
Lead Tetroxide
Lead tetroxide, Pb~0A, also known as red lead or minium, is a bright
O *T
red heavy powder. In sales, it is the second most important lead oxide.
In 1965, about 30,000 tons were produced in the United States. It is
produced by heating the lead monoxide in a reverberatory furnace in
presence of air at 450 to 500 C until the desired Pb-^O. content has been
reached. Its major uses are:
(1) in the manufacture of storage battery plates;
(2) as a pigment in paints for protecting metal surface against
corrosion and rust.
-------
Other uses are:
(1) in glass and ceramics industries;
(2) in the manufacture of lead dioxide and matches;
(3) as a preferred raw material for making hard ferrites
which are finding rapidly expanding use as permanent magnets.
Other Lead Oxides1433
Lead dioxide, PbO^, is a brown to black tetragonal crystal. It
decomposes to lower oxides upon heating to 300 C or above. It is produced
by anodic electrodeposition from solutions of lead salts or from lead
monoxide or red lead used anodically. It is sold commercially in relatively
small tonnage for use in high-voltage lightning arresters and as an
oxidizing agent in dye and chemical industries.
Lead sesquioxide, Pb^O^, is a black monoclinic crystal formed by
hydrothermal decomposition of lead dioxide at 350 C. It has no commercial
importance.
Sources and Types of Wastes
The lead oxides wastes may come from the following major sources:
(1) manufacturers of lead oxides and other lead compounds using the
lead oxides as raw materials;
(2) storage battery producers and users;
(3) formulators and consumers of paints containing lead oxides;
(4) industrial plants for rubber compounding, glass and ceramics
manufacturing;
(5) users of products containing lead oxides such as lead glasses,
certain insecticides and ceramic products, etc.
(6) refinery storage tanks and basins.
105
-------
Example of some typical waste streams containing lead oxides are:
(1) 1.5 percent lead oxide mixed with solvents, cleaners, and
resins from kettle washings and equipment cleanup in
paint manufacture;
(2) 1 to 2 percent lead oxide mixed with other pigments, acrylics,
organic solvents, water and approximately 2.5 percent solids
from paint manufacture;
(3) 15,000 ppm total lead as lead oxide and tetraethyl lead in
waste oil reclaiming basins;
(4) 1 percent mixture of tegraethyl lead and lead oxide with
20 to 80 percent bottom silt and water from refinery
storage tanks and basins.
Physical and Chemical Properties
The physical and chemical properties of the lead monoxide and
tetroxide are given in the attached worksheets.
2. TOXICOLOGY0766
Lead poisoning or plumbism is one of the oldest and best known of all
occupational hazards. It is caused by (1) inhalation of dusts, fumes,
mists or vapors; (2) ingestion of lead compounds; and (3) absorption
through the skin. However, there is no evidence that inorganic lead
compounds can be absorbed through the skin in sufficient quantities to
cause lead poisoning. When lead is ingested, much of it passes through
the body unabsorbeds and is eliminated in the feces. The greater portion
of the lead that is absorbed is caught by the liver and excreted, in part,
in the bile. For this reason, larger amounts of lead are necessary to
cause poisoning by the route of ingestion and a longer period of exposure
is usually needed to produce the poisoning symptoms. On the other hand,
when the lead is inhaled, absorption takes place easily from the respiratory
tract and symptoms tend to develop more quickly. So, from the standpoint
of industrial safety, inhalation of lead or lead compounds is much more
106
-------
Important and requires more serious attention than ingestion and skin
absorption of lead compounds.
Lead is a cumulative poison. Increasing amounts of lead could build
up in the body. The symptoms of lead poisoning may be classified according
to their clinical picture as (1) alimentary; (2) neuromotor: and
(3) encephalic. The alimentary type occurs most frequently. It is
characterized by abdominal discomfort or pain, constipation and/or diarrhea,
nausea and vomiting, joint and muscular pains, headache and dizziness. In
the neuromuscular type, the chief complaints are weakness, frequently of
the extensor muscles of the wrist and hand. Joint and muscular pains are
more severe. Gastroenteric symptoms are present, but not as severe.
Headache, dizziness and insomnia are frequently prominent. The lead
encephalopathy is the most severe but the rarest manifestation of lead
poisoning. It is caused by rapid and heavy lead absorption. It begins
abruptly and is characterized by signs of cerebral and meningeal involvement.
There is usually stupor, progressing to coma, with or without convulsion,
and often terminating in death.
For treatment of lead poisoning, it has been found that the chelating
agent, calcium ethylenediaminetetracetate (Ca EDTA), and related compounds
are highly efficacious in removing absorbed lead from the body tissues.
Ca EDTA is effective only when administered intravenously.
The Threshold Limit Value (TLV) for lead in air recommended by the
American Conference of Governmental Industrial Hygienists, 1971, is 0.15
3 0225
mg/M . The lethal doses reported for the lead oxides are given
below.1312
(1) lead monoxide
ip LD5Q: 400 mg/kg, rat
(2) lead tetroxide
ip LD5Q: 200 mg/kg, rat
107
-------
The U.S. Public Health Service has established the limits and ranges
of lead concentrations in public water affecting human health as follows:1752
(1) Physiologically safe:
Lifetime 0.05 mg/1
Short period, a few weeks 2-4 mg/1
(2) Harmful range:
Borderline 2-4 mg/1 for three months
Toxic 8-10 mg/1 for several weeks
Lethal Unknown, but probably more than
15 mg/1 for several weeks
Lead in soft water is highly toxic to certain fish; 0.1 mg/1 is toxic to
small sticklebacks', larger fish are somewhat less susceptible to lead
poisoning.
3. OTHER HAZARDS
Lead tetroxide is an oxidizing agent. It would cause slight fire
hazard by chemical reaction with reducing agents. Similarly, lead dioxide
would react with a reducing agent. It may also ignite some organic materials
when mixed. When heated to decomposition, it emits the highly toxic fume
of lead.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Since lead poisoning is caused more easily by inhalation than by
ingestion, adequate ventilation and dust control must be maintained to
minimize the hazard of lead poisoning. Avoid breathing the lead oxide
dust in handling. Wearing the dust mask approved by the U.S. Bureau of
Mines for this purpose is recommended. In storage, the lead oxides should
be kept away from feed or food products. As lead tetroxide is an oxidizing
agent, it should also be kept away from any reducing agent to avoid fire
hazards caused by chemical reactions. The lead oxides are stable chemicals
under ordinary temperatures. There is no specific requirement in
transportation.
108
-------
Disposal/Reuse
The lead oxides (litharge and red lead) are produced in large tonnage
1433
but at a very small profit margin. Therefore, it is not economically
feasible to reprocess the waste materials for reuse purpose under present
circumstances. Safe disposal of lead oxide wastes is defined in terms of
provisional limits as tabulated below:
Basis for
Contaminant in Air Provisional Limit Recommendation
Lead Monoxide 0.0015 mg/M3 as Pb 0.01 TLV for Pb
Lead Tetroxide 0.0015 mg/M3 as Pb 0.01 TLV for Pb
Contaminant in Water Basis for
and Soil Provisional Limit Recommendation
Lead Monoxide 0.05 mg/1 as Pb U.S. Public Health
Service, Drinking
Water Standard for
Pb
Lead Tetroxide 0.05 mg/1 as Pb U.S. Public Health
Service, Drinking
Water Standard for
Pb
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Landfill
Since the lead oxides are insoluble in water, and also are very stable
under ordinary temperatures, disposal of lead oxide wastes by means of land-
fill is acceptable. Mixed wastes of lead oxides such as glass and ceramic
products often do not contain any water-soluble toxic components. Hence,
the risk of contaminating the ground and surface waters by these waste
materials is very minimal.
109
-------
Option No. 2 - Conversion to Sulfide
Contaminated lead oxide wastes can be treated with nitric acid to form
the nitrate which is then converted to lead sulfide by hydrogen sulfide.
The sulfide precipitate can be removed by filtration and sent to lead smelter
to recover its lead content.
Option No. 3 - Conversion to Carbonate
Similar to Option No. 2, the contaminated solid waste can be treated
with nitric acid to yield the nitrate which is converted to lead carbonate
by ammonium carbonate. The insoluble carbonate is removed by filtration
and its lead content could be recovered by smelting.
In summary, the most practical method for disposal of lead oxide wastes
is by landfill. However, should it be desirable or economically advantageous
to recover the lead content, the waste material can be converted to lead
sulfide or carbonate from which the lead content can be recovered by the
smelting process. Treatment of waste streams containing both lead oxide
and tetraethyl lead is discussed in the Profile Report on tetraethyl and
tetramethyl lead.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Waste streams containing lead oxides and no other soluble toxic consti-
tuents or organo-lead compounds can be conveniently disposed of by landfill
or by simple chemical treatment to recover the lead content. On this basis,
lead oxides are not considered as candidate waste stream constituents for
national disposal. However, lead oxides have also often been found in waste
solvent based paint sludges, residual sludges from refinery storage tanks
and basins, and sludges containing tetraethyl lead and these are candidate
waste streams requiring treatment at National Disposal Sites.
110
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual
(revised May, 1970). Washington, Manufacturing Chemists Association,
1970. 176 p.
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971. Washingtons
U.S. Government PrThTing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck Company, Inc., 1960. 1,634 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
1752. Public Health Service. Drinking water standards, 1962. Washington,
U.S. Department of Health, Education, and Welfare, 1969.
Ill
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead Monoxide (242)
IUC Name
Common Names
Structural Formula
PbO
Molecular Wt. 233.19
(1)
Melting Pt. 888 C
(1)
Boiling Pt..
Density (Condensed) 9.53^) @ Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
IP @
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solub'il ity
Cold Water 0.0017 grams/100 ml @20Hfrt Water
Others: soluble in HN03> alkali, lead acetate.
Acid, Base Properties
ttr
Ethanol
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 1570
112
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead Tetroxide (242)
IUC Name
Common Names
Structural Formula
Pb3°4
Molecular Wt. 685.57(1)
decomposes
Melting Pt. at 500 C
Boiling Pt..
Density (Condensed) _ & __
Vapor Pressure (recommended 55 C and 20 0
Density (gas)_
Flash Point
Autolgnition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Solubility(l)
Cold Mater insoluble
Others:
Acid, Base Properties_
Hot Water insoluble
Upper_
Upper
Ethanol insoluble
Highly Reactive with_
Compatible with
Shipped in
ICC Classification_
Comments
Coast Guard Classification
References (1) 1570
113
-------
PROFILE REPORT
Manganese (499)
1. GENERAL
Production and Use
Although the United States possesses reserves of manganese ores
(greater than 35 percent Mn content) and manganiferous ores (5 to 35 per-
cent Mn content), direct importation of ores is considered more economical
than mining, so that the domestic production accounts for only 8 percent of
the annual consumption (256,000 short tons ore mined vs. 3,045,000 short
1288
tons consumed in 1968). Imports account for the balance. There is
virtually no recycling of used metal, although the United States Bureau of
Mines has invested a great amount of experimental effort over a period of
time in attempts to reclaim the 7 to 8 percent manganese contained in spent
slag from basic open-hearth furnaces.0101'0102'0103'01°8.0n8,0120
Manganese is chemically and metallurgically similar to iron, and it
is won from its ores by smelting in a blast furnace in a manner analogous
1433
to the smelting of iron. Occasionally low grade ores are beneficiated
1287
by leaching with sulfuric or nitric acid.
Over 90 percent of the manganese consumed is alloyed with iron and
used as an additive in the production of steel.1288'0642'1433 The most
popular alloy is ferromanganese (80 percent Mn-20 percent Fe). Others
include spiegeleisen (20 percent Mn-bal. Fe, C) and silicomanganese (65 to
70 percent Mn-15 to 20 percent Si). Ferromanganese and spiegeleisen are
produced mostly in blast furnaces9 while silicomanganese is produced in
electric arc furnaces. These alloys are made and sold by many of the
larger chemical companies, e.g., Foote Mineral Company, Kerr-McGee
Corporation, and Union Carbide Corporation. Many steel companies,
including Bethlehem Steel and U.S. Steel, produce their own.
115
-------
Approximately 1 percent of the manganese consumed (27,000 tons of
ore annually) is used in the smelting of pig iron. Welding rods and fluxes
<
account for an insignificant amount in terms of quantity, but may neverthe-
less pose a health hazard.0277'0642
The chemical industry accounts for approximately 7 percent of the
total annual consumption. Most of this is refined electrolytically and
converted to synthetic manganese dioxide for the production of dry cell
1288
batteries. A small amount is used as a feed additive to prevent
deficiencies in livestock and as fertilizer. The Ethyl Corporation is
currently in the preliminary phases of marketing manganese methylcyclo-
pentadienyltricarbonyl as a replacement of lead tetraethyl in gasoline
flfi/l? ?1 ?R
' for cars equipped with catalytic afterburners. Manganese
methylcyclopentadienyltricarbonyl is discussed in the Profile Report on
Manganese Methylcyclopentadienyltricarbonyl (502).
Manganese is a common impurity in coal (0.005 to 1 percent), and some
is released to the atmosphere when coal is burned.
2. TOXICOLOGY
Health and Safety Standards
The Threshold Limit Value (TLV) recommended by the American Council
of Governmental Industrial Hygienists is 5 mg/m air. It is likely
that this represents a maximum exposure limit rather than a uniformly safe
standard, since disease has been reported in workers exposed to this limit.
' The State of Pennsylvania requires a short-term maximum limit
3 2112
of 5 mg/m for 30 min. Chronic symptoms of manganese poisoning were
o f)?77
found at levels of 5, 6, 30, and 59 mg/nr air. ' The 1971 Annual List
1312 3
of Toxic Substances reports that 11 mg/m by inhalation produced toxic
effects in man. Both the central nervous system and the lungs were affected.
Similarly, serious chronic symptoms were produced in two manganese steel
workers, even though environmental assays showed manganese concentrations
ranging from 2.3 to 4.7 mg/m air.
-------
Epidemiology
The only significant mode of entry is by inhalation of dusts and fumes.
2110,2111,2112,2114 The Cl1n1cal symptoms have been well documented.0277'
' * They primarily involve malfunctioning of the central nervous
system, probably by enzyme inhibition. Warning and diagnosis is complicated
by an incubation period of 6 to 30 days prior to the onset of symptoms.
Definitive confirmation of manganism is by urinalysis; manganese is
cumulated temporarily in the body and then discharged gradually in yg/ml
quantities. CaNa^ EDTA administered intravenously is effective treatment in
early stages of disease. Clinical evidence shows a marked increase in
urinary concentrations on administration of CaNa2 EDTA, which indicates that
CaNa2 EDTA promotes elimination of the metal through the kidneys. A con-
trolled, clinical study of Chilean miners suggests that a positive corre-
lation exists between nutritional deficiency and susceptibility to
manganism.
Pulmonary damage and high incidence of pneumonia have been reported
among persons living in the neighborhood of manganese steel plants in Great
Britain, Norway, Italy, and the U.S.S.R., but none has been reported in the
United States. ' Laboratory experiments in Great Britain and the
U.S.S.R. involving intratracheal injections of manganese oxides in rats
have confirmed the clinical evidence.
Inorganic and/or insoluble manganese and manganese salts administered
orally are passed virtually unabsorbed. Oral administration of 100 ppm Mn
stimulates animal growth, while 600 ppm proves deleterious.
3. OTHER HAZARDS
Manganese dust is a moderate hazard with respect to explosion.
3
The minimal explosive concentration is 125 oz/1000 ft and the minimum
required oxygen concentration is 15 percent. At 450 C manganese dust will
ignite spontaneously.
117
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
On a worldwide basis, industrial manganese poisoning is most
prevalent in the mining industry, where the mining, transporting, crushing,
and sieving of the ore generate considerable quantities of dust containing
manganese mixed with arsenic, lead cobalt,
provisions attend the shipment of the ore.
manganese mixed with arsenic, lead cobalt, and nickel. No special
In the manufacturing of ferromanganese, steel, other metallurgical
products, and in the chemical industry, waste management should involve
controlling the quantity of dust emitted. Standard industrial techniques
such as baghouses, electrostatic precipitators, forced ventilation, face
masks, and respirators should be used to minimize worker exposure.
Disposal/Reuse
Manganese mine tailings containing less than 5 percent manganese can
be discarded in the vicinity of the mine.
In steel plants, control of manganese dust is treated as part of the
larger problem of general particulate emissions. Steel mill tailings
contain 7 to 8 percent manganese, but as yet, despite considerable
efforts, means have not been found for reclaiming the manganese
economically.010' ,0102,0103,0108,0118,0120 .T|ia,e „,, un,ngs Conta1n
almost all the manganese waste generated within the United States.
Manganese waste as a component of steel mill tailings is discussed in
the Profile Report on Mill Tailings, Lead and Zinc (276).
For the release of manganese dust particles into the environment,
the acceptable criteria are defined in terms of the recommended
provisional limits.
Contaminant and Environment Provisional Limit Basis for Recommendation
3
Manganese in air 0.05 mg/m 0.01 TLV
Manganese in water and soil 0.05 ppm (mg/1) Drinking Water Standard
118
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Since the predominant danger with regard to manganese poisoning is by
inhalation, the burial of unsegregated, nearly insoluble wastes does not
constitute a significant hazard.
Disposal of Manganese Wastes
Option No. 1 - The Discarding of Manganese Dusts and Mine Tailings in
the Vicinity of the Mine. These wastes are insoluble. While the situation
nationalIy9 with regard to mine tailings, is in general unsatisfactory,
manganese tailings pose no special problems of their own, and comprise a
small fraction of the total amount of tailings in existence. No
documentary evidence was found for manganese poisoning among mine workers
in the United States. This may be attributable in part to the ever-
decreasing size of this industry domestically. 256,000 short tons of
manganese ore were mined in the United States in 1968, compared to 302,000
tons in 1967 and 339,000 tons in 1966.1288
Option No. 2 - The Burial of Manganese as a Component of Steel Mill
Tailings. This procedure is evaluated in the profile Report on Mill
Tailings, Lead and Zinc (276).
Option No. 3 - The Collection and Burial of Manganese Dusts at Local
Plant Sites. With regard to industrial exposure, waste management practices
range from satisfactory to unsatisfactory. In response to several clearly
pi I p pi I A
diagnosed cases of mancfanism from a broad segment of industry, '
the Division of Occupation Health, Pennsylvania State Department of Health,
undertook an investigation of manganese-using plants within the State of
2112
Pennsylvania. Generally, poor housekeeping and malfunctioning, poorly-
maintained equipment combined to create hazardous conditions in many plants.
o
The number of plants not complying with the Threshold Limit Value of 5 mg/m
listed on an industry-by-industry basis, has been presented by Tanaka and
Lieben (Table I).2112
119
-------
TABLE 1
MANGANESE AIR EMISSIONS IN INDUSTRIAL PLANTS
Type of Industry
Steel
Nonferrous metals
Metal manufacturing
Ceramics, brick, etc.
Chemical manufacturing
Processing of ore or ferromanganese
Miscellaneous
Total No. Plants
24
11
22
6
5
4
3
No. Above TLV
2
0
2
1
3
4
0
% in Violation
8.4
0
9.1
16.7
70.0
100.0
0
Total
75
12
-------
In each case, compliance would not have been inherently difficult or
expensive. The seriousness of the statistics is compounded by the fact
that the present TLV is too high, and at best constitutes a ceiling value,
rather than a true index of safety.
The situation apparently has not improved markedly in the four years
2129
since this study was made. In 1971, two new cases of manganism were
diagnosed in the State of Pennsylvania. In view of the rarity of this
disease and the non-specificity of its symptoms, it is probable that more
were misdiagnosed. Pennsylvania may be considered typical of other
2129
states/1"
These dusts are insoluble, and once they are collected, their burial
does not constitute a significant hazard.
With regard to the general public, extensive studies indicate that
there is no air or water pollution problem at present.0642'0768'2107'2108'
2109 2118
' No documentary evidence was found for manganism among the general
public. Spectrographic analyses of the water supplies of the 100 largest
cities in the United States indicated a median manganese concentration of
5.0 yg/1 (0.005 ppm) and a maximum manganese concentration of 1,100 pg/1
(1.1 ppm). The American Water Works Assocation specifies that ideal water
2118
should contain a maximum of 0.01 ppm Mn, while the U.S. Public Health
0285
Service regards 0.05 ppm as the Drinking Water Standard. Air pollution
studies indicated an average of 0.10 ug/m in one study and a range of
"3 pi nc
0.005 to 1.44 yg/m in another. These findings and recommendations
have been summarized (Table 2). It is seen that air emissions are well
below the recommended provisional limit. Water emissions are also well
below the recommended provisional limit, except for several city water
supplies which depend on natural ground water. These are found to be
borderline acceptable.
121
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TABLE 2
GENERAL PUBLIC EXPOSURE TO MANGANESE AIR AND WATER EMISSIONS
Mean (or Median) Range Recommended
Air emissions 0.10 yg/rrT0542 o7o05-l .44 yg/m3 2106 50
npoc 0?85
Water emissions 0.005 ppm 0-1.1 ppm o.05 ppm
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
At present, manganese does not constitute a hazard to the general
public. There is evidence, however, that current industrial practices may
involve exposures of workers to levels which are presently regarded as
unsafe. These exposures are in the form of atmospheric dust and constitute
a serious industrial health threat, since the current Threshold Limit Value
itself is in need of revision downward. The problem is primarily one of
dust control and ample technology is presently available to solve it with
minimal economic impact.
Manganese mine tailings containing less than 5 percent Mn are not
significantly different than other tailings. The suitability of taconite
tailings for National Disposal Sites is discussed in the Profile Report on
Taconite Tailings (419).
Similarly, the manganese contained in steel mill tailings is discussed
in the Profile Report on Mill Tailings (276). Although the tailings only
contain 7 to 8 percent manganeses they account for almost all the manganese
waste generated in the United States.
The inadequacy of dust control within industrial plants is a problem
amenable to solution by education and by application of current technology.
Manganese and manganese compounds are relatively insoluble and inert unless
inhaled, and while some control of their disposal as solid waste would be
desirable, burial in an unsegregated manner with other wastes does not
constitute a significant hazard. Manganese is therefore not a candidate
waste stream constituent for national disposal.
123
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7. REFERENCES
0074. Booz, Allen, and Hamilton. An appraisal of the problem of handling,
transporting, and disposal of toxic and other hazardous materials.
Environmental Quality Council. 1970.
0101. Ruppert, J. A. Manganese concentrates from open-hearth slags by
lime-clinkering (Sylvester) process. U.S. Bureau of Mines Report
RI 4847. 1952. 26 p.
0102. Heindl, R. A., et al. Manganese from steel plant slags by a lime-
clinkering and carbonate-leaching process: Part I. Laboratory
development. U. S. Bureau of Mines Report RI 5124. 1955. 48 p.
0103. Heindl, R. A. et al. Manganese from steel plant slags by a lime-
clinkering and carbonate-leaching process: Part II. Pilot plant
development. U. S. Bureau of Mines Report RI 5142. 1955. 80 p.
0108. Stickney, W. A. and C. W. Sanders. Recovering manganese from mill
rejects. U. S. Bureau of Mines Report RI 5692. 1960. lip.
0118. Buehl, R. C., et al. The recovery of manganese from open hearth
slags and low-grade ores by smelting and selective oxidation.
U. S. Bureau of Mines Report RI 6596. 1965. 37 p.
0120. Cochran, A. A. and W. L. Falke. A one-step operation for recovery
of manganese as chloride from ores and slags. U. S. Bureau of
Mines Report RI 6859. 1967. 22 p.
0277. Patty, F. A. Comp. Industrial hygiene and toxicology. New York,
Interscience Publishers, 1963.
0285. Lund, H. F. Industrial pollution control handbook. New York,
McGraw-Hill, 1971.
0642. Sullivan, R. J. Air pollution aspects of manganese and its compounds,
Bethesda, Maryland, Litton Systems, Inc., September 1969. 92 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
0768. Murthy, G. K., et al. Levels of antimony, cadmium, chromium, cobalt,
manganese, and zinc in institutional total diets. Environmental
Science and Technology, 5(5):436-442, May 1971.
1287. Mineral facts and problems. U. S. Bureau of Mines Bulletin 650.
1970. 1,291 p.
1288. Minerals yearbook. U. S. Bureau of Mines. 1969. 1,208 p.
124
-------
REFERENCES (CONTINUED)
1312. Christensen, H. E. Toxic substances: Annual list. U. S. Department
of Health, Education, and Welfare, Health Services and Mental Health
Administration, National Institute for Occupational Safety and
Health, Rockville, Maryland. 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966. 899 p.
2106. Schroeder, H. A. A sensible look at air pollution by metals. Archives
of Environmental Health, 21:798-806. 1970.
2107. Delfina, J. J. and H. F. Lee. Chemistry of manganese in Lake
Wendota, Wisconsin. Environmental Science and Technology,
2(12):1094-1100.
2108. Wiley, R. H. and H. Proelss. Manganese ESR signal in air particulate
samples. Environmental Science and Technology, 2(9):705. 1968.
2109. Turekian, K. K. and M. R. Scott. Concentrations of Cr, Ag, Mo, Ni,
Co, and Mn in suspended material in streams. Environmental
Science and Technology, 1(11 ):940-942. 1967.
2110. Data sheet D-306 (D-Chem 26). Manganese. National Safety Council.
2111. Hygienic guide series. Manganese and its inorganic compounds.
American Industrial Hygiene Assocation.
2112. Tanakas S. and J. Lieben. Manganese poisoning and exposures in
Pennsylvania. Archives of Environmental Health, 19:674-684. 1969.
2113. Mera, J., et al . Chromic manganese poisoning-industrial susceptibility
and absorption of iron. Neurology, 19(10):1000-1006. 1969.
2114. Whitlock, C. M., et al . Chronic neurological disease in two manganese
steel workers. American Industrial Hygiene Assocation Journal,
27(5):454-459. 1966.
2115. Jonderko, G. and Z. Szczurek. Pathomorphological changes in the
brain as a result of experimental chronic manganese poisoning.
Internationales Archiv fur Gewerbepathologie und Gewerbehygiene,
23(2):106-116. T96T
2116. Jonderko, G. and Z. Szczurek. Pathomorphological changes in the brain
as a result of experimental chronic manganese poisoning.
Internationales Archiv fur Gewerbepathologie und Gewerbehygiene,
25(2):165-180. 1969.
125
-------
REFERENCES (CONTINUED)
2118. Durfor, C. N. and E. Becher. Public water supplies of the 100
largest cities (1962). U. S. Geological Survey Water Supply
Paper 1812. Washington, U. S. Government Printing Office, 1964.
2128. Personal communication. L. B. Andrew, Ethyl Corp. to M. Appel, TRW
Systems, July 10, 1972. Manganese methylcyclopentadienyltricarbonyl
2129. Personal communication. S. Tanaka, Pennsylvania Department of
Environmental Resources to M. Appel, TRW Systems, July 10, 1972.
Manganese poisoning.
2130. Personal communication. W. Bucciarelli, Pennsylvania Department of
Environmental Resources to M. Appel, TRW Systems, July 10, 1972.
Disposal of manganese wastes.
126
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name Manganese (499)
Common Names Manganese
Structural Formula
Mn
54.9
(1)
Melting Pt. 1260 C
Molecular Wt.
Density (Condensed) 7.20 q/cc @ 20 C_ Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
1 mm @ 1292 C
(1)
Boiling Pt. 1900 C
Flash Point
Autoignltion Temp.450 C
Flammability Limits in Air (wt %) Lower moderate (as Upper_
Explosive Limits in Air (wt. %)
Lower dust)!25 oz/1000 Upper <15%
Solubility
Cold Water insoluble
ftj (as dust)
Hot Water insoluble
Ethanol insoluble
Others: sol, acids, insol. bases
Acid, Base Properties slightly basic
Highly Reactive with acids
Compatible with metals, oxides
Shipped in no special requirements
ICC Classification not classified
Coast Guard Classification
Comments fumes and dust hazardous if
References (1) 766
127
-------
PROFILE REPORT
Manganese Sulfate (252) and Manganese Chloride (501)
1. GENERAL
Production
There are several producers of MnSOA in the United States, including
?17ft ?1Q1
the Diamond Shamrock Chemical Company, Baltimore, Maryland, °' ' '
Eastman Chemical Products, Inc., Kingsport, Tennessee, and the Carus
2279
Chemical Company, Inc., La Salle, Illinois. Diamond Shamrock makes
MnSO. by leaching oxide ores with sulfuric acid and concentrating the fil-
trate. The acid insoluble residues, which consist mostly of silicon
2178
dioxide, are dried by evaporation and carted away to serve as landfill.
Eastman Chemical Products and the Carus Chemical Company produce MnSO, as a
2279
byproduct of their production of hydroquinone. Aniline is oxidized by
in the presence of H2$04 to quinone. The quinone is then vacuum-
distilled and reduced by iron metal filings to hydroquinone. The solid
residue contains MnSO^, which is isolated, crystallized, packaged, and
shipped. In 1964, 34,169 tons of MnS04 were produced. Current prices range
from $82 to $100/ton, depending on the manganese content.
Diamond Shamrock is the only producer of manganese chloride. The
process is the same as that used for the sulfate with hydrochloric acid
replacing sulfuric acid as the leaching agent. Production of MnClo amounts
to under 2,000 tons/yr, which currently sells for 21 cents/lb.
Use
Manganese sulfate is used almost exclusively for agricultural
purposes.21 8> 1433 It is applied as a spray containing 4 Ib MnS04/50 gal
water to citrus fruits and truck crops grown in Mn-deficient soils, e.g.,
Florida and Rhode Island. It is an essential element in plant and animal
growth. In plants it appears to catalyze the production of chlorophyll,
129
-------
even though it is not an integral part of the molecule, as is magnesium.
Manganese sulfate is also beneficial in the neutralization of alkaline
soils. Applications vary from 30 Ib/acre for Rhode Island truck crops to
1433
100 Ib/acre for Florida citrus fruits. The addition of manganese
sulfate to livestock feed prevents skeletal and reproductive abnormalities
-al ne
1492
and disorders of the central nervous system. Typical additions are
60 mg/lb feed for poultry.
A small, undisclosed amount of manganese sulfate is used in the
manufacture of Pharmaceuticals.
Small quantities of manganese chloride are used in the electrolytic
refining of magnesium metal. ' The manganese alloys with the
1433
magnesium and induces the precipitation of iron impurities. Kirk-Othmer
reports that another use for manganese chloride is in the manufacture of
bricks; the manganese chloride is volatilized in the kiln to impart a dark-
red finish to face brick. However, communications with the Los Angeles
??fift
County Air Pollution Control District and three Southern California
brick manufacturers2265' 2266' 2267 indicates that MnCl2 is not used in
the industry. One manufacturer does»on occasion,add manganese oxide to
his charge to impart the red color. It is unlikely that brick manufacturing
in other parts of the United States is conducted substantially differently,
so it may be concluded that the use of MnCU in this industry has stopped.
2. TOXICOLOGY
Manganese and manganese compounds have Threshold Limit Values (TLV) of
o
5 mg/M . Laboratory experiments with mice have shown that the approximate
LD50 for MnClp is 210 mg/kg administered subcutaneously and the LD5Q for
MnSO. is 44 mg/kg administered intraperitoneally.
130
-------
The epidemiology of Manganese and manganese compounds is discussed
flAOO
more fully in the Profile Report on manganese.
3. OTHER HAZARDS
Manganese chloride and manganese sulfate are quite stable. Manganese
chloride vapor reacts slowly with moist air to form HC1 and MnO.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
The U.S. Department of Transportation has no special requirements or
restrictions for the transportation of manganese chloride or manganese
sulfate. The materials can be handled and stored with no special
precautions.
Disposal/Reuse
There are no significant sources of manganese sulfate and manganese
chloride wastes that could be reclaimed for their manganese values. The
acceptable criteria for the release of these materials into the environment
are defined in terms of the following provisional limits:
Contaminant in Air Provisional Limit Basis for Recommendation
Manganese chloride 0.05 mg/M as Mn 0.01 TLV for Mn
Manganese sulfate 0.05 mg/M as Mn 0.01 TLV for Mn
Contaminant in Water Provisional Limit Basis for Recommendation
and Soil
Manganese chloride 0.05 ppm as Mn Drinking Water Standard for Mn
Manganese sulfate 0.05 ppm as Mn Drinking Water Standard for Mn
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Laboratory studies have shown that manganese chloride and manganese
sulfate are relatively non-toxic. No incidences of poisoning in man
attributable to these substances were found. These materials are quite
stable and well-character!" zed, so it is unlikely that a future problem
will arise. It may therefore be concluded that their handling, storage,
and transportation are adequate.
Option No.l - Use of Acid Insoluble Residues as Landfill
The use for landfill of the insoluble residues from the production of
manganese sulfate and manganese chloride by acid leaching is satisfactory.
These residues consist mostly of silicon dioxide, with some highly-insoluble
manganese oxides included. There is no air emission or leaching into any
ground water.
Option No. 2 - Permanent Storage in a Lagoon
of Solid Waste from Hydroquinone Production
All Mn-containing waste from the production of MnSO. as a byproduct of
hydroquinone is moved to a lagoon, where the manganese is precipitated with
lime as Mn(OH)2. The overflow from the lagoon contains less than one ppm
Mn, which is below the limit set by the State of Illinois.2279 This does,
however, exceed the drinking water standard so the water should not be used
as a potable source. There is no air emission except for an occasional,
accidental release of quinone.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Since manganese chloride and manganese sulfate can be handled and
treated adequately at the industry level, they are not candidate waste
stream constituents for national disposal.
132
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7. REFERENCES
0277. Patty, F. A., comp. Industrial hygiene and toxicology. New York,
Interscience Publishers, 1963.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966.
1492. The Merck index of chemicals and drugs. 7th ed. v. 11. Rahway, New
Jersey, Merck and Company, Inc. 1960. 1,643 p.
2118. Durfor, C. N. and E. Becher. Public water supplies of the 100
largest cities (1962). U. S. Geological Survey Water Supply
Paper 1812. Washington, U. S. Government Printing Office, 1964.
2178. Personal communication. D. Hanson, Diamond Shamrock Chemical Company
to M. Appel, TRW Systems, July 21, 1972. Manganese sulfate and
manganese chloride.
2191. Personal communication. M. Appel, TRW Systems to F. Lickteig,
Diamond Shamrock Chemical Company, July 27, 1972. TRW letter
4742.3.72-102. Request for information on manganese sulfate and
manganese chloride.
2263. Personal communication. A. L. Gregoric, Diamond Shamrock Chemical
Company to M. Appel, TRW Systems, Aug. 14, 1972. Response to
request for information on manganese sulfate and manganese chloride.
2264. Personal communication. M. Appel, TRW Systems to J. A. Mitchell,
Tennessee Eastman Company, Aug. 25, 1972. TRW letter 4742.3.72-118.
Request for information on manganese sulfate.
2265. Personal communication. Higgins Brick and File Company to M. Appel,
TRW Systems, Aug. 25, 1972. Manganese chloride.
2266. Personal communication. Listen Brick Company to M. Appel, TRW
Systems, Aug. 25, 1972. Manganese chloride.
2267. Personal communication. Dick Smith, Pacific Clay Products to
M. Appel, TRW Systems, Aug. 25, 1972. Manganese chloride.
2268. Personal communications. Herb Simon, Los Angeles County Air
Pollution Control District to M. Appel, TRW Systems, Aug. 25, 1972.
Manganese chloride.
2278. Personal communication. Tom Walton, Carus Chemical Company to
M. Appel, TRW Systems, Aug. 28, 1972. Manganese sulfate.
2279. Personal communication. Walt Starnes, Florida State Air and Water
Pollution Control Board to M. Appel, TRW Systems, Aug. 30, 1972.
Manganese sulfate.
133
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name Manganous Sulfate (252)
Common Names Manganese Sulfate
Structural Formula
MnSO,
Molecular Wt.
151
o:
Melting Pt. 700 c
;D
Density (Condensed) 3.25 g/cc @ _ 20 j: _ Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
Boiling Pt. decomposes
„ 850 C
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubil ity
Cold Water 52 g/100 ml
Others: insoluble in ether
Hot Water 70 g/100 ml
Ethanol soluble
Acid, Base Properties acidic
Highly Reactive with_
Compatible with
Shipped in_
tank cars
ICC Classification None
Coast Guard Classification None
Comments no restrictions on shipment
References (1) 1433
134
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name 501
IUC Name Manganese Pi chloride
Common Names Manganese Chloride
Structural Formula
MnCl,
Molecular Wt. 125-8
Melting Pt. 650 C
(1)
Boiling Pt. 1190 C
Density (Condensed) 2.977 @ _ 25_ C _ 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 62.2 g/100 ml Hot Water 123.8 q/100 ml
Others: insoluble in ether. NH3
Acid, Base Properties acidic
Ethanol soluble
Highly Reactive with
Compatible with_
Shipped in tank cars
ICC Classification None
Coast Guard Classification None
Comments no restrictions on shipment
References (1) 1433
135
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PROFILE REPORT
Nickel Ammonium Sulfate (290). Nickel Chloride (294).
Nickel Nitrate (296), and Nickel Sulfate (298)
t
1. GENERAL
Introduction
Nickel ammonium sulfate [NiS04 • (NH4)£ S04 • XHgO]; nickel chloride
(NiCl2 • XH20); nickel nitrate [N1(N03)2'. XHgO]; and nickel sulfate
(NiSO« • XHpO); are compounds of varying toxicity that find wide use in
metal finishing, catalyst manufacture and battery manufacture, as well as
minor uses in ceramics and general laboratory chemistry. Of the four
compounds, nickel chloride and nickel sulfate are industrially important
and their wastes are more widely spread. Nickel nitrate has limited uses
while the ammonium sulfate is of little commercial significance. These
four compounds represented 10 to 20 percent of the 273 million Ib of
nickel consumed in the United States for all purposes in 1971. The bulk of
nickel is used in ferrous, non-ferrous•> and high temperature alloys.
Manufacture
The production methods for nickel ammonium sulfate, nickel chloride,
nickel nitrate, and nickel sulfate can be generally characterized as
reactions in which the appropriate acid is reacted with a source of pure
nickel metal, nickel oxide, or nickel hydroxide. The desired nickel salt
products are precipitated from the mother liquor which can be reused a
?ifin ?ifi?
number of times but finally must be dumped. '
The purification procedures are the focal point of the technology of
providing pure salts and are believed to be the major source of nickel
waste from their manufacture. Due to the proprietary nature of the
critical purification stepss neither the details nor their waste outputs
137
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were available. However, the major manufacturers are recovering
nickel values from their waste streams before final discharge. The
majority of the production is on a batch scale and soda ash (anhydrous
sodium carbonate) is added to the mother liquor. The precipitated nickel
2162
carbonate is washed and is used as starting material. The contacted
manufacturers also had neutralization and clarification equipment at the
plant for recovering nickel and other metal ions from the unsegregated
waste streams flowing from all operations at the plant. The sludges from
the in-plant treatment along with insoluble filter cakes and filter aids
are landfilled.2162'2163 The levels of nickel in plant effluents after
final treatment were not available because of the reluctance of plant
personnel to reveal them.
Electroplating and Metal Finishing
The electroplating industry is a significant contributor, if not the
major source of waterborne nickel wastes. Nickel sulfate and nickel
chloride are the principal nickel salts used in the industry. Nickel
ammonium sulfate has minor use to make "black nickel" surfaces. Water
borne wastes in the metal finishing industry occur in six basic areas:
(1) rinse water; (2) concentrated plating tanks accidentally or
intentionally dumped; (3) washings from cleaning the plant equipment and
facilities; (4) sludges, filter cakes, etc.; (5) regenerants or concentrates
from in-plant water treating or recovery equipment; and (6) vent scrubber
waters.
The predominant sources are the rinse waters, the concentrated
plating baths, and sediments arising from purity maintenance on the tanks.
The rinse waters are very dilute solutions containing nickel and other
metals and anions, but because of their tremendous volumes, they represent
the most serious pollution problem in the electroplating industry. The
actual nickel plating baths can be maintained for long periods of time by
means of procedures to remove impurities and maintain the effectiveness
of the tank8 but occasionally they are dumped and the effects of dumping
such a large amount of plating solution at one time without treatment can
138
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have a disastrous effect on sewage lines, sewage treatment plants or
aquatic life in open waterways. Typical effluents from metal finishing
plants doing nickel plating are presented below:
TYPICAL NICKEL EFFLUENTS FROM PLATING SHOPS
Volume Ni Content
Type of Work Plated gal/day ppm
Office machine 50S000 39
Silverware 40„000 33
Automobile manufacture 620S000 80
Metal fasteners 89,000 302
Only a very small percentage of plating shops are making any significant
attempt to recover or treat waste nickel. The industry cites the lack of
rigid discharge controls or limits of discharge set by municipal, state,
and federal water pollution control authorities. Another reason for the
prevailing discharge practices is that it is not economical to install
recovery systems or plant-wide water treatment systems in the average size
plating shop. Only the high waste volume platers can benefit from recovering
01 C"7
water and metal values. Furthermore sewer authorities more or less
welcome certain metal ions in their sewer lines, nickel included, which
react with and precipitate free sulfides within the sewer. This removes
some of the corrosive and malodorous sulfides from the domestic sewage
lines. The precipitated sulfides are recovered in primary clarification
steps at the sewage treatment plant and thereby do not significantly effect
the operation of the plant itself. More detail on the current situation
within the metal finishing industry is presented in a large number of
articles, reports and books. Notably among these, are Lund's book on
QOQC
industrial pollution control „ Metal Finishing Waste Disposal (article
by Ceresa and Lancy) and a state-of-the-art review of metal finishing
waste treatment With an extensive bibliography prepared by Batelle
Memorial Institute.0783
133
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Catalyst Preparation
Nickel nitrate and nickel sulfate are used as starting materials in
the preparation of nickel catalysts for the petroleum and chemical
industry. The big users buy these starting materials for captive
production using proprietary processes. Examples are: (1) nickel sulfate
chemically reduced to a catalyst powder; and (2) nickel nitrate solution
saturated on a ceramic support and gently ignited to yield the desired
impregnated nickel catalyst. These processes are believed to be on a
batch basis with virtually no wasting of the starting materials.
Batteries
Nickel nitrate is combined with cadmium nitrate and saturated on
inert fillers for "solid" electrolyte, nickel-cadmium batteries. The
consumption of nickel nitrate in batteries is minor and significant
wastes from the production of these batteries or their ultimate scrapping
is not believed to occur.
2. TOXICOLOGY
Generally speaking, the chloride, nitrate, sulfate and ammonium ions
that are combined with nickel in the subject compounds assume the
toxicological properties of the cation nickel. That is to say, if these
compounds are inhaled or ingested, the toxicological effects of the nickel
constituent would more likely cause a harmful effect before the ammonium,
sulfate, nitrate, or chloride ions with which they are compounded.
Nickel compounds have been responsible for a variety of skin
abnormalities among workers in refining plants, plating shops, and other
industries where workers are in contact with them. Nickel salts have also
been linked to carcinogenesis, especially when inhaled, but other materials
were involved in these cases and the nickel compounds have not been proven
as being singly responsible. The recommended Threshold Limit Value
for airborne nickel or nickel compounds is 1 milligram per cubic meter of
140
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air.0 Good discussions, of the health and toxicological aspects of nickel
._ . ..'•.. _. ~ ,_•,.,_ j , 0356,0615,0633
and its compounds are (.found in a number of published works. ' '
Studies have been made to investigate the toxic effects of nickel on
plant life. In general, pi ants are more sensitive to nickel than lead.
There also is a correlation between nickel and the iron content, copper
content and pH of the soil which cause significant deleterious effects.
3. OTHER HAZARDS
The sulfate and nitrate anion constituents of the compounds being
discussed in this Profile Report can release toxic fumes of S02 or N02 if
they are exposed to intense heat. This represents a moderate disaster
hazard if large amounts of these materials are involved in a very hot fire.
The nitrate ion also is a source of oxygen and if combined with combustible
materials, could represent a dangerous hazard from self-sustained combustion.
In general, however, these compounds are considered to be stable and present
no significant hazard when stored or transported under normal conditions.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Storagea Handling and Transportation
The subject nickel salts do not require severely restrictive storage,
handling and transportation procedures. All four compounds are shipped in
100-lb plastic-lined paper bags. Nickel nitrate is also commonly shipped
in 400-1b steel drums. Nickel chloride and nickel sulfate are also
prepared in aqueous solution convenient for electroplaters. These solutions
are shipped in 5-gal pails and 50-gal steel drums. It is recommended that
personnel who handle open containers of these materials be provided with
protective clothings face shields and dust filtering breathing equipment
to guard against possibility of skin contact and inhalation. Solid spills
should be swept up and packaged for return to the manufacturer. Liquid
spills require the addition of soda ash to precipitate nickel carbonate
which can be sewered with additional large amounts of water.
141
-------
Disposal
The acceptable criteria for the release of nickel compounds into
the environment are defined in terms of the following provisional limits:
Contaminant in
Air
Nickel ammonium
sulfate
Nickel chloride
Nickel nitrate
Nickel sulfate
Contaminant in
Water and Soil
Nickel ammonium
sulfate
Nickel chloride
Nickel nitrate
Nickel sulfate
Provisional Limit
0.01 mg/M3 as Ni
0.01 mg/M3 as Ni
0.01 mg/M3 as Ni
0.01 mg/M3 as Ni
Provisional Limit
Basis for Recommendation
0.01 TLV for Ni
0.01 TLV for Ni
0.01 TLV for Ni
0.01 TLV for Ni
Basis for Recommendation
0.05 ppm (mg/1) as Ni Chronic toxicity drinking
water studies
0.05 ppm (mg/1) as Ni Chronic toxicity drinking
water studies
0.05 ppm (mg/1) as Ni Chronic toxicity drinking
water studies
0.05 ppm (mg/1) as Ni Chronic toxicity drinking
water studies
Reuse
Nickel prices are currently about Sl.SB/lbj, a level where it is
apparently economical only for manufacturers and large consumers to reclaim
nickel values from waste solutions.028501243'2162 The smaller plating and
metal finishing shops normally do not have any water recovery or solution
concentrating equipment. The only conservation procedure widely used is
the "save rinse" method wherein rinse water in the firsts, most concentrated
rinsing tank is added to the electroplating tank to make up for evaporative
water losses.
142
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Introduction
The nickel compounds being considered here are almost always found as
wastes in aqueous solutions and two different approaches are typically
employed in the management of these solutions. The first approach of
waste management is reduction of these compounds in the final plant
effluent or reduction of the volume of the stream itself. This is done
by: (1) changing the processes to reduce waste outputs; (2) improving
housekeeping; (3) segregating waste streams with specific recovery
procedures; or (4) installing equipment for recovering water and
concentrating the waste stream. The concentrated waste stream can then be
more easily handled. The second approach is applied to the final plant
effluent to remove the contaminants with no possibilities of reusing them.
This usually means removal by precipitation of sludges. Firms trying to
reduce and/or recover nickel wastes employ various techniques from both
approaches when dealing with their wastes. Three good sources which
provide overviews of the scope of the metal finishing waste problem and
the state-of-the-art on treatment methods are presented in Lund's book,
an article by Ceresa and Lancy, and a report prepared by Battelle
Memorial Institute.0285'0783'1"119
Option No. 1 - Recycling and Reuse. The loss of large amounts of
nickel compounds from the metal finishing industry, manufacturers and
large consumers has created the need to adopt methods and equipment for
recovering nickel values from these solutions. One of the easiest procedures
for nickel conservation which is used in a great number of plating shops
is that of "save rinse" which was described earlier. Other, more
sophisticated equipment is commercially available to concentrate and
recover nickel salt solutions for immediate reuse in the plant or to sell
to an outside reclaiming firm. This equipment includes reverse osmosis,
where the contaminated solutions are pressure-forced through a semi-permeable
membrane. The permeate is recovered for rinse water and the concentrate
is available for reuse or sale to a reclaimer. Multiple effect evaporators
are used to concentrate solutions; thereby recovering the condensate for
143
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reuse or sale to a reclaimer as economics and purity of the concentrate
dictate. The equipment also includes ion exchange which incorporates a bed
of activated-beads through which the dilute aqueous solutions flow. Sites
on these beads selectively attract and hold the desired ions. Periodically
a regeneration solution is passed through the ion exchange beds and the
adsorbed ions are desorbed from the bed in a concentrated solution. These
concentrated solutions can be reprocessed for their metal values.or otherwise
recycled. Other newer methods are in various stages of development.
Option No. 2 - Precipitation and Clarification. Precipitation of
insoluble nickel carbonate with soda ash (anhydrous sodium carbonate), or
pH adjustment with caustic to yield the sludge-like, insoluble nickel
hydroxide is a widely used method for treating aqueous nickel effluents.
This process can produce treated effluents containing 1 to 5 ppm heavy
metals when performed properly. The chemical companies manufacturing
these nickel salts are actively recovering nickel from their large volume,
?lfifi ?lfi?
batch, manufacturing processes for credit. s Whenever feasible
plating shops also use soda ash to recover nickel values when a plating
tank is completely rennovated. The NiCcO-Jo can be redissolved in an
appropriate mineral acid for immediate reuse, or may also be packaged, as
is, for return to a reclaimer.0285'1243'2162
When caustic or an alkaline stream in the plant is combined with an
acid plating shop effluents the heavy metal hydroxides precipitate. These
precipitates are normally gelatinous sludges with very high water content
(70 to 80 percent). These sludges normally contain a wide mixture of
materials and treatment after precipitation includes passage through a
sand bed or similar clarifier. The sludge is removed for laqdfilling and
the effluent is discharged to a municipal sewer or open waterway if
permitted by the regulating authorities.
Option No. 3 - Direct Discharge to Municipal Sewers. Nearly all the
small and medium size plating shops, and even some of the large ones,
discharge their metal laden aqueous effluents to municipal sewers.
Some plants have facilities to precipitate and clarify before discharge,
-------
as discussed above, but they are estimated to be about 15 percent of the
2134
total shops. In many areas, especially large metropolitan areas, this
practice is allowed to continue as long as the toxicity of the nickel
discharges has little or no effect on the continuous operation of any of
the biological waste treatment processes of the sewage treatment plant.
Many of the metal cations, nickel included, precipitate with sulfides in
the domestic sewer lines while in transit to the sewage treatment plant.
Thus, a great proportion of them are removed in the primary treatment
process and most of the remainder are bound up in the sludge resulting
from the secondary treatment processes.
The method is considered adequate provided that: (1) the sewage
treatment authorities can effectively regulate the discharge of toxic
metal compounds into the sewer system at a rate which will not disturb the
efficiency of the sewage treatment processes; and (2) the operation and
design of the sewage treatment plant is such that effective treatment is
accomplished and the effluent from the treatment plant complies with the
local purity regulations for discharge to open waters. The secondary sludge
must be landfilled such that the provisional limits are not exceeded or they
must be placed in a California Class 1 type landfill.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
National Disposal Site Facilities should not be made available to
handle the subject nickel salts for the following reasons: (1) untreated
wastes occur in dilute solutions that cannot be economically transported,
(2) technology and waste handling techniques are available for those
industries that choose to use them, and (3) wastes recovered from aqueous
streams (precipitates) are being accepted by commercial dumps for landfill
disposal. Landfill ing these insoluble sludges or precipitates is adequate
providing that the provisional limits are not exceeded or that the landfill
has a proper geological location and further in either case that no materials,
such as acids, are landfilled with the sludges which would cause them to
redissolve and leach out. As a footnote, however, a National Disposal Site
will be an excellent choice to process dried, metal laden sludges when the
145
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technology becomes available and the economics of processing are favorable.
The potential for recovering metals from the tremendous volumes of these
presently cumbersome and worthless materials would help in reducing the
operating costs of a National Disposal Site system.
146
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7. REFERENCES
0095. Laboratory waste disposal manual. Washington, Manufacturing
Chemists Association, 1970.
0225. American Conference of Governmental Hygienists Threshold Limits
for 1971. Adopted at 33rd Meeting, Toronto, Canada, May 1971.
Occupational Hazards» p. 35-40, Aug. 1971.
0285. Lund, H. F. ed., Industrial pollution control handbook. New York,
McGraw-HilFBook Co., 1971. 864 p.
0356. Mastromatteo, E. Nickel: a review of its occupational health
aspects. Journal of Occupational Medicine, 9(3):127-136. Mar. 1967,
0458. Mineral facts and problems, 1965 ed., Washington, Bureau of Mines,
1965. 1,118 p. '
0615. Schroeder, H. A. Metals in the air, Environment, 13 (8): 18-24S
299 Oct. 1971. '
0633. Sullivan, R. J. comp. Air pollution aspects of nickel and its
compounds. Report prepared for National Air Pollution Control
Administration by Litton Systems, Inc., Bethesda, Maryland
under Contract No. PH-22-68-25. Washington, National Technical
Information Service, 1969. 89 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.,
New York, Reinhold Publishing Corp., 1968. 1,296 p.
0783. Battelle Memorial Institute, A State-of-the-art review of metal
finishing waste treatment. Prepared for the Federal Water
Quality Administration and the Metal finishers Foundation under
grant No. WPRD 201-01-68. Washington, National Technical
Information Service, 1968. 43 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.
1243. Personal communication. D. Hutchinson, Harshaw Chemical Co.s to
J. F. Clausen, TRW Systems, Feb. 16, 1972.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Cfiimical Rubber Company, 1969. 2,100 p.
2134. Personal communication. D. Hutchinson, Harshaw Chemical Co., to
J. F. Clausen, TRW Systems, July 10, 1972.
2160. Personal communication. R. Halvedal, Harshaw Chemical Co., to
J. F. Clausen, TRW Systems, July 13, 1972.
147
-------
2162. Personal comnunication. H. Beckemeyer, Chemetron Inc., to J. F. Clausen,
TRW System, July 17, 1972.
2163. Personal communication. M. Goss, J. T. Baker Chemical Co., to
J. F. Clausen, TRW Systems, July 17, 1972.
148
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Nickel Ammonium Sulfate (290)
IUC Name
Common Names double nickel salts
Structural Formula
ammonium nickel sulfate
NiS04-(NH4)2S04-6H20
Molecular Wt. 395g/mole(2)
Density (Condensed) 1.923g/cc^e
Melting Pt.
Boiling Pt..
Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignitlon Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 10.4q/100cc 20
Others: Sol (NHj-SO.
Hot Water 30g/100cc 80
Ethanol insol
Acid, Base Properties
Highly Reactive w1th_
Compatible with_
Shipped in
ICC Classification
Comments used in electroplating
Coast Guard Classification
References (1) 1570
(2) 0766
149
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nickel Nitrate hexahydrate (296)
Structural Formula
IUC Name
Common Names
Ni(N03)2-6H20
Molecular Wt. ZQO.Slg/mole^ Melting Pt. 56.7 C^ Boiling Pt. 136.7
Density (Condensed) 2.05(1) @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
@ 0 @
Flash Point _ Auto1gnit1on Temp. _
Flammability Limits in Air (wt %) Lower _ Upper_
Explosive Limits in Air (wt. %) Lower_ _ Upper_
Solubility
Cold Mater, 238.5g/100cc @ 0 Cu; Hot Water very soluble^' Ethanol.
Others: NH^OH
Acid, Base Properties ag soln:pH4
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification
Comments
References (1) 1570
(2) 0766
150
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. rf. Name Nickel Sulfate (2981
v ; Structural Formula
IUC Name
Common Names
N1S0
*
4
Molecular Wt. 154.78g/mo1et ' Melting Pt. d 84ft C() . Boiling Pt..
Density (Condensed) 3.68g/cc^ 9 Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
@ @ G
Flash Point Auto1gn1t1on Temp.
Flanrnability Limits in A1r (wt X) Lower . Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 29.3g/100cc @ 0 C(1)' Hot Mater 83.7q/100cc @ 100 C(1Ethanol Insol
Others : _
Acid, Base Properties _
Highly Reactive with
Compatible with
Shipped in_
ICC Classification Coast Guard Classification
Comments h^xa and hepta hydrates lose water at 103 C and are more soluble in wat-.pr and
alcohol^
* Commerci al prnduct'S normall
References (1) 1579
0766
151
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nickel Chloride (294)
IUC Name
Common Names
Structural Formula
Ni Cl *
Molecular Wt. 129.62 C
i:
Melting Pt. 1001
,0)
Density (Condensed) 3.55g/cc^ '@ Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
@ 9
Boiling Pt. Sub 973 C
1mm
(2)
& 671
(2)
Flash Point Auto1gn1tion Temp._
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %} Lower
Upper_
Upper_
Solubility
Cold Water 64.2g/100cc @ 20
Hot Waters?.6g/100cc & 100 C^Ethanol Sol
Others:
NH4OH
Acid, Base Properties ag soln is acid pH4
Highly Reactive with_
Compatible w1th_
Shipped in_
ICC Classification
Coast Guard Classification
Comments Not considered a systemic poison, can cause nickel itch in plating areas
* Commercial product normally hyHratpH ;
(2)
References (1)
(2)
1570
0766
152
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PROFILE REPORTS ON THE
ANTIMONY, ARSENIC, AND SELENIUM COMPOUNDS OF NICKEL
Nickel Antimonide (291). Nickel Arsenide (292). and Nickel Selem'de (297)
1. GENERAL
Nickel antimonide, nickel arsenide and nickel selenide are laboratory
curiosities used in gram quantities for research and development. It is
believed that the major research and development activities employing the
2135
arsenide and selenide is in semiconductors. The laboratory activities
using the antimonide are not known. Sources at Rocky Mountain Research
indicated that they are the sole manufacturers of these materials in the
United States and they knew of no imports. They estimate that the national
demand for these compounds is no more than 5 to 10 Ib per year for each
material. The actual details of manufacture for these compounds were not
available, but it is believed that the method is either to: 1) roast the
nickel in antimony, arsenic or selenium vapor, or; 2) combine the elements
2133
in a sintering process. Their very small production and value would
indicate, that in all likelihood, no significant amounts of the material
are being lost to the environment as waste products. In addition, no
evidence of any of these compounds being produced as a waste product from
other unrelated processes was found.
Nickel arsenide, even though it is commercially produced in high purity,
also occurs naturally as niccolite, the least of the three principal nickel
ores; the others being the nickel sulfides and nickel oxides. Niccolite is
said to have no current commercial importance as a nickel bearing ore.
Niccolite ores are not processed in the United States and any study on
NiAs wastes from foreign processing is outside the scope of this study.
2. TOXICOLOGY
The antimony, arsenic, and selenium constituents of the subject
materials are the principal source behind the hazardous nature of these
153
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compounds. Most arsenic compounds are poisons whereby the systemic effects
are normally caused by ingestion. As little as 0.1 grams can be fatal if
taken internally. Both nickel and arsenic can be responsible for a variety
of skin abnormalities on contact. Acute poisoning symptoms from ingesting
arsenic compounds may include difficulty in swallowing, severe abdominal
pain resulting from corrosion of the stomach lining, vomiting, with pain
in the limbs and muscle cramps. A cold damp skin, a rapid and Weak pulse,
shock, unconsciousness and convulsions are the indicators of impending
death. The symptoms caused by chronic low level arsenic exposure are
difficult to diagnose due to the wide variety of unpredictable symptoms
which may arise.
Selenium compounds with nickel are considered as moderate toxicological
hazards that when taken orally can cause both irreversible and reversible
changes that are not severe enough to cause death or permanent injury.
Selenium compounds have low systemic toxicity but in dust form, they can
be dangerous respiratory tract irritants as are most nickel compounds. All
three compounds, when inhaled, can cause death or permanent injury even
after very short exposure to small quantities. The recommended Threshold*
Limit Value (TLV) of 0.2 milligrams per cubic meter of air represents
the maximum concentration to which personnel should be exposed in an 8-hr
period. Nickel has been identified with respiratory carcinogenesis, but
that is subject to debate since the cited cases involved other materials
... . , , . 0633
with nickel compounds.
Antimony compounds are also highly toxic when ingested or inhaled.
Small amounts can cause permanent injury or death. The recommended TLV is
0.5 mg per cubic meter of air. Information on the toxicity of these
compounds towards other animals and plant life was not found.
3. OTHER HAZARDS
Nickel arsenide and nickel selenide both exhibit moderate to serious
fire, explosion, and disaster hazards as a result of being heated or exposed
to water, steam or acids. These reactions will emit the highly flammable
154
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arsines and hydrogen selenides which, if present in the right proportions
with air, could explode if ignited. Stibine (H2Sb), arsine (HJ\s), and
hydrogen selenide (H^Se) vapors are all extremely toxic and represent a
serious disaster hazard if released in areas where they might be inhaled
by humans or animals. Nickel antimonide and the potentially evolved
hydrides of all compounds react violently with oxidizing agents.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
The toxicological and flammable hazards of these materials require
careful handling when they occur as waste products in a concentrated form.
They should be stored in containers in which they are compatible, i.e.
screwtop glass bottles or ampules. They should be stored in cool areas
with no prevalent acid mists. The use of protective clothing, eyewear
and dust filtering respiratory equipment are recommended for handling these
materials outside fume hoods. Spills of the solid materials should be
cleaned up using a vacuum cleaner with a disposal paper dust bag. No
Department of Transportation (DOT) regulations are prescribed by Sax, but
common sense recommends careful labeling on both the bottle and shipping
container.
Disposal/Reuse
The disposal of the antimonides, arsenides and selenides of nickel
into the air, water or soil must be carefully regulated from the standpoint
of the toxic nature of antimony, arsenic, selenium, and the somewhat less
toxic but still significant hazard of nickel. The U.S. Public Health Service
has established 0.05 mg/1 arsenic content as grounds for rejecting a drinking
1752
water supply. The ideal maximum is 0.01 mg/1. The Public Health
Service in its publication on drinking water standards recommended that
the limits for selenium be lowered from the present value of 0.05 mg/1
to 0.01 mg/1 and concentrations in excess of this lower value be used as
1750
grounds for rejection of the water supply. The acceptable criteria
for the release of these compounds into the environment are defined in
155
-------
terms of the following provisional limits:
Basis for
Contaminant in Air Provisional Limit Recommendation
Nickel Antimonide 0.005 mg/M3 as Sb 0.01 TLV for Sb
Nickel Arsenide 0.005 mg/M3 as As 0.01 TLV for As
Nickel Selenide 0.002 mg/M3 as Se 0.01 TLV for Se
Contaminant in Water Basis for
and Soil Provisional Limit Recommendation
Nickel Antimonide °-05 PPm Ong/1) as Sb Chronic Toxicity
Drinking Water
Studies
Nickel Arsenide 0.01 ppm (mg/1) as As Proposed Drinking
Water Standard
Nickel Selenide 0.01 ppm (mg/1) as Se Drinking Water
Standard
All three compounds are expensive (estimated prices for ten grams
each of the antimonide, arsenide, and selenide being $40, $33 and $9
respectively), and in light of this, it would appear that reasonable
attempts would be made to prevent indiscriminate wasting of the compound.
Small amounts of these materials, if occurring as wastes in a concentrated
form, should be packaged and returned to the supplier or manufacturer for
reprocessing, purification, or ultimate disposal. Considering the low
levels of use for these compounds (5 Ib per year), it is not expected
that these materials would occur as wastes in any significant amounts.
Shipping waste concentrates back to the manufacturer is the cheapest and
safest way of handling them. Rocky Mountain Research, currently the only
apparent manufacturer of these materials, expressed its willingness to
accept returned waste concentrates.
156
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Return to Vendor or Manufactuer
The amounts of concentrated waste nickel antimonide, arsenide, or
selenide which could arise are expected to be very small. For this reason,
careful packaging and shipment back to the vendor or manufacturer by prior
arrangement is an easy and safe means of disposal. The manufacturer can
either reprocess the material, if economically feasible, or could dispose
of it in his own facilities. Return to the manufacturer or vendor should
be considered before any other disposal option is considered.
Option No. 2 - Encapsulation and Landfill
Some landfills are chartered to accept these compounds for ultimate
encapsulation and landfill. They would most likely be combined with other
compliant materials in a steel drum, and the steel drum would be given
a concrete collar before burial. Landfill ing is adequate in California
Class 1 type facilities.
Option No. 3 - Laboratory Decomposition to Reduce Hazard
The subject materials can be roasted in air or oxygen to produce the
condensable poisonous oxides of antimony, arsenic, selenium, and non-
volatile nickel oxide. The fire hazards are lower with these products, ,
but there remains the problem of disposing the toxic products. This
option offers no real advantage over Option 1 or 2.
6. APPLICABILITY OF NATIONAL DISPOSAL SITES
No recommendation is made for any equipment or waste treating
processes to treat waste nickel antimonide, nickel arsenide, or nickel
selenide at a National Disposal Site. It is estimated that the annual
157
-------
production of these materials, as wastes, does not exceed 10 pounds,
Furthermore, they are rather expensive compounds and it is doubtful
that they would be wasted.
158
-------
7. REFERENCES
0300. Rich, E. The production of nickel. Chemistry and Industry, No. 47,
1856-1862, Nov. 23, 1963.
0356. Mastromatteo, M. Nickel: a review of its occupational health aspects.
Journal of Occupational Medicine. 9(3):127-136, Mar. 1967.
0615. Schroeder, H.A. Metals in the air. Environment, 13(8):18-24,
Oct. 1971.
0633. Sullivan, R.J. Comp. Air pollution aspects of nickel and its compounds,
Report prepared for the National Air Pollution Control Administration
by Litton Systems, Inc. Bethesda, Maryland under Contract No. PH-22-
68-24. Washington, U.S. Government Printing Office, 1969. 69 p.
0766. Sax, N.I. Dangerous properties of industrial materials.3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1570. Weast, R.C. ed Handbook of Chemistry and Physics. 48th ed.
Cleveland, The Chemical Rubber Co., 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. 61 p.
2133. Mellar, J.W. A comprehensive treatise on inorganic and theoretical
chemistry, v. 10. New York, John Wiley and Sons, Inc., 1930. 958 p.
2135. Personal communication. G. Thompson, Rocky Mountain Research, Inc.,
to J. F. Clausen, TRW Systems Group, July 10, 1972.
2140. Personal communication. .6. Thomspon, Rocky Mountain Research, Inc.,
to J. F. Clausen, TRW Systems, July 10, 1972.
159
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nickel antimonide (291)
IUC Name
Common Names Breithauptite '
Structural Formula
NiSb
(1)
Molecular Wt.
180.6
^
Melting Pt. 1158
Density (Condensed) 7.sa(1) @
Density (gas)
Boiling Pt. dl400
@
Vapor Pressure (recommended 55 C and 20 C)
G»
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water_
Others:
Hot Water
reacts
Ethanol.
Acid, Base Properties
Highly Reactive with steam to form stibine^. Can aUn
agents. *-2' __
violentl with oxidizin
Compatible with
Shipped in
ICC Classification
Coast Guard Classification
Comments slight explosive hazard when exposed to flame, can evolve stibine
antimony vapors when heated to decomp temp.
^' re1eases
References (1) 1570
(2) 0766
160
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Nickel Arsenide (292)
IUC Name
Structural Formula
Common Names Niccolite
(2)
NiAs
Molecular Wt.
133.60
(2)
Melting Pt. 966 C
Density (Condensed) 7.57 q/cc & 0 C Density (gas)
Vapor Pressure (recommended 55 C and 20 Q)
.@ 6>
,(2)
Boiling Pt.
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water insoluble
Others:
Hot Water reacts with steam Ethanol
acids (reaction)
Acid, Base Properties
Highly Reactive with hot water, steam and acids to produce toxic and flammable vapors of
arsenic hydrides
Compatible with
Shipped in glass bottles
ICC Classification
Coast Guard Classification
Comments Highly toxic, moderate chem. reaction to form arslne. a fire and explosion hazard.
References (1) 1570
(2) 0766
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nickel Selenide (297)
Structural Formula
IUC Name
Common Names
Molecular Wt. 137.67^ Melting Pt. Red heat^ Boiling Pt._
Density (Condensed) 8.46 @ Density (gas) & '
Vapor Pressure (recommended 55 C and 20 C)
Flash Point . Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %} Lower Upper_
Solubility'
Cold Water insoluble Hot Water reacts Ethanol_
Others: soluble in acids; reaction
Acid, Base Properties__
Highly Reactive with water steam and acids to produce toxic and flammable vapors of hydrogen
selenide •
Compatible with glass
Shipped in glass bottles
ICC Classification Coast Guard Classification
Comment'; Fire hazard: evolves hydrogen selenide, a toxic gas.
References (1) 1570
(2) 0766
162
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PROFILE REPORT
Phosphorus, White or Yellow (332)
1. GENERAL
Introduction
Elemental phosphorus has four allotropic forms, all tetra-atomic at
room temperature. This Profile Report covers only the white allotrope,
which is the most hazardous common form of the four, because it is highly
poisonous and extremely inflammable.
White phosphorus turns yellow upon heating. It is a wax-like substance,
of low melting point, very low heat of fusion, and high volatility. White
phosphorus smolders and ignites spontaneously in dry air, and is usually
kept under water from which all of the oxygen has been expelled by boiling.
The material glows in the dark, with a yellow light.
White phosphorus is manufactured by condensing the phosphorus vapor
obtained by electrothermal (electric furnace) reduction of phosphate rock
with coke. The raw materials for the process are phosphate rock, coke,
and silica. In 1968, over 650,000 tons of phosphorus were produced in
electric furnaces in the United States by the following reaction:
3Ca3(P04)2-C'aF2 + 9Si02 + 15 C I5UUC * 1-1/2 P4+ + 9(CaO'Si02) + 15COT
The phosphorus produced is employed almost completely as an
intermediate product. The largest single use is the manufacture of
furnace H3PO». The condensed elemental phosphorus is burned in air to
produce phosphorus oxide vapor, which is reacted with water to yield
phosphoric acid.
163
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Physical and Chemical Properties •
The physical and chemical properties of white phosphorus are
summarized on the attached worksheet.
2. TOXICOLOGY
Elemental white or yellow phosphorus and phosphine (PH^) are the only
inorganic phosphorus compounds with recognized systemic toxicity. Skin
contact with white phosphorus produces painful, slow-healing, second and
third degree burns, due to both chemical and thermal damage. White
phosphorus is a general protoplasmic poison when introduced via either
inhalation or ingestion. Its toxicity is enhanced when the material is
dissolved in solvents such as alcohol, fats or oils, or when the material
is finely divided.
The acute fatal dose of white P-, for an adult is between 50 and 100 mg,
poyc
although recovery has occurred after 1.5 gm. Fatality rates are about
50 percent. Acute poisoning occurs typically in three stages. The first
stage produces symptoms due to local irritation. The effects are not
immediate, except for thermal burns due to contact with the body surface.
Nausea, vomiting, diarrhea, and severe abdominal pain occur. If the
quantity inhaled or ingested is very large, shock is severe and death may
2028
occur from cardiac collapse in the first 24 to 48 hours. The second
stage is frequently symptom free, and may last from 8 hours to several
weeks, with apparent recovery during this period. The third stage,
involving symptoms of systemic toxicity due to the action of elemental
phosphorus as a general protoplasmic poison, is normally terminated by
death in 4 to 8 days, but may last as long as three weeks before death
occurs. Symptoms include nausea, vomiting, diarrhea, massive hematemesis,
hemorrhages into the skin, mucous membranes and viscera, liver damage
including hepatic failure, cardiovascular collapse, and central nervous
system involvement. If the victim survives, cerebral symptoms may continue
for a protracted period.
164
-------
Chronic poisoning, due to ingestion or inhalation of sub-lethal
dosages produces cachexia, anemia, bronchitis, general debility and
.necrosis of the mandible-known as "phossy jaw".
The Threshold Limit Value (TLV) for white phosphorus is 0.1 mg per
cubic meter. The provisional limits recommended for air and water are
0.001 mg per cubic meter and 0.005 mg per liter respectively.
3. OTHER HAZARDS
Phosphorus is not explosive nor is the smoke generated from its
combustion. It does ignite spontaneously upon contact with air or oxygen
and gives off great clouds of white smoke during combustion. Phosphorus
melts at 44.1 C and when thoroughly melted, it becomes a liquid which flows
and spreads even more readily than light penetrating oils or gasoline. In
this form it combines readily with oxygen and burns rapidly in air. Fires
1881
can be controlled by covering with water, sand or earth to exclude air.
The P^-JQ fumes produced by burning phosphorus are extremely irritating,
and react with any source of water to form corrosive phosphoric acid. If
combustion occurs within a confined space, asphyxiation may occur due to
consumption of oxygen by the burning phosphorus.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
In the manufacture of phosphorus by the electric furnace method
"phossy water" containing suspended phosphorus and ferrophosphorus ore
formed as waste and by-products. In handling phosphorus under water, small
bits of phosphorus break off the edges of phosphorus lumps and "phossy
water" is formed. The other waste stream from phosphorus production is
the ferrophosphorus obtained as a by-product due to the iron content of the
phosphate ores. The phosphorus content of ferrophosphorus is about 23 to
25 percent.
165
-------
Phosphorus, white or yellow, is classified by the U. S. Department of
Transportation (DOT) as an inflammable solid with a yellow label. It is
shipped either under water or dry, by rail, water or highway. Dry phos-
phorus may not be shipped by rail-express, but dry shipment is rarely, if
1881
ever, used.
The Manufacturing Chemists' Association in Chemical Safety Data Sheet
SD-16 summarizes the information required for white phosphorus plant design,
1881
handling, storage and shipping. Personnel handling phosphorus wastes
should wear the prescribed protective clothing.
Many rat poisons and other vermin poisons contain as much as 1 to 4
percent white phosphorus, combined with such diluents as oil, flour, sugar,
2028
and coloring matter. These economic poisons remain a major source of
phosphorus poisoning in humans.
Phosphorus should not be released to the environment at levels higher
than those noted below. Abatement processes should convert recovered
phosphorus to phosphoric acid.
The safe disposal of white or yellow phosphorus is defined in terms
of the recommended provisional limits in the atmosphere and in water and
soil environments. These recommended provisional limits are as follows:
Contaminant in
Air
White or Yellow
Phosphorus
Contaminant in
Water and Soil
White or Yellow
Phosphorus
Provisional Limit Basis for Recommendation
0.001 mg/Mv
0.01 TLV
Provisional Limit Basis for Recommendation
0.005 ppm
Stokinger and Woodward
Method
166
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The current disposal technique most frequently employed for "phossy
water" is to lagoon the material in a pond within the boundaries of the
electrothermal phosphorus plant. The phosphorus particles settle to the
bottom of the basin, and are slowly oxidized by the oxygen dissolved in
the water to hypophosphorous, phosphorous and phosphoric acids, which enter
the water table. This method of disposal is not acceptable.
Ferrophosphorus is generally used as an alloying constituent in the
manufacture of certain steels. The material is also subjected to
destructive distillation at 1400 to 1500 C, and the phosphorus vapors
produced are condensed under water. ' The white phosphorus thus
produced is used for the same purposes as normal electric furnace
phosphorus. Both of these techniques are acceptable processes for
disposal via recycle and reuse.
The options listed below are those recommended for the disposal of
phossy water, rat and other vermin poisons based on white phosphorus,
and contaminated bulk white phosphorus.
Option No. 1 - Oxidation of Suspended
Particles in Water, "Phossy Water"
Phosphorus in "phossy water" is oxidized by spraying into an incinerator
equipped with an alkaline scrubber or it is oxidized by blowing through a
1881
flame followed by an alkaline scrubber.
Option No. 2 - Open Burning
Rat and verriin poisons and other solid or pasty residues containing
phosphorus should be burned in an isolated location, the residue neutralized
and diluted with water to a phosphate concentration less than 50 mg per'
liter.0095
167
-------
21485-6013-RU-UO
Option No. 3 - Conversion to Phosphoric Acid
Contaminated phosphorus should be purified by distillation in an
inert gas stream at temperatures over 280 C. The phosphorus vapor
produced should be condensed under water, and recycled for sale to the
furnace phosphoric acid industry. Alternatively, the contaminated
phosphorus can be charged to the electric furnace used for phosphorus
production.
Option No. 4 - Controlled Incineration-Municipal Incinerators
Rat and vermin poisons which contain white phosphorus and other small
lots of wet phosphorus wastes, if properly segregated to permit safe
handling, can be burned in municipal incinerators equipped with automatic
conveying equipment and scrubbing and mist removal devices. The fly ash
produced in such incinerators will generally neutralize the H3PO» made.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that small quantities of white phosphorus
contaminated wastes can be treated adequately by municipal incinerators
as per Option No. 4 if transported sealed or under water. If large
quantities of phosphorus wastes must be treated, the wastes should be
shipped in air tight containers to the nearest manufacturing plant capable
of recovering phosphorus via Option No. 3. It is, therefore, not
recommended that provision be made at National Disposal Sites for the
disposal of phosphorus.
168
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7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40. Aug., 1971.
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.
0955. Sittig, M. Inorganic chemical and metallurgical process encyclopedia.
Park Ridge, New Jersey, Noyes Development Corporation, 1968. 833 p.
1416. Ross, A., and E. Ross. The condensed chemical dictionary. 6th ed.
Ross and Ross, 1961.
1662. Shreve, R. N. Chemical process industries. 2d ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
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. TRW Systems Group, Jan. 1972. 560 p.
1881. Manufacturing Chemists' Association. Properties and essential
information for safe handling and use of phosphorus, elemental.
Washington, D. C., Safety Data Sheet SD-16, 1947. 13 p.
2028. Gonzales, T. A., M. Vance, M. Helpern, and C. J. Umberger. Legal
medicine pathology and toxicology. 2d ed. New York, Appleton-
Aubury-Crofts Inc. 1,349 p.
2376. Gleason, M. N., R. E. Gosselin, H. C. Hodge, and R. P. Smith.
Clinical toxicology of commercial products. 3d ed. Baltimore,
The Williams & Wilkins Company, 1969.
169
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Phosphorus, white or yellow (332i
v ' Structural Formula
IUC Name phosphorus, white
Common Names
P
4
Molecular Wt. 124.08 Melting Pt. 44.1 C(}' Boiling Pt. .280
Density (Condensed) 1.82g/cc @ 20 C/1* Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
0 9 &
Flash Point Autoignltion Temp. 30 C
FlammablHty Limits in Air (wt %) Lower Upper_
Explosive Limits in A1r (wt. X) Lower Upper_
Solubility
Cold Waterinsoluble^ Hot Water Ethanol
Others: soluble - carbon disulfide^
Add, Base Properties
Highly Reactive with oxidizing substances, air"
Compatible w1th_
Shipped in sealed container*
ICC Classification Flammable solid' ^ Coast Guard Classification Flammable
Comments -
References (1) 1416
170
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PROFILE REPORTS ON
HALOGENATED PHOSPHORUS COMPOUNDS
PHOSPHORUS CHLORIDES
Phosphorus Oxychlorlde (333), Phosphorus Pentachloride (334)
Phosphorus Trichloride (336)
1 . GENERAL
Introduction
Phosphorus halides were discovered and investigated by Gay Lussac and
i 1 g2fl
Thenard in France at the beginning of the 19th century. The best
known and most studied compounds are the tri halides, pentahalides and
oxyhalides. The phosphorus halides of commercial importance today are
phosphorus trichloride, PCU; phosphorus pentachloride, PCU; and phosphorus
1433
oxychloride, POCl-j. All are used extensively in manufacturing organic
phosphorus compounds and in chlorinating organic compounds to give acid
chlorides. ^3»15<::o Demand for the phosphorus chlorides has been steady
over the past five years with phosphorus trichloride fluctuating between
50,000 to 55,000 tons per year and phosphorus oxychloride varying from
31,000 to 35,000 tons per year.1751 '2202 Production figures for phosphorus
pentachloride are unavailable. The major U.S. producer is Hooker Chemical
2201
Company, Industrial Chemicals Division in Niagara Falls, New York.
Future market importance and production will be affected by possible
regulations on chlorinated pesticides and gasoline additives which con-
22Q2
stitute another major outlet for the phosphorus chlorides.
Manufacture
Phosphorus Trichloride: Phosphorus trichloride is manufactured by a
direct union of liquid red or white phosphorus and gaseous chlorine
according to the reaction:
2P + 3C12
171
-------
Gaseous chlorine is blown into a reactor containing the liquid phosphorus
and a precharge of phosphorus trichloride. The highly exothermic reaction
is controlled by either refluxing cooled phosphorus trichloride or by adding
carbon disulfide as an inhibitor. Crude phosphorus trichloride is then
fractionally distilled to remove traces of oxychloride and organic chloride
i con
compounds. t •«*<>•>»£ uu ^^ reaction vessels are closed to the atmosphere
and vents are equipped with refrigerated condensers to eliminate any discharge
of trichloride vapors. The final vapor stream is water scrubbed to remove
221 6
any final traces of trichloride. Pi
was approximately 50,000 tons per year.
2216
any final traces of trichloride. Production over the last five years
Phosphorus Pentachloride: Phosphorus pentachloride is manufactured either
batchwise or continuously by contacting phosphorus trichloride with gaseous
chlorine according to the following reaction:
PC13 + C12 ^PC15
In the batch reaction phosphorus trichloride is first dissolved in carbon
tetrachloride. Chlorine is then blown over the surface of the solution
causing phosphorus pentachloride crystals to form. The crystals are removed,
filtered, dried (carbon tetrachloride strips off and is returned to the reaction
vessel in this step) and sent to storage. The continuous reaction process
produces phosphorus pentachloride by passing chlorine gas countercurrent to
the phosphorus trichloride and collecting the resultant crystals at the
bottom of the reaction tower. ' Yearly United States production
figures are not available in the literature and could not be ascertained
during our investigation. The major producer of the pentachloride is
Hooker Chemical Company in Niagara Falls, New York. Other previous
manufacturers who have not continued their production are Monsanto Company
2202
and FMC Incorporated.
172
-------
Phosphorus Oxychloride: Phosphorus oxychloride (also called phosphoryl
chloride) is most commonly manufactured by oxidizing phosphorus trichloride
.with pure oxygen or air.
Oxygen bubbled through liquid phosphorus trichloride at 20 to 50 C will
result in a 95 to 97 percent complete reaction, so that only 3 to 5 percent
trichloride remains in the oxychloride. Another well-known method of
phosphorus oxychloride manufacture consists of a reaction between phosphorus
pentachloride and phosphorus pentoxide:
P4°10 + 6PC15
The two solids are slowly heated and mixed until the liquid oxychloride is
n^oo I KOf]
formed. Pure oxychloride is distilled off, cooled and sent to storage. '
Yearly production in the United States has varied between 31,000 and 35,000
tons over the past five years with no great changes expected in the
future. 1606-2202
The bulk of the phosphorus chlorides are manufactured by four major
United States corporations:1506'2201'1411
Monsanto Industrial Chemicals Company; Sauget, Illinois
FMC Incorporated, Organic Chemicals Division;
Nitro, West Virginia
Hooker Chemical Co.; Industrial Chemicals Division
Niagara Falls, New York
Stauffer Chemical Co.; Specialty Chemicals Division
Morrisville, Pennsylvania
173
-------
Uses
All of the phosphorus chlorides are used in the manufacture of
organic-phosphorus compounds. Phosphorus trichloride is used primarily
as a chlorinating agent in the manufacture of organic acid chlorides.
When reacted with alcohols or phenols a phosphite or phosphate ester is
produced. Certain end use products are dyestuffs, organic antioxidants,
vinyl stabilizers and plasticizers. Phosphorus pentachloride is similarly
used as a chlorinating agent and catalyst in organic synthesis. The
pentachloride is essentially a more reactive chlorinating agent than the
trichloride. It recently has found additional uses as a catalyst in lubricant
additive production and insecticide manufacture. Phosphorus oxychloride is
one of the phosphorus-containing intermediates that may become of greater
importance with an expanding plastics industry. The major portion of
oxychloride produced is presently used in organic synthesis; chiefly in
manufacturing phosphate esters (tricresyl phosphate, a common plasticizer).
The second most important use for oxychloride is in production of cresyl
*l /) O O
diphenyl phosphate and triisopropyl phosphite, gasoline additives. I4JJ»
1620,2200,1411,0636,1501
More recent uses include the organic phosphorus insecticides, parathion
and methyl parathion. Other less known but increasing uses include fire
resistant hydraulic fluids and flame retardants.1433'2206
Sources and Types of Waste
The main source of phosphorus trichloride, pentachloride and oxychloride
waste is the material remaining in shipping containers after emptying. That
is, the thin film left in drums and the "heel" left in tank cars and tank
trucks. There are essentially no production wastes generated since all
production equipment is either closed loop or equipped with refrigerated
condensers to eliminate chemical emissions to the atmosphere. Storage
tanks are nitrogen blanketed, pumps utilizing mechanical seals and drums are
purged of air before sealing.
174
-------
There are no aqueous dilute wastes. Since all three compounds rapidly
decompose upon contact with water, the only source of aqueous pollution
is the decomposition products, namely, hydrochloric and phosphoric acids.
The concentrated wastes, however, include the unused or contaminated materials
left in emptied containers and any "off-spec" production material.
Physical/Chemical Properties •
Phosphrous trichloride is a fuming liquid that boils at 76 C, phosphorus
pentachloride is a solid that sublimes at 148 C, while the oxychloride is a
fuming liquid that boils at 107 C. Each has a specific gravity of approximately
1.6 (water = 1.0). They react violently (highly exothermic) when contacted
with moisture and usually produce hydrogen chloride gas, steam, phosphoric
acid and hydrochloric acid. Detailed physical and chemical properties of
all three chlorinated phosphorous compounds can be found on the attached
worksheets.
2. TOXICOLOGY
Phosphorus trichloride and phosphorus pentachloride are similar in
toxicity in that a small amount in the atmosphere will cause prompt irritation
of the eyes, nose, throat and lungs (all mucous membrane). Suffocation,
bronchitis, edema and lung inflammation may all result from extended exposures.
Severe exposure in a concentration of 600 ppm is lethal within a few minutes.
The vapors are also irritating to the skin, while the liquid (or solid)
1RQ7 ??nR p?flfi
can cause severe skin burns immediately upon contact. ' ' The
American Conference of Governmental Industrial Hygienists 1971 recommends
Threshold Limit Values (TLV) for phosphorus trichloride in air at 0.5 ppm
^ ^ 02?*! Dfi3fi
or 3 mg/m ; and for phosphorus pentachloride in air at 1 mg/m . '
Phosphorus oxycloride causes similar effects to the trichloride and
pentachloride in that its vapors are very irritating to all mucous membranes
and to the lungs. The liquid itself can cause severe burns of the skin.
Inhalation symptoms range from coughing to delayed wheezing due to bronchial
2206 2207
irritation or pulmonary edema. '
175
-------
There is no aquatic toxicity possible from the three pure chlorinated
phosphorus compounds. All readily decompose upon contact with water into
hydrochloric acid and phosphoric acid. The level above which fish are
affected by aqueous phosphoric acid is 0.1-10 ppm. The level above which
aqueous hydrochloric acid will affect fish is 1.0 ppm.
3. OTHER HAZARDS
Phosphorus trichloride and phosphorus pentachloride by themselves are
neither flammable nor explosive. However, each reacts violently with small
amounts of water liberating heat, spontaneously flammable phosphine gas,
hydrogen chloride, phosphorus acid and even free spontaneously flammable
phosphorus. They will also react violently with slight moisture, oxidizing
agents, fibrous organic matter and alkalies. The hydrochloric and
phosphoric acids generated on reaction with water can attack most metals to
18Q7 ??0'
form hydrogen gas which is both highly flammable and explosive. o:">"u
Phosphorus oxychloride can be classified along with the other chlorinated
phsophorus compounds in that it is neither flammable nor explosive. It is,
however, much more corrosive in its pure state than either phosphorus
trichloride or phosphorus pentachloride. Phosphorous oxychloride reacts
violently with water giving off hydrogen chloride gas and steam. One gallon
of water added to an excess of Phosphorus oxychloride will liberate in excess
1433
of 100 cu ft of hydrogen chloride. The reaction products, hydrochloric
and phosphoric acids, can react with metals to form highly flammable hydrogen
gas. Oxychloride has also displayed violent reactions with alkalies and
2206
fibrous organic matter.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
Phosphorus trichloride, phosphorus pentachloride and phosphorus
oxychloride are all toxic by inhalation or skin contact. It is extremely
irritating to mucous membranes and the lungs. Body moisture is sufficient
to decompose them into acids which will cause severe acid burns. Full
176
-------
protective clothing, including gas-tight safety goggles, face shields,
rubber shoes, rubber gloves and rubber apron,are required in their handling.
In cases of accidental contact all contaminated clothing should be removed
at once and exposed skin washed thoroughly with large quantities of water.
To avoid vapor inhalation an acid-gas canister type respirator is
recommended. In the event of severe exposure by inhalation,pure oxygen
should be administered for at least 30 minutes.1897'2205'2206'2207'2208
Phosphorus trichloride and oxychloride are loaded into drums, tank
cars and tank trucks at stations equipped with fume-scrubbing devices to
2203
prevent harmful vapors from reaching either the operator or the atmosphere.
Storage of small quantities of all three chemicals should be in cool,
dry,well ventilated areas. Although each has a relatively high boiling point
they are all very reactive with moisture in the atmosphere. Because of its
corrosive nature, lead-lined, ceramic-lined or nickel-lined steel drums should
be used and kept sealed from potential contact with any moisture. Large
quantities are usually stored in nickel- or lead-lined steel tanks and
blanketed with nitrogen. Since phosphorus pentachloride is a solid it may
be stored in ordinary steel carboys or steel drums; however, the drums must
be sealed tightly to avoid any contact of the pentachloride with moisture.
1897,2207
Phosphorus trichloride and phosphorus oxychloride are classified by
the U. S. Department of Transportation (DOT) as corrosive liquids. As such
they must be packaged and shipped in accordance with Title 49 of the Code of
Federal Regulations, Section 73.271. Phosphorus pentachloride is classified
by DOT as a flammable solid and must be packaged and shipped according to
A07O
Title 49 of the Code of Federal Regulations, Section 73.191.
Additional detailed information on the safe handling, storage and
shipping of phosphorus trichloride and phsophorus oxychloride may be obtained
by referring to Chemical Safety Data Sheets SD-27 and SD-26 published by the
Manufacturing Chemists Association.
177
-------
Disposal/Reuse
Contaminated lots of phosphorus trichloride, oxychloride and penta-
chloride are sold as contaminated or "off-spec" material. Manufacturers
generally recycle and repurify any material if found to be contaminated or
off-specification. The current method for disposing of small quantities
of the phosphorus chlorides is to douse with copious amounts of water.
Every manufacturer contacted utilizes water to dispose of small quantities
of waste material.2201'2203'2204'2216 Monsanto Industrial Chemical Division
in Sauget, Illinois disposes of larger quantities (a heel from a tank car)
in the following manner: They slowly add phosphoric acid to the material
and then very slowly neutralize the entire mass with a sodium carbonate
solution. The neutralized mass is then sewered to the waste treatment
plant. The only other method feasible for disposal of large quantities
is to react the phosphorus chloride slowly with copious amounts of water
and neutralize the resultant acids with caustic, limestone or other basic
material.
The safe disposal of these phosphorus compounds is defined in terms
of the recommended provisional limits:
Contaminant in
Air
Provisional Limit
Phosphorus oxychloride 0.07 mg/M as HC1
3
Phosphrous trichloride 0.03 mg/M
Phosphrous penta- 0.01 mg/M
chloride
Contaminant in
Water and Soil
Phosphorus oxychloride 0.35 ppm (mg/1)
Phosphorus trichloride 0.15 ppm (mg/1)
Provisional Limit
Phosphorus penta-
chloride
0.05 ppm (mg/1)
Basis for Recommendation
0.01 TLV for HC1
0.01 TLV
0.01 TLV
Basis for Recommendation
Stokinger and Woodward Method
Stokinger and Woodward Method
Stokinger and Woodward Method
178
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Generally, phosphorus trichloride, phosphorus pentachloride and
phosphorus oxychloride do not present serious pollution problems to the
chemical industry because of their low volatility, easy recovery and
simple decomposition as discussed below.
Removal From Air
Option No. 1 - Refrigerated Condensation. When present in sufficiently
high concentrations, phosphorus trichloride and phosphorus oxychloride
has been removed from vapor streams by refrigerated condensation. FMC
Incorporated employs such a system in its Nitro, West Virginia production
facility to control phosphorus trichloride and oxychloride emissions from
its reaction equipment. The bulk of vapor is condensed and collected
and trace material is removed by a final water scrubbing system.
Option No. 2 - Decomposition With Water. Most vapor streams resulting
from loading operations are decomposed by a reaction of the particular phosphorus
chloride compound with large volumes of water. Since phosphorus trichloride,
phosphorus oxychloride,and phosphorus pentachloride rapidly decompose to
hydrochloric and phosphoric acids upon contact with water.it is the cheapest
most efficient method utilized. The resultant dilute acid stream is easily
neutralized with caustic, soda ash, or limestone and sent to the plant sewage
wastewater stream.2201'2204'2216
Removal From Water
All three chemicals, the trichloride, the pentachloride and the oxychloride
of phosphorus readily decompose into phosphoric and hydrochloric acids upon
contact with water. Consequently they do not present a water pollution
hazard in their pure state. Standard neutralization techniques and dilution
of the resultant stream is the simplest and cheapest technique. The
danger is thereby limited to the increase of phosphate concentration leading
to a possibly increased rate of eutrophication. See the Profile Report on
Sodium Orthophosphates (401). .
179
-------
Disposal/Recovery of Concentrated Wastes
The major manufacturers of phosphorus pentachloride and phosphorus
oxychloride admit that they have never had the problem of disposing of
??m ??Dd ?216
large quantities of concentrated waste material. '' The
major sources of concentrated wastes are spills in loading, material left
in emptied containers and "heels" left in tank cars or tank trucks.
Option No. 1 - Recycle. Waste material is easily recycled to the
plant production system. Drums, tank cars and tank trucks can be drained
or vacuumed to holding tanks, returned to the production process and
purified. FMC Inc., Monsanto and Hooker Chemical Co. said all material
returned to them is handled in this manner.2201'2204'2215
Option No. 2 - Decomposition. All three phosphorus compounds decompose
readily in water. Therefore, flushing with water is an extremely effective
and economical method of disposal. Under controlled conditions, utilizing
large amounts of water, phosphorus trichloride, pentachloride and oxychloride
are reacted to phosphoric and hydrochloric acids which are easily neutralized.
Option No. 3 - Chemical Degradation. Monsanto Industrial Chemicals Co.
in Sauget, Illinois occasionally uses a degradation technique to scrap
phosphorus trichloride and phosphorus oxychloride. The plant practice is to
slowly add phosphoric acid to the material and then very slowly neutralize
the mass with a sodium carbonate solution. The neutralized mass is then
sewered to the waste treatment plant. This proves to be an adequate disposal
technique for largerquantities of waste material.
6. APPLICABILITY TO NATIONAL DISPOSAL
It is anticipated that disposal systems to handle concentrated or dilute
phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride
waste material will not be required at National Disposal Sites. All waste
material generated is easily decomposed, neutralized or recycled at the
plant operation level.
ISO
-------
In the event large quantities must be disposed (e.g., tank car quantity)
several manufacturers said that they would recycle and reuse the "waste"
material. Even without recycling, decomposition with large volumes of water
would prove to be the most efficient method of disposal.
181
-------
7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists. Threshold
Limit Values for 1971. Occupational Hazards, Aug. 1971.
0278. Code of Federal Regulations. Title 49--Transportation, parts 71 to
90. (Revised as of January 1, 1967). Washington, U.S. Government
Printing Office, 1967. 794 p.
0636. Air Pollution aspects of phosphorus and its compounds. Technical
Report, Litton Systems Inc., Bethesda, Maryland. Sept. 1969. 86 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation. 1957. 1,467 p.
1411. Chemical Meek. 1972 Buyers Guide Issue Pt. 2. 109(17) :618
Oct. 27, 1971.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v.
New York, Interscience Publishers, 1966. 899 p.
1501. Faith, W. L., D. B. Keyers, and R. L. Clark. Industrial chemicals.
3d ed. New York, 1965. 852 p.
1506. Chemical profiles. Oil, Paint and Drug Reporter. New York, Schnell
Publishing Company Inc., 1969. 200 p.
1570. Weast, R. C. ed. Handbook of chemistry and physics. 51st ed.Cleveland,
The'Chemical Rubber Publishing Company, 1970. 1,500 p.
1620. Van Wazer, J. R. Phosphorus and its compounds. 2 v. New York,
Interscience Publishers Inc., 1958. 2,046 p.
1673. Perry, R. H., C. H. Chilton, and S. D. Kirkpatrick ed. Perry's
chemical engineers' handbook. 4th ed. New York, McGraw-Hill
Book Company, 1963.
1751. Chemical statistics handbook. 7th ed. Washington, Manufacturing
Chemists Association, 1971. 475 p.
1897. Chemical Safety Data Sheet SD-27—Properties and essential
information for safe handling and use of phosphorus trichloride.
Washington, Manufacturing Chemists Association, 1972. 19 p.
2200. Kent, J. A. ed. Reigels industrial chemistry. New York, Reinhold
Publishing Corporation, 1964. 963 p.
2201. Personal communication. J. Lemen, Hooker Chemical Company to
W. L. Niro, TRW Systems, July 25, 1972. Phosphorus trichloride,
phosphorus pentachloride, phosphorus oxychloride and phosphorus
pentasulfide waste treatment.
18Z
-------
7. REFERENCES (CONTINUED)
2202. Personal communication. J. Williams, Monsanto Company to W. L. Niro .
TRW Systems, July 24, 1972. Phosphorus trichloride, phosphorus
pentachloride, phosphorus oxychloride and phosphorus pentasulfide
waste treatment.
2203. Personal communication. J. Boehm, Monsanto Company to W. L. Niro
TRW Systems, July 25, 1972. Phosphorus trichloride and phosphorus
oxychloride waste disposal.
2204. Personal communication. P. Heisler, Monsanto Company to W. L. Niro,
TRW Systems, July 26, 1972. Phosphorus trichloride, phosphorus
oxychloride and phosphorus pentasulfide waste treatment.
2205. Material Safety Data Sheet No. 804-A, Phosphorus trichloride. Niagara
Falls, New York, Hooker Chemical Company, 1972. 2 p.
2206. Material Safety Data Sheet No. 799-A, Phosphorus oxychloride. Niagara
Falls, New York, Hooker Chemical Company, 1972. 2 p.
2207. Chemical Safety Data Sheet SD-26--Properties and essential information
for handling and use of phosphorus oxychloride. Washington,
Manufacturing Chemists Association, 1968. 17 p.
2208. Material Safety Data Sheet 800-A, Phosphorus pentachloride. Niagara
Falls, New York, Hooker Chemical Company, 1972. 2 p.
2216. Personal communication. L. Cavender, FMC Inc. to W. L. Niro, TRW
Systems, July 31, 1972. Phosphorus trichloride and phosphorus
oxychloride waste disposal.
183
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Phosphorus Oxychloride
Structural Formula
IUC Name
Common Names Phosphoryl Chloride
POC1
3
Molecular Wt. 153.35^ Melting Pt. 1.22 C^ Boiling Pt. 107.2
Density (Condensed) 1.675 (3 20 C/4 C Density (gas) 5.30 @ 0_C
(air = 1.0)
Vapor Pressure (recommended 55 C and 20 C)
40 mm Hg @ 27.3 C 100 mm Hg @ 47.4 C 400 mm Hg @ 8.43 C
Flash Point none Autoignition Temp, none
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower : Upper
Solubility (1)
Cold Water Decomposes Hot Water Decomposes Ethanol Decomposes
Others: Carbon tertrachloride
(2)
Acid, Base Properties Very corrosive to most common metals except nickel and lead
Highly Reactive with water, alkalies or fibrous organic matter.
Compatible with nickel and lead
Shipped in nickel lined tank cars and steel drums; 316 stainless steel tank _
ICC Classification Corrosive liquid Coast Guard Classification Corrosive liquid
Comments A clear, colorless fuming liquid that hydrolyzed into phosphoric and hydrochloric
acids. It volitizes quickly upon contact with water giving off hydrogen chloride gas.
Acids formed can react with metals to give off highly flammahlp hyrirogpn gas.
References (1) 2206, 1570
(2) 2207
(3) 2216
184
-------
. ( h
H. M. Name Phosphorus Pentachloride
IUC Name
Common Names same
Molecular Wt. 208.3
Density (Condensed) 1.6 @
AZARDOUS WASTES PROPERTIES
WORKSHEET
(334)
Structural Formula
PClr
under 0 ) /-.\
Melting Pt. 148 C pressure Sublimes at 160 rv
20 C/4 C Density (gas) 4.65 a/1 9 296 C
Vapor Pressure (recommended 55 C and 20 C)
(2)
1 mm Hg @ 55.5 C 10 mm Hq @ 83.2 C 100 mm Ha @ 117 C
Flash Point
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Solubility
Cold Water Decomposes
Others: Carbon tetrachloride,
Autoignition Temp.
Lower Upper
Lower Upper
Hot Water Ethanol
Carbon disulfide, Benzoyl chloride
Acid, Base Properties not corrosive per se--upon reaction with water hydrochloric and
phosphoric acids are created.
Highly Reactive with water (moisture) to form toxic and corrosive fumes—potentially
explosive if phosphine is formed.
Compatible with non-corrosive materials (e.g., nickel, 316 stainless steel, lead).
Shipped in plastic lined steel drums or carboys.
ICC Classification flammable solid
Coast Guard Classification inflammable solid
Comments Decomposes upon contact with water or heat into hydrogen chloride, phosphorus
oxides, phosphorus oxychlor.ides
vellow white crystalline <;uh<;ta
; flammable phosphine possible. PentarhlnHHp ic 9
nre ovtremely morp rpartivp than phosphorus trirhlnririp.
References (1) 1570, 2208
(2) 1673
(3) 0766
185
-------
H. M. Name Phosphorus Trichloride
IUC Name
Common Names Phosphorus Chloride
Molecular Wt. 137.35(1)
Density (Condensed) 1.575 @
HAZARDOUS WASTES PROPERTIES
WORKSHEET
(336)
Structural Formula
PCI
3
Melting Pt. -118.5 C^ Boiling Pt. 75.5 C^
20/4 C(1 Density (gas) 4.75 @ 0 C^)
(ref = water) (air = 1.0)
Vapor Pressure (recommended 55 C and 20 C)
400 mm HQ 9 56.9 C~(1) 100 mm Ha 9 ?i r.^1) 9
Flash Point Nonflammable'^
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Solubility (1)
Cold Water Decomposes
Autoignition Temp, none
Lower Upper
Lower Upper
Hot Water Decomposes Ethanol Soluble
Others: Chloroform, Ether, Benzene, Carbon Disulfide, Carbon Tetrachloride
Acid, Base Properties Corrosive to most metals except nickel and lead^2'
Highly Reactive with water and aqueous solutions, oxidizing agents, fibrous organic
matter, alkalies.
Compatible with nickel, lead, 316
stainless steel
Shipped in Carbon steel tank cars
. lead or nickel lined steel drums
ICC Classification Corrosive liquid Coast Guard Classification Corrosive liauid
CommpntQ Colorless fuming liauid
with ounaent. irHtaHnn nHnr resemblina that of
hydrochloric acid. Contact with water rWnmnncoc PCI., into hvdrnrhlnnV and
phospheric acid. (3)
J
References (1) 2205, 1570
(2) 1897
(3) 2?16
186
-------
PROFILE REPORT
Phosphorus Pentasulfide (335)
1. GENERAL
Phosphorus pentasulfide is one of only four phosphorus-sulfur compositions
which are definite chemical entities. It is the largest volume phosphorus
sulfide produced. Phosphorus pentasulfide (chemical name, tetraphosphorus
decasulfide) is referenced in the literature as P-S^, however, the yellow-green
1620 1433 2209
crystals manufactured in bulk quantity exist in the P^S,,, state. ''
Modern commercial preparation of phosphorus pentasulfide is carried out
by reacting white phosphorus and elemental sulfur continuously at about 350 C.
It is also made in commercial quantities by heating elemental sulfur with
red phosphorus in a batch process. When the molten phosphorus pentasulfide
is cooled properly it consists almost completely of crystalline PAS-JO-
The crystals are then purified by washing with carbon disulfide to remove
small percentages of phosphorus sesquisulfide and free sulfur. In 1971
approximately 70,000 tons of phosphorus pentasulfide was produced by these
three major manufacturers:
Monsanto Company: Industrial Chemicals.Unit,
Sauget, Illinois
Hooker Chemical Co.: Industrial Chemicals Division
Niagara Falls, New York
Stouffer Chemical Co. .-Specialty Chemicals Division
Morrisville, Pennsylvania
This represents almost a 100 percent increase in production since 1965 when
U.S. production was marked at 34,000 tons.
187
-------
The major impetus behind the growth of phosphorus pentasulfide has been
its continued demand in the expanding manufacture of organic phosphorus
compounds used as plasticizers and in insecticide production. A more recent
and expanding use is in the production of thio-phosphate esters used in
gasoline and oil additives.1433'1620'2200 The largest single-volume items
produced are the dithiophosphates used in the manufacture of parathion and
methyl parathion and oil additive zinc dithiophosphate. Extensive government
pollution control legislation could materially affect the use of parathion,
methyl parathion and zinc dithiophosphate which, in turn, would reduce the
production of phosphorus pentasulfide significantly.
Sources and Types of Wastes
The main sources of phosphorus pentasulfide waste may include: (1) the
manufacturer of the chemicals; (2) pesticide formulators; (3) oil additive
producers; (4) storage facilities and (5) shipping containers.
In generals the only wastes possible are the concentrated crystalline
pentasulfide material. Consequently, unused or contaminated materials left
in shipping containers or spillage constitute the major sources of concentrated
waste.
There are essentially no diluted wastes associated with phosphorus
pentasulfide due to its rapid decomposition upon contact with water. The
following equation typifies the reaction of phosphorus pentasulfide with water:
16H20—MH3P04 + 10H2S
Physical and Chemical Properties
Phosphorus pentasulfide is a gray to yellow-green solid with a specific
gravity of 2.03 (water = 1.0), a melting point of 296 C and a boiling point
of 513 C. It exists as a dry non-corrosive powder which is flammable.1620
2209 2217
' Detailed physical and chemical properties are contained in the
188
-------
attached worksheet.
2. TOXICOLOGY
Phosphorus pentasulfide is only a mild irritant in its pure solid state.
It can cause slight skin irritation upon contact and serious irritation to
the eyes and mucous membranes. Effects of inhalation or ingestion range
from minor irritation and coughing, to respiratory failure.0766'2217
The American Conference of Governmental Industrial Hygenists recommends a
Threshold Limit Value (TLV) of 1.0 mg/m of air.
The major hazard associated with phosphorus pentasulfide is a result of
the rapid decomposition of P^S-JQ upon contact with moisture into toxic and
flammable hydrogen sulfide and phosphoric acid.
P4S]0 + 16H20 MH3P04 + H2S
o
The ACGIH recommended TLV for H«S is 10 ppm or 15 mg/m . At high concentrations
it has a paralyzing effect of the olfactory nerves and therefore cannot be
detected by odor. Phosphorus pentasulfide is also extremely dangerous when
heated. The fumes emitted are phosphorus pentoxide which has a recommended
TLV of 0.1 mg/m3 of air
(TLV of 5 ppm for S02).
TLV of 0.1 mg/m of air, and oxides of sulfur which are also toxic
Water pollution hazards associated with pure phosphorus pentasulfide
are negligible because of its rapid decomposition.0766'2209*2217
3. OTHER HAZARDS
Phosphorus pentasulfide is ignitable by friction, by static, and by
struck sparks at room temperature. It will spontaneously ignite at
temperature near its melting point of 280 C. At low temperatures it burns
slowly unless it is dispersed in air where it burns rapidly. The dust of
189
-------
pentasulfide presents an explosion problem. In addition, flammable hydrogen
sulfide gas is liberated in the presence of moisture. Phosphorus pentasulfide
has also been known to react with acids and oxidizing agents to yield the
2209
same products as the reaction with water.
4. DEFINITION OF ADEQUATE WASTE 'MANAGEMENT
Handling, Storage and Transportation
Phosphorus pentasulfide must be handled with care to avoid the generation
of hydrogen sulfide vapors, the hazards of dust explosion and hazards of
spontaneous ignition. However, since phosphorus pentasulfide is not corrosive
it does not require any special materials of construction in its production.
It must, however, be stored in a cool, dry, non-combustible ventilated area
separated from other combustibles, acids or oxidizing materials. Equipment
must be grounded to avoid friction sparks. Inert nitrogen is recommended
2217
as the best protection against explosion, toxicity and hydrolysis dangers.
Personnel should have chemical safety goggles, rubber gloves and rubber shoes
to prevent contact with the skin. Also self-contained breathing apparatus
or externally supplied air masks should be located nearby in the event of
^S emission.
Phosphorus pentasulfide is not classified as a dangerous article by
the Department of Transportation for the purpose of transportation. The
usual shipping containers are fiber or steel drums and aluminum tote bins.
Most manufacturers and users who utilize tote bins design their equipment
so that the tote bin is filled, sealed, shipped and emptied without ever
being open to the atmosphere. This eliminates most of the hazards associated
2201
with the chemical.
190
-------
Disposal/Reuse
Contaminated or degraded phosphorus pentasulfide is usually not
considered for reprocessing, although manufacturers would normally accept
it for disposal. As mentioned in the previous section, manufacturers and
users minimize their waste material by using equipment which minimizes
contact with the atmosphere.
The safe disposal of phosphorus pentasulfide is defined in terms of
the recommended provisional limits:
Basis for
Contaminant and Environment Provisional Limit Recommendation
Phosphorus pentasulfide in 0.01 mg/M3 0.01 TLV
air
Phosphorus pentasulfide in 0.05 ppm (mg/1) Stokinger and
water and soil Woodward Method
Careful consideration must also be given to the decomposition product hydrogen
sulfide which has a recommended provisional limit of 0.15 mg/M in air.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Since phosphorus pentasulfide is a powdered solid with a very low vapor
pressure it does not present an air pollution problem. The only source of
waste is the solid scrap material accumulated from spills in manufacturing
or loading.
Option No. 1 - Decomposition with Water
Several manufacturers of phosphorus pentasulfide recommend dousing small
quantities of the chemical with copious amounts of water, while taking
2201 2204
precautions to keep hydrogen sulfide generation at a low level. '
Large volumes of water keep the decomposition temperature low .thereby reducing
the H2S emission rate. The aqueous decomposition product (phosphoric acid)
can then be treated by standard industrial wastewater treatment techniques
(e.g., neutralization).2201'2217
191
-------
Option No 2. - Burial
Phosphorus pentasulfide can be buried in a sanitary landfill disppsal
site. This essentially is a slow hydrolysis process which must be carefully
done to minimize the evolution of hazardous hydrogen sulfide. Very small
quantities may be adequately handled in this manner.2204'2209
Option No. 3 - Incineration
Phosphorus pentasulfide can be incinerated to yield phosphorus pentoxide
^P2°5^ an<* su^fur dioxide (SOp). Large quantities of waste material should
be disposed of by incineration only where the combustion equipment is capable
2217 2209
of removing the combustion products from the exhaust gas stream. '
Option No. 4 - Neutralization
Phosphorus pentasulfide rapidly decomposes upon contact with water into
phosphoric acid and gaseous hydrogen sulfide. Therefore, it does not present
a water pollution hazard in its pure chemical state. Standard neutralization
techniques and dilution of the resultant stream are the simplest and cheapest
method of disposal. The danger is thereby limited to the increase in phosphate
concentration which could possibly lead to an increased rate of water
eutrophication.
6. APPLICABILITY TO NATIONAL DISPOSAL SITE
It is anticipated that disposal systems to handle waste streams con-
taining phosphorus pentasulfide will not be required at National Disposal
Sites. All waste material generated is easily decomposed, neutralized
or recycled at the plant operation level.
192
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7. REFERENCES
0225. American Conference of Governmental Industrial Hygiem'sts. Threshold
limit values for 1971. Occupational Hazards, Aug. 1971.
0636. Air pollution aspects of phosphorus and its compounds. Technical
Report, Litton Systems Inc., Bethesda, Maryland. Sept. 1969. 86 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation. 1957. 1,467 p.
1411. Chemical Week. 1972 Buyers Guide Issue, Pt. 2. 109(17):442-443,
Oct. 27, 1971.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v.
New York, Interscience Publishers, 1966. 899 p.
1506. Chemical profiles. Oil, Paint and Drug Reporter. New York, Schnell
Publishing Company Inc., 1969. 200 p.
1620. Van Wazer, J. R. Phosphorus and its compounds. 2 v. New York,
Interscience Publishers Inc., 1958. 2,046 p.
2201. Personal Communication, J. Lemen, Hooker Chemical Company to
W. L. Niro, TRW Systems, July 25, 1972. Phosphorus trichloride,
phosphorus pentachloride, phosphorus oxychloride and phosphorus
pentasulfide waste treatment.
2202. Personal Communication. J. Williams, Monsanto Company to W. L. Niro,
TRW Systems, July 24, 1972. Phosphorus trichloride, phosphorus
pentachloride, phosphorus oxychloride and phosphorus pentasulfide
waste treatment.
2204. Personal Communication. P. Heisler, Monsanto Company to W. L. Niro,
TRW Systems, July 26, 1972. Phosphorus trichloride, phosphorus
oxychloride and phosphorus pentasulfide waste treatment.
2209. Chemical Safety Data Sheet SD-71. Properties and essential
information for handling and use of phosphorus pentasulfide.
Washington, Manufacturers Chemists' Association, Inc., 1958. 15 p.
2216. Personal Communication. L. Cavender, FMC Inc. to W. L. Niro, TRW
Systems, July 31, 1972. Phosphorus trichloride and phosphorus
oxychloride waste disposal.
2217. Material Safety Data Sheet. Phosphorus pentasulfide, Niagara Falls,
Hooker Chemical Company, 1972. 1 p.
193
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Phosphorus Pentasulfide (335)
IUC Name Tetrophosphorus Decasulfide
Common Names Thiophosphoric Anhydride
Structural Formula
P4S10
444.56
(1)
Molecular Wt.
Density (Condensed) 2.03
Melting Pt. 286 C
(1)
(1)
Boiling Pt. 513 C
(2)
20 C
Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
1 mm Hg @ 300 C
Flash Point
Autoignition Temp. 260 290 C (dust)
275 C (liquid)
Flammability Limits .in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %)
(2)
Solubility
Cold Water Decomposes
Others:
Lower 0.050 oz/cuft Upper_
(200 mesh dust in air)
Hot Water
Ethanol
Acid, Base Properties dry powder noncorrosive
Highly Reactive with water to form toxic, corrosive, flammable hydrogen sulfide. Reactive
with acids and oxidizing agents also.
Compatible with mild steel.
Shipped in fiber and steel drums or aluminum tote bins.
ICC Classification
Coast Guard Classification
Comments A ye11ow green powder which will: (1) react with water to form hydrogen sulfide;
(2) ignite by spark or friction; (3) explode when dispersed as a dust; (4) decomposes
into tOXJC and corrosive sulfur dinxide and
References (1) 2209, 2217
(2) 1620
194
-------
PROFILE REPORT
Potasslurn Permanganate(3491
1. GENERAL
Potassium permanganate forms glittering dark purple crystals with a
sweetish astringent taste. It is a strong oxidizing agent that decomposes
at 240 C with the liberation of oxygen.
Potassium permanganate is prepared in two stages. In the first stage
manganese dioxide (tetravalent Mn), is oxidized to manganate (hexavalent Mn)
by passing an ore containing manganese dioxide mixed with a 50 percent
solution of potassium hydroxide and steam through a series of rotary kilns.
In the second stage of the process, the potassium manganate is dissolved
in water, filtered and oxidized to potassium permanganate, either in an
electrolytic cell or in a chemical process, In the chemical oxidation
process, the filtered solution of potassium manganate is neutralized with
carbon dioxide and heated; two-thirds of the potassium manganate is
oxidized to potassium permanganate and one-third is reduced to manganese
dioxide.1433
The uses of potassium permanganate depend on its oxidizing power.
Important quantities are used for production of saccharin and benzoic acid
since potassium permanganate oxidizes the methyl group of toluene and
toluene derivatives to a carboxylic acid group. Manganese dioxide is
obtained as a by-product. Potassium permanganate is also used for bleaching
and decolorizing such materials as oils, fats, waxes and natural sponge.
It is also used in textile bleaching, as a disinfectant and antiseptic
for staining wood, and for forming tightly adherent oxide coatings on
aluminum. Recently it has found considerable use in treating wastes
such as phenols, aldehydes, ketones, esters, olefins, mercaptans, amines,
tannins, lignins, hydrogen sulfide and lower oxides of nitrogen.
The physical/chemical properties of potassium permanganate are
summarized on the attached worksheet.
195
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2. TOXICOLOGY
Potassium permanganate solutions and dust are strong irritants to
the eyes, nose and throat, and ingestion must be avoided during ordinary
handling and storage operations. Prolonged ingestion of manganese com-
pounds can produce chronic manganese poisoning, but the irritant effects
from potassium permanganate would be so prdnouced as to require treatment
prior to the onset of any chronic toxic effects.
Drinking water standards limits KMnO^ concentration to 0.05 mg/1.
The critical KMn04 concentration for fish toxicity is 3 mg/1.
3. OTHER HAZARDS
Potassium permanganate is a powerful oxidizing agent that is
spontaneously flammable on contact with glycerin, ethylene glycol, and
numerous other organic materials. It may detonate when severely shocked
or exposed to high temperature. Storage of potassium permanganate
in a cool, dry, fireproof building is recommended. Dry concrete floors
are preferred to wooden floors. The material should be stored away from
acids, organic solvents, oils and combustible materials.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Direct contact of potassium permanganate with reducing agents and
organic materials should be avoided. Dry potassium permanganate is not
corrosive to most metals. It may etch glass because it contains traces
of potassium hydroxide. In neutral solutions, it is not corrosive to
iron, aluminum, lead, zinc and alloys containing these metals. It attacks
rubber and most fibers.
Potassium permanganate is shipped under Department of Transportation
(DOT) regulations for an oxidizing material. Small quantities are packaged
in bottles or jars, with larger quantities shipped in steel drums con-
196
-------
taining 85 to 600 Ib. The bulk material may also be shipped in hopper
. . , 2300
cars and trucks.
Disposal/Reuse
Potassium permanganate is an oxidizing agent commonly employed in
waste water treatment and its presence up to a certain concentration in
waste streams could be considered as beneficial. Because manganese
dioxide, the reduction product of potassium permanganate, is insoluble,
the manganese in potassium permanganate waste streams may be a mixture
of soluble potassium permanganate and manganese dioxide sludge. The
acceptable criteria for the release of potassium permanganate into the
environment is defined in terms of the following provisional limits:
Basis for
Contaminant and Environment Provisional Limit Recommendation
q
Potassium permanganate in air 0.05 rog/M as Mn 0.01 TLV for Mn
Potassium permanganate in 0.05 ppm (mg/1) Drinking water
water and soil as Mn standard for
Mn
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Potassium permanganate is a valuable material that is often used to
treat waste streams containing oxidizable substances. It is not anticipated
that large quantities of potassium permanganate will ever require treatment
as a waste. When disposal of waste or contaminated potassium permanganate
is required, reducing substances such as phenolic wastes, sugar solutions
or formaldehyde wastes can be added to a dilute solution of the potassium
permanganate waste, maintaining a pH of 9 to 10. The potassium permanganate
is reduced to the insoluble, colloidal hydrous manganese dioxide which
should be removed by flocculation and lagooning, and placed in an appropriate
landfill.2300
137
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Since most potassium permanganate wastes are likely to be discharged
as relatively dilute solutions, the material is not considered economically
feasible for National Disposal Site processing, and is not recommended as
a candidate waste stream constituent for National Disposal Sites. The
simple method outlined in Section 5 for the reduction of potassium
permanganate to insoluble manganese dioxide can be performed by any firm
that handles potassium permanganate wastes.
198
-------
7. REFERENCES
0536. Federal Water Pollution Control Administration. Water quality
criteria, Washington, 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. 22 v. and
supplement. New York, Wiley-Interscience Publishers. 1963.
2300. Personal communication, R. A. Brenner, Carus Chemical Company,
to R. S. Ottinger, TRW Systems, August 28, 1972
199
-------
1
H. M. Name Potassium Permanganate
IUC Name Potassium Permanganate
Common Names
Molecular Wt. 158'03
Density (Condensed) 2.7 g/cc @ 23
Vapor Pressure (recommended 55 C and
e
ARDOUS WASTES PROPERTIES
WORKSHEET
(349)
Structural Formula
KMnO.
...__. n
Melting Pt. 24° C ^composes0 ^^ pt
C(1)Density (gas) e
20 0
0 @
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. X)
Solubility
Cold Water 6.3 g/100 g at 20 C(1}
Others: reacts with most organic
Acid, Base Properties
Lower Upper
Lower Upper
Hot Water Ethanol reacts^1'
solvents' '
Highly Reactive with reducing substances1'^
Compatible with
Shipped in Hopper cars or steel drums^
ICC Classification oxidizing material
Comments
veilow labpiO) oxidizing Material.
>yellow labe^t 6uard Classif1cat1onyenow label H)
References (1) 1433
H
200
-------
PROFILE REPORT
Potassium Peroxide (350). Sodium Peroxide (400), Sodium Monoxide (508)
1 . GENERAL
There is apparently only one domestic manufacturer of sodium peroxide,
Reactive Metals J296 Ashtabula, Ohio, a subsidiary of U.S. Industrial
Chemicals, which in turn is a subsidiary of the National Distillers and
Chemical Corporation. The peroxide is produced by controlled oxidation of
sodium metal with no waste. The primary use is for bleaching in the pulp
and paper industry. No production figures are available, but the market is
decreasing as paper manufacturers are switching to hydrogen peroxide and
sodium hypochlorite, and it is anticipated that the demand will approach
1296
zero within several years. Except for the odd 5-1 b can, none has been
T295
sold in California for several years. Three major pulp and paper
1289 1290
producers were contacted, Crown Zellerbach, Weyerhauser, and
I
Georgia-Pacific. Their environmental staffs and purchasing agents
know of no sodium peroxide use at present.
Neither Sitting ' nor Kirk-Othmer report any commercial use for
sodium monoxide. It can be prepared by the controlled burning of sodium in
air at temperatures less than 160 C. It appears in the waste sludge in the
1433
production of sodium metal in an intimate mixture with Na, Ca, and CaO '
05 and in used sodium as the principal contaminating material. In this
latter form, it promotes corrosion and fouls pumping equipment. With sodium
0398 0399
now selling at 230/lb, Atomics International, ' a large sodium user,
finds it more economical to dispose of the sodium metal than to repurify it.
Thus, sodium monoxide* waste disposal is part of the sodium metal disposal
problem, which is discussed in the Profile Report on sodium metal (374).
201
-------
There are two commercial uses for potassium in the United States—as a
component of NaK for catalysis and cooling systems and for the production
of K909 for use in breathing apparatus. Total potassium production is 100
0395
tons/yr by a sole supplier, MSA, and is expected to remain constant
over the next 10 years. The quantity breakdown of this production into
1433
NaK and ^2 1's unavailable. Kirk-Othmer reports the production
process to be:
Na + KCl-*NaK + (Na, K) Cldistil1aV°VryJ£ K02 decomposition ^
There is no appreciable K^Og waste either at the source or from any
individual spent breathing apparatus.
The waste products from the NaK and K production are the oxides and
chlorides of sodium and potassium. MSA would not release any waste pro-
duction figures, but did say that the oxides are neutralized in settling
ponds and then discharged into nearby rivers. The mixed chlorides are
trucked to a nearby abandoned mine.
2. TOXICOLOGY
These materials are dangerous due to their caustic properties. The
1971 Annual List of the U.S. Department of Health, Education, and Welfare
does not list these as toxic substances.1312 Sax0766 does not report a
Threshold Limit Value (TLV) for these materials, but NaOH, which forms
vigorously on contact of Na^O or NagO^ with moisture or human tissue, has
a TLV of 2 mg/m , as recommended by the American Conference of Governmental
Industrial Hygienists. The hydroxides themselves are caustic in concentrated
form, but neutralization with acid renders them harmless.
202
-------
3. OTHER HAZARDS
The oxides and peroxides of sodium and potassium react vigorously
with water, acids, and powdered metals.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
Sodium peroxide and potassium peroxide are strong oxidizing agents and
sodium monoxide is a strong drying agent and caustic. Extreme caution
should be exercised in their handling. Protective clothing, rubber gloves,
a full face shield, and a dust respirator should be worn. In case of heavy
dust concentration in air, the use of chemical safety goggles is recommended.
Contaminated clothing, including shoes, should be immediately removed and
thoroughly cleaned before reuse. In cases of fire, only dry chemicals
should be used as extinguishing agents.
All three oxides should be stored in cool, dry, well-ventilated, and
preferably fire-resistant areas. The containers for these chemicals should
also be kept off from the floor, and away from any possible contacts with
water, combustibles, and organic or readily oxidized substances.
Sodium peroxide and potassium peroxide are classified by the U.S.
Department of Transportation (DOT) as Oxidizing Material. As such, both
chemicals must be packed in DOT specification containers when shipped
by rail, water, or highway and all DOT regulations governing loading,
handling, shipping and labeling must be complied with. Sodium monoxide
is not classified by DOT, but as a strong caustic, the regulations
governing the handling, loading, and shipping of sodium hydroxide should
be followed.
Disposal/Reuse
Sodium monoxide, sodium peroxide, and potassium peroxide all react
violently with water to form either sodium or potassium hydroxides. No
203
-------
Threshold Limit Value (TLV) for these chemicals have been reported. For
the safe disposal of these materials, the recommended provisional limits
are as follows:
Contaminant in Air
Sodium monoxide
Sodium peroxide
Potassium peroxide
Contaminant in Water
and Soil
Sodium monoxide
Sodium peroxide
Potassium peroxide
Provisional Limits
0.02 mg/M3 as. NaOH
0.014 mg/M3 as H20-2
0.014 mg/M3 as H0
Provisional Limits
0.1 ppm as NaOH
0.1 ppm as NaOH
0.1 ppm as KOH
Basis for Recommendation
Provisional limit for NaOH
0.01 TLV for H202
0.01 TLV for H202
Basis for Recommendation
Provisional limit for NaOH
Provisional limit for NaOH
Provisional limit for KOH
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The oxide waste from the production of NaK by MSA is neutralized
with sulfuric acid in settling ponds and discharged into nearby rivers.
The small concentration of several percent Na20 which appears as a
contaminant of Na metal is treated with the metal in an unsegregated
manner. As a component of breathing apparatus, K202 is converted to KOH
and 02. The KOH produced is likely present in too small amounts to be
considered a significant hazard.
Any Na202 used for bleaching in the pulp and paper industry would be
reduced in the effluent streams to NaOH. "1289,1290,1291 If the
stream is caustic it should be neutralized with acid prior to sewering.
204
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Sodium peroxide and potassium peroxide are not found in any
appreciable amounts as waste stream constituents. The only significant
source of sodium monoxide waste is in the waste sludges of sodium metal
production, and these are currently disposed of by dumping at sea in
perforated drums so that complete reaction to sodium hydroxide is attained.
Since all three compounds are adequately handled at the industrial level,
they are not considered as candidate waste stream constituents for
national disposal.
205
-------
7. REFERENCES
0274. Sittig, M. Sodium; its manufacture, properties, and uses. New York,
Reinhold Publishing Company, 1956. 529 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.
0395. Personal communication. Mine Safety Appliances, to M. Appel, TRW
Systems, Jan. 12, 1972.
0398. Personal communication. Atomics International, to M. Appel, TRW
Systems, Jan. 12, 1972.
0399. Personal communication. AI Liquid Metals Engineering Center, to
M. Appel, TRW Systems, Jan. 10, 1972.
0595. Personal communication. B. Bryden, Ethyl Corporation, to M. Appel,
TRW Systems, Feb. 8, 1972.
0596. Personal communication. Mr. Hoyle, Du Pont, to M. Appel, TRW Systems,
Feb. 9, 1972.
0664. Personal communication. M. B. Burton, El DuPont De Nemours Company,
to M. Appel, TRW Systems, Feb. 17, 1972.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1289. Personal communication. Mr. Dowdy, Crown Zellerbach, to M. Appel,
TRW Systems, Mar. 17, 1972.
1290. Personal communication. J. McClintdck, Weyerhauser, to M. Appel,
TRW Systems, Mar. 17, 1972.
1291. Personal communication. M. Gould, Georgia-Pacific, to M. Appel,
TRW Systems, Mar. 17, 1972
1295. Personal communication. Mr. Rumfel, U. S. Industrial Chemicals, to
M. Appel, TRW Systems, Mar. 13, 1972.
1296. Personal communication. Mr. Toth, U. S. Industrial Chemicals, to
M. Appel, TRW Systems, Mar. 13, 1972.
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.
206
-------
REFERENCES (CONTINUED)
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
207
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. K. Name
IUC Name ' SODIUM MONOXIDE (508)
Common Names SODIUM OXIDE
Structural Formula
Na20
Molecular Wt.
61.99
Melting Pt. 920 C Boiling Pt. 1350 C(decoro:-
Density (Condensed) 2.27 g/ccg Density (gas) . @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower not flam.
Explosive Limits in Air (wt. Z) Lower not flam.
Upper not flam.
Upper not flam.
Solubility
Cold Mater decomposes
Others:
Hot Mater decomposes
Ethanol deconioosos
Acid, Base Properties strongly basic
Highly Reactive with water, powdered metals, steam, acids
iCompatible with oxides
Shipped in_
ICC Classification none
Comment<: obtained v;hen Na burned <160 C
Coast Guard Classification hazardous
material
.•^%^-.»»'OTacivr»^'7.^-*i^&wj^vTWrjssiK^^
208
-------
r
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name
Structural Formula
IUC Name SODIUM PEROXIDE (400)
Common Names SODIUM DIOXIDE. SODIUM SUPEROXIDE,
Molecular Wt. 77.99 Melting Pt. 460 C Boiling pt. decomposes 651
Density (Condensed) 2.805g/cc@ Density (gas) @
Vapor Pressure (recommended 55 C and 20 0
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Dangerous Upper_
Explosive Limits in Air (wt. %) Lower Moderate Upper_
Solubility
Cold Water decomposes Hot Water decomposes Ethanol decomposer '
Others: dil. acid, decomposes in NH_ (aq.)
Acid, Base Properties strongly basic .
Hi9hly Reactive with water, powdered metals, steam, acids evolving heat, combustible material '
Compatible with oxides
Shipped in ?q -[^ steel pails and 400 Ib steel drum: @ "2dt/1b
ICC Classification oxidizing material, yellow Coast Guard Classification oxidizing material.''
label, 100 Ib yellow label
Comments Sec. 78.187 . : yeiiow laoei ,
obtained when Na burned >160 C i
_ ___ _ . -.
209
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
'
rl. M. Name .
Structural Formula
IUC Name POTASSIUM PEROXIDE (350)
Common Names POTASSIUM PEROXIDE
K00
2U2
Molecular Wt. 110-19 Melting Pt. 49° c Boiling Pt._
Density (Condensed) @ Density (gas) 6
Vapor Pressure (recommended 55 C and 20 J)
& 8 C
Flash Point Autoignition Temp,_
Flammability Limits in Air (wt %) Lower Dangerous Upper_
Explosive Limits in Air (wt. %) Lower Moderate Upper_
Splubil ity
Cold Water Decomposes Hot Water Decomposes Ethanol Decomposes
Others:_
Acid, Base Properties Strongly basic .
Highly Reactive with Spontaneously, water, steam, acids, powdered metals
Compatible with oxides
Shipped in steel pails
ICC Classification Oxidizing material, yellow Coast Guard Classification oxidizing material.
label, 100 ibyellow label,
Comments s^r 7?..lRd .. _ *
Obtained either by oxidizing K in liq. NH, sol, or decomposing KOg-disproportionat
easily , , 1:
. . t!
-------
PROFILE REPORT
Selenium (367)
1. GENERAL
Production
1288
There are five selenium producers in the United States : American
Metal Climax, Carteret, New Jersey; American Smelting and Refining Company,
Baltimore, Maryland; International Smelting and Refining Company, Perth
Amboy, New Jersey; Kennecott Copper Company, Garfield, Utah; and KBI
Industries, Boyertown, Pennsylvania. KBI processes materials produced
by the mining operations of the other four, supplemented by imports.
Almost all production is as the by-product of the electrolytic refining
of copper, gold, nickel, and silver ores, with copper ore accounting for
over 90 percent of the 600,000 Ib produced annually in the United States.
An additional 400,000 Ib is imported to make up the 1,000,000 Ib annual
domestic consumption. A small amount is also produced as a by-product
of lead refining and sulfuric acid production. The weakness of the market
precludes the exploitation of selenium ores directly and this situation
1287
is likely to continue indefinitely. In fact, demand is so slack
relative to the copper market, that only 60 percent of the potentially
winnable selenium is recovered as the by-product.
At $4.50/lb of the commercial grade (99 % pure) and $6.00/lb for
1 ?ft8
the high purity grade (99.99 % pure), selenium is considered of
sufficient value for secondary recovery. Approximately 30,000 Ib are
recovered each year from spent catalysts, factory scrap, and xerographic
cylinders, and sold back to the primary producers for recycling.
211
-------
Typically, selenium is won from the anode mud or slime resulting
from the electrowinning of copper. There are two basic methods: (1)
smelting or roasting the mud with soda ash to form the water soluble
Na2Se03, followed by neutralization with acid to precipitate tellurium
metal, and filtration and acidification with S02 gas to precipitate
selenium metal or (2) heating the mud with FUSO^ to volatilize the
selenium as Se02, followed by collection as H2SeO~ in a wet Cottrell
precipitator, and further acidification with SCL gas to precipitate
selenium metal. Approximately 250 people are employed in selenium
production, purification, and fabrication in the United States.
Uses1433,1748,1287,1288,0277
Two unique properties make selenium virtually irreplaceable for a
wide variety of applications. It is an excellent decolorizer for glass
and it is a semiconductor whose electrical conductivity varies strongly
as a function of the incident light. This light sensitivity makes
selenium and its compounds ideal for "electric-eye" systems and for
xerography, where a selenium-containing powder is charged and exposed
selectively to light to discharge the exposed areas. The undischarged areas
are then fixed. Selenium rectifiers are popular because selenium can be
easily made to conduct current in the forward, but not in the reverse direction.
The glass industry accounts for about 31 percent of the annual
selenium consumption, duplicating machines account for another 22 percent,
electronics and power transmission account for 16 percent, and the
paint and pigments industry (as'cadmium sulfoselenide) accounts for 14
percent. The remainder finds use in the steel industry for improving
ductility, in the rubber industry as an alternative to sulfur for vulcan-
ization, for improving the stability of explosives, and as a fungicide
in dandruff removers and agricultural chemicals. It is a necessary trace
element in the diets of livestock, and livestock raised in selenium-
deficient areas must have their diets supplemented.
212
-------
Sources and Types of Selenium Wastes
The major sources of selenium wastes that have been identified in-
clude the following: (1) manufacture and reconditioning of xerox drums;
(2) paint and pigments industry; and (3) paint residues left in containers.
The selenium and arsenic coated xerox drums are manufactured and
reconditioned exclusively at Xerox's Rochester, New York facility.
About 700,000 Ib of solid wastes containing cotton linter, steel,
aluminum, and 300 to 400 Ib of selenium and arsenic are generated each
year during these operations. Of the selenium and arsenic found in these
wastes, there is usually more selenium present than arsenic and approximately
25 percent of the selenium is combined with arsenic chemically (e.g.,
arsenic triselenide), with the remaining selenium containing less than 1
percent arsenic in them. In addition, there are 50,000 Ib of liquid
wastes consisting primarily of caustic solutions and 0.3 percent selenium
and arsenic generated each year from the same operations.
Cadmium sulfoselenide accounts for nearly all the selenium used in
pigments. In the manufacture of solvent-based paints, sludges are
generated from both the washing system and the solvent recovery stills.
The combined solvent-based paint sludge is characterized by the following
composition: 4.5 percent inorganic pigment (excluding titanium dioxide),
8.5 percent titanium dioxide, 14.5 percent pigment extenders, 25.0 percent
binders and 47.5 percent organic solvents. It is estimated that a total
of 370 Ib of selenium are lost through 37 million Ib of solvent-based
*
paint sludges every year.
Selenium containing paint residues left in containers normally
discarded in municipal dumps constitute another source of selenium waste.
It is estimated that a total of 2,560 Ib of selenium are lost as paint
*
residues every year.
The basis for these estimates are discussed in detail under "Toxic
Paint Wastes" in the appendix volume on Waste Forms and Quantities.
213
-------
Possible sources of trace selenium include natural fuels, leather
goods, cloth materials, paper and other wood products, etc. Coal has
been found with as much as 7.4 ppm Se and significant amounts have
been found in newsprint. In general, materials derived from terrestrial
-4 1745
sources have a Se/S ratio of approximately 1 X 10 . A comprehensive
1745
study of selenium contained in solid waste has been made. The
principal means of access to the environment is by incinerator stack
emission, where emissions of 0.002 mg/m were found. Quench water samples
showed 0.014 mg/1. These levels compare favorably with the present TLV
of 0.2 mg/m and drinking water recommendation of 0.01 mg/1. No information
is available, however, on the seasonal and geographical variations of
these emissions.
2. TOXICOLOGY
Health and Safety Standards
Commercial elemental selenium is relatively inert and is handled
143-3 1747
without special precautions. l'+oc>'l/'f/ The 1971 HEW Annual List of
1312
Toxic Substances does not list selenium metal as a toxic substance.
The Threshold Limit Value, (TLV) as recommended by the American
o
Conference of Governmental Industrial Hygienists in 1968 was 0.1 mg/m .
3 1745
This was recently raised to 0.2 mg/m . Most industrial absorption
occurs by inhalation of dust, vapors, and fumes, and care therefore
should be taken to scrub exhaust gases and employ good housekeeping pro-
cedures. Care should also be taken that volatile or soluble selenium
compounds not be formed, since these are many times more toxic than the
metal itself. Organoselenium compounds are particularly dangerous.
Epidemiology
The principal cause of selenium poisoning in the United States is the
consumption of vegetables and grains grown in selenium-rich soils, parti-
cularly in the Northwest plains states. Industrial exposures are
apparently rare. The common symptoms are a characteristic garlic
breath, often accompanied by dermatitis, gastrointestinal disturbances,
214
-------
and/or damage to the lungs, liver, and other viscera. ' Fifty to
eighty percent of ingested selenium is excreted through the kidneys and
a conclusive diagnosis may be obtained from urinalysis. Persons not
exposed industrially to selenium average 0.01 to 0.15 mg Se/liter urine,
depending on their geographical location. Industrial workers average
0.069 mg/1. It has been determined that humans can excrete 2.00 mg/1
without exhibiting symptoms.
3. OTHER HAZARDS
In common with almost all metals, sufficiently fine selenium powder
may explode in air to form the water-soluble SeOo- Selenium will react
with acids to form the highly toxic H2Se gas. If another metal is present,
a selenide may form, which would then react with water vapor to form H^Se.
4. DEFINITION AND EVALUATION OF WASTE MANAGEMENT PRACTICES
Handling, Storage, and Transportation
There are no special shipping regulations for selenium metal. '
Metal should be stored in such a way as to avoid contact with water, and
fine powder should be sealed under inert gas to avoid the possibility of
an explosion. A fire involving selenium can be handled as any metal
fire would. Anytime there is a possibility of the evolution of airborne
dusts or fumes or the possibility of an uptoward chemical reaction,
controlled exhaust .ventilation should be provided.
Disposal Reuse
At $4.50/lb for commercial grade selenium metal, the metal is an
attractive candidate for secondary recovery and resale to the primary
producers, and 30,000 Ib/yr are recycled in this way. For the disposal
of selenium wastes, the acceptable criteria is defined in terms of the
recommended provisional limits:
Contaminated and Provisional Limits Basis for
Environment Recommendation
Selenium in Air 0.002 mg/M3 0.01 TLV
Selenium in Water Drinking Water
and Soil 0.01 ppm (mg/1) Standards
215
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Selenium waste may be divided into two categories, that which comes
from the refining or manufacture of selenium and selenium products and that
which arises incidentally from the disposal of wastes containing trace
quantities of selenium.
Option No. 1 - Scrubbing with Hydrobromic Acid. Selenium refineries
are typically equipped with wet scrubbers containing 40 to 48 percent HBr
in aqueous solution with 5 to 10 percent free bromine added. The acid
vapors are absorbed in a soda lime train, while the selenium is separated
from the HBr solution by a straightforward distillation. The recovered
selenium is then recycled. On an industrial level, the hazards asso-
ciated with selenium are apparently handled adequately, as evidenced by
the lack of disease associated with the selenium producers.
Option No. 2 - Sanitary Landfill. The selenium containing solid
wastes from the manufacture and reconditioning of xerox drums are currently
disposed of by burial in a segregated section of a landfill site for
industrial wastes. Waste sludges containing selenium and toxic heavy
metals from the manufacture of paint and pigments are also disposed of in
approved sanitary landfill sites. It is felt that sanitary landfill is an
acceptable and adequate method for the disposal of selenium wastes, provided
that the sites used are located over nonwater-bearing sediments or have
only unusable ground water underlying them and are completely protected
from flooding, surface runoff or drainage, so that all waste materials
and internal drainage are restricted to the site. In other words, any
sanitary landfill sites approved for the disposal of selenium wastes must
meet the criteria for a Class 1 disposal site in California.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Despite intensive investigations, no correlation has been found
between selenium-related disease and employment in the selenium industry.
Similarly, no incident disease has been attributed to air or water
emissions or other wastes emanating from plant sites.
-------
Selenium-related diseases in man and livestock have been found in
certain areas of the country (e.g., the Northwest plains states), whose
indigenous soils contain an unhealthily high concentration of selenium.
Likewise, selenium deficiencies have induced pathologies in livestock
in other areas. This is not a disposal problem, but rather a problem
involving health screening of the indigenous animal and human populations
and appropriate dietary recommendations. It indicates, however, that the
disposal of selenium should be accomplished such that water and soil
contamination with soluble selenium compounds is avoided.
Studies to date indicate that the disposal of municipal and other
wastes containing trace quantities of selenium does not generally result
1745
in unsafe levels in the environment. These studies, however, were
not extended to an investigation of seasonal and geographical variations.
Also, while it has been determined that terrestrial mammals, including
man, do not concentrate the metal, no information was found regarding
the possible concentration of selenium in plants.
At this time, selenium is not considered as a candidate waste
stream constituent for National Disposal Sites. However, no investigations
have been conducted to determine what seasonal and geographical variations
exist in the emission of trace selenium from the disposal of municipal
and other wastes, and whether these variations are sufficient to cause
occasional emissions at an unsafe level. Furthermore, the ability of
plants and animals to assimilate and concentrate selenium has not been
investigated to determine if unsafe levels can be attained in this way.
If it is determined that a combination of circumstances can lead to
unsafe levels, intermittent or permanent controls will have to be imposed
on the time and place of disposal and the content of general wastes (e.g.,
newsprint and other paper) now disposed of without regard of their selenium
content. In this eventuality, National Disposal Sites might prove economical
for the disposal or recycling of these wastes.
217
-------
7. REFERENCES
0277. Patty. F. A., ed. Industrial hygiene and toxicology. 2d ed. 2 v.
New York, Interscience Publishers, Inc., 1963.
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.
0766. Sax. N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1287. U. S. Bureau of Mines. Mineral facts and problems. Bulletin No. 650.
U. S. Bureau of Mines, 1970. 19291 p.
1288. U. S. Bureau of Mines. Metals, minerals, and fuels. In Minerals
Yearbook, 2 v. U. S. Bureau of Mines, 1969. 1,208 p.
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.
1745. Johnson. H. Determination of selenium in solid waste. Environmental
Science and Technology, 4(10):850-853. 1970.
1747. National Safety Council. Selenium and its compounds. National Safety
Council Data Sheet 578. National Safety News. 93(5):42-45. May 1966.
1748. Stahl, J. R. Air pollution aspects of selenium and its compounds.
PB-188-077. Bethesda, Maryland, Litton Systems, Inc., Sept. 1969.
218
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Selenium Powder (367)
Common Names Selenium Powder
Se (solid)
Seg (liquid)
Se (gas) with
x < 1 x 18
Molecular Wt. 78.96 Melting Pt. 217 C Boiling Pt. 685 C
Density (Condensed) 4.82 @ 25 _C Density (gas) &
Vapor Pressure (recommended 55 C and 20 C) log Pmm = 8.0886-4989.5/T(K)
nun
1 mm @ 356 CS,
Acid, Base Properties Weakly acidic ___
Highly Reactive with Acids to form toxic H?Se gas; may react similarly with water or
water vapor; finely divided powder may explode
Compatible with steel, plastic
Shipped in steel drums (may be plastic-lined for ultimate purity)
ICC Classification None Coast Guard Classification,
Coirments
219
-------
PROFILE REPORT
Sodium Acid Sulfite (380), Sodium Nitrite (397), Sodium Sulfite (405)
1. GENERAL
Introduction
The inorganic chemicals in this report are basically nontoxic. However,
when dissolved in water in sufficiently large quantities they may create a
hazard or nuisance. They are grouped together here in one report because
they can be handled by similar disposal processes.
Manufacture and Uses
Sodium Acid Sulfite. Sodium acid sulfite, NaHSOg, is prepared as white
crystals or as crystalline powder that has a slight sulfurous odor and a
disagreeable taste. It is prepared by saturating sodium carbonate solution
with sulfur dioxide gas. The product is obtained as a suspension which is
removed from the solution by centrifuging. The dried product is really the
sodium metabi sulfite, Na2S20g, which yields NaHS03 upon solution in water.
It finds industrial use either as a solution or as a solid. The solutions
may be shipped, stored and handled in lead-lined equipment. In the tanning
industry sodium acid sulfite is used as a reducing agent for chrome solutions.
In the textile industry it is a bleaching agent, a dechlorinating agent, and
a raw material for the manufacture of hydrosulfite solutions. It is also
consumed in the paper, photographic and organic chemical industries. '
Sodium Nitrite. Sodium nitrite, NaN02» is prepared as slightly yellowish
or white crystals, pellets, sticks or powder that oxidizes upon exposure to
air. In the dye industry sodium nitrite is a very important chemical, used
for the diazotization of amines for making azo dyes. It is also used in the
preparation of nitric oxide, pickling metal, medicine, rustproofing and
cutting oils. Formerly sodium nitrite was prepared by the reaction,
NaN03 + Pb - NaN02 + PbO.
221
-------
Now it is manufactured by passing NO, obtained by oxidation of ammonia,
into soda ash solution.
Na2C03 + 2NO + 1/202 -> 2 NaN02 + C02
Sodium nitrate is also formed and is separated from sodium nitrite by
crystallization in lead lined equipment. '
Sodium Sulfite. Sodium sulfite, Na9SO,, is manufactured as white
" "" £ w
crystals or powder. It is a compound that is easily oxidized. For this
reason it is employed in many cases where a gentle reducing agent is desired.
It is employed to bleach wool, silk and as an "antichlor" (deehlorinating
agent) after bleaching of yarns, textiles, and paper, as a preservative
for foodstuff and to prevent raw sugar solutions from coloring upon
evaporation. It is also used in photography, medicine and to remove oxygen
from boiler water. The most important commercial manufacturing process
starts by passing sulfur dioxide into a solution of soda ash until the
product is acid. Then sodium sulfite is formed by adding the stoichiometric
quantity of soda ash, and boiling until carbon dioxide is evolved. After
the carbon dioxide has been evolved, the solution is concentrated, whereupon
the crystals of Na2S03'7H20 settle out upon cooling. Another commercial
source of sodium sulfite is as a byproduct from the preparation of phenol by
the fusion of sodium benzene sulfonate with sodium hydroxide.
S03Na ^-vONa
+ 2NaOH •* 11 I + Na9SO~ + H,0
U. S\^) (.3 £.
Sodium sulfite is also recovered from paper mill cellulose waste liquors. '
1416,1662
Physical and Chemical Properties
The physical and chemical properties of the inorganic chemicals treated
in this report are summarized on the attached worksheets.
222
-------
2. TOXICITY
The materials treated in this report are not highly toxic. However, they
are all soluble in water to yield solutions that are corrosive and in high
concentrations are irritating to the skin and mucous membranes. Two of the
compounds, sodium nitrite and sodium sulfite, are employed as food additives.
No Threshold Limit Values (TLV's) have been recommended by the American
/•jpoc
Conference of Governmental Industrial Hygienists for these compounds.
Sodium nitrite has a lethal dose reported as "or ID™ 480 mg/Kg rat".
3. OTHER HAZARDS
The three compounds covered by this report are generally considered to
be reducing agents. Sodium nitrite, however, is also an oxidizing material
that is a fire hazard when in contact with organic or other easily oxidized
material. All three compounds are corrosive to most metals and require
0955
lead-lined equipment for storage of concentrated solutions.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handlings, Storage and Transportation
The three materials covered by this report may be handled and stored as
strong solutions in lead-lined equipment. Sodium acid sulfite must be
protected from air to avoid oxidation. Sodium nitrite is classified by the
Department of Transportation (DOT) and the U. S. Coast Guard as oxidizing
material that required a Yellow Label. The other materials do not have
shipping regulations.
Disposal/Reuse
Industrially contaminated materials covered in this report, when in
sufficient quantity, can be reprocessed for reuse. Usually the materials
can be purified by recrystallization. The safe disposal of these materials
are defined in terms of the recommended provisional limits in the atmosphere
; and in water and soil environments. These recommended provisional limits
are as follows:
223
-------
Contaminant in Air
Provisional Limit
Basis for
Recommendation
Sodium Bisulfite
Sodium Nitrite
Sodium Sulfite
0.02* mg/Mv
0.02* mg/M3
0.02* mg/M3
0.01 TLV*
0.01 TLV*
0.01 TLV*
Contaminant in
Water and Soil
Sodium Bisulfite
Sodium Nitrite
Sodium Sulfite
Provisional Limit
0.10* mg/1
0.10* mg/1
0.10* mg/1
Basis for
Recommendation
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
*Estimated
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The disposal of the reducing agents covered by this report is
accomplished by diluting the materials with a large volume of water containing
soda ash and then adding calcium hypochlorite. The solution is decanted or
siphoned into another container if sulfate is present. The solution is then
neutralized with 6M-HC1, diluted and discharged into a sewer or stream. The
sludge, if any, is added to a Class 2 type landfill. This method is considered
satisfactory for the three materials covered by this report.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The chemical compounds discussed here have been classified on a pre-
liminary basis as probable candidate waste stream constituents for municipal
disposal. Based on the disposal process described in Section 5, it may be
concluded that waste treatment for these compounds can be handled adequately
locally and no consideration for treatment at National Disposal Sites is
warranted.
224
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Washington, 1969. 176 p.
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, 35:35-40, Aug. 1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 2d ed.
New York, Reinhold Publishing Corporation, 1957. 1,467 p.
0955. Sitting, M. Inorganic chemical and metallurgical process encyclopedia,
Park Ridge, New Jersey, Noyes Development Corporation, 1968. 883 p.
1416. Ross, A. and E. Ross. Condensed Chemical Dictionary. 6th. ed. New
York, Reinhold Publishing Corporation, 1961. 1,256 p.
o
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.
225
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodl"um acid sulfite(380)
Structural Formula
IUC Name Sodium acid sulfite
Common Names Sodium bisulfite
NaHSO
'3
Molecular Wt. 190-11 Melting Pt. decomposition Boiling Pt._
Density (Condensed) 1.48g/cc @ 20_c"^ Density (gas) @
Vapor Pressure (recommended 55 £ and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water very soluble^ Hot Water very soluble^ Ethanol slightly soluble
Others:
Acid, Base Properties
Highly Reactive with ozidizing materials
Compatible with_
Shipped in 500 Ib barrels; 500-, 600-lb drums; solution in 500-lb barrels^ '
(2)
ICC Classification none' Coast Guard Classification^
Comments When dried sodium metahiMilfitp, Na s 0 i^ fnrmpH' '
^ ^ 3-
References (1) 1570
(2) 1416
zzs
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium nitrite (397)
IUC Name
Common Names Diazotizing salt
Structural Formula
NaNO,,
69.01
(1)
271 C
(1)
Molecular Wt. ba'ul Melting Pt.
Density (Condensed) ; @ Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
Boiling
0
pt 320 decomp'1'
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water 72g/100 g at 0 C^ Hot Water 163q/100q at 100 C^Ethanolsliqhtlv soluble
Others: 0.3g/100 q ether at 20 C^
Acid, Base Properties
Highly Reactive with Reducing or oxidizing materials^ '
Compatible with_
Shipped in 25-. 100-lb drums; 150-lb kegs; 400-1b barrels^
ICC Classification oxidizing material;2)
Coast Guard Classification oxidizing material
Comments.
References (1) 1570
(2) 1416
227
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium sulfite (405)
Structural Formula
IUC Name Sodium sulfite
Common Names
Na2S03
Molecular Wt. 126.05^ Melting Pt. decomposes. Boiling Pt._
Density (Condensed) 2.633g/cc @ 15.4 C^ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
@ 9 (
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility.
1
Cold Water 12.54g/100 ml at 0 Cu;Hot Water 28. 3g/ 100 ml at 80 C Ethanol slightly
Others:
Acid, Base Properties
Highly Reactive with Oxidizing materials
Compatible with
Shipped in 100-,200-lb bags; 234-. 450-lb barrels; 400-1b
ICC Classification N°"e( _ Coast Guard Classification
Commen ts
References (1) 1570
(2) 1416
228
-------
PROFILE REPORT
Sodium Alloy (374) and Sodium-Potassium Alloy (402)
1. GENERAL
Chemical Profiles0767 and contacts with the Ethyl Corporation0595
indicate that sodium is produced at five plants in the United States: two
DuPont plants at Niagara Falls, New York, and Memphis, Tennessee, two
Ethyl plants at Baton Rouge, Louisiana and Houston, Texas, and a Reactive
Metals plant at Ashtabula, Ohio. Total annual production is 180,000 tons
of which 90 percent is used in the production of tetraethyl lead with no
associated waste metal or metal oxide. If or when tetraethyl lead
production ceases in 1975, Ethyl estimates that Na production will shrink
to 15 to 30,000 tons/year and four of the five plants will probably close.
Kirk-Othmer reports that all of the Na production in the United
States is by the Downs process. A representative at the Ethyl Corporation
plant in Baton Rouge, Louisiana estimates that his waste amounts to about
1 percent of his total Na production and is in the form of a sludge
containing Na, Ca, CaO, and Na20. This translates to a generated waste
of about 3,000 Ib sludge/day. This sludge is drummed and dumped at sea
with perforations to assure complete reaction and destruction. The DuPont
plant at Niagara Falls, New York °596'0664 generates waste of 100 Ib
Na/day for a plant of similar size. This material is mixed with kerosene
and burned in a closed reactor. The exhaust gases are scrubbed with water
and sewered.
The use of sodium as a coolant and heat transfer medium in nuclear
reactors has declined in recent years, but the Atomic Energy Commission
expects that it may again become important as fast breeder reactors become
onstream around 1980. It is impossible to judge the magnitude of this use
229
-------
at this time, because it will be affected by many policy decisions to be
made between now and then. In this event, they envision closed loop
purification processes, perhaps similar to that invented by the De Vries
.and Scarborough. Their invention purifies Na or NaK in a continuous
process by taking advantage of the virtual insolubility of ^0 just above
the melting point (97.9 C). The material is heated or cooled to the
appropriate temperature; the pure metal is pumped from the bottom and the
less dense impure metal oxides are skimmed from the top.
The Sodium Reactor Experiment at Atomics International, Canoga Park,
California0398'0399 inventories about 100,000 Ib of Na, of which about
30,000 Ib is disposed of as waste every year by dumping at sea.
There are two commercial uses for potassium in the United States --
as a component of NaK for catalysis and cooling systems and for the
production of K90« for use in breathing apparatus. Total potassium
0395
production is 100 tons/year by a sole supplier, MSA, and is expected
1433
to remain constant over the next 10 years. Kirk-Othmer reports the
production processes to be:
distillation
Na + KC1 -NaK + (Na.K) CL - K
The waste products from the NaK and K production are the oxides and
chlorides of sodium and potassium. MSA would not release any waste
production figures, but did say the oxides are neutralized in settling
ponds and then discharged into nearby rivers. The mixed chloride salts
are trucked to a nearby abandoned mine. The largest NaK customer in the
United States is the Union Carbide Corporation, Charleston, West Virginia.0665
2. TOXICOLOGY
The materials are not toxic in a strict sense, but are dangerous
because of their caustic properties. The oxides or hydroxides are formed
vigorously on contact with air or moisture or human tissue. The reported
o
Threshold Limit Value (TLV) for sodium hydroxide is 2 mg/M , as
230
-------
recommended by the ACGIH. The hydroxides themselves are caustic in
concentrated form, but neutralization with acids, such as hydrochloric
acid, eliminates this hazard.
3. OTHER HAZARDS
Na and NaK are spontaneously flammable in contact with moisture to
evolve \\2 with sufficient heat to ignite the H,,. They ignite spontaneously
in Clp and react vigorously with moisture, acids, and human tissues.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Procedures for adequate handling, storage, and transportation of
these materials are well documented by the Manufacturing Chemists
Association, the Liquid Metals Handbook,
Handbook - Na Supplement.
and the Liquid Metals
Disposal/Reuse
The safe disposal of wastes containing sodium and sodium-potassium
alloys is defined in terms of the recommended provisional limits:
Basis for Recommendation
Provisional limit for NaOH
Contaminant in Air
Provisional Limits
Sodium
Sodium-potassium alloy
0.02 mg/jr as NaOH
0.02 mg/M3 as NaOH
and KOH
Provisional limits for
NaOH and KOH
Contaminant in Water
or Soil
Sodium
Sodium-potassium alloy
Provisional Limits Basis for Recommendation
0.1 ppm as NaOH
Provisional limit for NaOH
0.1 ppm as NaOH and Provisional limits for NaOH
KOH and KOH
231
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Primary Na producers either drum their waste and dump it at sea with
perforation in the drums to assure complete reaction and destruction
(Ethyl Corporation, Baton Rouge, Louisiana) or burn it mixed with
kerosene in a closed chemical reactor (DuPont Corporation, Niagara Falls,
New York). >Uob4 y^ use Qf fl reactor allows the burning to be
controlled by varying the feed rates of sodium and air to prevent a
violent conflagration and also allows the exhaust gases to be scrubbed
with water to remove the sodium oxide and carbonate.
The 30,000 Ib/year of Na waste produced by Atomics International is
packed in barrels on site. The California Salvage Company picks up
this material under contract, fits the barrels with concrete collars and
dumps them at sea off Santa Catalina Island. The cost of this service is
$2,200 on an annual basis. This method of disposal is currently considered
satisfactory to all parties concerned, including the California Water
ty d
0401
Quality Control Board and the California Department of Fish and
Game.
NaK and K?09 production by MSA at their single location in Evans City,
0395
Pennsylvania is reported to be under control. No toxic materials are
generated by the production of these materials and the hydroxide effluent
is neutralized in settling ponds to whatever pH is acceptable. The (Na,K)
Cl waste is a neutral salt and deposition in an abandoned mine poses no
problems. As the sole supplier of 100 tons K/year with NaK selling for
$1.55/lb in 200 Ib barrels, the economics of these disposal processes
certainly aren't constricting.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The disposal processes for sodium and sodium-potassium alloys are
currently adequate at the industrial level, and these materials should
not be considered as candidate waste stream constituents for national
disposal.
232
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7. REFERENCES
0384. Personal communication. California Water Quality Control Board,
Los Angeles region9 to M. Appel, TRW Systems, Jan. 14, 1972.
0395. Personal communication. Mine Safety Alliances Corporation, to
M. Appel, TRW Systems, Jan. 12, 1972.
0398. Personal communication. Atomics International to M. Appel, TRW
Systems, Jan. 12, 1972.
0399. Personal communication. AI Liquid Metals Engineering Center, to
M. Appel, TRW Systems, Jan. 10, 1972.
0400. Personal communication. J. Hutchinson, Murry H. Hutchinson & Sons,
to M. Appel, TRW Systems, Jan 12, 1972.
0401. Personal communication. Capt. Putman, California Department of
Fish and Game, to M. Appel, TRW Systems, Jan. 12, 1972.
0463. Lyon, R. N. Liquid metals handbook. U. S. Office of Naval Research,
June 1952.
0464. De Vries, P. E., and J. M. Scarborough. Sodium purification process.
U. S. Patent 3S 600, 155.
0593. Personal communication. Atomic Energy Commission, Gaithersburg,
Maryland, to M. Appel, TRW Systems, Feb. 18, 1972.
0595. Personal communication. B. Bryden, Ethyl Corporation, to M. Appel,
TRW Systems, Feb. 8S 1972.
0596. Personal communication. Mr. Hoyle, DuPont Corporation, to M. Appel,
TRW Systems, Feb. 9, 1972.
0664. Personal communication. M. B. Burton, E. I. Du Pont de Nemours and
Company, to M. Appel3 TRW Systems, Feb. 17, 1972.
0665. Personal communication. W. P. Samuels, Union Carbide Corporation,
to M. Appel, TRW Systems, Feb. 14, 1972.
0765. Manufacturing Chemists Association. Sodium. Chemical Safety Data
Sheet SD-47, 1952. 12 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
0767. Sodium. 2d rev. ed. 1^ Chemical Profiles. New York, Schnell
Publishing Company, Oct. 1, 1969.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
233
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
ri. M. Name
btructura
IUC Name ^OPTUM (374)
Common Names SODIUM Na
1 Formula
Molecular Wt. 23.0 Melting Pt. 97-9 C Boiling Pt. 892 c
Density (Condensed) 0-971 @ 20 C Density (gas) °-003 NaNH, + 1/2 H,
3 22
Acid, Base Properties stropglv basic
' Highly Reactive with Moisture, human tissue, spontaneously flammable
heat, ianites in Cl». CS~. POCK, acids
r c c- -3
Compatible with metals
in air, evolves H~ and;
! Shipped in Pumped in and out of tank cars molten; shipped under N0
ICC Classification Flammable solid, yellow Coast Guard Classification Flam, solid. I
_ 70 one label, 25 Ib
Comments See. 73.206
for 1155-1735 K: loq P (atm) = 6. 67176-5544. 97/T-O. 61344 log T
yellow label i
.
234
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name SODIUM-POTASSIUM ALLOY (402)
Common Names NaK
Structural Formula
NaK
Molecular Wt. 77%K, 23%Na .
Melting Pt.
-12.5 C
Boiling Pt._
1446 F
Density (Condensed) 0.732 g/ml @ 950 F Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
0.46 psiag 950 F &
Flash Point
Autoignition Temp._
Flammability Limits in Air (w.t %) Lower dangerous
Explosive Limits in Air (wt. %) Lower dangerous
Upper_
Upper_
Solubility
Cold Water Reacts to evolve Hg Hot Water reacts
Others: NH3(aq.)
Acid, Base Properties strongly basic
Ethanol
reacts
Highly Reactive with
moisture, human tissure., spontaneously flammable in air, evolves
H, and heat
Compatible with metals
Shipped in under inert gas in steel containers with valves and downpipes
ICC Classification flam, solid, yellow label, Coast Guard Classification
Comments.
Sec. 73.206
ID
Forms explosive mixtures with chlorinated hydrocarbons
235
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PROFILE REPORT
Sodium Azide (378)
1. GENERAL
Sodium azlde, NaN3, is a colorless crystalline substance described as
being highly toxic.0766
Sodium azide is prepared from sodium amide and nitrogen monoxide
according to the following reaction :
2NaNH2 + N20 -*• NaN3 + NaOH + NH3
Fairmont Chemical Company in Newark, New Jersey is the only
manufacturer of sodium azide in the United States. Last year they
produced about 500,000 Ib of the chemical for domestic use.
Sodium azide is used mainly as a reactant in the production of lead,
silver, antimony, and mercury azides. It also has a medical use in
treating hypertensive encephalopathy and other conditions which demand
immediate lowering of blood pressure (dose 0.2 to 4.0 micrograms/kg body
weight/minute intravenous).
The sources of sodium azide wastes may include the following:
(1) sodium azide manufacturers; (2) sodium azide wholesalers; (3) manu-
facturers that use sodium azide as a reactant in their production process.
However, DuPont claims that in their process for making lead azlde, sodium
2025
azide does not appear in the waste stream. This is because there 1s
essentially a 100 percent conversion of sodium azide to lead azlde in the
reaction process.
237
-------
The physical and chemical properties of sodium azide are summarized
in the attached worksheet.
2. TOXICOLOGY
The toxicity of sodium azide is due to the azide group (-NNN). Much
of the knowledge of azide toxicity has been gained from industrial
exposures and laboratory studies involving hydrazoic acid, HNg. Dilute
aqueous solutions and hydrazoic acid vapors from azide reactions have
caused noticeable and measurable effects in industrial and laboratory
workers.
Hydrazoic acid is easily adsorbed into the bloodstream after
inhalation of the vapor or spray. The chief physiological effect is a
marked lowering of the blood pressure with an accompanying rise in heart
beat and an increase in the respiration rate. Eye and nose irritation,
headache, weakness, and unsteadiness have also been reported following
continued industrial exposures. Recovery from these effects is rapid and
low level (less than 4 ppm) exposures which cause these symptoms do not
?n?fi
appear to produce any permanent abnormal conditions.
The estimated oral ID™ value to the rat fo^ sodium azide is 46 mg/kg
1312
of body weight. The 48-hour Median Tolerance Limit (TL ) of sodium
azide for bluegills is 980 micrograms/liter as established by the Federal
Water Pollution Control Administration, and is indicative of the
water pollution hazard associated with sodium azide.
3. OTHER HAZARDS
The explosive hazard of sodium azide is moderate when shocked or
exposed to heat. However, the explosiveness of sodium azide increases
somewhat when it is contaminated with certain materials. When heated to
decomposition in air, sodium azide emits toxic fumes of nitrogen • oxides.
238
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Care should be exercised in handling sodium azide because of the
high toxicity and explosive nature of the compound. The use of leather
gloves, a heavy face shield, and a laboratory coat is recommended in
handling the material. It is advisable to work behind a barricade (body
shield or wall). Avoid unnecessary heat, friction or impact.
2024
Sodium azide should be stored in a warehouse in metal containers.
It should be stored away from foodstuffs, feeds, or any other material
intended for human or animal consumption.
Sodium azide must be transported in wooden boxes with inside
containers which are securely closed paper bags, placed within a
waterproof duplex bag. The net weight of material in one outside box
should not
every box.
0272
should not be over 100 Ib. There must be a "Poison B" label on
Disposal/Reuse
Fairmont Chemical Company has a policy of accepting excess amounts
of sodium azide and contaminated sodium azide for reprocessing.
In the laboratory, small quantities of waste azide solutions can
be discharged into the sink if adequate cold water dilution is provided.
The safe disposal of sodium azide is defined in terms of the recommended
provisional limits.
Basis for
Contaminant and -Provisional Limit Recommendation
Environment
3
Sodium Azide in air 0.02 mg/m Provisional limit for
NaOH
Sodium Azide in water 0.1 mg/1 Provisional limit for
and soil NaOH
239
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Concentrated Wastes
Option No.1 - Reprocessing/Disposal. Fairmont Chemical Company, the only
major producer of sodium azide in the United States has indicated its
willingness to accept excessive or waste sodium azide for reprocessing,
purification or disposal. The details of the reprocessing technique
were not revealed. Fairmont Chemical's method for disposal of sodium
azide is to react it with sulfuric acid solution and sodium nitrate in
1 p^c
a hard rubber or teflon vessel. Nitrogen dioxide is generated by
this reaction and the gas is run through a scrubber before it is
released to the atmosphere. It is conceivable that any industry that
handles sodium azide in significant amounts would probably have
facilities for reacting the sodium azide and treating the evolved
nitrogen dioxide gas.
Option No.2 - Incineration. The complete and controlled oxidation of
sodium azide in air or oxygen with adequate scrubbing and ash disposal is
possible if the sodium azide is mixed with other combustible wastes.
Since the combustion process produces nitrogen and sodium oxides, an
adequate gas clean-up system must be installed to alleviate the air
pollution problem.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Considering the small production and consumption of sodium azide,
as well as provisions for return of waste sodium azide to the producer,
it is felt that sodium azide is not a candidate waste stream constituent
for national disposal. The high cost of sodium azide is in itself an
incentive to the manufacturers that use the compound to minimize the
amount of waste material. The simple method of disposing of sodium azide
by reaction with sulfuric acid and sodium nitrate can easily be performed
by any firm that handles the compound. In summary, processes for the
exclusive treatment of wastes containing sodium azide are not recommended
for inclusion in the National Disposal Site scheme.
240
-------
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. Apr. 1, 1968.
Washington, Federal Water Pollution Control Administration. 234 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1236. Personal communication. B. Pick, Fairmont Chemical Company to
J. Clausen, TRW Systems, Mar. 16, 1972. Sodium azide waste
treatment.
1492. The Merck index of chemicals and drugs. 7th ed. Rathway,
New Jersey, Merck Co., Inc., 1960. 1,634 p.
2024. Personal communication. B. Pick, Fairmont Chemical Company to
D. DalPorto, TRW Systems, June 16, 1972. Sodium azide production
data and reprocessing information.
2025. Personal communication. Mr. Patterson, DuPont Chemical Company to
D. DalPorto, TRW Systems, June 19, 1972. Aqueous sodium azide
waste treatment.
2026. Safety in handling hazardous chemicals. Los Angeles, Matheson,
Coleman and Bell, 1969. 24 p.
241
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Azide (378)
Structural Formula
IUC Name
Common Names.. Sodium Azide
NaN3
cc no . decomposes in
Molecular Wt. 65'02 _ Melting Pt. decomposes Boiling Pt. a vacuum
Density (Condensed) 1.846 @ 20 __ Density (gas) _ & __
Vapor Pressure (recommended 55 C and 20 C)
Flash Point _ Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 41.7g/100cc @ 17 C Hot Water _ Ethanol 0.314/100cc
Others: _ 16 C
Acid,' Base Properties
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification Pois°n B Coast Guard Classification Poison B
Comments Shock will explode it; when heated to decomposition, it emits toxic fumes
of nitrogen oxides, and may explode.
References (1) 0766
242
-------
PROFILE REPORT
Sodium Chlorate (385)
1. GENERAL
Introduction
Sodium chlorate, NaC103, is a white crystalline solid which is slightly
hygroscopic. The compound is a soluble oxidizing agent in acid and neutral
solutions, but in basic solutions at room temperature it does not show
oxidizing properties.
In acid solutions, sodium chlorate is a source of chloric acid, a
powerful oxidizing agent. Chlorates are strong oxidizers, comparable
to manganese materials and chlorine. They are stronger than bromates or
2122
iodates. The molten salt is also a powerful oxidizing agent.
In '1969, there were 187,125 tons of sodium chlorate produced in the
United States. In 1970, the production was 221,000 tons and the projected
annual demand for sodium chlorate by 1974 is 265,000 tons.
Manufacture
All of the chlorate produced in the United States is prepared by
electrolysis of a solution of chloride and chlorate in a diaphragmless
cell.1433
A number of reactions take place at the anode. Chlorine is liberated
and reacts with hydroxide 1on to produce hypochlorite and chloride ions,
and with water to form hypochlorous and hypdrochloric acid:
243
-------
2e"
n j- u n — "^i n i u n~
i< I o T n^u " riL. i u ~ n L.I
By maintaining the electrolyte at pH 6.2 to 7, favorable conditions
for the reaction between hypochlorous acid and hypochlorite ions can be
maintained, so that chlorate is formed. This is a slow reaction, and
takes place in the body of the cell rather than at or near the anodes.
The reactions for the electrolyses of sodium chloride, and for the
formation of hypochlorus acid and hypochlorite ion from the evolved
chlorine, may be combined with the reaction for the hypochlorous acid-
hypochlorite ion to form chlorate, giving the overall reaction:
NaCl + 3H20
Six faradays are required per mole of sodium chlorate formed; the overall
1433
reaction is 100 percent efficient.
Large scale commercial facilities for the manufacture of sodium chlorate
include the following :
Kerr-McGee Chemical Corporation; Hamilton, Mississippi and Henderson,
Nevada
Hooker Chemical Corporation; Columbus, Mississippi
Penn-Olin Chemicals; Calvert City, Kentucky.
244
-------
Uses
Sodium chlorate is used extensively as a source of chlorine dioxide
for paper pulp bleaching. It is used in tanning and finishing leather,
in processing of furs, in the preparation of dyes, as a mordant in textile
dyeing and printing, for production of bromine from brines, for medicinal
purposes, in metallurgy operations, processing of uranium ore, and as an
intermediate in the production of perchlorates. In agriculture, it is
used as a cotton and tomato defoliant, and it is used as a weed killer.
Battery-active manganese dioxide can be made by a chemical process using
sodium chlorate oxidation of manganese. It is also a selective oxidizing
2122
agent in organic synthesis.
Sources and Types of Sodium Chlorate Wastes
The sources of sodium chlorate wastes may include the following:
(1) sodium chlorate manufacturers, (2) agricultural users, (3) government
facilities that.store, transport, and use sodium chlorate, and (4) commercial
and industrial processes including those from paper manufacturers, textile
dyeing and printing operations, metallurgy operations, etc.
In general, most of the sodium chlorate waste will be in concentrated
form as a result of spills occuring in the transporting and handling of
the materials or as a partially degraded or contaminated surplus material.
For example, the U. S. Army currently has 12,000 Ib of sodium chlbrate-
borate mixture stored in Pennsylvania awaiting disposal. The electrolytic
process used in manufacturing sodium chlorate is a closed process and no
waste is generated other than accidental spills or the small amount of
chlorate, mixed with other solids, which is left as residue after the fil-
tering process. In the bleaching process (in paper manufacturing) there
is essentially a 100 percent conversion of sodium chlorate to chlorine
dioxide, so that there is no waste chlorate other than spills involved in
handling the material/'^
245
-------
Dilute sodium chlorate wastes include those generated in agricultural
runoffs and possible spent solutions used to clean empty containers.
Physical and Chemical Properties
The physical and chemical properties of sodium chlorate are included
in the attached worksheet.
2. TOXICOLOGY
Sodium chlorate is not highly toxic, but ingestion or excessive
inhalation of dust should be avoided. Ingestion of relatively large
quantities (15-30 gm) of the material may prove fatal. Abdominal pain,
nausea and vomiting, diarrhea, pallor, blueness, shortness of breath,
unconsciousness and collapse are the immediate symptoms following ingestion
of toxic amounts of sodium chlorate. Prolonged exposure to sodium chlorate
dust may cause skin irritation to the mucous membranes of the eyes, nose
and throat.2123
The intraperitoneal LD5Q value of sodium chlorate to the mouse is
550 mg/kg of body weight.1312
3. OTHER HAZARDS
Sodium chlorate is a strong oxidizing agent and constitutes an
extreme fire and explosion hazard if allowed to come in contact with
organic or combustible materials„ acids, or reducing substances.
Dry materials such as wood, clothing, paper, and leather contaminated
with sodium chlorate may easily be ignited by friction, percussion, or
any source of heat such as flames, sparks, welding torches, lighted
cigarettes, and hot surfaces. Ignition can also occur when sodium chlorate
dust comes in contact with clothing that is damp with perspiration and
which then dries.
-------
Mixtures of sodium chlorate with oxidizable organic substances such
as oils, greases, waxes, solvents, paints, sugars, alcohols, wood dust,
lint, and vegetable dusts are potential fire and explosion hazards.
Certain easily oxidizable or finely divided inorganic materials such
as ammonium compounds, sulfur and its compounds, sulfides, phosphorous,
powdered metals, and metal salts (especially copper) are potential fire
2124
and explosion hazards when mixed with sodium chlorate.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, Transporation
In handling chlorates, workers should wear clean coveralls daily, as
well as washable rubberized gloves, boots or shoes. A washable head
covering should also be used. In dusty conditions, goggles and an approved
dust respirator should be used. Use of leather shoes or gloves is not
recommended because when contaminated it may not be possible to remove
completely all traces of chlorate from the leather. Workers should avoid
using oils, greases or protective creams on skin, as flammable mixtures
2123
may develop on prolonged contact of these materials with chlorates.
Dry bulk sodium chlorate should be stored in lined steel, concrete
or tight glazed tile silos or tanks. Dessicated air should be supplied
to prevent caking from atmospheric moisture. Storage of sodium chlorate
in drums should be in a cool, dry, fireproof building. Dry concrete
floors are preferable to wooden decks. Spillage should be swept up and
removed at once. Sodium chlorate solutions or slurries may be stored
2123
in steel-lined tanks.
247
-------
Sodium chlorate is shipped in metal drums (returnable and single trip)
and in tank cars. It is classified by the Department of Transportation
(DOT) as an oxidizing material and must be packed in DOT specification
containers when shipped by rail, water or highway. All of the DOT regulations
2123
regarding loading, handling, and labeling must be followed.
Disposal/Reuse
Contaminated or degraded sodium chlorate is not currently reprocessed.
Contaminated sodium chlorate is disposed of by one of the methods described
in Section 5.
Although sodium chlorate is very soluble in water, it does not appear
to be a serious water pollution problem. The small amount of sodium chlorate
that is discharged into sewers, lakes, or streams will readily supply oxygen
to the BOD or COD present in the water and be reduced to the chloride ion.
Chlorate ion will be rapidly reduced to the chloride ion by any reducing
2120
agent present in the water.
For the safe disposal of sodium chlorate, the acceptable criteria for
its release into the environment are defined in terms of the following
provisional limits:
Contaminant and Basis for
Environment Provisional Limit Recommendation
3
Sodium chlorate 0.02 mg/M Provisional
in air limit for NaOH
Sodium chlorate 0.10 ppm (mg/1) Provisional
in water and soil limit for NaOH
248
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Reduction
The most acceptable method for disposing of both solid and aqueous
sodium chlorate waste is to reduce it with a reducing agent in a plastic
vessel. If the waste is present in the solid form, it is first dissolved
and then reduced in the vessel. The most economical and readily available
reducing agent is iron filings. Pickle liquor from the iron and steel in-
dustry is also a good reducing agent. The sodium chlorate is reduced to
sodium chloride in the reduction process and the resulting iron precipitate
can be removed with a lime slurry, soda ash, or sodium hydroxide followed
2121
by a lagooning operation.
Option No. 2 - Incineration
A small amount of sodium chlorate waste can be incinerated if it is
mixed with a large quantity of other combustible waste. An adequate gas
clean up to remove the gaseous combustion products must be installed to
2121
alleviate the air pollution problems.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Considering the small amount of waste sodium chlorate present in in-
dustry and the lack of a water pollution problem associated with the
compound, it is felt that sodium chlorate waste streams do not warrant
National Disposal Site treatment. The simple method of disposing of
sodium chlorate by reduction with ferrous ion can easily be performed by
a firm that handles the compound. In summary, processes for the exclusive
treatment of sodium chlorate are not recommended for inclusion in the
National Disposal Site scheme.
243
-------
7. REFERENCES
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.
1506. Sodium chlorate. JJT_ Chemical Profiles. New York, Schnell Publishing
Company, 1970. 200 p.
2120. Personal communication. Dick Wohletz, Kerr-McGee Corporation, to
D. Dal Porto, TRW Systems, June 26, 1972.
2121. Personal communication. G. Gruber, TRW Systems, to D. Dal Porto,
TRW Systems, June 28, 1972.
2122. Sodium chlorate as an oxidizing agent. Bulletin No. A-ll. Los
Angeles, Kerr-McGee Corporation, 1966. 16 p.
2123. Manufacturing Chemists Association. Properties and essential infor-
mation for safe handling and use of sodium chlorate. Chemical
Safety Data Sheet SD-42. Washington, 1952. 11 p.
2124. Technical data sheet on sodium chlorate. Bulletin EC-1. Los Angeles,
Kerr-McGee Corporation, 1968. 4 p.
250
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Chlorate (385)
IUC Name
Common Names Sodium Chlorate
Structural Formula
NaCIO,
Molecular kit.
106.45
Melting Pt. 248 C
Density (Condensed) 2.490 9 15 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 Q)
(? 0
Decomposes @
Boiling Pt. 300C
9
Flash Point
Auto1gn1t1on Temp._
Flammabmty Limits 1n A1r (wt %) Lower_
Explosive Limits 1n A1r (wt. X) Lower
Upper_
Upper_
Solubility
Cold Water 79 g/100 g & PC
Others:
Hot Water 140g/100 g (350 C Ethanol
Add, Base Properties,
Highly Reactive with organic substances, solvents, oils, sulfur sulfides, phosphorous, powderet
metals and ammonium salts.
Compatible with Sulfates, carbonates, nitrates and oxides.
Shipped 1n metal drums (returnable and single trip), tank cars.
oxidizing material,
ICC Classification oxidizing material.yellow Coast Guard Classification yellow label
I abel
Comments
References (1) 0766.
251
-------
PROFILE REPORT
Sodium Iodide (395)
1. GENERAL
Introduction
Sodium iodide, Nal, is a white, deliquescent crystalline solid.
Sodium iodide is prepared by treating ferroso-ferric iodide (see discussion
in Section 5) with sodium carbonate. Iron hydroxide is removed from the
reaction product by filtration. The filtrate, which contains the sodium
iodide in solution, is concentrated and the sodium iodide recovered by
crystallization. Sodium iodide is used in photography, medicine, analytical
chemistry, and (in solution) as a solvent for iodine.1492'1662
Physical/Chemical Properties
The physical/chemical properties of sodium iodide are summarized in
the attached worksheet.
2. TOXICITY
Sodium iodide is generally nontoxic, unless an overdose is ingested.
3. OTHER HAZARDS
Sodium iodide becomes dark if exposed to light due to the liberation of
molecular iodine. The toxicity reactivity and corrosive characteristics are
sharply due to the free iodine present.
253
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
Sodium iodide should be protected from moisture and light. There
are no other special handling or storage requirements. Sodium iodide is
shipped in 25-, 100-, and 300-1b drums. There are no Department of
Transportation (DOT) shipping regulations covering this material.
Disposal/Reuse
Because of economic considerations, iodides are usually recovered for
reuse. The methods for recovery are discussed in Section 5. The safe
disposal of Nal is defined in terms of the recommended provisional limits
in the atmosphere and in water and soil environments. These recommended
provisional limits are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Sodium Iodide 0.02 mg/M3* 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Sodium Iodide 0.10 mg/1* Stokinger & Woodward Method
^Estimated
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Iodine can be recovered from concentrated sodium iodide wastes or
waste streams by the processes used to recover iodine from brines. The
processes used are discussed in the following paragraphs as Options No.l
and No.2.
*. ; Option No. 1 - Silver Iodide Process
Sodium iodide in dilute aqueous solution (either as a waste stream
or from off-specification' sodium iodide) is reacted with a 2 percent
254
-------
silver nitrate solution in the presence of ferric chloride solution as a
coagulant. A wood tub is usually used. The mixed AgI-Fe(OH)~ precipitate
produced by the reaction settles and is treated with concentrated
hydrochloric acid to dissolve the iron hydroxide precipitate. Iron scrap
is added, forming ferrous iodide and silver metal, the reaction being
completed within an hour. The silver is removed by filtration and converted
to silver nitrate. The ferrous iodide solution is treated with an oxidant
such as chlorine to precipitate the iodine. The iodine is separated
and melted under concentrated sulfuric acid; the purified iodine is taken
off, freed of residual H,,S04 and packaged.
Option No. 2- Blow Out Process
A dilute solution containing sodium iodide is acidified with sulfuric
acid to a pH under 3.5. The acidified brine is chlorinated and stripped
in an acidproof brick-lined blowing-out tower, by passage through the tower
countercurrent to a stream of air. The iodine-laden airstream is then
passed through an absorbing tower countercurrent to recirculating dilute
sulfuric acid. Sulfur dioxide is added to the sulfuric acid effluent from
the tower to reduce the free iodine:
I2 + S02 + 2H20 +2HI + H2S04
The iodine is reprecipitated by chlorinating the HI-H2SO. liquor. The
precipitated iodine is filtereds dried with concentrated sulfuric acid,
and heated to melt the iodine, which is taken off, freed of residual
H9SO,, and packaged. This process is in operation in the California oil
1662
fields and is a continuous process. Waste sodium iodide can be sent
to plants operating this process, but the process cannot be used
economically to treat small batches of sodium iodide.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Sodium iodide wastes can be treated at plants recovering iodine from
brines using the processes described in Options No. 1 and 2, or small quantities
255
-------
of sodium iodide contaminated wastes can be accumulated at National
Disposal Sites and sold to iodine recovery plant operators for recovery
via Options 1 or 2. Because of the value of iodine, it is not anticipated
that sodium iodide will be sent to National Disposal Sites, but it is
anticipated that most wastes will be treated at existing iodine recovery
plants or at the point of origin by Option No. 1.
?56
-------
7. REFERENCES
1492. Ross, A. and E. Ross. Condensed chemical dictionary. 6th ed. New
York, Reinhold Publishing Corporation, 1961. 1,256 p.
1662. Shreve, R. N. Chemical Process industries. 2nd ed. New York, McGraw-
Hill Book Company, 1956. 1,004 p.
257
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Iodide (395)
Structural Formula
IUC Name
Common Names N T
Molecular Wt. 149.92 Melting Pt. 651 C Boiling Pt.1300
Density (Condensed) 3.667g/cc @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
@ 9 G>
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 158.7g/100 ml at 0 C Hot Water 256.8g/100 ml at 10° £thanolslightly soluble
Others:
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in Drums
/2) • I?}
ICC Classification Nonev Coast Guard Classification Nonev '
Comments.
References (1) 1570
(2) 1492
258
-------
PROFILE REPORT
Sodium Silicates (403)
1. GENERAL
Introduction
The sodium silicates, Na20 ' X Si Op(X = 2,3,4,5), are made by fusing
sodium carbonate and silica (sand) in a furnace resembling that used for
the manufacture of glass. The reaction that takes place at 1,300 C is
as follows:
Na2C03 + X Si02 + Na2 0 • X Si02 + C02
The most common commercial silicates are those where X equals 2.0 and 3.2.
The product upon cooling forms a clear light bluish-green glass. To make
sodium silicate solutions, the product is ground and dissolved in water
in a steam injected, pressurized reactor. Alternatively, the melt from
the furnace is passed directly without chilling into an open rotary
dissolver where solution is effected at atmospheric pressure.
The silicates as 32 to 47 percent solutions find considerable use as
adhesives for many kinds of materials, especially plywood and paperboard
for corrugated containers. Water glass solutions are also used in
detergents, metal cleaning, fireproofing and sizing. '
Physical/Chemical Properties
The chemical/physical properties of the silicates are summarized in
the attached worksheet.
259
-------
2. TOXICITY
The sodium silicates are generally nontoxic. In water, their
solutions are strongly basic, corrosive, and will cause irritation to the
skin and respiratory system.
3. OTHER HAZARDS
When dissolved in water, the silicates are strongly alkaline and will
attack aluminum.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT;
Handlings Storage, and Transportation
Solutions of the silicates, due to their alkalinity, attack aluminum.
There are no other special handling and storage problems. The silicates
may be shipped in solution in drums or dry in bags or fiber drums. There
are no Department of Transportation (DOT) shipping regulations covering the
silicates.0766
Disposal/Reuse
Industrially contaminated materials will probably not be considered
for reprocessing for reuse based on economic consideration. The safe dis-
posal of the sodium silicates is defined in terms of the recommended pro-
visional limits in the atmosphere and in water and soil. These recommended
provisional limits are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Sodium Silicate 0.02 mg/M3* 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Sodium Silicate 0.10 mg/1* Stokinger & Woodward Method
*Estimated
260
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The disposal of the sodium silicates is both simple and effective.
The silicates are dissolved in water9 acidified with 6M-HC1 and allowed to
stand for at least a day. The liquid is decanted into another container,
neutralized, diluted, and discharged into a sewer or stream. The sludge
(silica gel) is added to a landfill.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The sodium silicates have been classified on a preliminary basis as
probable candidate waste stream constituents for municipal disposal. Based
on the disposal process described in Section 5, it may be concluded that
waste treatment for the sodium silicate can be handled adequately locally
arid no consideration for National Disposal Site treatment is warranted.
261
-------
7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal
manual. 2d ed. Washington,, 1969. 176 p.
0776. Sax, N. I. Dangerous properties of industrial materials. 2d ed.,
New York, Reinhold Publishing Corporation, 1957. 1,467 p.
0955. Sittig, M. 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.
1662. Shreve, R. N. Chemical process industries. 2nd ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
262
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Sodium Silicates (402)
Structural Formula
IUC Name
Common Names Water Glass
NaO . XSi02 (X=2,3,4,5)
Not.a .fixed
Molecular Wt. composition Melting Pt. Boiling Pt.
Density (Condensed) @ Density (gas)_ &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water miscible Hot Water misclble Ethanol miscible
Others:
Acid, Base Properties strongly alkaline in aqueous solution
Highly Reactive with Gels form below pH 3 in water
Compatible with
Shipped in Paper bags, drums, tank trucks as solution
^
ICC Classification None^ - Coast Guard Classification
Comments
References (1) 1492
263
-------
PROFILE REPORT
Strontium (410)
1. GENERAL
1433
Kirk-Othmer reports that there is no known commercial use for
strontium metal- World annual production is approximately 1,000 Ib, which
currently sells for $10.80/lb. At this price concentrated waste is a very
attractive candidate for purification and recycling. The single primary
North American producer and distributor 1s Dominion Magnesium, Ltd.,
^\COO 1 /I OO
Toronto, Canada, ' who report that they generate no strontium waste.
Their principal customer is a secondary distributor, Ventron Corporation,
Beverly, Massachusetts, who purchase about 200 Ib annually. They report
that this quantity is broken down and sold in 10 to 15 Ib lots to various
research laboratories scattered throughout the country.
2. TOXICOLOGY
No toxicological information pertaining to strontium metal was found
1312
in the open literature and the 1971 HEW Toxic Substances Annual List
does not list strontium as a toxic substance. It is suggested that strontium
probably resembles calcium physiologically and that it only represents a
toxicological hazard as the radioactive isotope strontium 90.
3. OTHER HAZARDS
Strontium resembles calcium chemically. It reacts with water to
release hydrogen, which represents a fire and explosive hazard in itself,
and form SrfOH^ which is caustic. Metallic strontium represents a
moderate fire hazard when in the form of dust and exposed to direct flame.
265
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Strontium wastes resulting from occasional laboratory use of small
portions (generally less than 1 Ib) of the metal are chemically
reacted with water whereupon small amounts of hydrogen are evolved and
the-hydroxide is formed. The hydrogen is generally evolved in small
quantities at sufficiently slow rates so that it is immediately diluted
with room air and vented to the atmosphere in concentrations well below
its flammability limits. The hydroxide [SrCOHjg] is then further diluted
with water and washed down the drain. The SrCOH^ in solution in the
sewer system is very dilute and causes no problems.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The practice of conversion of metallic strontium to strontium
hydroxide utilizing water addition with subsequent dispersion of evolved
hydrogen (in concentrations well below its flammability limit) to the
atmosphere and the hydroxide to the sewer system is judged to be an
adequate method of disposal.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Because of the small quantities of waste involved, the lack of
toxicological hazard, and the simplicity of the disposal technique,
metallic strontium is not judged to a candidate waste stream constituent
requiring National Disposal Site treatment.
266
-------
7. REFERENCES
0601. Personal communication. Mr. Fraser, Ventron Corporation, to M. Appel,
TRW Systems, Feb. 10, 1972.
0602. Personal communication. Dominion Magnesium Ltd., to M. Appel,
TRW Systems, Feb. 9, 1972.
1312. Christensen, H. E. ed. Toxic substances annual list 1971. Washington,
U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encylcopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1963-1971.
267
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
. M. Name
IUC Name STRONTIUM (410)
Conroon Names STRONTIUM
Structural Formula
Sr
Molecular Wt. 87.63
Melting Pt. 770 C
Boiling Pt. 1380 C
Density (Condensed) 2.6 g/cc @ 20. _C Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
10 mm @ 898 C ?
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower Moderate (dust) Upper_
Explosive Limits in Air (wt. %) Lower Moderate (dust) Upper_
Solubility
Cold Water reacts to form Sr(OH)Hot Water reacts
t i /M i * flrt
Ethanol slightly
Others:
Acid, Base Properties basic
Highly Reactive with water to evolve H.
Compatible with Most metals
Shipped in metal drums or barrels not exceeding 25 1b net
ICC Classification flam, solid
Comments
_ Coast Guard Classification _
rnntainp^ rnnt.pnt.^ mu<:t hp lahplpH if chippprf nypr yiatpf Spr 7?-153t 73.154
268
-------
PROFILE REPORT
Tacom'te Tailings (419)
1. GENERAL
The processing of taconite follows the classic extractive metallurgical
method of crushing, grinding and separation (in this case by magnetic and
hydraulic methods). The concentrates are then mixed with small amounts of
clay and pelletized for shipment to iron smelters while the tailings, ap-
proximately two-thirds of the input ore, are left for disposal. A flow
sheet .for the taconite concentration portion of the Reserve Mining Company's
operation at Silver Bay, Minnesota, which is fairly typical of today's
taconite concentration plants, is presented (Figure 1).
i,
As described by Aleshin and Schwartz, taconite ore averages 27
percent iron and 48 percent silica. The Mesabi range of Minnesota is the
largest producer in the United States and annually produces some 66 million
tons of tailings.
Concentrates contain some 99+ percent of the magnetic iron in the ore
1975
and the magnetic portion of the ore constitutes some 70 percent of the
total iron content.
As previously noted, some two-thirds of the original ore is disposed
of as tailings. Both coarse and fine tailings are produced by the concen-
tration operation with some 90 percent of the ore being ground to -325
mesh. The tailings contain approximately 8 percent iron and a remainder,
which is primarily the original siliceous gangue. "Some lime (1 Ib/ton
of tailings solids) or a proprietary cationic flocculating agent (1/8 ppm
of pulp ) are currently used to thicken the effluent from the concentrator
to about 45 percent solids."
-------
RAILROAD FROM
MINE
-tiiiiiiiiim
ROTARY
DUMP
PAN FEEDER
CONVEYOR
PAN FEEDER
CAR DUMPER PLANT
FINES
ICONE CRUSHER
I
VIBRATING SCREEN
CONVEYOR/
o
FINE CRUSHER PLANT
FINISHING HYDRO
CONCENTRATE PLANT
SUMP TANK (_^
TAILINGS TAILINGS
u CONVEYOR
Figure 1. Reserve Mining Company; Silver Bay Operation
2488
-------
2. TOXICOLOGY
Tacom'te tailings constitute a negligible toxicological hazard.
3. OTHER HAZARDS
Although taconite tailings present no toxicological hazard, they do
constitute an environmental problem on the basis of two elemenst: (1) the
sheer volume of the materials involved and (2) the dust problems encountered
because of the fineness of the material.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Taconite tailings are presently disposed of by collection in tailings
ponds (see Profile Report on Copper [275] Lead and Zinc [276] tailings) or,
in one major case, by discharging the tailings into Lake Superior. The
discharge into the lake was premised on a phenomenon known as the "heavy
2487
density current". As a result the discharge waters carry the tailings,
which are heavier than the surrounding waters, into an area off shore where
the lake depth is approximately 900 feet. It is indicated that the density
of tailings in the waters discharged is 14,000 milligrams per liter.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Of the two disposal methods described in Section 4 of this report, only
that of ponding is judged to be an acceptable method. The acceptability of
the discharge of tailings into large potable water sources has not been
determined. The discharge should be curtailed until the environmental
effects of this practice are determined.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Because of the negligible toxicological effect, taconite tailings
are not considered candidates for National Disposal Sites.
271
-------
The recommendations for research and development to alleviate the
environmental effects contained in the Profile Report on Copper (275),
Lead and Zinc (276) Tailings also apply to taconite tailings. The dis-
posal of tailings into bodies of water is presently in litigation question-
ing the environmental damage caused by this method.
272
-------
7. REFERENCES
0169. ITT Research Institute for the U.S. Bureau of Mines. Techno-economic
analysis of mining and milling wastes. Contract No. G6027. 1969.
1975. U.S. Bureau of Mines. Mineral facts and problems. Bulletin No. 650,
1970.
2487. Environmental Reporter. State of Minnesota vs. the Reserve Mining
Company. 1972.
2488. Engineering and Mining Journal. Portfolio of flowsheets, June 1969.
273
-------
PROFILE REPORT
Thallium (430) and Thallium Sulfate (431)
1. GENERAL
Production
There is one producer of thallium and thallium sulfate (TIgSO*) in
the United States, the American Smelting and Refining Company, Denver,
Colorado. 1433' 2179' 2239' 2182 Its thallium department "operates on
a very intermittent basis, having produced thallium in five short
campaigns over the past twenty years. The department is not now in
2242
operation and is not scheduled for the foreseeable future."
Thallium is produced as a byproduct of the production of cadmium,
which, in turn is produced as a byproduct of the production of zinc. The
zinc dross remaining from the smelting of lead and zinc sulfide ores is
leached with sulfuric acid to solubilize the cadmium and thallium, which is
present in concentrations ranging from several ppm to 2000 ppm in the dross.
The solution is electrolyzed to produce a cadmium-thallium alloy containing
5 to 20 percent thallium. This alloy is then solubilized as the hydroxides
by the addition of hot water, and the cadmium is then precipitated by the
addition of sodium bicarbonate. The filtrate is then treated with hydrogen
sulfide to precipitate thallous sulfide, which in turn is dissolved in
sulfuric acid. Electrolysis of the thallous sulfate solution yields
pure thallium metal. The commercial sulfate is made by redissolving
this metal in sulfuric acid and crystallizing from the saturated
solution. 1287' 1433> 2239' 2242> 224°
Use
Historically, thallium and thallium sulfate have been used as
depilatories and in rodenticides and insecticides. However, their extreme
toxicity has caused the U.S. Food and Drug Administration and the
275
-------
U.S. Department of. Agriculture to ban their use for these purposes.
Customers for thallium sulfate must furnish an affidavit stating that
the material will not be used for rodenticide or insecticide
manufacture. 1433» 2242
These were the only uses for these materials, so that currently there
is no commercial use of any significant extent. Parts per billion
quantities of thallium have been used as dopants in Nal crystals for
y-ray scintillation counting and the U.S. Army is experimenting with Hg-Tl
alloys for arctic thermometers, since the eutectic temperature of -59 C
is 20 C lower than the freezing point of pure mercury.
In the first seven months of 1972, total thallium metal sales amounted
??&?
to 10 Ib, while thallium sulfate sales were 90 Ib. Definite
information is not available with regard to the ultimate disposition of
these sold materials, but it has been reported that thallium is present
in minor concentrations in various electrical connections, solders and
fusible alloys. 1288 In 1964 it retailed for $7.50/lb.
2. TOXICOLOGY
Health and Safety Standards
The Threshold Limit Value (TLV) for thallium and thallium compounds is
0.1 mg/m3. °766 On contact with the skin, thallium and thallium compounds
are readily solubilized by formation of the chloride, which then penetrates
into the body. The toxicity and epidemiology of thallium and its compounds
2238 2241
are not influenced by the mode of entry. '
131 2
The HEW 1971 Annual List of Toxic Substnaces * reports the LD5Q of
29 mg/kg in the mouse and 15.8 mg/kg in the rat for T12S04 administered
orally. Since thallium rapidly solubllizes on contact with skin and
276
-------
clinical symptoms seem independent of mode of entry, it may be concluded
that the pure element or other compounds would give approximately the same
results.
The most dramatic clinical symptom is alopecia (baldness), and it is
for this very property that is was widely used in patent medicine
applications until its toxicity forced it off the market. It diffuses
readily through the body and produces widespread damage to the nervous
system and the gastrointestinal tract. Respiratory failure and cardiac
depression have been noted in laboratory animals.
Diagnosis is complicated by the fact that it takes several days for
symptoms to appear. The mechanisms are unknown, but as with most heavy
metals, enzyme-poisoning is suspected. The metal is eventually excreted
via the kidney, but removal is very slow, so that it may be classified as
a "somewhat cumulative" poison. There is no known antidote; i.e., no way
has been found either to precipitate and immobilize it within the body or
to hasten its elimination through the kidney.
3. OTHER HAZARDS
Thallium and thallium compounds are relatively unreactive. On heating
fumes of the toxic, water-soluble TlgO are generated.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
Thallium and thallium sulfate are extremely toxic chemicals and the
use of full protective clothing, goggles, and respirators is recommended
in their handling. If clothing has been contaminated, it should be
removed as soon as possible and the skin should be immediately washed with
plenty of water and soap.
277
-------
Thallium and thallium sulfate should be stored in cool, dry, well-
ventilated places, and away from any area of high fire hazard. The producer
stores the refined thallium and thallium sulfate in Denver„ Colorado in a
prefab steel structure with asphalt paving and in a brick building with a
2242
concrete floor.
Thallium metal is marketed as stickss 3/8-in.-diameter by 9 in.,
weighing approximately 6-1/2 oz, or as ingots, 2 in. by 3-9/16 in. by
7-9/16 in., weighing approximately 20 Ib. These shapes are sealed in
polyethylene plastic and packed in wooden boxes as required. Thallium
sulfate is sold in 2-1/2-lb amber glass bottles and shipped in sawdust-
filled mailing tubes packed in wooden boxes. Twenty-five-lb orders may
2242
be packed in polyethylene-lined steel pails, 9 in. by 7-1/2 in.
Thallium and thallium sulfate are classified as Class B poisons by
the Department of Transportation (DOT) and the rules and regulations
governing their transportation are given in the Code of Federal Regulations
(CFR) Title 49-Transportation, Part 71-90.0278
Disposal/Reuse
The zinc dross containing the trace quantities of thallium (2 to
2000 ppm) is not disposed of; rather it is stockpiled in anticipation of
future use. Since thallium is not currently ir production, no waste is
being generated from the refining process. Previous experience indicates
that airborne emissions from thallium production are nils and the liquid
effluent averages <0.1 ppm on delivery to the waste storage facility.
The small amounts (<200 Ib annually) of thallium and thallium compounds
used commercially are widely dispersed in very small quantities. For
the disposal of wastes, which incidentally contain small amounts of thallium
and thallium sulfate, the acceptable criteria for their release into the
environment are defined in terms of the following provisional limits:
278
-------
Basis for
Contaminant in Air Provisional Limit Recommendation
Thallium 0.001 mg/M3 0.01 TLV
Thallium Sulfate 0.001 mg/M3 as Tl 0.01 TLV for Tl
Contaminant in Basis for
Water and Soil Provisional Limit Recommendation
Thallium 0.005 ppm (mg/1) Stokinger and Wood-
ward Method
Thallium Sulfate 0.005 ppm (mg/1) Stokinger and Wood-
as Tl ward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Stockpiling of Zinc Dross
Containing Trace Quantities of Thallium
This may be judged satisfactory. There is no evidence that thallium
from this stockpile has become airborne or has leached into any ground
water.
Option No. 2 - Production of Thallium from Stockpiled Zinc Dross
The procedures used in the past may be judged satisfactory, as can be
seen from the following comparison:
Tl Released2242 ILV0766
2
airborne emission nil 0.1 mg/M
liquid effluent <0.1 ppm 0.5 ppm
If and when production resumes, care must be taken to minimize worker
exposure in the refining operation. The extractive metallurgy is
relatively straightforward and well within the state-of-the-art, so worker
protection should not present any untoward technical or economic problems.
27S
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The handling, storage, and transportation of thallium and thallium
ulfate are adequate at present and for the foreseeable future. If and
hen production resumes, worker exposure in the refining operation should
e carefully monitored. Health and safety should not prove a problem.
Information on the disposal of incidental quantities of thallium
fter use is not available. While no incidences of thallium poisoning
ave been uncovered, it is nevertheless advisable for these disposals to
e pinpointed in location and quantity. Additional education of users with
egard to the hazards of thallium and thallium sulfate may prove desirable.
mall quantities may easily be disposed of by sealing in polyethylene bags
nd burying in Class 1 landfills, i.e., landfills with no access to ground
ater.
Thallium and thallium sulfate can be handled quite adequately at the
ndustrial level and are therefore not candidate waste stream constituents
or national disposal.
280
-------
7. REFERENCES
0278. Code of Federal Regulations. Title—transportation, parts 71 to 90.
(Revised as of January 1, 1967.) Washington, U.S. Government
Printing Office, 1967. 794 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1287. Mineral facts and problems. U.S. Bureau of Mines Bulletin 650.
1970. 1,291 p.
1288. Minerals yearbook. U.S. Bureau of Mines. 1969. 1,208 p.
1312. Christensen, H. E. Toxic substances: Annual list. U.S. Department
of Health, Education, and Welfare, Health Services and Mental Health
Administration, National Institute for Occupational Safety and
Health, Rockville, Maryland. 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966 899 p.
2179. Personal communication. M. Coats, American Smelting and Refining Co.
to M. Appel, TRW Systems, July 24, 1972. Thallium and thallium
sulfate.
2180. International Occupational Safety and Health Information Centre.
Four citations on thallium. CIS-34, CIS-40, CIS-41, CIS-67,
no date.
2182. Personal communication. M. Coats, American Smelting and Refining
Company, to M. Appel, TRW Systems, July 24, 1972.
2238. Heyroth, F. F. Thallium: A review and summary of medical literature.
U.S. Public Health Service Report Supplement 197. 1947.
2239. Prater, J. E., et al. Recovery of thallium from smelter products.
U.S. Bureau of Mines Report RI-4900. 1952.
2240. Teats, R. Process for recovering thallium/treating sulfate solutions
of thallium and cadmium. U.S. Patent Numbers 2,060,453 and
2,011,882. Nov. 10, 1936 and Aug. 20, 1935.
2241. Pfizer Laboratories. Thallium poisoning. Pfizer Spectrum. 6(20):558.
1958.
2242. Personal communication. M. Coats, American Smelting and Refining Co.
to M. Appel, TRW Systems, August 10, 1972.
281
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Thallous Sulfate
IUC Name .Thallium Sulfate (431)
Common Names
Structural Formula
T12S04
Molecular Wt. 505
(1)
Melting Pt. 632 C
;D
Boiling Pt. decomposes
Density (Condensed) 6.77 g/cc @ 20 C Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
I? @
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %} Lower_
Upper_
Upper_
Solubility
Cold Water 4.87 g/100 ml
Others:
Hot Water 15.57 g/100 ml Ethanol
Acid, Base Properties_
Highly Reactive with_
Compatible with_
Shipped in metal drums, wooden barrels either lined with paper or tongue-and-grooved
ICC Classification Poison B; poison label. 200 IbCoast Guard Classification Poison B; poison
label
Comments ,
Code Of Federal Regulations, Ser. 73.3fiA anri 73 3fiR \
References (1) 1433
282
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name
430
Thallium (430)
Structural Formula
Common Names
Tl
204
Melting Pt. 303 C
Molecular Wt.
Density (Condensed) 11.85 g/cc @ 20 _C Density (gas)_
Vapor Pressure (recommended 55 C and 20 Q)
1 mm @ 825 C @
(1)
Boiling Pt. 1457 C
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower moderate (as dust) Upper
Explosive Limits in Air (wt. %} Lower Upper_
Solubil ity
Cold Water insoluble
Hot Water insoluble
Ethanol insoluble
Others: HN03. HoSOr slightly in HC1
Acid, Base Properties slightly basic
Highly Reactive with
Compatible with
Shipped in metal drums, wooden barrels either lined with paper or tongue-and-grooved
ICC Classification Thallium salts, solid:
Commen ts
Poison B; poison label, 200 Ib
Coast Guard Classification Thallium salts,
Poison B; poison label
Code of Federal Regulations, Sec. 73.364 and 73.365
References (1) 1433
2'83
-------
PROFILE REPORT
ZINC COMPOUNDS
Zinc Chloride (456), Zinc Nitrate (459).
Zinc Permanganate (461), Zinc Peroxide (462). Zinc Sulfide (463)
1. GENERAL
The zinc compounds with specific exceptions, do not have serious
toxicities and can be adequately handled by current industrial or commercial
treatment methods. These compounds will be discussed as a class in this
Profile Report and important exceptions to general remarks will be cited.
Zinc chloride is the second most commercially important zinc compound
after zinc oxide. Most, if not all, of the zinc chloride produced in the
United States is derived from secondary zinc sources such as zinc dross
and sal skimmings. They are normally treated with muriatic acid and the
product solution is filtered off. The nearly dry residue is then
chlorinated. The resulting, additional zinc chloride is leached with water
and added to the original filtrate. Concentration and purification follows.
Zinc chloride is used in combination with other compounds as a wood
preservative and fire proofing lumber. It is used as a deodorant, in
disinfectants, embalming fluids, as a fungicide, in the manufacture of
vulcanized fiber and parchment paper, as a dyeing mordant, in oil
2377
refineries, galvanizing and manufacture of dry batteries. Zinc is
the largest plating commodity and zinc chloride is widely used in the
industry. Production of ZnCl2 in the United States was 28,000 tons in
1966.
285
-------
Zinc sulfide is used as a pigment in paints and plastics. It exhibits
phosphorescence when very pure and is,used in cathode ray tubes, TV picture
tubes and luminous watch dials. It is insoluble in water and does not
constitute a hazard unless exposed to acids.
Zinc nitrate is believed to be made by reacting a zinc source with
nitric acid. The pattern of purchase by industries indicate that it is
used in textile dy
was not available.
used in textile dyeing and engraving. Its consumption for all purposes
Zinc permanganate is classed as a rarely used compound by its sole
commercial manufacturer. Its use is believed to be confined to
Pharmaceuticals as an oxidizing agent where it is much more soluble than
the commonly used potassium permanganate. Sales are certainly less than
1,000 Ib annually and probably less than 50 lb.2361
Zinc peroxide is used in Pharmaceuticals and as a curing agent for
polysulfides. It is consumed in the reactions where it is added and is
not believed to occur anywhere as a specific waste. It slowly decomposes
to zinc oxide. In polymer formulation the zinc residues are of course
bound up and present no significant hazard.
Physical Properties
The available physical and chemical properties of the materials
discussed in this Profile Report are included in the attached worksheets.
2. TOXICITY
Zinc compounds in general are not inherently very toxic. The general
toxic effects of the zinc compounds are noted in three distinct areas of
exposure: inhalation, ingestion and skin contact.
286
-------
Inhaled zinc compounds can cause a mild reaction called "metal fume
fever," "brass chills.,", "oxide shakes" and other colorfully descriptive
illnesses. Zinc chloride irritates the mucosa probably because HC1 is
liberated from hydrolysis. All these symptoms readily disappear when
airborne zinc is controlled.
Small amounts of zinc have a metallic taste and can cause illness and
digestive tract disorders. Small amounts of concentrated zinc peroxide or
permanganate can also cause localized tissue infTarnation.
Skin contact with these compounds may result in rare and minor
symptoms of zinc poisonings but in general the epidermis is resistant to
zinc compounds and any localized disorders are most likely to be caused by
the anion.
The recommended Threshold Limit Value (TLV) for zinc chloride fume is
1 mg per cubic meter of air.0225 The drinking water standards have been set
at 15 mg per liter.
3. OTHER HAZARDS
Zinc nitrate, zinc peroxide and zinc permanganate are moderately
strong oxidizers. They should not be allowed to contact reducing material
or a fire could result. No other hazards have been found to exist.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
o
Handling, Storage and Transportation
The zinc compounds can be handled with relative ease. These materials
should be handled and stored in a well ventilated area. The containers
should not be agitated when open, and when stored, should be sealed to
prevent the hazard of airborne particles. The nitrates, peroxides and
permanganates are classed as oxidizing materials and require yellow labels.
The producers of these material can supply details on container information
but in general fiber drums are sufficient for these materials.
287
-------
y
Disposal/Reuse
Zinc chloride can be recovered from plating operations or other
processes'when the waste stream is segregated or free from other
contaminants. However, the proportion of firms who are recovering zinc is
2350
estimated to be small. The commercial applications of zinc nitrate,
peroxide and permanganate indicate that they will be consumed, or transformed
to the degree that they are no longer easily recoverable. However, the use
of sulfides to precipitate pigment grade zinc sulfide from zinc-containing
waste streams should always be considered whenever it is technically possible
and economically justifiable.2359'2361
For the release of these zinc compounds into the environment, the
acceptable criteria are defined in terms of the following provisional
limits:-
Contaminant in Air
Zinc Chloride
Zinc Nitrate
Zinc Permanganate
Zinc Peroxide
Zinc Sulfide
Provisional Limit
0.01 mg/M3
0.05 mg/M3 as HN03
0.05 mg/M3 as Mn
0.014 mg/M3 as H20
0.15 mg/M3 as H$
Basis for Recommendation
0.01 TLV
0.01 TLV for HN03
0.01 TLV for Mn
0.01 TLV for H202
0.01 TLV for H2S
Contaminant in
Water and Soil
Zinc Chloride
Zinc Nitrate
Zinc Permanganate
Zinc Peroxide
Zinc Sulfide
Provisional Limit
5 ppm (mg/1) as Zn
5 ppm (mg/1) as Zn
5 ppm (mg/1) as Zn
5 ppm (mg/1) as Zn
5 ppm (mg/1) as Zn
Basis for Recommendation
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
288
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - By-Product Recovery and Recycling
Effluent streams from industries such as metal finishing and electro-
plating often contain zinc wastes that can be readily recovered as a by-
product. Equipment which can be utilized to concentrate a stream for
reuse include reverse osmosis, multiple effect evaporation, and ion
exchange. In some cases usable water is also recovered. Precipitation
of zinc sulfide, a useful pigment, is also possible. Recycling and by-
product recovery is an acceptable and favored treatment option inasmuch as
it reduces overall waste loads.
Option No. 2 - Destructive Precipitation
The use of lime, soda ash and similar materials to render waste
streams alkaline, leading to the precipitation of heavy metal hydroxide
sludges, is in widespread use today. The sludges present a handling and
disposal problem which has been previously discussed in the Profile
Reports on the chromates, nickel compounds, copper compounds, (21,22, etc.),
The procedure produces effluents with satisfactory zinc levels and is
adequate for waste streams where recovery is not feasible.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The treatment of zinc compounds can be carried, out adequately at the
site of generation and hence the need for centrally treating these
compounds is not indicated. A facility for destructive precipitative by
pH adjustment has been recommended for the treatment of wastes generated
within National Disposal Sites. This facility could also be used to
handle non-routine shipments of zinc wastes to National Sites.
289
-------
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 Corporation, 1968. 1,251 p.
1492. Merck index of chemicals and drugs. 7th ed. Rahway, New Jersey,
Merck 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.
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.
2350. Personal communication. Don Hutchinson, Harshaw Chemical Company,
to J. F. Clausen, TRW Systems, Sept. 26, 1972.
2359. Personal communication. George Kurma, Lucidol Division of Pennwalt
Corporation, to J. F. Clausen, TRW Systems, Oct. 3, 1972.
2360. Personal communication. Jim Anderson, J. T. Baker Chemical Company,
to J. F. Clausen, TRW Systems, Oct. 3, 1972.
2361. Personal communication. Mrs. C. E. Anderson, Carus Chemical Company,
to J. F. Clausen, TRW Systems, Oct. 3, 1972.
2377. Mathewson, C. H., ed. 71nc: the science and technology of the
metal, its alloys and compounds. New York, Reinhold Publishing
Corp., 1959. 721 p.
290
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Zinc Chloride (456)
IUC Name
Structural Formula
Common Names Butter of Zinc
(3)
ZnCl,
Molecular Wt. 136.30
(1)
(1)
Melting Pt. 262 C
Density (Condensed) 2.91 @ 25_C_00 Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Boiling Pt. 732 C
(1)
1 mm @ 428 C
(1)
Flash Point
Auto1gnit1on Temp._
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 432 9/100 cc
Hot Water 615 g/100 cc
Ethanol 100 g/100 cc
Others: ether
Acid, Base Properties Aqueous solution is acid to litmus
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 0766
291
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Zinc Nitrate Trihydrate (459)
Structural Formula
IUC Name
Common Names
Zn(N03)2-3H20
Molecular Wt. 243.43(1) Melting Pt. *5.5 C(1) Boiling Pt.
Density (Condensed) @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 Q
9 9
Flash Point Autoignitlon Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. X) Lower Upper
Solubility
-(1).
Cold Water 327.3 g/100 cc 9 40 C^ 'Hot Water Ethanol.
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in fiber drums - poly lined
oxidizing material,
ICC Classification yellow label. 100 Ib Coast Guard Classification same
Comments.
References (1) 1570
292
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Zinc Nitrate Hexahydrate (459)
Structural Formula
IUC Name
Common Names
Zn(N03)2-6H20
-6H,0
/1\ i->\ '
Molecular Wt. 297.47u; Melting Pt. 36.4 CUJ Boiling Pt. 105-13
Density (Condensed) 2.065 g/cc @ 14 C,"' Density (gas) &
Vapor Pressure (recommended 55 C and 20 0
0 9 2_
Flash Point Autoignition Temp.
Flanmability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water 184.3 g/100 cc @ 20 C^Hot Mater infinitely sol.^1^ Ethanol very soluble^1*
Others:
Acid, Base Properties solution is acid to litmus, pH of 5 percent aq. soln. is 5.r3'
Highly Reactive with_
Compatible with
Shipped in
ICC Clas
Comments
oxidizing material , /,.
ICC Classification yellow label. 100 lbl ' Coast Guard Classification
References (])
(2) 0766
(3) 1492
293
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Zinc Permanganate (461)
IUC Name
Common Names
Structural Formula
Zn(Mn04)2-6H20
Molecular Wt. 411.33
^
Density (Condensed) 2.47
Melting Pt. -5H20 @ 100 C Boiling Pt._
& __ Density (gas) _ @ _
Vapor Pressure (recommended 55 C and 20 C)
&
9
Flash Point
Autolgnition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper
Upper
Solubility
Cold Water 33.3 g/100
Hot Water very soluble
(1)
Others: decomposes in acids '
Acid, Base Properties
Ethanol decomposes
^
Highly Reactive with reducing agents
Compatible with
Shipped in
oxidizing mtl. ,~\
ICC Classification yellow label. 100 Ib ^ '
Comments Chrystaline form deliquesces' '
Coast Guard Classification same
References (1) 1570
(2) 0766
294
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Zinc Peroxide (462)
Structural Formula
IUC Name
Common Names ZPO, zinc superoxide
Zn02-l/2H20
Molecular Wt. 106.38(1) Melting Pt. -0; with vac.(1^ Boiling
Density (Condensed) 3. 00u; @ __ Density (gas) _ &
Vapor Pressure (recommended 55 C and 20 Q
Flash Point _ Autoignition Temp.
Flammability Limits in Air (wt %) Lower ' JJpper_
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water slowly decomposes^ ' Hot Water decomposes^ ' Ethanol decomposes^ '
Others: decomposes in ether, acetone* '
Acid, Base Properties_
Highly Reactive with heat or reducing materials explodes.at 212 C^
Compatible with (Not dangerous unless mixed with combustiblesr
Shipped in fiber drums, no liner required
yellow label
ICC Classification oxidizing material, 100 1b Coast Guard Classification same
Comments Toxicity similar to ZnO
coml. prod. 50 to 60 percent ZnO^ remainder is ZnO
coml. prod. 50 to 60 perce
^Decomposes above 150 C* '
References (1) 1570
(2) 0766
(3) 1492
295
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Zinc Sulfide (463)
IUC Name
Structural Formula
Common Names Wurtzite
(2)
ZnS
Molecular Wt. 97.45
(1)
Density (Condensed) 4.087UJ
(-,\ sublimes at' '
Melting Pt. 1850 C 9 150 atmufoiling Pt. 1183 C
Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
0
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. X) Lower_
Upper_
Upper_
Solubility
Cold Water insoluble
Others:
(1)
Acid, Base Properties_
Hot Water insoluble
0)
Ethanol
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 1579
296
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-m
3. Recipient's Accession No.
4. Title and Subtitle Recommended Methods or Keducti on, Neutra 11 zati on,
Recovery, or Disposal of Hazardous Waste. Volume XIII, Indus-
trial and Municipal Disposal Candidate Waste Stream Constituent
Profile Reports - Inorganic Compounds (continued)
5. Report Date
Issuing date - Aug. 197;
6.
7. Author(s) R. S. Ottihger, J. L. BlumenthaTTD. F. Dal Porto,
G. I. Gruber, M. J. Santy. and C. C. Shih
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/Gram 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 XIII 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, th,e
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. Descriptors
Hazardous Wastes
Inorganic Compounds
Industrial Disposal Candidate
Municipal Disposal Candidate
Domestic Bauxite Mud
Trivalent Chromium Salts
Copper, Lead, and Zinc Mill Tailings
Acids
Lead Compounds
Manganese Compounds
I7b. Identifiers/Open-Ended Terms
Nickel Compounds
Halogenated Phosphorous Compounds
Sodium Compounds
Zinc Compounds
Selenium
Strontium
Thallium
Thallium, Sulfate
Potassium Compounds
Taconite Tailings
I7c. COSATI Field/Group Q6F; 06T; 07B; 07C; 07E; 13B; 13H; 19A; 19B
8. Availability Statement
Release to public.
- 297 -
19.. Security Class (This
Report)
UNC1 ASSIFIF.D
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
303
22. Price
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