EPA-670/2-73-053-n
August 1973
Environmental Protection Technology Series
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY OR
DISPOSAL OF HAZARDOUS WASTE
Volume XIV Form and Quantities
Office of Research and Development
U.S. Environmental Protect ion Agency
Washington, D.C. 20460
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EPA-670/2-73-053-n
August 1973
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY
OR DISPOSAL OF HAZARDOUS WASTE
Volume XIV. Summary of Waste Origins,
Forms, and Quantities
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
e 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 also 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
iii
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TABLE OF CONTENTS
VOLUME XIV
SUMMARY OF WASTE ORIGINS, FORMS AND QUANTITIES
Page
Introduction . 1
Toxic Paint Wastes 5
Cadmium, Copper, Cyanide, and Chromium Wastes from the
Electroplating Industry 19
Cadmium, Lead, and Mercury Wastes from the Manufacture of
Batteries .29
Pesticide Wastes 39
Wastes of Mercury and Mercury Compounds 63
Wastes of Arsenic and Arsenic Compounds 75
Wastes of Cadmium and Cadmium Compounds 85
Wastes of Lead Compounds ....... 91
Wastes of Soluble Copper Compounds 97
Wastes of Selenium and Selenium Compounds 107
Wastes of Boron Hydrides 115
Wastes of Chromium Compounds 119
Wastes of Inorganic Cyanides 133
Wastes of Hydrofluoric and Fluoboric Acids 137
Wastes of Specific Organic Chemicals 141
Wastes of Explosive, Propel 1 ant and Chemical Warfare Materiel ... 153
Radioactive Wastes 163
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INTRODUCTION
This volume summarizes th§ TRW effort 1n the determination of the
origins, forms, and quantities of hazardous wastes. The volume contains
16 separate reports.
The waste streams from soms of the Industries, such as the waste
sludges from paint manufacture, were found to contain several hazardous
waste stream constituents. To provide a complete treatment, and to avoid
duplications 1n d1scussionB the first three reports 1n this volume describe
the waste forms and quantity Information according to the waste generation
source. Wastes from paint manufacture and paint residue left 1n used paint
containers are discussed In the report "Toxic Paint Wastes". Likewise, the
manufacturing wastes from the electroplating and the battery Industries are
discussed separately In the reports "Cadmium, Copper, Cyanide, and Chromium
Wastes from the Electroplating Industry" and "Cadmium, Lead, and Mercury
Wastes from the Manufacture of Batteries". In the report on copper wastes,
for example, detailed discussions of the copper wastes from electroplating
are specifically referenced to the separate report on electroplating wastes.
The other 13 reports 1n this volume provide waste forms and quantity
Information for each group of hazardous waste stream constituents under
Investigation (such as the report "Wastes of Lead Compounds"). Each of
these 13 reports consists of: (1) a short introductory section on the
principal sources of the hazardous wastes; (2) a table (or tables) sum-
marizfng the total waste quantity information from each waste source and
the geographical distribution of these wastes; (3) wherever applicable, a
summary table (or tables) describing the forms and composition of the
typical waste streams; and (4) for each major waste stream or waste source
identified, an individual section discussing the data bases and the methods
of estimation utilized in deriving the waste forms and quantity information,
as well as the results of the findings.
1
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The geographical distributions of the hazardous wastes are generally
presented in terms of the standard U.S. Regions as Identified by the
Bureau of Census (Figure 1). The exceptions are the pesticide waste dis-
tributions, which are presented in terms of USDA Regions (described in the
report "Pesticide Wastes"), and explosive wastes which are presented by
state.
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NORTH
SOUTH
DAKOTA
UTAH i
/
»
/--— »
<" "~T
i
COLORADO
/ARIZONA ' NEW
_._J / MEXICO
X-i-
"*
NEBRASKA \ IOWA
Figure 1. U.S. Bureau of Census Regions
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TOXIC PAINT WASTES
Waste Sludges Containing
Toxic Ingredients from Paint Manufacture
A paint is generally defined as a liquid vehicle containing a
suspended pigment which is converted to an opaque solid film after
application as a thin layer. The liquid vehicle consists basically of
two components: (1) a binder, which forms the film and is composed of
natural resins, synthetic polymers, or drying oils; and (2) a solvent, which
is either water or an organic solvent. Other ingredients present in the
paint may include driers to accelerate the drying of the film, plastidzers
to give elasticity to the film, fungicides to inhibit the growth of mildews,
and various other additives such as pigment-dispersing agents, antiskinning
agents, defoamers, freeze-thaw stabilizers, etc.
Pigments are used in paint formulations to obscure the substrate, to
impart color for aesthetic purposes, and to improve durability of the
film. Millions of pounds of inorganic oxides, sulfates, and carbonates
are consumed by the paint industry annually for the use of pigmentation
(Table 1). In addition, materials such as talcs, clays, and chalks are
used to aid processing and to maintain formulation stability. These
materials are called extenders, fillers, or supplemental pigments. The
inorganic pigments containing lead, cadmium, selenium, chromium (chromates
and chromium oxide), and cyanides (Table 2) are mainly responsible for the
toxicity of paints and the waste sludges from paint manufacture. With the
exception of chrome oxide green, however, all the other pigments containing
these toxic ingredients are normally only used for sol vent-type paints.
Both the chromate based pigments and the iron blues cannot be used in
emulsions or water-based paints because they are unstable under the
conditions of contact with aqueous solutions and alkalinity.
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TABLE 1
PIGMENTS CONSUMED BY THE COATINGS INDUSTRY - 1970
Pigments and Extenders
millions of Ibs.
White pigments:
Titanium dioxide 800
Zinc Oxide - lead free 50
Zinc oxide - leaded 10
White lead 10
Other 5
Total ~87?
Colored and black pigments:
Carbon blacks 15
Red lead 20
Chrome green 5.4
Chrome oxide green 10.4
Chrome yellow and orange 63.5
Molybdate chrome orange 21.7
Zinc yellow 15.6
Iron blue 10.0
Cadmium red, yellow, and orange* 0.7
Other inorganic colors 116
Organic colors 12
Metallics (aluminum pastes, etc.) 20
Zinc dust 50
Total 367
Extenders:
Calcium carbonate 350
Magnesium silicate (talc) 330
Clay 280
Barium sulfate (barytes) 100
Mi ca 60
Others 200
Total 1,320
Total pigments and extenders 2,562
*The estimates are based on the assumption that 25
percent of the cadmium pigments produced is consumed by the
paint industry. Consumption figure of 0.7 million Ib is as
the cadmium metal. About 51,000 Ib of selenium are used in
the cadmium pigments.
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TABLE 2
PIGMENTS CONTAINING TOXIC INGREDIENTS
Pigment
Principal Chemical Component Toxic Ingredient
White lead
Leaded zinc oxide
Red lead
Cadmium yellow
Cadmium orange
Cadmium red
Chrome yellow
Chrome orange
Z1nc yellow
Molybdate orange
Chrome green
Chrome oxide green
Iron blue
2PbC03-Pb(OH)
2PbS04-PbO + ZnO
Pb304
CdS
CdS + CdSe
CdS + CdSe
PbCr0
PbO-PbCr04 + PbCr04
PbCr04 + PbMo04
PbCr04 + Fe(NH4)Fe(CN)6
Cr203
. Fe(NH4) Fe(CN)6
lead
lead
lead
cadnrl um
cadmium, selenium
cadmium, selenium
lead, chromate
lead, chromate
chromate
lead, chromate
lead, chromate, cyanide
chromium oxide
cyanide
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Solvent- and water-based paint films are formed differently and
employ different materials as binders. Solvent-based paint forms a film
through a combination of organic solvent evaporation and the catalytic
polymerization of the drying oil. Binders or film forming materials used
for solvent-based paints contain natural and synthetic resins, drying oils
and fatty adds. Resins used in solvent-based paints Include alkyds,
epoxies, rosin-esters, urea-melamines, and to a lesser extent acrylics,
phenolics, urethanes, hydrocarbons, vinyl-acetate and vinyl-chloride
copolymers, and vinyl formal and butyral acetal resins (Table 4). Drying
oils and fatty acids used in solvent-based paints Include Unseed oil and
its fatty acid, soybean oil and its fatty acid, tall oil, tung oil, castor
oil, safflower oil and oltlcica oil (Table 5). Water-based paints, on the
other hand, form a continuous film through evaporation of their water
content and subsequent coalescence of the synthetic polymer particles.
The formulation of the water-based paint consists basically of combining
pigments and synthetic resin dispersions or latexes. The four major types
of latexes used are polymers based on esters of acrylic acid, polyvinyl
acetate, polyvinyl chloride, and styrene-butadiene.
In addition to the toxic inorganic pigments, phenyl mercury compounds
have been added to paints for use as a mildewcide and to extend the shelf
life of paints and constitute another major hazard associated with paints
and waste sludges from paint manufacture. Phenyl mercuric acetate,
phenyl mercuric oleate, and di (phenyl mercuric) dodecenyl succinate
represent the three types most commonly employed as paint additives. These
phenyl mercury compounds are currently used almost exclusively for water-
based paints in low concentrations of 0.004 to 0.1 percent (as mercury),
?R7fi ?R77
with 0.01 to 0.05 percent being the average. ' Mercury consumption
by the paint industry amounted to 654,000 Ib in 1971.
*
Organic solvents used include aliphatic and aromatic hydrocarbons,
ketones, esters, alcohols and glycols (Table 3).
It is believed that mercury is no longer used in antifoul ing paints.
8
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TABLE 3
SOLVENTS CONSUMED BY THE COATINGS INDUSTRY - 19702495
Solvents
millions of Ibs.
Hydrocarbons:
Aliphatic 600
Aromati c 690
Total TT290
Oxygenated:
Ketones 815
Esters 250
Alcohols 555
Glycols 50
Glycol esters 10
Glycol ethers 95
Glycol ether-esters 80
Total 1,855
Other:
Chlorinated products
Miscellaneous (terpenes, etc.)
Total
Total solvents
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TABLE 4
RESINS CONSUMED BY THE COATINGS INDUSTRY - 19702495
Resins
millions of Ibs.
(dry basis)
Resin:
Synthetics
Alkyds 600
Acryli cs 220
Vinyls (PVac, PVC, etc.) 210
Cellulosics 75
Epoxies 68
Rosin esters 70
Urea-melamines 60
Phenolics 33
Styrenes 37
Urethanes 45
Hydrocarbons 30
Polyesters 7
Others 50
Total 1,505
Natural:
Shellac
Rosin and others
Total
Total resin
10
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TABLE 5
FATTY A(
THE COATINGS INDUSTRY = 1970'
DRYING OILS AND FATTY ACIDS CONSUMED BY
,2495
Drying 011s and Fatty Adds
millions of Ibs.
! Oils:
j , Linseed oil
I Soybean oil
! Tall oil
I Tung oil
I Castor oil
Fish/marine oil
1 Safflower oil
i
! Coconut oil
Oiticica oil
Other oils
i Total
i
Fatty acids
Total
Excludes oils in coating resins.
11
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The various operations in paint manufacture are wholly physical. The
weighing, assembling, and mixing of the pigments and vehicles are normally
done on the top floor of a paint plant. The batch masses are conveyed to
the floor below, where grinding and further mixing take place. The paint
is then transferred to the next lower floor, where it is thinned and tinted
in agitated tanks, before being strained into a transfer tank or directly
into the hopper of the filling machine on the floor below. Centrifuges,
screens, or pressure filters are used to remove nondispersed pigments.
The paint is poured into cans or drums, labeled, packed and moved to storage,
each of these last few steps being completely automatic.
Solid wastes are generated from the manufacture of paints and allied
products as a result of kettle washings and equipment clean-up. In the
latex washing system, the waste water is first sent to a settling tank,
where alum is added to facilitate flocculation. The waste water Is then
decanted, and drained into the sewers after any necessary pH adjustment.
Sludge from the latex washing system are mainly disposed of 1n sanitary
2575
landfills, in spite of the fact that the toxic constituents in paint
are not biodegradable and the leaching of these pollutants by percolating
water could lead to gross ground and surface water contamination. Industry
sources indicated that 1 gal-of sludge is produced for every 170 gal- of
water-based paint product, and that the water-based paint sludge has the
257fi
following general composition:
2.5 percent inorganic pigment (excluding titanium dioxide)
4.5 percent titanium dioxide
8.0 percent extenders
20.0 percent binders
65.0 percent water
The mercury concentration in the water-based paint sludge ranges from 0 to
700 ppm, the estimated average being 100 to 150 ppm.*
In the solvent washing system, the waste stream is normally pumped
over to a storage tank and decanted. The solvent is recovered by
California State Water Resources Control Board. !
*Based on confidential data from a state-wide survey conducted by the
itrol
12
i
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; distillation. The sludge obtained from the decantation step typically
i contains 20 percent inorganic pigment and extenders, 20 percent binders,
i and 60 percent organic solvents, with a heating value of 14,000 to 18,000
i . ?t\1fi
i Btu/lb. The residue sludge from the solvent stills, however, has a
j higher solids content, and typically contains 35 percent inorganic pigment
and extenders, 30 percent binders, and 35 percent organic solvents, with
i 91576
i a heating value of 10,000 to 15,000 Btu/lb. Industry sources indicated
! that a total of 1 gal. of sludge is obtained from the decantation and
solvent recovery operations for every 120 gal. of solvent-based paint
| product.2575'2576'2578 The combined solvent-based paint sludge is
| characterized by the following composition:
I 4.5 percent inorganic pigment (excluding titantium dioxide)
! 8.5 percent titanium dioxide
j 14.5 percent extenders
• 25.0 percent binders
i 47.5 percent solvent
1 The solvent-based paint sludges are currently disposed of in sanitary
! landfills. As indicated previously, this is not a satisfactory procedure
and incineration systems to handle solvent-based paint sludges are now under
i p^yfi
: development. The solvent recovered from the still is used for cleaning
: purposes only, and contains 70 percent aliphatic hydrocarbons and 30 percent
aromatic hydrocarbons.
i Based on the waste generation factor of 1 gal. of sludge for every
;
120 gal. of solvent-based paint product, the quantity of pigments consumed
; by the coatings industry (Table 1), and a U.S. solvent-based pa.int produc-
. tion of 442 million gal. in 1971, it was estimated that 637,000 Ib of lead,
i 137,000 Ib of chromium (mostly in the form of chromates), 5,100 Ib of
! cadmium, 370 Ib of selenium, and 44,900 Ib of cyanides are lost through
; 36,800,000 Ib of solvent-based paint sludges per year (Table 6). In
j water-based paints, chrome oxide green and the phenyl mercury compounds
I are normally the only toxic ingredients of concern found in the paint
i product and the waste paint sludges. Again, based on the waste generation
\ factor of 1 gal. of sludge for every 170 gal. of water-based paint product,
; the quantity of chrome oxide green and mercury consumed by the coatings
i industry, and a U.S. water-based paint production of 442 million gal. in
i
!• 13
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TABLE 6
WASTE SLUDGES CONTAINING TOXIC INDGREDIENTS FROM PAINT MANUFACTURE
Material
Solvent-Based
Paint Sludge
Lead
Chromium
Cadmium
Selenium
Cyanides
Sludge
Water-Based
Paint Sludge
Chromium
Mercury
Sludge
I
16,000
3,000
150
10
1,100
0.92 x 106
240
45
0.65 x 106
II
140,000
30,000
1,100
80
9,900
8.12 x 106
2,160
395
5.74 x 106
III
196,000
42,000
1,550
115
13,800
11.32 x 106
3,010
555
7.99 x 106
Bureau of
IV
Annual Waste
42,000
9,000
350
25
2,900
2.40 x 106 3
640
120
1.70 x 106 2
Census Regions
V VI
Production (Ib/yr)
55,000
12,000
450
30
3,800
.16 x 106
840
155
.23 x 106
30,000
7,000
250
15
2,150
1.76 x 106
470
.85
1.24 x 106
VII
47,000
10,000
400
25
3,350
2.74 x 106
730
135
1.93 x 106
VIII
8,000
2,000
50
5
550
0.44 x 106
120
20
0.31 x 106
IX
103,000
22,000
800
60
7,300
5.97 x 106
1,590
290
4.21 x 106
Total
637,000
137,000
5,100
370
44,900
36.83 x 106
9,800
1,800
26.0 x 106
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1971, 1t was estimated that 9,800 Ib of chromium {as chromium oxide) and
1,800 Ib of mercury are lost through 26,000,000 Ib of water-based paint
sludges per year (Table 6). The geographical distribution of these waste
paint sludges was computed on the basis of the regional distribution of
"value added by manufacture" dollar amounts for paints and allied products
and by Bureau of Census regions (Table 6).
Old Paint
The paint residues left in containers discarded in municipal dumps
often contain toxic ingredients and could lead to possible contamination
of the soil and ground water. The composition of the old paint, after
evaporation of the solvents, is approximately described by the pigment
volume concentration (PVC) of the paint. The pigment volume concentration
1s defined simply as:
pvc volume of pigment in paint ^_^
~ volume of pigment in paint + volume of nonvolatile vehicle
constituents in paint
PVC is generally considered as the most important indicator in paint
formulation, and controls such factors as gloss, reflectance rheological
properties, washability, and durability. As a consequence, there is
usually a range of PVC for a given paint, varying between 25 and 45 percent.
The amount of paint residues and their toxic constituents were computed
with the assumptions that (1) 5 percent of the paint is unused and left in
the containers; and (2) the nonvolatile portion accounts for 50 percent of
the paint. It is estimated that 4,410,000 Ib of lead, 963,000 Ib of chromium
(mostly as chromates); 35,300 Ib of cadmium; 2,560 Ib of selenium; 311,000
Ib of cyanides; and 32,700 Ib of mercury could be lost each year through
the 221,000,000 Ib of paint residue left in paint containers (Table 7).
The geographical distribution of these paint residue wastes was calculated
on the basis of the population distribution in the United States by
Bureau of Census regions (Table 7).
As the old paints are normally discarded in their containers, the
types and numbers of containers used by paint manufacturers are also of
15
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Material
TABLE 7
OLD PAINT
ii
Bureau of Census Regions
in iv v vi
Annual Haste Production (Ib/year)
VII
VIII
IX
Total
Lead
Chromium
Selenium
2.58 x 105 8.13 x 105 8.81 x 105 3.28 x 105 6.69 x 105 2.77 x 105 4.22 x 105
1.81 x 105 5.81 x 105 4.41 x 106
0.56 x 105 1.78 x 105 1.92 x 105 0.72 x 105 1.46 x 105 0.61 x 105 0.92 x 105 0.40 x 105 1.27 x 105 9.63 x 105
2,100
150
6,500
470
7.000
510
2,600
190
5.400
390
2.200
160
3.400
240
1.400
110
4.700
340
35.300
2.560
Cyanides 0.18 x 105 0.57 x 1C5 0.62 x 105 0.23 x 105 0.47 x 105 0.20 x 105 0.30 x 105 0.13 x 105 0.41 x 105 3.11 x 105
Karcury 1,900
Old Paint 13 x 10°
6.000 6.500 2.400 5.000 2.100 3.100 1.400
41 x 106 44 x 106 16 x 106 34 x 106 14 x 106 21 x 106 9 x 106
4.300 32.700
29 x 106 221 x 106
(75
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some concern. Extrapolation of the data presented in the recent survey
by the National Paint and Coatings Association indicates that the
containers used are predominantly of the 1 quart and 1 gallon size metal
2498
type. For the year 1970, the quantities of each size container used
are: 1 pint containers, 60 million; 1 quart containers, 160 million,
1 gallon containers, 320 million; 5 gallon containers, 16 million; and
55 gallon drums, 3.7 million.
17
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REFERENCES
2495. Chemicals in coatings. Chemical Week, 109(16) :35-51, Oct. 20, 1971.
2498. Raw materials usage survey for the year 1970. Washington, National
Paint, Varnish, and Lacquer Association, Inc., 1971. 15 p.
2575. Personal communication. F. A. Lei bold, Sherwin-Williams Company, to
C. C. Shih, TRW Systems, Nov. 10, 1972. Wastes from paint
manufacture.
2576. Personal communication. C. Cooper, PPG Industries Coatings and
Resins Division, to C. C. Shih, TRW Systems, Nov. 13, 1972. Wastes
from paint manufacture.
2577. Personal communication. C. W. Finegan, Ameritone Paint Corporation,
to C. C. Shih, TRW Systems, Nov. 13, 1972. Wastes from paint
manufacture.
2578. Personal communication. E. Davis, National Lead Company, to C. C. Shih,
TRW Systems, Nov. 14, 1972. Wastes from paint manufacture.
18
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CADMIUM, COPPER, CYANIDE, AND CHROMIUM WASTES
FROM THE ELECTROPLATING INDUSTRY
Electroplating and metal finishing waste streams can contribute directly
ream pollution resulting from the conten
materials such as cyanide, acids, and metals.
to stream pollution resulting from the content of toxic and corrosive^
Wastes from an electroplating plant may range from nontoxic to highly
toxic and/or corrosive. Innocuous effluents are obtained only by the use of
thorough in-plant waste treatment methods. Highly lethal or corrosive
effluents are generally the result of the accidental or intentional dis-
charge of concentrated solutions. The Incidence of this type of discharge
is minor in the metal finishing field.
The sources of the liquid, solid, and semi-solid wastes generated
in the electroplating industry include the following:
(1) rinse waters from plating, cleaning, and other surface
finishing operations;
o
(2) concentrated plating and finishing baths that are Intentionally
or accidentally discharged ;
(3) wastes from plant or equipment cleanup ;
(4) sludges, filter cakes, etc., produced by naturally
occurring deposition in operating baths or by inten-
tional precipitation in the purification of operating
baths, chemical rinsing circuits, etc., when flushed
down sewers ;
19
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(5) regenerants from ion exchange units; and
(6) vent scrubber waters.
The most important of these wastes, especially from the standpoint of
0783
the smaller plater, is the rinse water. This is the constantly flowing,
production oriented stream which is generally so large in volume that some
form of concentration is warranted before it can be economically transported
to a central disposal facility for treatment.
Some of the general methods used to treat or reduce the volume of rinse
waters from electroplating shops include ton exchange, precipitation, chemical
destruction, chemical reduction, biological destruction on trickling filters,
evaporation, and adsorption with activated-carbon beds. These treatment
methods are described 1n more detail 1n the Profile Reports on cadmium,
copper, cyanide, and chromium compounds.
The wastes from the electroplating industry include liquid, slurry,
sludge, and solid forms depending upon the degree of concentration. Rinse
waters, for example, may be concentrated by passing through evaporators.
Information on the forms and composition of some typical waste streams from
electroplating that contain cadmium, copper, and cyanide compounds was pro-
vided by Rollins Environmental Services and is summarized here (Tables 1,
2, 3). The forms and composition of chromium containing waste streams from
metal finishing are discussed separately in the report "Wastes of Chromium
Compounds".
i
Cadmium Wastes
It is estimated that there are 1,440,000 Ib of water soluble cadmium
waste (as cadmium) generated per year by the electroplating industry. This
number was computed by applying a 18 percent waste generation factor to the
total amount of cadmium used in the electroplating industry each year.
The waste generation factor was supplied by L. E. Lancy of Lancy
2287
Laboratories. The total waste quantity was based on cadmium consumption
of approximately 8,000,000 Ib per year by the electroplating industry
20
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TABLE 1
TYPICAL ELECTROPLATING WASTES
CONTAINING CADMIUM
Waste Description
1.5 % cadmium cyanide and 8.5 % sodium cyanide in a 3 % caustic solution,
with trace of other metals.
Solid waste containing 3 % cadmium oxide and 16 % cadmium metals with
alkali carbonates—hangers from plating bath.
300 to 500 ppm cadmium chromate with aluminum alkaline salts, organic
cleaners, and 95 % water—wash water.
Liquid slurry containing 5 % cadmium cyanide and 5 % sodium cyanide in
10 % aqueous sodium hydroxide.
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TABLE 2
TYPICAL ELECTROPLATING WASTES CONTAINING COPPER
Waste Description
2 % copper cyanide, 6 % sodium cyanide, sodium sulfonate, hydrocarbons,
and zinc phosphate in 83 % water.
Alkaline cyanide solutions having copper concentrations of 50 to 10,000 ppm,
alkaline concentrations of 1 to 20 % as sodium hydroxide, and chromium
nickel, and lead.
Solid crystalline waste containing 15 % copper in a copper cyanide-sodium
cyanide salt and traces of other metals.
2 % copper cyanide and 5 % sodium cyanide in a 10 % sodium hydroxide solution.
5 % copper in 17 % sulfuric acid.
-------
TABLE 3
TYPICAL ELECTROPLATING WASTES CONTAINING CYANIDES
Waste Description
Liquid waste containing 15 % sodium cyanide, a 10 % mixture of sodium
ferro and sodium ferrlcyanides, and traces of nickel and zinc.
Stripping solution containing 13 % sodium cyanide, sodium hydroxide,
and 600 ppm copper.
0.8 % cyanide, 3,300 ppm zinc, 165 ppm nickel, and trace of silver 1n a
1 % sodium hydroxide solution.
Slurry containing 20 % sodium ferrocyanide, 2% zinc and insoluble material,
and 50 % water.
Slurry containing 2.5 % zinc ferrocyanide, 2 % calcium fluoride, 3 %
chromic hydroxide, and 80 % water.
1 % potassium ferrocyanide and less than 50 ppm lead, nickel, chromium,
and copper combined in an aqueous 10 % sodium hydroxide solution.
3 to 5 % sodium cyanide and 1 to 3 % nickel, cadmium, copper, and zinc
in an aqueous 10 % sodium hydroxide solution.
23
-------
(this figure represents the amount of cadmium compounds used to make up the
plating baths and the amount of cadmium metal used in the plating elec-
trodes).2286
The geographical distribution of these wastes was computed on the basis
of the distribution of "value added by manufacture" dollar amounts for
finished metal products in the United States and by Bureau of Census
regions (Table 4).
Copper Wastes
It is estimated that there are 2,106,000 Ib of copper wastes (as copper)
generated by the electroplating industry each year. This number was computed
by using the same 18 percent waste generation factor that was used for
cadmium electroplating. Industry sources indicated that the 18 percent
figure is the representative copper waste factor within the electroplating
industry. The total waste quantity was based on copper consumption of
11,700,000 Ib per year by the electroplating industry (this figure includes
ocno
the amount of copper compounds and copper metal electrodes used).
The geographical distribution of these wastes was computed on the basis
of the distribution of "value added by manufacture" dollar amounts for
finished metal products in the United States and by Bureau of Census
regions (Table 4).
Cyanide Wastes
Cyanide compounds (cadmium cyanide, copper cyanide, etc.) are used
extensively to make up the plating baths in the electroplating industry
because cyanide compounds are good coraplexing agents. This complex!ng
action increases the solubility of the metal cyanide salts and makes the
electroplating operation more effective.
It is estimated that there are 21,320,000 Ib of cyanide westes (as
cyanide) generated in the electroplating industry each year, 'his number
-------
TABLE 4
ELECTROPLATING WASTES
Material
ii
in
Bureau of Census Regions
IV V VI VII
Annual Waste Production (Ib/year)
VIII
IX
Total
Cadmium
Copper
Cyanide
1.88x10 4.10X10^ 4.64 x 105 0.65 x 105 0.70 x 105 0.33 x w* 0.52 x ^ 0.10 x 105 1.48 x,05 14 40xx 10*
2.75 *10 5.99 x,05 6.78 * 105 0.95 x ^ ,M*tf 0.48 x ^ 0.76 x 105 0.15 x 105 2.17 x 105 21 06 x 105
2.78 x 10 6.07 x 106 6.86 x 106 0.96 x 106 1.04 x 10* 0.49 x 10« 0.77 x rf 0.15 x 106 2.20 x 106 21 32 x 106
cn
-------
was estimated from information presented in a report by the Battelle
Memorial Institute. The mean cyanide waste load per plant (8,170 Ib
per year) was calculated from a graph in this report that was prepared
2224
using data collected from 162 plating shops in the United States.
This mean waste load was then multiplied by the number of plants in the
United States that use cyanides in their electroplating operation (approx-
2fiO?
imately 2,600 plants*) to obtain the total waste quantity.
The geographical distribution of these wastes was computed on the basis
of the distribution of "value added by manufacture" dollar amounts for
finished metal products in the United States and by the Bureau of Census
Regions (Table 4).
Chromium Wastes
Chromium compounds are formulated for use as cleaning agents, oxidizing
agents and surface preparation agents as well as the chemicals used to
electroplate the decorative chrome surface. The wastes are generated
from the washing of the metal parts as well as spills, tank leakage, etc.
Many of the metal treatment tanks become exhausted and have to be periodically
drained and this is a major portion of the waste load.
It is very difficult to distinguish between the amount of chromium
wastes generated in electroplating and the amount generated in the other
metal finishing processes. More detailed information on the quantities of
chromium wastes and forms and composition of the waste streams can be found
in the report "Wastes of Chromium Compounds".
*Eighty-seven percent of the plating shops in the United States use
lirfp^ in thpir nnpratinn 2602
cyanides in their operation.1
26
-------
REFERENCES
0783. A state-of-the-art review of metal finishing waste treatment.
Technical Report, Battelle Memorial Institute. Nov. 1968. 53 p.
2224. An investigation of techniques for removal of cyanide from electro-
plating wastes. Report prepared for the Environmental Protection
Agency by Battelle, Inc. Columbus, Ohio under Contract No. WPRD
201-01-68. Nov. 1971. 87 p.
2286. Personal communication. Bob Ruhlman, U. S. Tariff Commission to
D. Dal Porto, TRW Systems. Aug. 21, 1972. Cadmium compound
production data.
2287. Personal communication. Leslie E. Lancy, Lancy Laboratories to
D. Dal Porto, TRW Systems. Aug. 21, 1972. Cadmium waste production.
2602. Personal communication. Peter Kovatis, National Association of
Metal Finishers to D. Dal Porto, TRW Systems. Dec. 7, 1972.
Copper wastes from the electroplating industry.
2603. Personal communication. Bob Trees, Metal Finishing Suppliers
Assoc. to D. Dal Porto, TRW Systems. Dec. 7, 1972. Amount of
copper used in electroplating annually.
2604. Personal communication. Jim Zievers, Industrial Filter Corporation
to D. Dal Porto, TRW Systems. Dec. 7, 1972. Copper wastes from
electroplating.
-------
CADMIUM, LEAD, AND MERCURY WASTES
FROM THE MANUFACTURE OF BATTERIES
Nickel-Cadmium Batteries
There are two distinct types of nickel-cadmium cells—the pocket plate
(Jungner type) cell and the sintered-plate cell.
The positive and negative plates of the Junger cell are usually similar
in construction, consisting of perforated pockets which contain the active
materials. The pockets for both positive and negative plates are made from
perforated steel ribbon which has been nickel-plated and annealed 1n hydrogen.
Pockets of the negative plates are filled Initially with cadmium oxide or
cadmium hydroxide, either of which is reduced to metallic cadmium on the first
charge. Most manufacturers of these cells add iron (5 to 30 percent) to
the cadmium in order to obtain the required degree of fineness of the
cadmium.
The pockets for holding the active material of both positive and
negative plates of Nicad batteries are standardized at half an inch, but
the length may be varied. These are pressed into grids, usually called
frames, made of nickel-plated steel. The plates are assembled into elements
with rods of polystyrene being used as separators between plates.of
opposite polarity. Sheet hard-rubber separators are used between the sides
of the element and the inside of the steel container of the cell. The
container is welded along all seams and at the top and bottom. Terminal
?fil fi
posts are sealed through rubber glands.
Industry sources indicate that the production of pocket-plate type
batteries does not generate much cadmium waste. This is because the
active chemicals used are solids and not solutions or pastes. When good
housekeeping methods are used within the plant, there is almost no waste
generated.
-------
The manufacture of sintered-plate batteries, however, does generate
some waste. This type of cadmium battery differs materially in construction
and performance from the pocket-opiate battery described above.
The plates consist of a highly porous structure of nickel impregnated
with the active materials nickel oxide and cadmium. The plates are called
plaques before being impregnated with the active materials. To obtain plaques
of 60 to 90 percent porosity, it is necessary to use a nickel powder of
low apparent density. The powder sinters in a protective atmosphere without
the need for compacting at temperatures as low as 500 C, but higher
temperatures are generally used.
Grids are usually a coarsely woven wire cloth of about 20 mesh and may
have a frame around the wire. A thin nickel strip is welded to the cloth
to provide the lug. The grids are usually of nickel, but nickel-plated
iron has been used.
The plaques are cut (in the form of the plate) from a block of graphite
about 1 in. thick. The carbonyl nickel is sifted into the opening to
about half depth, and then the grid is laid on it and covered with the other
half of the powder. A graphite cover closes the mold. The sintering
furnace is provided with a cooling chamber into which the graphite block
passes after 10 minutes' heating. In the protective atmosphere of nitrogen
and dissociated ammonia the plaque is finished, and it then has about 80
percent porosity.
Impregnation is accomplished in solutions of nickel and cadmium salts.
Electrolysis is done in an electrolyte of 25 percent sodium or potassium
hydroxide heated to nearly 100 C. The current density is nigh and maintained
for about 20 minutes while vigorous gassing occurs. The washing that
follows is done with deionized water (the components of tap water are
detrimental to the lifetime performance of the battery) and may last 3 hours
until the effluent water has a pH of 9. The plates are dried at 80 C.2609
This cycle of impregnation is repeated 4 or 5 times, each succeeding cycle
making the washing more difficult. The finished plates are assembled into
cells, using plastic rods as separators.
30
-------
A typical impregnation bath may be composed of 8 percent cadmium oxide,
0.6 percent nicklic oxide, 14 percent potassium hydroxide, and trace metals.
Industry contacts indicate that the major source of waste in the
manufacture of sintered-plate batteries is the wash water that is used
2609
to remove excess material from the plates. A typical wastewater
effluent may contain cadmium hydroxide, potassium hydroxide (as high as
1000 ppm), and potassium nitrate. The concentrations are fairly high
because the deionized water commonly used is expensive and minimal
quantities are applied.
It is estimated that there are 3,700 Ib of cadmium waste (as cadmium)
generated in the production of sintered plate nickel-cadmium batteries
annnually by the seven U.S. manufacturers (Table 1). This estimate is
based on a waste generation factor of 4 Ib of cadmium waste (as cadmium)
produced for every 3,000 gal. of wash water effluent. The waste
factor was applied to a combined wash water effluent of approximately 2.8
million gal. per year for the seven U.S. manufacturers. The largest
battery manufacturer has an effluent of 1 million gal. per year and the
other 6 manufacturers have a combined effluent of 1.8 million gal. per
year. All of the above data was supplied by A. D. Little, Inc.
The geographical distribution of these wastes was determined on the
basis of the plant locations of the Nicad battery manufacturers and by
Bureau of Census Regions (Table 2).
Lead-Acid Batteries
The battery industry is the largest consumer of lead in the United
States—about 500,000 tons were used in 1968. Eighty percent of this is
returnable, however, as secondary metal when the batteries are discarded.2616
There are basically two types of lead-acid batteries—pasted plates
and PI ante plates. The essential difference between the two is that the
active materials of PI ante plates are derived from the body of the plate
31
-------
TABLE 1
NICKEL-CADMIUM BATTERIES
Firm
Location
Alkaline Batteries Corporation
Eagle Richer Industries, Incorporated
Precision Products Department
General Electric Company
Battery Business Division
Goulton Industries, Incorporated
Marathon Battery Company
Nicad Division, Gould Incorporated
NIFE Incorporated
Easthampton, Massachusetts
Colorado SpringsB Colorado
Gainsville, Florida
Metuchen, New Jersey
Cold Spring, New York
St. Paul, Minnesota
Copiagne, New York
32
-------
TABLE 2
WASTES FROM BATTERY MANUFACTURE
Bureau of Census Regions
Material I II III IV V VI VII VIII IX Total
Annual Waste Production (Ib/year)
Cadmium 530 1,600 - 530 530 - 530 3,720
Lead .2.56 x 105 4.70 x 105 2.29 x 105 0.46 x 105 0.70 x 105 0.08 x 105 0.25 x 105 0.15 x 105 2.21 x 105 13.40 x 105
CO
CO
-------
itself, whereas for pasted plates they are formed from oxides or other
pastes applied to the plate mechanically. The manufacture of pasted
plate batteries contributes the major portion of the lead wastes generated
from battery manufacturing. For this reason, the following discussion is
limited to pasted plate batteries.
The grids of lead acid batteries serve as supports for the active material
of the plates and conduct the electric current. They also have an important
function in maintaining a uniform current distribution throughout the mass
of the active material. The grids are cast, for the most part, of an alloy
of lead and antimony.
The pastes now commonly used in making the pasted-plate batteries are
prepared by mixing some particular lead oxide or a blend of oxides with a
dilute solution of sulfuric acid. Reactions occur that result in the
formation of basic lead sulfate and the liberation of considerable heat.
The lead sulfate is the cementing material which makes a firm plate that
can be handled in the processes to follow. The lead sulfate also expands
the paste and this has an important effect on the subsequent operating
characteristics of the finished battery. Too little expansion results in
hard, dense plates and needless limitation of the ampere-hour capacity
of the battery. They may fail in service by buckling. On the other hand,
too great expansion may result in shedding of the active material and thereby
p/-1 C
shorten the useful life of the battery.
The paste is applied to the grids by hand labor in many of the
smaller manufacturing plants and by machine pasting equipment in most of
the larger plants. When the work is done by hand, the paste is spread
upon the grids with a wooden spatula or a smoothing trowel. Sufficient
pressure must be applied to force the paste into intimate contact with
the cross bars of the grid. The grids must be free from grease and dirt
before pasting is begun. Sometimes they are washed and dipped in a dilute
solution of sulfuric acid before being pasted.
34
-------
Machines of several types have been developed for pasting the plates.
In the machine operation, the grids pass under a hopper from which approximately
the right amount of paste 1s received. This 1s pressed Into the grids as
they pass along, and the excess paste 1s removed. Sometimes the plates
2616
are partially dried before leaving the machine.
The lead wastes from the battery Industry are generated largely 1n the
mixing of the pastes and the application of the pastes to the grids. A
typical waste sludge may contain 2,500 ppm of lead sulfate, a trace of copper
hydroxide, and neutralized sulfuric acid.*
It is estimated that there are 1,340,000 Ib of lead waste (as lead)
generated in the manufacture of lead-acid batteries each year. This
number was computed by employing the same waste generation factor (0.67
percent of the material input is wasted) as for the manufacture
of cadmium-nickel cells and assuming that of the total amount of lead used
each year in the battery industry, 20 percent of it is used to make the
lead-acid battery paste.
The geographical distribution of these wastes was determined on the
basis of the distribution of "value added by manufacture" dollar amounts
for electrical supplies produced in the United States and by Bureau of
Census regions (Table 2).
Mercury Cell Batteries
Confidential industry sources indicated that mercury wastes from
battery manufacturing are insignificant. The only mercury waste stream
generated in the production of mercury cell batteries comes from the wash
water used to clean mechanical equipment in the assembly line. This is a
very low volume waste stream. The methods for treating this waste stream
are: (1) addition of sodium sulfide to precipitate out mercuric sulfide;
*Rollins Environmental Services data.
35
-------
and (2) reduction to elemental mercury with sodium borohydride or zinc.
The mercury or mercuric sulfide is then collected by filtration and
reclaimed for its mercury value.
The larger battery manufacturers also make their own mercury chemicals
(mercuric oxide) to be used in the production of their mercury cell
batteries. In this case, there is an aqueous waste stream which may con-
tain 0.1 to 0.5 percent mercury (mostly mercuric oxide with some mercuric
chloride), and sodium chloride. This waste stream is usually combined
with the waste stream from the battery production line and the treatment
methods described above are employed.
The same confidential sources from the battery manufacturing industry
also indicated that 10 to 20 percent of the mercury cells produced are
currently being recycled to the battery manufacturers for the reclamation
of the mercury value. This would imply that 80 to 90 percent of the
mercury contained in the batteries eventually end up in landfills, dumps
and incinerators and find their way into the environment.*
*The quantity of mercury used in batteries each year is not available.
Total mercury consumption for the general category "electrical apparatus"
amounts to 1.29 million Ib in 1971.
36
-------
REFERENCES
2609. Personal communication. John Parry, A. D. Little, to D. Dal Porto,
TRW Systems, Jan. 2, 1973. Cadmium wastes generated in battery
manufacturing.
2616. Vinal, G. W. Storage batteries. 4th ed., New York. John Wiley and
Sons, Inc., 1955. 446 p.
37
-------
PESTICIDE WASTES
The disposal of surplus pesticides and pesticide contaminated wastes
is a problem of growing concern in recent years. Pesticide wastes that
warrant transportation to National Disposal Sites for treatment come from
three major sources:
(1) manufacturing wastes from pesticide producers and formulators;
(2) empty pesticide containers with pesticide residues from
professional applicators and agricultural users;
(3) surplus pesticides stored in government facilities.
Manufacturing Wastes
Pesticide manufacturers produce a variety of pesticide wastes.
Although aqueous waste streams and gas streams containing pesticides and
related toxicants are usually treated at the production site, there are
other solid, semi-solid, and liquid pesticide contaminated wastes currently
disposed of largely in landfill sites without adequate prior detoxification.
Virtually every pesticide manufacturer produces contaminated solvents and
process solutions containing unreacted ingredients, unrecovered products
and undesired by-products and in spite of the extensive efforts made to
minimize these process losses, the wastes are generated because a point
is usually reached where further recovery and recycle of the waste streams
and their constituents are no longer economically or technically feasible.
Pesticide ingredients may often be found to be concentrated in still bottoms
or filter media. In addition, normal plant trash such as bags, rags,
empty containers also often contain an unknown amount of pesticide residue.
Several major pesticide manufacturers have incineration facilities to
dispose of these types of wastes.
39
-------
Formulating plants receive pesticide concentrates from manufacturers.
Pesticide formulation processes are primarily batch mixing operations where
the appropriate active ingredients, solvents, or carriers, and the necessary
additives such as emusifying agents are blended together in ratios needed
to give the desired product. Frequently,, the same equipment 1s used to produce
a number of pesticide formulations containing different active ingredients
and solvents and great care must be taken to prevent cross-contamination
during the formulation process. Cleaning of liquid formulation process
equipment generally Involves one to five rinses with 20 to 50 gal. of the
solvent used in the previous formulation. In most cases, the solvents
used for rinsing are collected in sumps or evaporative basins along with
liquid wastes from occasional washdown of other plant facilities. Evaporative
basins of this type could be used for several years in some parts of the
country before concentrated liquid wastes and the accumulated sludges have
to be removed by contract disposal services. Dry formulation plants, on
the other hand, generally clean their equipment by flushing with a dry in-
ert material before producing a different product and it is often possible
to save the flushing material for use in later production.
Information on the representative forms of pesticide manufacturing wastes
was provided by Rollins Environmental Services (Table 1). To summarize, the
principal types of wastes from pesticide manufacturers and formulators
are: (1) solid wastes containing 0.1 to 10 percent active ingredients on
rags, bags, paper, fiber drums, steel drums, filter solids, etc.; (2) still
bottoms containing active ingredients which are usually produced only in
small quantities; (3) solvent cleanup wastes containing 1 to 10 percent
active ingredients and inert carriers in aqueous or organic solutions which
are mainly produced by pesticide formulators: (4) spill cleanup and floor
washing wastes containing 1 to 10 percent active ingredients in aqueous
solution or organic solvent which are usually produced 1n very small quanti-
ties; (5) process wash water containing a few ppm to 0.1 percent active
ingredients in aqueous solution; (6) process solutions that may contain up
to 50 percent active ingredients, decomposition products, undesired by-products
etc.; and (7) off-spec material that can usually be reworked into the process.
40
-------
TABLE 1
REPRESENTATIVE PESTICIDE MANUFACTURING WASTES
Solid Wastes:
2 to 5 % Methomyl on fiber drums
2 % Temlk, 5 % Carbowax on solid matrix
0.1 to 10 % Methyl Parathion in plant trash
--contaminated paper, gloves, sample bottles, etc.
r
Semi-Solid and Liquid Wastes:
2.5 % Heptachlor and related compounds; 10 % diatomoceous
earth in aqueous slurry--solvent cleanup
• 10 % mixed Malathion and Parathion;5 to 7 % mixed intermediates;
3 to 4 % Carbaryls; 5 to 10 % diatomoceous earth; 3 to 5 % organic
solvent in aqueous slurries—solvent cleanup
11 to 40 % mixed phosphorothioates; 10 to 15 % phenates; 30 % alcohols;
sodium sulfate inorganic phosphites, filter aid and 0 to 20 % watej—
still bottoms and solvent cleanup
1 to 5 % 2,4-D and/or 2,4,5-T in mixed solvents including toluene
and xylene—solvent cleanup
5 to 10 % Atrazine; 5 to 10 % other triazines and by-products; 85 %
toluene—solvent cleanup
1 to 2 % Randox; 23 % trichlorobenzye chloride; 65 % aromatic solvent--
solvent cleanup
20 to 25 % 2,4-D; 20 to 25 percent 2,6-D; 10 to 15 % mono- and trichloro-
phenoxy acetic acids,sol vents and water-*plant shutdown residue
0.01 to 0.1 % methyl arsenate and other related compounds; 3 % soluble
organics in alkaline solution—process wash water
10 % Dithane in water with cleaning agents—spills and floor, washings
30 % DDT; 10 % trichloroethane and benzylchlorophenol; 60 % mixed
hydrocarbons—process solution
10 % DDT; 11 to 18 % DDT decomposition products; 5 % benzensulfonic
acid; 30 % aqueous sulfuric acid—process solution
45 % mixed methyl esters and thioesters of phpsphoro dithioate
compounds; 5 % mercaptans and hydrogen sulfide; 50 % organic solvent
--process solution
7 % Torpedo (dichloroethyl-dinitrotoluidene) in aqueous 38 % nitric
acid, 18 % phosphoric acid, 14 % hydrochloric acid—process solution
41
-------
Among the pesticide manufacturing wastes described here, only the
solid wastes, the contaminated solvents, and the process solutions are
produced in large volumes. A major pesticide manufacturer has indicated
that an average of 3 Ib of pesticide active ingredient are lost through
2290
these wastes per 1,000 Ib of pesticide active ingredient produced,
and the pesticide production wastes by USDA Regions (Table 2) have been
computed by using the information on the distribution of pesticide pro-
duction plants (Table 3), the estimated U.S. herbicide, insecticide, and
fungicide production figures (Tables 4, 5, 6), and the above production
loss figure (Table 7). For the specific pesticides which have been pro-
filed, the types and quantities of wastes generated in their manufacture
have been obtained from literature and industry sources and by TRW esti-
mates and are summarized in this report (Tables 8 and 9). In the absence
of any actual data, rough estimates on pesticide manufacturing wastes
could be made based on the following model:
(1) solid wastes —0.5 percent active ingredients on contaminated
fiber material and 0.2 Ib of waste per Ib of pesticide active
ingredient products;
(2) contaminated solvents--5 percent active ingredients in organic
solvents and 0.02 Ib of waste per Ib of pesticide active
ingredient formulated;
(3) process solutipn—10 percent active ingredients in organic solvent
and 0.01 Ib of waste per Ib of pesticide active ingredient
produced.
The solid waste generation factor of 0.2 Ib of waste per Ib of
pesticide active ingredient produced is the average of the figures provided
by the two sources where reliable and well-documented records of solid
waste quantity, information are available. The first source, a major organo-
phosphorus manufacturer, indicated that approximately 0.34 Ib of solid
waste are generated per Ib of pesticide active ingredient produced. The
second source, a DDT manufacturer, provided a lower waste generation factor
of 0.16 Ib of solid waste per Ib of pesticide active ingredient produced.2501
The estimate of 0.5 percent pesticide active ingredients in the solid wastes
was based on Rollins Environmental Services data.
41a
-------
TABLE 2
USDA REGIONS
*.
Region 1, North-Eastern Region 2. Appalachian Region 3, South-Eastern
New Hampshire Virginia South Carolina
Maine West Virginia Georgia
Vermont North Carolina Florida
New York Kentucky Alabama
New Jersey Tennessee
Pennsylvania
Delaware
Maryland
Massachusetts
Rhode Island
Connecticut
Region 4, Delta States Region 5, Corn Belt Region 6, Lake States
Mississippi Ohio Michigan
Arkansas Indiana Wisconsin
Louisiana Illinois Minnesota
Iowa
Missouri
Region 7, Northern Plains Region 8, Southern Plains Region 9, Mountain States
North Dakota Oklahoma Montana
South Dakota Texas Idaho
Nebraska Wyoming
Kansas Colorado
New Mexico
Arizona
Utah
Nevada
Region 10, Pacific States
Washington
Oregon
California
Alaska
Hawaii*
* Although Alaska and Hawaii are in Region 10, they were not included in
the pesticide waste estimates which refer to USDA regions.
-------
TABLE 3
PESTICIDE PRODUCTION PLANT*LOCATIONS IN 1969
0449
USDA Region & State
Region 1 , North-Eastern
New Hampshire
Maine
Vermont
New York
New Jersey
Pennsylvania
Delaware
.Maryland
Massachusetts
Rhode Island
Connecticut
Region 2, Appalachlna
Virginia
West Virginia
North Carolina
Kentucky
Tennessee
Region 3, South-Eastern
South Carolina
Georgia
Florida
Alabama
Region 4, Delta States
Mississippi
Arkansas
Louisiana
Region 5, Corn Belt
Ohio
Indiana
Illinois
Iowa
Missouri
Region 6, Lake States
Michigan
Wisconsin
Minnesota
No. of
Plant Sites
0
0
0
12
15
8
0
3
7
0
.1
5
1
16
1
3
5
18
18
12
9
5
7
10
1
15
7
9
7
7
5
USDA Region & State
Region 7, Northern Plains
North Dakota
South Dakota
Nebraska
Kansas
Region 8, Southern Plains
Oklahoma
Texas
Region 9, Mountain States
Montana
Idaho
Wyoming
Colorado
New Mexico
Ari zona
Utah
Nevada
*
Region 10, Pacific States
Washington
Oregon
California
Total U.S. Plant Sites = 340
.
No. of
Plant Sites
0
0
4
4
3
34
0
1
0
7
0
11
0
1
8
4
56
Although Alaska and Hawaii are in Region 10, they were not included in the pesticide waste
estimates.
43
-------
TABLE 4
ESTIMATED MAJOR U.S. HERBICIDE PRODUCTION IN igyi2276'2277
UNITS IN MILLION POUNDS.
Benzoic
Ami ben
Banvel
Betasan
Dacthal
Lasso
Nap ta lam
PCB and Salts
Picloram
Propani 1
Ramrod
Si 1 vex
2,3,6-TBA
Total
Chlorinated Aliphatic
Dalapon
Randox
TCA
Total
20
2
2
20
2
46
3
6
23
3
2
oTSlT
5
10
1
16
Triazine
Amitrole 1
Aatrex 90
Pri ncep 5
Propazine 4
Total VTOO"
Organic Arsenical
Cacodyllc Acid 2
DSMA-MSMA 35
Total 37
Phenyl-urea
Chlorobenzilate 2
Chloroxuron <1
Diuron 6
Monuron <1
Siduron <1
Linuron 2
Total ^13
Carbamate
Avadex <1
Avadex BW <1
Azak <1
Barban <1
Eptam 5
Ro-Neet <1
Sutan 6
Till am 1
Vegadex <1
Vernam 2
Total ^20
Phenoxy
2,4-D
2.4.5T
Total
Other Organic
Aqualin
Bromasil
Chloropropharm
Def
Endothall
Fluometuron
Fluorodifen
Folex
Herban
Maleic hydrazide
Ordam
Terbaci 1
Total
Dinitro
45 Benefin 1
6 Dinoseb 3
•\3T Planavin 2
Trifluralin 25
Total ^TT
,
<1
8
2
5
2
4
1
3
2
3
<1
<1
-.33
Total major herbicide production =i431 million pounds in 1971.
-------
cn
TABLE 5
ESTIMATED MAJOR U.S. INSECTICIDE* PRODUCTION IN 19712276'2277
UNITS IN MILLION POUNDS
Polychlorinated Hydrocarbon
Acaralate <1
Aldrin 10
Chlordane 25
Dicofol 4
Dieldrin <1
DDT 45
Endosulfan ' 2
Endrin <1
Heptachlor 6
Lindane <1
Methoxychlor 10
Mi rex <1
Para-dichlorobenzene 60
Toxaphen 50
Total -v-TTT
Organophosphorus
Abate
Aspon
Azodrin
Bidrin
Co Ral
Dasanit
Diazinon
Dichlorvos
Dimethoate
D-ioxathion
Disulfoton
Dursban
Dyfonate
Ethion
Fenthlon
Guthion
Malathion
Meta-Systox R
Methyl parathion
Mevinphos
Mocap
Naled
Parathion
Phorate
Phosphamidon
Ronnel
Ruelene
TEPP
Trithlon
Zinophos
Total
Carbamate
<1 Bux Ten
<1 Carbaryl
5 Carbofuran
<1 Total
<1
4
10
<]
2
<1
8
5
2
2
<1
4
30
<1
45
<1
<1
2
15
8
<1
2
2
<1
'2
<1
•vW
Other Oraanic
6 DBCP
55 DEET
8 Diphacin
6T~ Ethyl hexanediol
Me thorny 1
Methyl bromide
MGK 264
MGK 326
Nicotine
Pyrethrins
Rotenone
Temi k
Tropital
Warfari n
Total
10
<1
<1
<1
. 2
22
<1
<1
<1
<1
<1
2
<1
12
•,,57
Total major insecticide production = ^504 million Bounds in 1971
* Including miticides, nematocides, rodenticides, molluscicides, *umigants, soil conditioners, etc. The ma'or inoraanic
insecticides such as arsenates are becoming insignificant as the result of strict government controls.
-------
TABLE 6
MAJOR U.S. FUNGICIDE PRODUCTION IN igyi2276*2277
UNITS IN MILLION POUNDS
Fungicide
Benomyl <1
Captan 18
Chloroneb <1
Cyprex 2
DCNA <1
Difolatan 2
Diphenamic 3
Dithio-carbamates 40
Folpet 2
Karathane <1
PCNB 3
TCP and Salts 20
Total
Total major fungicide production = ^94 million pounds in 1971.
-------
TABLE 7
ESTIMATED* PESTICIDE PRODUCTION AND ASSOCIATED PRODUCTION
WASTE BY USDA REGION AND STATE0049'2276'2277
UNITS, 100 LB/YEAR
USDA Reaion
and State
Peoion 1, North-Eastern
New Hampshire
Maine
Vermont
New York
New Jersey
Pennsylvania
Delaware
Maryland
Massachusetts
Rhode Island
Connecticut
Reoion 2, Appalachian
Virginia
West Virginia
North Carolina
Kentucky
Tennessee
Region 3, South-Eastern
South Carolina
Georgi a
Florida
Alabama
Region 4, Delta States
Mississippi
Arkansas
Louisiana
Region 5, Corn Belt
Ohio
Indiana
Illinois
Iowa
Missouri
Region 6, Lake States
Michigan
Wisconsin
Minnesota
Region 7, Northern Plains
North Dakota
South Dakota
Nebraska
Kansas
Region 8, Southern Plains
Oklahoma
Texas
Region 9, Mountain States
Montana
Idaho
Wyomi ng
Colorado-
New Mexico
Arizona
Utah
Nevada
Region 10. Pacific States
Washington
Oregon
California
Herbicide
Production
_
.
15,200
19,000
10,100
3,800
8,900
1,300
6,300
1.300
20.300
1.300
3.800
6.300
22.800
22.800
15,200
11,400
6,300
8,900
12,700
1,300
19.000
8.900
11.400
8^900
6.300
_
_
5.100
5,100
3,800
43,100
_
' 1,300
-
8.900
_
13.900
_
1.300
10.100
5,100
71,000
Insecticide
Production
17,800
22,200
11,900
4.400
10,400 .
1.500
7,400
1,500
23.700
1.500
4,400
7,400
26.700
26.700
17,800
13,300
7,400
10,400
14,800
1.500
22,200
10,400
13,300
10,400
10,400
7,400
5.900
5.900
4,400
50,400
-
1.500
-
10.400
-
16,300
-
1,500
11,900
5.900
83.000
Fungicide
Production
3,300
4,200
1,200
800
1.900
300
1,400
300
4,400
300
800
1,400
5,000
5,000
3.300
2.500
1.400
1.900
2.800
300
4,200
1,900
2.500
1,900
1,900
1.400
1,100
1,100
800
9.400
-
300
.
1.900
_
3.000
_
300
2.200
1,100
15,500
Herbicide
Waste
"
~
46
57
30
11
27
3.9
19
3.9
61
3.9
11
19
68
68
46
34
19
27
38
3.9
57
27
34
27
27
19
-
15
15
11
129
-
3.9
-
27
-
42
-
3.9
30
15
213
Insecticide
_
_
53
67
36
13
31
4.5
22
4.5
71
4.5
13
22
80
80
53
40
22
31
44
4.5
67
31
40
31
31
22
-
18
18
13
151
-
4.5
-
31
-
49
-
4.5
36
18
249
Fungicide
-
9.9
12.6
6.6
2.4
5.7
0.9
4.2
0.9
13.2
0.9
2.4
4.2
15.0
15.0
9.9
7.5
4.2
5.7
8.4
0.9
12.6
5.7
7.5
5.7
5.7
4.2
-
3.3
3.3
2.4
28.2
-
0.9
.
5.7
-
9.0
-
0.9
6.6
3.3
46.5
These estimations are based on the followinp assumptions:
(1) Current operational plant sites are those presented 1n Table 3.
(2) All plant production rates are equal.
(3) An equal herbicide.to Insecticide to fungicide ratio in ell producing states.
(4) Total herbicide, insecticide and fungicide production rates are those nresented in Tables 4, 5, and 6.
(5) An average pesticide production waste factor of 3 pounds of waste per 1000 rounds of nroduct.
47
-------
TABLE 8
MANUFACTURING WASTES FROM THE PRODUCTION OF SELECTED PESTICIDES
Pesticide
Waste Form
Waste Quantity and
Distribution
Source
OD
DDT
Aldrin
Dieldrin
Chlordane
Heptachlor
Aqueous waste containing
unknown amount of DDT
and Na2S04
Solid waste, unknown
amount of DDT
Aldrin-containing liquid
wastes from spill cleanup
and floor washings
Solid wastes containing
0.5 % aldrin
Aqueous waste containing
dieldrin in ppm range
Solid wastes containing
0.5 % dieldrin
Liquid wastes containing
approximately 12 % NaCl,
2 %NaOCl, 2 % NaOH and
chlordane in ppm range
Solid wastes containing
0.5 % chlordane
Aqueous waste containing
0.5 ppm heptachlor at
pH = 4.0
Liquid residue waste from
solvent recovery by dis-
tillation
Solid wastes containing
0.5 % heptachlor
68.5 X 10° Ib/year, Region 10
7.7 X TO6 Ib/year, Region 10
Small amount, Region 9
2 X 10° Ib/year, Region 9
6.6 X 108 Ib/year, Region 9
2X10° Ib/year, Region 9
30 X 10° Ib/year, Region 5
5 X 10 Ib/year, Region 5
2.63 X 10s Ib/year, Region 2
Small amount, Region 2
1.2 X 106Ib/year, Region 2
2501
2501
2501
TRW Estimate
2501
TRW Estimate
2293
TRW Estimate
2293
2293
TRW Estimate
-------
Pesticide
TABLE 8 - CONTINUED
MANUFACTURING WASTES FROM THE PRODUCTION OF SELECTED PESTICIDES
Waste Form
Waste Quantity and
Distribution
Source
Endrin
CD
Parathion
and Methyl
Parathion
Demeton
and Guthion
aqueous waste containing
0.03 ppm endrin at pH = 11
Liquid residue waste from
solvent recovery by dis-
tillation
Solid Wastes containing
0.5 % endrin
Slurry containing para-
thions and parathion
intermediate products
such as (CzHcOkPSCl and
5 1.71 X 10y Ib/year, Region 2
Small amount, Region 2
2 X 105 Ib/year, Region 2
Small amounts, Regions 2,
3, 4, 10
c
(CH302) PSCT
Solid wastes containing 0.5
% parathions
Process solution con-
taining 10 % demeton
and Guthion and inter-
mediate products in
organic solvent
Solids waste containing
0.5 % demeton and Guthion
6 X 10° Ib/year, Region 2;
5 X 106 Ib/year, Region 3;
6 X 105 Ib/year, Region 4;
6 X 105 Ib/year, Region 10
5 X 10 Ib/year, Region 5
10 Ib/year, Region 5
2293
2293
TRW Estimate
1037
TRW Estimate
TRW Estimate
TRW Estimate
-------
Pesticide
TABLE 8 - CONTINUED
MANUFACTURING WASTES FROM THE PRODUCTION OF SELECTED PESTICIDES
Waste Form
Waste Quantity and
Distribution
Source
2,4-D
cn
©
Still bottoms containing
2,4-D, 2,6-D and chloro-
phenols
Solid wastes containing 0.5
% 2,4-D
Small amounts, Regions 4, 6,
10
6 X 105 Ib/year, Region *\
7 X 106 Ib/year, Region 6;
6 X 105 Ib/year, Region 10
2501
TRW Estimate
TRW estimates on solid wastes (contaminated rags, bags, filter solids, fiber drums, steel drums, etc)
are based on 0.2 Ib solid waste generated per Ib of pesticide active ingredient produced. TRW estimate
on process solution wastes is based on 0.01 Ib liquid waste per Ib of pesticide active ingredient
process
produced.
-------
01
TABLE 9
ESTIMATED* MANUFACTURING WASTES FROM THE FORMULATION OF SELECTED PESTICIDES
UNITS - ACTIVE INGREDIENT (LB/YEAR)
Pesticide
DDT
Lindane
Aldrin
Dieldrin
Chlordane
Heptachlor
Endrin
Parathioh
Methyl
Parathion
Guthion
Demeton
2,4-D
1
500
-
-
170
-
-
-
930
-
840
40
1,700
2
2,200
210
1,000
50
2,300
600
80
630
-
180
130
1,300
3 4
9,800 5,400
530
200
230
-
-
230 430
2,720
9,000 24,300
620
-
800 1 ,000
USDA
5
800
-
7,700
140
19,600 2
4,700
-
-
.
260
-
9,400 3
REGIONS
6 7
400
-
700 400
80 60
,100 1,000
500 200
-
- 1 ,640
-
390
-
,900 10,300
8 9
3,700 600
130
-
80 190
-
-
110
3,610 1,310
11,700
-
50
2,700 6,900
10
1,600
. 130
-
-
-
-
150
4,160
-
1,710
780
7,000
Total
25,000
1,000
10,000
1,000
25,000
6,000
1,000
15,000
45,000
4,000
1,000
45,000
These estimates are based on the following assumptions:
(1) 0.02 Ib organic liquid waste containing 5 percent pesticide active ingredient per Ib
of pesticide active ingredient formulated;
(2) the quantity of a pesticide formulated in a-ceaion is proportional to the quantity of
the pesticide used on crops in that region. ^
-------
The waste generation factor for contaminated solvents from pesticide
formulation was computed with the following assumptions: (1) a 40 percent
active ingredient concentration for formulated liquid pesticides;
(2) three organic solution rinses of 40 gal. each are used in process
equipment cleanup for every 1,500 gal. of liquid pesticide formulated*;
(3) a 0.1 percent active ingredient loss in the liquid pesticide formulation
process; and (4) 90 percent of the organic solutions used for cleanup pur-
poses are evaporated from the sumps before the liquid wastes are removed
for disposal.
The quantity of process solution wastes generated from pesticide
production varies from negligible amounts to several times the quantity
of pesticide active ingredient produced, depending on the chemical reac-
tions involved and the subsequent purification steps employed. The
composition of the process solution wastes, for the same reasons, is
equally difficult to characterize, although the organic solution con-
taining TO percent pesticide active ingredients represents a fairly
typical process waste stream (Table 1). The waste generation factor of
0.01 Ib process solution waste per Ib of pesticide active ingredient
produced was computed from the balance of the other two pesticide pro-
duction wastes, to make up for a total of 3 Ib of pesticide active
ingredient loss per 1,000 Ib of pesticide active ingredient produced,
as indicated previously.
Empty Pesticide Containers and Residual Pesticide Wastes
Although the number of empty pesticide containers throughout the
United States has been growing every year, current information on the
numbers and sizes of empty pesticide containers is not readily available.
* Liquid pesticide formulation normally involves mixing in 1,500 gal.
size tanks.
As a result of the evaporation process, the liquid wastes removed are
ten times more concentrated in the pesticide active ingredients than
the original cleaning solutions. Thus, the final pesticide active
ingredient concentration of the liquid waste could reach as high as
3o to 40 percent, although the average is closer to 5 percent (Table 1),
52
-------
Reasonable estimates on the numbers and types of pesticide containers and
the quantity and regional distribution of pesticide residues, however,
could be made by using the following information:
(1) data on the weighed percentage estimates of active
pesticide ingredients, proportional usage, and packaging
sizes for formulated pesticides by class and formulation
types (Table 10) developed by Jansen06'9;
(2) data on the total 1970 domestic fungicide, herbicide, and
insecticide use given in Pesticide Review 1738;
(3) data from a University of California, Davis study indicating
that liquid residues left in pesticide containers are 400 gm
for the 55-gal» container, 40 flfflQfor the 5-gal- container, and
14 gm for the l-ga% container2592;
(4) the assumption that the quantity of pesticide residues left in
empty dry packages and aerosol cans is small compared to the
quantity of pesticide residues left in liquid pesticide containers;
(5) the assumption that the regional distribution of pesticide residues
is proportional to the quantity of each pesticide used on crops
in that region.0449
The total number of pesticide containers of all sizes in 1970 has been
computed to be in excess of 199 million (Table 11). Of these, approximately
30 million are liquid pesticide containers which pose the greatest disposal
problem.
The total quantity of pesticide active ingredients in empty containers
has been estimated to be 868,000 Ib in 1970 (Table 12). To indicate the
significance of these pesticide residue wastes, the estimated 136,000 Ib
organophosphorus insecticide residue is sufficient to cause the death of
*
35 million people if taken internally.
Surplus Pesticides Stored in Government Facilities
Sizable quantities of surplus pesticides have been accumulated in
recent years due to the cancellation of certain use patterns. The most
significant of these to date has been DDT. Since then, suspension or
By assuming an acute oral ID™ of 14 mg/kg for the organophosphorus
insecticides. DU
53
-------
TABLE 10
WEIGHED PERCENTAGE ESTIMATES OF ACTIVE PESTICIDE INGREDIENTS,
PROPORTIONAL USAGE, AND PACKAGING SIZED FOR FORMULATED
PESTICIDES BY CLASS AND FORMULATION TYPES
Pesticide
Class and
Formulation
Type
Active
Ingred-
ient
Propor-
tional
Use
Package Sizes
Large
Inter-
mediate
Small
Fungicides
Liquid 23.8
Dry 33.7
Herbicides
Liquid 43.5
Dry 19.3
Insecticides
Liquid 35.9
Dry 9.2
Aerosol 98.0
46.9
53.1
55.5
44.5
70.5
26.6
2.9
78
16
31
75
42
53
15
52
40
7
84
17
25
18
47
100
*Liquid
Dry
Aerosol
55-gal
50-lb
5-gal
1-gal
4-lb
1-lb
54
-------
TABLE 11
ESTIMATED DISTRIBUTION OF PESTICIDE CONTAINERS
BY SIZE AND TYPE IN 1970
Package Size
cn
cn
Class of
Pesticides
Fungicides
Herbicides
Insecticides
and Others
Total by
Size
55-qal .
(1,000)
279.44
281.09
404.40
964.93
Liquid
5-gal.
(1,000)
591.13
5,186.57
4,236.68
10,014.38
1-gal-
(1,000)
1,373.71
8,478.06
9,532.52
19,383.69
Dry
50-1 b
(1,000)
403.33
10,815.02
6,611.96
17,830.31
1-lb
(1,000)
26,469.27
45,062.59
73,292.96
144,824.82
Aerosols
1-lb Total
(1,000) 0,000)
29,116.88
69,832.33
6,384.13 100,462.65
6,384.13 199,,402.86
-------
TABLE 12
ESTIMATED QUANTITY OF PESTICIDE RESIDUE LEFT IN EMPTY CONTAINERS
UNITS - ACTIVE INGREDIENT (LB/YEAR)
Pesticide Type
and Category
Herbicides
Inorganic
Benzoic
Triazine
Phenyl-urea
Phenoxy
Dinitro
Chlorinated
Aliphatic
Organic
Arsenical
Carbamate
Other Organic
Insecticides
Inorganic
Polychlorinated
Hydrocarbons
Organuphosphorus
Other Organic
Fungicides
Organic and
Inorganic
Total Pesticides
USDA REGIONS
1
7,280
-
14,850
1,390
1,830
15,540
6,170
-
20
480
2,840
910
5,910
24,710
3,900
85 ,830
2 .
4,220
-
12,210
1,110
1,710
2,120
.-
260
320
5,740
2,130
5,630
6,780
14,000
10,100
66,330
3
1,450
480
1,320
1,390
1,600
7,070
-
390
450
5,740
260
16,060
18,950
32,940
35,600
123,700
4
2,550
1,450
330
5,570
1,510
-
1,700
27,040
2,190
4,310
_
11,100
26,080
23,880
100
107,810
5
750
55,680
32,350
1,390
10,140
710
1,230
_
7,720
13,640
450
980
2,430
9,060
3.8QO
140,330
6
_
7,750
30,200
420
4,650
530
4,630
_
1,010
2,150
1,160
6,880
7,650
6,180
2,100
75,310
7
400
5,330
7,430
20
11,910
• .
2,160
_
400
240
_
360
9,390
410
150
38,200
8
1,500
1,160
560
3,450
90
150
7,720
6,500
1,430
4,200
6,970
23,820
24,710
2,900
85,160
9
11,390
730
160
40
7,250
180
_
_
400
480
_
1,280
6,610
2,880
600
32,000
10
810
13,560
1,160
1,260
7,540
5,100
150
_
1,220
1,200
710
2.330
28,340
28,420
21,500
113,320
Total
30,350
84,980
101,170
13,150
51 ,590
31 ,360
16,190
35,410
20,230
35,410
11,750
52,500
135,960
167,190
80,750
867,990
-------
cancellation of certain uses of 2,4,5-T, several mercury compounds, aldrln,
dieldrin, etc., has been effected, and this has contributed to the disposal
problem.
Surplus pesticides are currently stored in Department of Defense
facilities and state/Environmental Protection Agency (EPA) regional
facilities. Information on the quantities, types and locations of surplus
2222
pesticides was obtained from the Defense Supply Agency and EPA sources,
and the data has been summarized and separately tabulated for Department
of Defense surplus pesticides and state/EPA surplus pesticides (Tables 13,
14, 15). The quantity of surplus pesticides currently in storage in
Department of Defense facilities in the continental United States awaiting
disposal amounts to 10 million Ib, including 8.2 million Ib phenoxy herbi-
cides, 1.4 million Ib polychlorinated hydrocarbon insecticides, and 140,000
Ib organophosphorus insecticides. The quantity of surplus pesticides under
the custody of the regional Environmental Protection Agency offices and
requiring disposal amounts to 1.8 million Ib. In addition, there are also
25,000 55-gal. drums of 2,4-D and 2,4,5-T manufacturing by-product wastes
stored at Alkali Lake, Oregon.
57
-------
TABLE 13
DEPARTMENT OF DEFENSE SURPLUS ORGANIC PESTICIDE SURVEY
UNITS, LB TOTAL - LB ACTIVE INGREDIENT
(a)
Ul
00
USOA REGION
AND STATEl")
Region 1
North' Eastern
New york
New Jersey
Pennslyvania
NeM Hampshire
Maryland
Massachusetts
Washington D.C
Region 2
Appalachian
Virginia
North Carolina
Tennessee
Region 3
South-Eastern
South Carolina
Georgia
Florida
Alabama
Region 4
Delta States
Mississippi
Arkansas
Region 5
Corn Belt
Ohio
Indiana
Illinois
Missouri
Region 6
Lake State:
Michigan
Region 7
Northern Plains
South Dakota
Nebraska
Kansas
Region 6
Southern Plains
Oklahoma
Texas
Beaton 9
Mountain States
Wyoming
Colorado
New Mexico
Arizona
Utah
Region 10
Pacific States
Washington
Oregon
California
Alaska
Hawaii
HERBICIDES
Benzole Phenyl-Urea Phenoxy
450 - 450
1.100 - 900 1.200 - 1,100
80 - 80
350- 280 120-100 1,200- 1,000
1,200 - 1,200 700 - 200 4.500 - 4,500
2,000 - 1,600
6. 954, 000 - 6.815.000
120 - 120
25 - 20 570 - 570
5.000 - 5.000
1.222.000 - 1.161,000
60 - 50 1,600 - 1,600
600 - 500 . 50 - 40
2,900 - 2.900
Chlorinated Other
AliDhatic Carbamate Organic
950 - 850
300 - 260
3.100 - 2,600 2.000 - 2.000
50 - 40 5,000 - 2,500
130 - 110 200 - 120
50 - 1
50 - 40
120 -
75-60
200 - 200
1,200- 10
Polycnlor
Hydrocar
90,000
1,100
32,700
430
1,550
700
4.800
98.700 -
55,300 -
39,000 -
120 -
69.400 -
58.500 -
1.900 -
5.100 -
2.600 -
300 -
19,900 -
1,900 -
1,600 -
2.000 -
70 -
60 -
210 -
44.600 -
160
12.400 -
170 -
2.800 -
7,200 -
37,300
353.500
377.600
15,500
18,800
INSECTICIDES
nated Organo- °°""'.
bons Phosphorus Organic
8,200 100 - 50
800
30,200
100
1,550
50
1.100
35,100 1.900- 500
13,200 750- 750
15.300
20
11.300 4.500-4,300 7.400- 7,300
20,100
1.400 25- 1
1.100
160
80 840- 340 350- 350
3.000
1 .800 500- 80
850
100 60- 60
10
30
20
7.300
90 250- 130
3.300 500- 10
80
700
1 ,600 1 ,250- 660
3,100 10-5
30.800 20,000-20,000
65.500 30,100-25.000 200- 2
10,300 98,000-73,000
1 ,100
FUNGICIDES
Organic
150-130
Approximate
Total
Pesticides
90,000- 9,000
1,100- 800
35,000-32,000
400- 100
1,700- 1,600
800- 150
4,800- 1,100
92,900-37.300
56,000-14,000
39,000-15.300
120- 20
92,800-33,400
65,500-24,200
1.900- 1.400
6.959,000-6.816,000
120- 120
2,600- 160
2,500- 1.600
20.400- 8.000
2,400- 1.900
1 ,600- 850
2,100- 160
70- 10
60- 30
210- 20
,267,000-1,168,000
410- 220
13,000- 3,400
1.900- 1.800
3.400- 1.200
8,700- 2,500
37,300- 3.100
373,500-50.800
369,100-90,500
116,400-86,200
18,800- 1,100
(a) Basic data obtained from Department of Defense inventory of pesticide wastes.
Liquid pesticide density assumed equal to water density.
When no active ingredient concentration data available, 100 percent assumed.
(b) States not listed In appropriate USOA regions contain no DOO pesticide wastes.
-------
tfi
TABLE 14
DEPARTMENT OF DEFENSE SURPLUS INORGANIC PESTICIDE
UNITS, LB TOTAL - LB ACTIVE INGREDIENT
USDA Region Herbicides
and State
Region 1
North-Eastern
New York
New Jersey
Pennsylvania 12,000 - 12,000
Region 2
Appal achlna
Virginia
Region 3
South-Eastern
Georgia
Florida
Region 4
Delta States
Louisiana
Region 5
Corn Belt
Indiana
Illinois
Missouri
Region 6
Lake States
Michigan
Region 8
Southern Plains
Texas
Region 9
Mountain States
New Mexico
Region 10
Pacific States
Washington
Oregon
California
Alaska .
Insecticides
300 -
5 -
20 -
537 -
31,100 -2
60 -
650 -
10 -
16 -
1,624 -1
6 -
25,500-25,
160-
4,550- 4,
16,200-16,
300
5
14
470
.600
£0
£50
10
15
,591
6
500
160
550
200
Total
Fungicides Pesticides
300
100 - 100 105
12,000
20
537
31,100
60
10 - 0.3 10
25 - 25 675
110 - 110 120
16
1,624
6
25,500
160
4,550
1,200 - 960 17,400
- 300
- 105
- 12,000
- 14
- 470
-2,600
- 60
- 0.3
- 675
- 120
- 15
-1,591
6
- 25.500
160
- 4,550
- 17,160
-------
TABLE 15
SURPLUS PESTICIDES STORED BY VARIOUS STATES AND EPA REGIONAL OFFICES
USDA Region
and State
Types and Quantities of Pesticides in Storage
Region 1
New Hampshire
Rhode Island
New Jersey
New York
Delaware
Region 2
Virginia
North Carolina
Region 3
Florida
Georgia
Region 5^
Indiana
Region 6
Minnesota
Michigan
3 to 5 tons of unidentified pesticides
Small amount of DDT
1 ton of fire damaged pesticides, principally organophosphates, chlorinated hydrocarbons,
and carbamates
1,000,000 Ib of assorted pesticides, 100,000 Ib of water damaged pesticides including dieldrin
Small amounts of pesticides
115 tons of pesticides
82 tons of DDT and DDT-Parathion mixtures
86,000 Ib mixed pesticides
3,360 Ib Parathion
2,100 Ib Chlordane
800 Ib drum spray
5,950 Ib DDT-BHC-Trithon
3,840 Ib DDT-BHC
3,810 Ib DDT-BHC Ethion
2,850 Ib Chlordane-BHC-DDT
2,460 units Harris Ant Buttons (Arsenate)
1,488 units Tick Spray
1,351 containers DDVP Strips
8,360 Ib Veon-245
5,600 Ib Disinfectant
Unknown quantities of pesticides
Unknown quantities of pesticide wastes
111,228 Ib of material containing 27,065 Ib of DDT
-------
TABLE 15 - CONTINUED
SURPLUS PESTICIDES STORED BY VARIOUS STATES AND EPA REGIONAL OFFICES
USDA Region
and State Types and Quantities of Pesticides in Storage
Region 10
Alaska13,400 Ib of technical DDT
575 Ib of technical chlordane
100 Ib of technical toxaphene
300-500 Ib of insoluble complex of copper-chromium-arsenic
Oregon 13,750,000 Ib of 2,4-D and 2,4,5-T manufacturing by-product
1,200 Ib of arsenic trioxide
1,000 Ib of 10 % DDT
104 Ib of Parathion
Washington 96 Ib of 95 % lead arsenate
305 Ib of 70 % calcium arsenate
50 Ib of 5 % chlorthion
32 Ib of 27 % Phosdrin
25 Ib of technical grade mercury cyanide
-------
REFERENCES
0449. Finkelstein, H. Comp. Air Pollution aspects of pesticides. Report
prepared for the National Air Pollution Control Administration by
Litton Systems, Inc., under contract PH-22-68-25. U.S. Government
Printing Office, Sept. 1969. p. 114-122.
0619. Working Group on Pesticides. Proceedings of National Working
Conference on Pesticide Disposal, Baltsville Maryland, June 30
and July 1, 1970. Washington, U.S. Government Printing Office,
1970. 141 p.
1037. Stutz, C. N. Treating parathion wastes. Chemical Engineering
Progress, 62(10): 82-84, Oct. 1968.
1738. The pesticide review, 1971. U. S. Department of Agriculture,
Washington, Mar. 1972. 56 p.
2222. Defense Supply Agency. Department of Defense inventory of pesticides,
herbicides and related hazardous substances. June 1971. 242 p.
2276. Johnson, 0. Pesticides' 72-part 2. Chemical Week, lll(4):17-46,
July 26, 1972.
2277. Johnson, 0. Pesticides' 72- part 1. Chemical Week. 110(25):33-66,
June 21, 1972.
2290. Personal communication. K. Schulz, Velsicol Chemical Corporation, to
M. J. Santy, TRW Systems, Sept. 1, 1972. Pesticide waste generation.
2293. Personal communication. K. L. Schulz, Velsicol Chemical Corporation,
to C. C. Shih, TRW Systems, Aug. 21, 1972. Pesticide manufacturing
wastes.
2501. Lawless, E. W., T. L. Ferguson, and R. von Rumker. The Pollution
potential in pesticide manufacturing. Report prepared for the
Environmental Protection Agency by Midwest Research Institute,
Kansas City, Missouri under Contract No. 68-01-0142. Chamblee,
Georgia,Division of Pesticide Community Studies, Environmental
Protection Agency, 1972. 250 p.
2592. Hsieh, D. P. H. and T. E. Archer. Detoxification of metal drums
from emulsifiable concentrate formulations of parathion. Un-
published paper, 1972.
62
-------
WASTES OF MERCURY AND MERCURY COMPOUNDS
' The principal sources of mercury wastes in solid, semi-solid or
concentrated liquid forms have been identified as (1) brine sludges from
mercury cell chlor-alkali plants; (2) waste sludges from paint manufac-
turers; (3) paint residue left in used paint containers; and. (4) mercury
used in electrical apparatus, industrial and control instruments, etc.'
that are not currently recycled. In addition, there are also small quan-
tities of surplus mercury and mercury compounds stored in Department of
Defense and regional Environmental Protection Agency facilities (Table 1).
The constituents of the brine sludges from mercury cell chlor-alkali
plants include barium sulfate, calcium carbonate, calcium sulfate, magne-
sium oxide, magnesium hydroxide, graphite, some iron, aluminum, mud, rocks,
and typically 100 ppm mercury in the form of HgClT. An estimated 16,500 Ib
of mercury are lost through 56,800 tons of brine sludges per year (Table 1).
A detailed discussion of the mercury containing brine sludges is included in
a later section of this report.
Phenyl mercury compounds are still used as mildewcides in water-based
paints in concentrations of 0.004 to 0.1 percent (as mercury). Phenyl
mercuric acetate, phenyl mercuric oleate, and di(phenyl mercuric) dodecenyl
succinate represent the three types most commonly employed as paint addi-
tives. Solid wastes are generated from the manufacture of paint and allied
products as a result of kettle washings and equipment cleanup. In the
latex washing system, the waste sludges typically contain 15 percent pig-
ments, 20 percent binders, 65 percent water, and 100 to 150 ppm mercury.
It is estimated that 1,800 Ib of mercury are lost through 26 million Ib
of water-based paint sludges every year. The geographical distribution of
these waste paint sludges was calculated on the basis of the distribution of
"value added by manufacture" dollar amounts for paints and allied products
and by Bureau of Census regions (Table 1). A more complete discussion of
the sources and constituents of the mercury containing wastes from paint
manufacture, along with the assumptions used in the computation of the total
quantity of the wastes, can be found in the report "Toxic Paint Wastes."
63
-------
TABLE 1
WASTES OF MERCURY AND MERCURY COMPOUNDS
Source and
Material
I
II
III
Bureau of Census
IV V
Regions
VI
VII VIII
IX
Total
Annual Waste Production (Ib/year)
Brine Sludge
Mercury
Sludge
Paint Sludge
Mercury
Sludge
Paint Residue
Mercury
110
1.1 x 106
45
0.65 x 106
1,900
3,120
31.2 x 106
395
5.74 x 106
6,000
1 ,010
10.1 x 106
555
7.99 x 106
6,500
1 ,385
13.9 x 106 44
120 155
1.70 x 106 2.23 x 106 1.
2,400 5,000
3,260
.7 x 106
85
24 x 106
2,100
5,510
8.9 x 106
135 20
1.93 x 106 0.31 x 106
3,100 1,400
2,115
3.7 x 106
290
4.21 x 106
4,300
16,510
113.6 x 106
1,800
26.0 x 106
32,700
Old paint 13 x 106 41 x 106 44 x 106 16 x 106 34 x 106 14 x 106 21 x 106 9 x 106 29 x 106 221 x 106
Mercury from
electrical
apparatus,
industrial and
control instru- . . . . . . . . 4 ' 4
ments, etc. 5.8 x 10* 18.4 x 10* 20.0 x 10* 7.4 x 10* 15.2 x 10* 6.3 x 10* 9.6 x 10* 4.1 x 10* 13.2 x 10* 100.0 x 10*
Stored Wastes (Ib)
Mercury - 3,700 25 9.5 - - - - - 3,735
Mercuric Nitrate ..._.__. 55
Mercuric and
mercurous
chloride 100 - - 110 - - - - - 210
Mercuric Cyanide -.._._._ 25 25
-------
The paint residues left in used paint containers discarded in municipal
dumps often contain 0.02 to 0.10 percent mercury and is another major source
of mercury waste. It is estimated that as much as 32,700 Ib of mercury are
lost through these paint residues per year. The geographical distribution
of these paint residue wastes was calculated on the basis of the population
distribution in the United States (Table 1). Again, a more complete dis-
cussion of the paint residue wastes can be found in the report "Toxic
Paint Wastes".
Of the mercury used for other potentially recyclable uses, such as
electrical equipment, measurement and control apparatus, and general lab-
oratory uses, approximately 1 million Ib per year (in batteries, fluores-
cent tubes, switches, etc.) are disposed of in landfills, dumps and incin-
erators. This was estimated by assuming that only 44 percent of the
1,800,000 Ib of mercury consumed for these purposes in 1971 were actually
recycled. The geographical distribution of these mercury wastes was
calculated on the basis of the population distribution in the United
States (Table 1).
Mercury compounds in relatively low levels are also found in the
liquid effluents from pharmaceutical and battery manufacturing plants.
The mercury compounds present are usually either reduced to metallic
mercury by the use of sodium borohydride (or zinc) or precipitated as
mercuric sulfide by the addition of sodium sulfide, and then collected by
filtration and reclaimed for their mercury value. Mercury wastes from
these manufacturers are therefore insignificant.
Mercury Containing Brine Sludges from the
Mercury Cell Chior-Alkali Plants
Approximately 25 percent of the U.S. supply of chlorine comes from
mercury cells, which produce a higher grade caustic soda that is highly
concentrated and essentially free of chlorine impurities. The total
chlorine capacity of mercury cells in the United States is about 7,000 tons
65
-------
per day from 29 installations around the country*9 with plant capacities
ranging from 6 to about 700 tons per day. In the mercury cell process, a
circulating sodium chloride solution is electrolyzed in the cell in which
mercury serves as the cathode; the anode is usually graphite. Sodium ion
reacts with mercury to form an amalgam, and chlorine gas is produced at
the anode. The mercury flows through the cell, picking up sodium on the
way, and is pumped to a regeneration cell, where the amalgam is mixed with
water and forms one-half of a self-shorted electrolytic cell, with iron
serving as the other electrode. The regeneration cell removes sodium from
the amalgam and produces caustic soda (approximately 50 percent solution)
and hydrogen gas. The regenerated mercury is then returned to the mercury
cell and the process is repeated. The brine solution leaves the mercury
cell and is vacuum de-chlorinated and then purged with air to remove the
last of the chlorine. The solution is then saturated with salt, and this
is followed by a purification step, in which various impurities from the
newly added salt are precipitated. The brine is then passed through a
filter and back to the mercury cell.
For resaturation of the partly depleted brine from electrolysis, solid
salt is required by the mercury cell process. If only brine is available,
this must be evaporated first to produce solid salt. Typical sources of
salt include shaft mined rock salt, vacuum pan salt, solar pond salt, and
salt recovered from the cell liquor evaporator in an adjacent diaphragm
cell plant. The ideal raw material for the mercury cell process is, of
course, highly purified recrystallized salt with a purity of 99.99 +
percent NaCl.
If the salt feed is of extremely high purity, the brine need only be
filtered before returning it to the cells. If salt recovered from the
diaphragm cell caustic evaporators is used, brine purification normally
involves the addition of caustic soda followed by filtration, the sludge
obtained is mainly graphite, along with some CaCOg, Mg(OH)2, and iron.
When either high purity recrystallized salt or recovered salt from the
*Five of the installations also have diaphragm cell chlorine plants
at the same location.
66
-------
diaphragm cell caustic evaporator is used, smaller quantities of mercury
containing brine sludges are generated. These can often be treated and
disposed of safely on the property.
If rock salt or solar salt is used, the full brine stream is treated
for the removal of Mg, Fe, CaClg and CaSO, equivalent to the pickup from
the salt dissolved. Brine purification includes the addition of barium
carbonate to remove sulfates, the addition of sodium carbonate or carbon
dioxide to precipitate calcium, the addition of caustic soda to remove
magnesium and heavy metals, and the addition of flocculents to cause
settling of the precipitates. Depending on the impurities initially
present in the salt, the constituents of the brine sludge include barium
sulfate, calcium carbonate, calcium sulfate, magnesium oxide, magnesium
hydroxide, graphite, some iron, aluminum, mud, rocks, and typically 100 ppm
mercury in the form of HgCl«~. Mercury losses through the brine sludges
from the mercury cell chlor-alkali plants range from 0.001 to 0.04 Ib per
ton of chlorine produced. The mercury containing brine sludges are currently
being pumped into settling basins awaiting the development and installation
of adequate treatment processes.
The location, producer, chlorine production capacity, the rate of
brine sludge production, and the rate of mercury loss through the brine
sludges of all the 29 mercury cell chlorine plants in the United States
have been summarized (Table 2). In addition, the annual chlorine production
capacity, the annual mercury loss through brine sludges, and the annual
brine sludge production by state are also presented (Table 3). The data
used in both tables were obtained through contacting the individual chlor-
alkali plants.2643-2662'2664
67
-------
TABLE 2
MERCURY LOSSES THROUGH BRINE SLUDGES FROM MERCURY CELL CHLOR-ALKALI PLANTS
OD
State & City
Alabama
Le Moyne
Mclntosh
Mobile
Muscle Shoals1'
Delaware
t
Delaware City
Georgia
Augusta
Brunswick
Illinois
East St. Louisf
Kentucky
Calvert City
Calvert City
Louisiana
Geismar
Lake Chalres
St. Gabriel
Chlorine Production Mercury Loss Through
Capacity BHne sludges
Producer (tons/day) Source of Salt (lb/day)
Stauffer Chemical Co.
01 in Corp.
Diamond Shamrock
Diamond Shamrock
Diamond Shamrock
01 in Corp.
Allied Chemical Corp.
Monsanta Co.
B. F. Goodrich Chemical
Corp.
Pennwalt Corp.
BASF Wyandotte Corp.
PPG Industries, Inc.
Stauffer Chemical Co.
190
350
100
285
400
390
285
100
330
300
no
700
430
Rock Salt, 99% Nad 0.15
Rock Salt (high purity)
Rock Salt 0.25 - 1.50
? 1.88
? ' 2.64
? 2.52
Recrystallized solar pond salt
? 0.66
Rock Salt 1.1
Rock Salt 1.35
recovered salt from diaphragm cell 0.7
caustic liquor
Recovered salt from diaphragm cell
caustic liquor
Rock Salt, 99. U Nad 14.4
Quantity of Brine
Sludges Produced
(tons/day)
2.5
•
: 2
9.4
13.2
' 12.6
-
3.30
; ' 11.7
21
0.25
-
12
-------
TABLE 2 - CONTINUED
MERCURY LOSSES THROUGH BRINE SLUDGES FROM MERCURY CELL CHLOR-ALKALI PLANTS
State & City
Maine
Orrington
New Jersey
Linden f
New York
*
Niagara Falls
Niagara Falls f
Syracuse
North Carolina
Acme
Pisgah*
Ohio
*
Ashtabula
Tennesse
Charleston
Texas
Deer Park
Point Comfort
Washington
Bellingham
*
Longview
Chlorine Production Mercury Loss Through
Capacity Brine Sludges
Producer (tons/day) Source of Salt (lb/day)
Sobin Chlor-Alkali Inc.
Linden Chlorine Products
Hooker Sobin Chemical
01 In Corp.
Allied Chemical Corp.
Allied Chemical Corp.
01 in, Ecusta Operations
Detrex Chemical Industries
01 in Corp.
Diamond Shamrock
Aluminum Co. of America
Georgia-Pacific Corp.
Weyerhaeuser Co.
160
500
140
250
250
165
6
60
455
250
400
135
265
Solar pond salt 0.18 - 0.30
Rock Salt 3.32
? 0.92
Rock salt . 1.66
Recovered salt from diaphragm
cell caustic liquor
Recovered salt from diaphragm
cell caustic liquor
Rock Salt, 99* purity 0.02
Mined salt, 98* purity 0.40
? 2.96
Recovered salt from diaphragm
cell caustic liquor
Evaporated salt (NaCl > 99.9*)
Solar pond salt 5
Solar pond salt 0.80
Quantity of Brine
Sludges Produced
(tons/day)
1.50
16.6
4.6
8.3
-
0.1
2
14.8
-
.
1
4
-------
TABLE 2 - CONTINUED
MERCURY LOSSES THROUGH. BRINE SLUDGES FROM MERCURY CELL CHLOR-ALKALI PLANTS
State & City
Producer
Chlorine Production
Capacity
(tons/day)
Source of Salt
Mercury Loss Through
Brine Sludges
(Ib/day)
Quantity of Brine
Sludges Produced
(tons/day)
West Virginia
Moundsville
New Martinsvilie
Wisconsin
Port Edwards
Allied Chemical Corp.
PPG Industries Inc.
BASF Wyandotte Corp.
250-300 Purified evaporated salt
190 ?
168 97-98% NaCl Salt from Detroit
1.26
1.7
6.3
8.5
Means both mercury loss and brine sludge production are negligible because highly purified salt is used.
When insufficient data is supplied, the quantity of brine sludges produced is estimated on the basis
that the salt is 98 percent NaCl. The mercury loss through brine sludges is estimated by
assuming that the mercury in the brine sludges is 100 ppm.
The mercury loss is estimated by assuming that the mercury concentration in the brine sludge is 100 ppm.
-------
TABLE 3
REGIONAL DISTRIBUTION OF MERCURY CONTAINING BRINE SLUDGE PRODUCTION
State
Alabama
Delaware
Georgi a
Illinois
Kentucky
Louisiana
Maine
New Jersey
New York
North
Carolina
Ohio
Tennesses
Texas
Washington
West
Virginia
Wisconsin
Total
Annual Chlorine
Capacity
(Tons)
337,600
146,000
250,000
36,500
230,000
452,600
58,400
182,500
233,600
62,400
21 ,900
166,000
•237,000 "
146,000
178,000
61 ,300
2,799,800
Annual Mercury
Loss
(lb)
1,288
964
920
241
894
5,512
no
1,212
942
7
146
1,080
-
2,117
460
621
16,514
Annual Production
of Brine Sludge
(Tons)
5,070
4,820
4,600
1,200
11,900
4,470
550
6,060
4,710
40
730
5,400
-
1,825
2,300
3,100
56,775
71
-------
REFERENCES
2105. Wallace, R. A., W. Fulkerson, W. D. Shults, and W. S. Lyon. Mercury
in the environment—the human element. ORNL NSF-EP-1. Oak Ridge,
Tennesses, Oak Ridge National Laboratory, Jan. 1971. 61 p.
2643. Personal communication. E. Dahlgren, Georgia-Pacific Corporation, to
C. C. Shih, TRW Systems, Sept. 22, 1972.
2644. Personal communication. W. Wallace, PPG Industries, Inc., to C. C.
Shihs TRW Systems, Sept. 25, 1972.
2645. Personal communication. F. Bahl, Linden Chlorine Product, to C. C.
Shih, TRW Systems, Sept. 26, 1972.
2646. Personal communication. C. Schmiege, Olin Corporation, to C. C. Shih,
TRW Systems, Sept. 26, 1972.
2647. Personal communication. B. Campanaro, Stauffer Chemical Company, to
C. C. Shih, TRW Systems, Sept. 27, 1972.
2648. Personal communication. C. Hovater, OUn Corporations to C. C. Shih,
TRW Systems, Sept. 27, 1972.
2649. Personal communication. G. Noce, Diamond Shamrock Chemical Corporation,
to C. C. Shih, TRW Systems, Sept. 27, 1972.
2650. Personal communication. J. Miller, Diamond Shamrock Chemical Corpora-
tion, to C. C. Shih, TRW Systems, Sept. 28, 1972.
2651. Personal communication. P. Armstrong, Wyandotte Chemicals Corporation,
to C. C. Shih, TRW Systems, Sept. 28, 1972.
2652. Personal communication. A. Macmillan, Sobin Chlor-Alkali Inc., to
C. C. Shih, TRW Systems, Sept. 29, 1972.
2653. Personal communication. D. Dmery, Aluminum Company of America, to
C. C. Shih, TRW Systems, Sept. 29, 1972.
2654. Personal communication. J. Kehn, Detrex Chemical Industries, Inc.,
to C. C. Shih, TRW Systems, Sept. 29, 1972.
2655. Personal communication. B. Conorry, Allied Chemical Company, to
C. C. Shih, TRW Systems, Oct. 2, 1972.
2656. Personal communication. H. Olfon, Wyandotte Chemicals Corporation,
to C. C. Shih, TRW Systems, Oct. 3, 1972.
2657. Personal communication. J. Barter, Stauffer Chemical Company, to
C. C. Shih, TRW Systems, Oct. 3, 1972.
-------
REFERENCES (CONTINUED)
2658. Personal communication. J. Tomllnson, Olin Corporation (Ecusta
Operation), to C. C. Shih, TRW Systems, Oct. 6, 1972.
2659. Personal communication. W. Epting, Allied Chemical Corporation, to
C. C. Shih, TRW Systems, Oct. 6, 1972.
2660. Personal communication. H. Houtz, Weyerhaeuser Company, to C. C.
Shih, TRW Systems, Oct. 9, 1972.
2661. Personal communication. W. Holbrook, B. F. Goodrich Chemical Company,
to C. C. Shih, TRW Systems, Oct. 25, 1972.
2662. Personal communication. C. Overbey, Pennwalt Corporation, to C. C.
Shih, TRW Systems, Nov. 3, 1972.
2664. Personal communication. E. Conant, Stauffer Chemical Company, to
C. C. Shih, TRW Systems, Jan. 30, 1973.
73
-------
WASTES OF ARSENIC AND ARSENIC COMPOUNDS
The principal sources of arsenic wastes have been identified as:
(1) flue dust from coal combustion; (2) flue dust from metal smelters;
(3) production of food grade phosphoric acid; (4) pesticide manufacture
and pesticide residues left in used containers; and (5) surplus arsenic
pesticides in storage and arsenic contaminated soil. Detailed discussions
of the quantities, forms, composition, and geographical distribution of the
arsenic containing waste streams from these sources are included in the
following sections of this report.
Arsenic Wastes from Coal Combustion
Coal contains 0.8 to 16 micrograms of arsenic per gram of coal and
for this reason the air of most large cities contains a small amount of
arsenic, probably as arsenic trioxide. Based upon the average arsenic
content of coal and a 400 million ton annual consumption of coal, the
total quantity of arsenic trioxide emitted from coal combustion amounts
to-8.5 million Ib per year. The fraction of this amount that is being
trapped by particulate removal systems is difficult to estimate, but is
expected to increase as tighter emission standards are enforced. The form
that this waste material is likely to take depends on the scrubbing method,
but in any case, the particulate residues will consist mainly of calcium
oxide, iron oxide, and other oxides. The geographical distribution of the
arsenic wastes from coal combustion was calculated on the basis of the
regional distribution of coal fired power plants in the United States
(Table 1).
Arsenic Hastes from Metal Smelting
Arsenic is present, normally as the sulfide, in most of the copper,
lead, zinc and other ores that are processed in the United States. In
the smelting of the metals, arsenic is oxidized to the more volatile arsenic
trioxide which exits up the flue stacks where most of it is recovered.
75
-------
TABLE 1
WASTES OF ARSENIC AND ARSENIC COMPOUNDS
Source and Bureau of Census Reg1ons
Material I II III IV V VI VII VIII IX Total
Annual Waste Production (Ib/year)
Coal combustion, /- , , , , fi fi ,
as As203 0.14x10° 1.25x10° 3.21x10° 0.61x10 1.72x10° 1.27x10° - 0.30x10° - 8.50x10°
Metal smelting ztzeiKKKKf.
as As203 - 0.6 x 10° 0.3 x 10° 2.1 x 10° 0.1 x 10° 0.2 x 10° 2.4 x 10° 16.7 x 10° 1.6 x 10° 24.0 x 10°
Production of
food grade
phosphoric
Asosl 0.2 x 104 0.8 x 104 1.0 x 104 0.2 x 104 0.2 x 104 0.2 x 104 0.4 x 104 0.2 x 104 0.8 x 104 4.0 x 104
23
Pesticide
residue in
used paint
containers,
as active ' 444
ingredient - - - - - 0.9 x 10 2.6 x 10 - - 3.5 x 10H
Stored Waste (Ib)
As-O, from metal 7 7
imiltlng - - - - - - - 4 * 10.' 4 x 107
Cacodyl ate
contaminated
solid waste 7 7
(1.5% cacodylate) - - 6 x 10X - - - - - - 6 x 10
-------
TABLE 1 - CONTINUED
WASTES OF ARSENIC AND ARSENIC COMPOUNDS
Source and
Material I
Still bottom
residue
(15% As)
Lead arsenate
Calcium arsenate
Sodium arsenlte
Copper
aceto»rsenite
Bureau of Census Regions
II III IV V VI VII VIII IX
1.6 x 104
12 1,600 - 24,100
-214
150 "325 - 550 - - - 8,100
1,500 - . -
Total
1.6 x 104
25,712
214 •
9,125
1 ,,500
-------
American Smelting and Refining Company (ASARCO) at Tacoma, Washington
is the largest producer of arsenic trioxide and until recently has acted
as a single point processing agent for the arsenic trioxide containing
flue dusts from virtually every smelter in the United States.* ASARCO
recovers 800 to 19000 tons of arsenic trioxide per month from flue dusts
1559
normally containing about 30 percent arsenic trioxide. Assuming that
ASARCO has almost 100 percent efficiency in arsenic trioxide recovery,
the amount of arsenic trioxide contained in the flue dusts received by
ASARCO would be approximately equal to the amount of arsenic trioxide
recovered. This indicates that the total quantity of arsenic containing
flue dusts collected from the smelting of copper, lead, zinc and other
arsenic-bearing ores amounts to 80 million Ib per year.
In addition to the crude arsenic trioxide, the flue dusts from metal
smelting contain mineral oxides, silica, and other materials. The geographical
distribution of the 24 million Ib of arsenic trioxide contained in these
flue dusts was calculated on the basis of the regional distribution of
copper, lead, and zinc refineries in the United States and by Bureau of
Census regions (Table 1). At the present time, as the result of low market
demand, there is also a stockpile of estimated 40 million Ib of arsenic
trioxide at ASARCO's Tacoma Site.
Arsenic Wastes from Phosphoric Acid Production
Nearly all phosphate rocks contain arsenic to some extent. Low level
arsenic wastes are generated from the production of phosphoric acid by
either the wet process or the furnace method, but these are of little
concern and can be safely disposed of into lagoons or landfills. In the
purification of the crude phosphoric acid to yield the food grade product,
however, arsenic wastes of much higher concentrations are obtained.
*These smelter flue dusts are sent to ASARCO for reclamation of their
metal values.
78
-------
The wastes from the wet process consist of a slurry of spent gypsum,
aluminum and iron phosphate sludges as well as the residual arsenic. The
arsenic content can be expected to range widely but is estimated to average
6 ppm as arsenic.* In addition, the spent, extracted rock also contains
residual amounts of arsenic.
The wastes from the furnace process consists primarily of spent rock
from the thermal reduction. Most of the arsenic in the rock is reduced
to the element and is recovered along with the elemental phosphorus. The
subsequent burning of the phosphorus creates only small quantities of
wastes and most of the arsenic is carried over with the resultant P«0C and
c. o
is thereby included in furnace grade acid.
Approximately 500 million lb of phosphoric acid-, primarily the
furnace grade product (50 ppm As), are annually treated for arsenic removal
to yield the food grade product. Hydrogen sulfide is bubbled through the
2587
acid to precipitate the highly insoluble arsenic sulfide, and a typical
waste stream from this process contains 8 percent arsenic sulfide, 7 percent
activated carbon, 29 percent filter acid, 35 percent phosphoric acid, and
water.f Based on an arsenic concentration of 50 ppm in the furnace acid,
it is estimated that approximately 40,000 Ib of arsenic sulfide are pro-
duced annually from this purification step. The geographical distribution
of these arsenic wastes was calculated on the basis of the industry infor-
PCQ7
mation on cities in which purification is performed (Table 1).
Arsenic Wastes from Pesticide Manufacturing and Usage
Industrial awareness for the hazardous properties of the arsenic
compounds has an important influence upon the design of industrial pro-
cesses for the manufacture of arsenic pesticide compounds. Batch processes
are normally employed in the production of these materials. The modern
*Based on mass balance calculations and the following assumptions:
(1) 1/3 of the phosphate rock is available phosphorus; (2) phosphate rock
contains an average of 10 ppm arsenic; and (3) wet process acid contains
5 ppm arsenic.
Rollins Environmental Services data.
-------
plants that produce these materials can generally be characterized by their
complete containment of any by-products or contaminated effluents that
result from these processes. More often than not, the only liquid effluents
from any of these processes are small amounts of contaminated water from
equipment washout and these are held in evaporating ponds at the plant
site. In the formulation of dry products, the water is driven off
by means of steam-heated, continuous drum dryers or of spray drying ap-
paratus. Scrubbing equipment treats the steam effluent from the drying
equipment and the scrubbing liquids are recycled for use as makeup solutions
for the next batch. Grinding and bagging of the products are performed in
a closed area with devices to control the emission of particulates from the
operation. "Bag filters are in common use and particulates removed from the
bags are packaged for sale. Because of the caution and control exercised
in the production process, the only major sources of arsenic wastes from
pesticide manufacture are: (1) arsenic contaminated filter cakes when
purification of a liquid formulation is required; and (2) arsenic contam-
inated by-products.
Of the four major inorganic arsenic pesticides, no arsenic containing
wastes have been identified in the manufacture of lead arsenate, calcium
arsenate, or copper acetoarsenite. Sodium arsenite is always sold commer-
cially as a liquid formulation and the liquid solution is usually filtered
before drumming. The resulting filter cake is buried in public dumps. The
quantity and composition of the waste filter cake generated are not known,
but is believed to be of low volume and contain both sodium arsenite and
arsenic trioxide, along with filter aid and water.
Among the organic arsenicals, solid wastes containing sodium chloride,
sodium sulfate, and 1 to 1.5 percent cacodylate contaminants are generated
2215
in the cacoylic acid production process. The rate at which this waste
material is produced is not known, but at the present time--there are
60,000,000 Ib being stored in concrete vaults in the Marinette, Wisconsin
area. There are currently no plans for the waste material other than to
2214
store it indefinitely. Arsenic wastes f
organic arsenicals have not been identified.
2214
store it indefinitely. Arsenic wastes from the manufacture of other
80
-------
Aerojet General Corporation manufactures arsenic fungicide products
and still bottom residues are generated from the process. The waste
amounts to about 16,000 Ib, contains approximately 15 percent arsenic in
various chemical forms, and is currently stored in 55-gal. drums at
Sacramento, California.
The use of formulated pesticides packed in containers always results
0
in some residue remaining in the containers. The arsenate pesticides are
usually formulated as dusts, granules, or wettable powders and packed in
sift proof, multiwall paper bags. The amount of pesticide residue left
in these containers after emptying is relatively small. The arsenites
and organic arsenicals, however, are normally formulated as liquid solutions.
As such, there are usually 0.5 oz to 1 Ib of liquid residue left in the
empty containers, depending on the shapes and sizes of the containers. At
the present time, arsenic pesticide usage is dominated by the three major
organic arsenicals--cacodylic acid, and the mono- and di-soliurn salts of
methane arsonic acid. The amount of these organic arsenicals left as
residues in used pesticide containers is estimated to be about 35,000 Ib
(as active ingredient) per year. The geographical distribution of these
pesticide residue wastes was calculated on the basis of the proportional
regional usage of organic arsenicals on crops by farmers (Table 1). The
assumptions and methods of computation employed in estimating the total
quantity and geographical distribution of the pesticide residue wastes are
described in detail in the report "Pesticide Wastes" elsewhere in this Volume,
Surplus Arsenic Pesticides and Arsenic Contaminated Soil
®
Surplus arsenic pesticides currently in storage awaiting disposal
include the following2222'2243: (1) Department of Defense - 1,624 Ib of
98 percent lead arsenate in Texas, 12 Ib of 98 percent lead arsenate in
Michigan, 110 gal. of sodium arsenite in Florida, 30 gal. of sodium arsenite
in New York, 65 gal. of sodium arsenite in Illinois, 1,620 gal. of sodium
arsenite in Alaska, and 30,000 Ib of 5 percent copper acetoarsenite solution
in Florida; (2) state/regional Environmental Protection Agency - 96 Ib of
95 percent lead arsenate and 305 Ib of 70 percent calcium arsenate in
81
-------
Washington, and 2,460 units of arsenate containing Harris Ant Buttons in
Georgia; and (3) pesticide manufactures - an estimated 24,000 Ib of lead
arsenate at South Gate, California.
The extensive use of arsenic pesticide in the past, particularly lead
arsenate, has also led to soil sterilization and rendered large acreages
2271
of farm land unusable for the growth of future crops. In addition,
the bottoms of evaporation ponds and lagoon systems for the treatment of
waste water from arsenic pesticide manufacturers are often contaminated
with arsenic in the form of arsenic trioxide. The lagoon system at Rocky
Mountain Arsenal, for example, has been used over the years by pesticide
manufacturers as well as the military for the discharge of their waste
water, and its bottom mud now contains 10 to 100 ppm arsenic.
82
-------
REFERENCES
0634. Sullivan, J. R. Air pollution aspects of arsenic and Its compounds.
Report prepared for the National Air Pollution Control Administration
by Litton Systems, Inc. Bethesda, Maryland under contract No.
PH 22-68-25. Washington, U.S. Government Printing Office, 1969.
72 p.
1559. Personal communication. K. Nelson, American Smelting and Refining
Company, to J. Clausen, TRW Systems, Mar. 3, 1972.
1643. Personal communication. T. Foster, Aerojet General Corporation, to
J. Clausen, TRW Systems, Aug. 17, 1972.
1740. Personal communication. D. Barem, Chevron Chemical Company, to J.
Clausen, TRW Systems, May 12, 1972.
2214. Personal communication. R. Gottschalk, Ansal Chemical Company, to
J. Clausen, TRW Systems, July 31, 1972.
2215. Personal communication. F. Wedge, Ansul Chemical Company, to J. Clausen,
TRW Systems, July 28, 1972.'
2222. Defense Supply Agency. Department of Defense inventory of pesticides,
herbicides, and related hazardous substancaes. June 1971, 242 p.
2243. Personal communication. H. Stevens, Los Angeles Chemical Company,
to J. Clausen, TRW Systems, Aug. 17, 1972.
2271. Benson, N. R. Re-establishing apple orchards in the Chelan-Mason
area. Panel Report to U.S. Bureau of Reclamation, Oct. 1968.
32 p.
2587. Personal communication. J. Taylor, Monsanto Chemical Company, to
J. Clausen, TRW Systems, Dec. 10, 1972.
83
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WASTES OF CADMIUM AND CADMIUM COMPOUNDS
The principal sources of cadmium wastes have been identified as: (1)
rinse water and dragout from the electroplating industry; (2) waste sludges
from paint manufacture; (3) paint residue left in used paint containers;
and (4) wash water from the manufacture of nickel-cadmium batteries.
Detailed discussions of the cadmium wastes from the electroplating
industry and battery manufacture can be found elsewhere in this volume
in the reports "Wastes from the Electroplating Industry" and "Wastes from
the Manufacture of Batteries", respectively. Likewise, a more complete
discussion of the cadmium wastes from paint manufacture and paint residue
left in used paint containers as well as the assumptions used in the
computation of the waste quantities can be found in the report "Toxic
Paint Wastes". A brief summary for these is given below followed by a
discussion of other sources.
The electroplating industry is the largest user of the cadmium metal
and is at the present also the largest source of cadmium wastes. The cadmium
wastes are generated primarily as the result of the rinsing operations, and
the typical aqueous waste stream contains 100 to 500 ppm cadmium, along with
other heavy metals, cyanides, and metal surface cleaning agents. Large
volumes of liquid waste streams having a much higher cadmium content, however,
have also been reported. An example of such a waste stream contains 1.5
percent cadmium cyanide, 8.5 percent sodium cyanide, 3 percent sodium
hydroxide, and traces of other metals. The total amount of cadmium wastes
(as cadmium) from the electroplating industry has been estimated to be 1.44
million Ib per year. The geographical distribution of the electroplating
wastes was calculated on the basis of the distribution of "value added by
manufacture" dollar amounts for finished metal products in the United States
(Table 1).
Cadmium wastes are generated in paint manufacture as a result of the
kettle washings and equipment cleanup. The two most important cadmium pig-
ments are the cadmium sulfide and the cadmium sulfoselenide. Cadmium in
85
-------
TABLE 1
WASTES OF CADMIUM AND CADMIUM COMPOUNDS
00'
Source and
Material
Bureau of Census
I II III IV V
Regions
VI VII VIII IX
Total
Annual Waste Production (Ib/year)
Paint Sludge
Cadmium
Sludge
Paint Residue
Cadmi urn
Old paint
Cadmium from
electroplating
Cadmium from
battery
manufacture
Cadmi urn
oxide
150 1,100 1,550 350 450
0.92 x 106 8.12 x 106 11.32 x 105 2.40 x 106 3.16 x 106
2,100 6,500 7,000 2,600 5,400
13 x 106 41 x 106 44 x 106 16 x 106 34 x 106
1.88 x 105 4.10 x 105 4.64 x 105 0.65 x 105 0.70 x 105
530 1,600 - 530 530
Stored Wastes
. ...
250 400 50 800
1.76 x 106 2.74 x 106 0.44 x 106 5.97 x 10^
2,200 3,400 1,400 4,700
14 x 106 21 x 106 9 x 106 29 x 106
0.33 x 105 0.52 x 105 O.lOxlO5 1.48xl05
530
(lb)
200
5,100
36.83 x 106
35,300
221 x 106
14.40 x 105
3,720
200
-------
these forms are found in the solvent-based waste paint sludges, which
typically contain 27.5 percent pigments, 25.0 percent binders, and 47.5
percent organic solvents. It is estimated that 5,100 Ib of cadmium are
lost through 37 million Ib of solvent-based paint sludges per year. The
geographical distribution of these waste paint sludges was calculated on
the basis of the regional distribution of "value added by manufacture"
dollar amounts for paints and allied products (Table 1).
The paint residues left in used paint containers constitute another
source of cadmium waste. It is estimated that as much as 35,300 Ib of
cadmium are lost through these paint residues each year. The geographical
distribution of these paint residue wastes was calculated on the basis of
the population distribution in the United States (Table 1).
The major source of cadmium waste in the manufacture of nickel-cadmium
batteries (sintered-plate type) is the wash water that is used to remove
excess material from the plates. The typical waste water effluent contains
cadmium hydroxide, potassium hydroxide, and potassium nitrate, usually in
fairly high concentrations since the deionized water often used is expen-
sive and is applied in minimum quantities. Cadmium losses from battery
manufacture amount to 3,720 Ib per year. The geographical distribution of
the cadmium losses from battery manufacture was calculated on the basis of
the regional distribution of "value added by manufacture" dollar amounts
for electrical supplies produced in the United States (Table 1).
Cadmium containing flue dusts are released to the atmosphere from the
metallurgical processing of cadmium-bearing ores. Cadmium is often found
as the sulfide greenockite dispersed in zinc sulfide ores, and also in lead
ores, copper ores, and other ores that contain zinc minerals. As a result,
the zinc metallurgical processing plants and the lead and copper smelters
have been found to be the largest sources of cadmium emissions to the
atmosphere, in spite of the fact that all these refineries are normally
equipped with electrostatic precipitators and/or bag filters for dust
collection, i'-lost of the atmospheric emissions of cadmium occur during the
roasting and sintering of zinc concentrates. The emissions are composed of
87
-------
cadmium and other metals, and the cadmium contained in the dusts emitted ,
may be in the form of cadmium oxide, or combined with sulfur as cadmium
sulfate. Based on material balance data obtained from processing companies,
the total cadmium emissions from metallurgical processing has been estimated
to be 2.1 million Ib in 1968 by Davis. These cadmium containing flue
dusts, however, are not to be considered as a solid waste problem. Cadmium
containing flue dusts are currently being sent to cadmium recovery plants
for processing, and in the event that more stringent air pollution standards
were adopted, the additional quantity of cadmium dusts collected could
be treated accordingly.
Under normal circumstances, there are only small quantities of surplus
cadmium chemicals in storage awaiting disposal. At present, this includes
only. 100 Ib of cadmium oxide flakes and 100 Ib of cadmium oxide powder in
Department of Defense facilities in New Mexico.
88
-------
REFERENCES
1086. National inventory of sources and emissions—cadmium, nickel, and
asbestos. Report prepared for the National Air Pollution Control
Administration by W. E. Davis & Associates, Leawood, Kansas, under
Contract CPA-22-69-131. Washington, U. S. Government Printing
Office, 1970. 44 p.
89
-------
WASTES OF LEAD COMPOUNDS
The principal sources of lead wastes of concern have been Identified
as: (1) waste sludges from petroleum refineries; (2) waste sludges from the
manufacture of alkyl lead compounds; (3) waste solvent-based paint sludges
from paint manufacture; (4) paint residue left in used paint containers;
(5) waste sludges from the manufacture of lead acid batteries; and (6)
solvent and water washes from printing ink production.
Detailed discussions of the lead wastes from paint manufacture and
paint residue left in used paint containers as well as the assumptions
used in the computation of the waste quantities can be found in the report
"Toxic Paint Wastes" elsewhere in this volume. Likewise, a more complete
discussion of the lead wastes from battery manufacture can be found in the
report "Wastes from the Manufacture of Batteries". Included in later
sections of this report are discussions on the lead wastes from petroleum
refineries, alkyl lead manufacturers, and printing ink production.
The major lead containing pigments include white lead, red lead,
leaded zinc oxide, chrome green, chrome yellow, chrome orange, and molyb-
date orange. Lead is present in these pigments as the oxide, the carbonate,
the hydroxide, the chromate, and the molybdate. In paint manufacture, lead
is found in the waste solvent-based paint sludges which typically contain
27.5 percent pigment, 25.0 percent binders, and 47.5 percent organic sol-
vents. It is estimated that a total of 640,000 Ib of lead are lost through
37 million Ib of solvent-based paint sludges per year. The geographical
distribution of these waste paint sludges was calculated on the basis of
the regional distribution of "value added by manufacture" dollar amounts
for paints and allied products (Table 1).
The paint residues left in used paint containers constitute another
source of lead waste. It is estimated that 4.4 million Ib of lead are
lost through these paint residues each year. The geographical distribution
of these paint residual wastes was calculated on the basis of the population
distribution in the United States (Table 1).
91
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TABLE 1.
WASTES OF LEAD COMPOUND
Bureau of Census Regions
Material * " "I IV V VI VII VIII IX Total
Petroleum • Annual Waste Production (Ib/year)
refineries,
waste lead c c K. c. P. F. n f, fi
sludge - 1.16 x 106 1.72 x IO6 0.66 x IO5 0.05 x 10b 0.14 x 10b 4.19 x 10° 0.39 x 10° 1.35 x 10° 9.66 x 10°
Alkyl lead
manufacture,
l.OxlO5 - - - - 3.2 x 105 - l.OxlO5 5.2 x 105
Waste paint
sludge
Lead 16,000 140,000 196,000 . 42,000 55,000 30,000 47,000 8,000 103,000 637,000
Sludge 0.92 x 106 8.12 x 106 11.32 x 106 2.40 x TO6 3.16 x 106 1.76 x 106 2.74 x 106 0.44 x 106 5.97 x 106 36.83 x 106
Paint
residue
Lead 2.58 x 1Q5 8.13 x 105 8.81 x 105 3.28. x 105 6.69 x 105 2.77 x 105 4.22 x 105 l.SlxlO5 5.81 x 105 4.41 x 106
Old
paint 13 x 106 41 * 106 44 x io6 16 x 106 34 x io6 14 x 106 21 x 106 9 x 106 29 x 106 221 x 106
Battery
manufacture ccc ccccccc
as lead 2.56 x IO5 4.70 x IO5 2.29 x IO5 0.46 x io5 0.70 x io5 0.08 x io5 0.25 x io5 0.15 x 105 2.21 x io5 13.40 x 1Q5
Printing
ink ofo-
duction,
as lead - 11,500 6,000 - - - - - 3,500 21,000
-------
Lead wastes from the manufacture of lead add batteries are generated
as a result of the mixing operation of the lead add pastes and the ap-
plication of these pastes to support grids. It 1s estimated that over
1.3 million Ib of lead, mostly as lead sulfate 1n neutralized sulfuric
add, are lost through the waste sludges from battery manufacture each
year. The geographical distribution of the lead losses from battery manu-
facture was calculated on the basis of the regional distribution of
"value added by manufacture" dollar amounts for electrical supplies pro-
duced in the United States (Table 1).
Lead Wastes from Petroleum Refineries
Tetraethyl lead 1s the major antiknock agent that 1s normally added
to the finished product of gasoline in tank cars or storage tanks. After
an extended period of time, sludges containing tetraethyl lead accumulate
at the bottom of the storage tanks of the leaded gasoline. When it becomes
necessary to take the storage tank out of service for repair or cleaning,
the sludges are pumped out and become the major lead wastes from the
petroleum refineries. The sludges typically contain a 1 percent mixture
of tetraethyl lead and lead oxide, along with gasoline hydrocarbons, iron
oxide, silt, and water.
On a survey of four major petroleum refineries in Contra Costa County,
California, conducted by the Western 011 and Gas Association and the
California Department of Public Health 1n 1967,°469 the total tetraethyl
lead wastes were found to amount to 270 tons per year. Based on the gas-
oline production rates, the tetraethyl lead wastes for the State of
California and the United States were calculated to be 675 tons per year
and 4,800 tons per year, respectively. Using the 1 percent figure as the
typical tetraethyl lead concentration in the waste sludge, the net tetra-
ethyl lead waste was determined to be 96,000 Ib per year. The geographical
distribution of the total waste was calculated on the basis of the gaso-
line production in each region as classified by the Bureau of Census
(Table 1).
93
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Lead Wastes from Alkyl Lead Manufacture
In addition to the petroleum refineries, organic lead sludges are
also generated 1n manufacturing facilities where alkyl lead compounds
are produced. These organic lead sludges are now being stored in holding
basins at the manufacturing plants awaiting the development of technically
and economically feasible lead recovery methods.
The organic lead waste sludges from alkyl lead manufacture contain
an average of 0.5 to 1.0 percent tetraethyl and tetamethyl lead. The
annual production of organic lead waste from an alkyl lead manufacturing
plant at Antioch, California has been reported to be 50 tons per year.
Assuming the same waste production factor at the other five alkyl lead
manufacturing plants, the total annual production of organic lead waste
sludge was estimated to be 260 tons. These organic lead wastes were
distributed geographically according to the locations and production capacities
of the alkyl lead' manufacturing plants in each Bureau of Census region
(Table 1).
Lead Wastes from Printing Ink Production
In printing ink production, the majority of manufacturers have either
phased out or curtailed the use of lead pigments in their products. There
are, however, a number of manufacturers that still produce certain types
of printing inks with lead pigments, and lead containing wastes are generated
as a result of the operations to clean up the ball mills, mixing tanks,
and other equipment. These liquid wastes typically contain 0.5 to 1.5
percent lead pigment mixed with varying amounts of other metals 1n organic
T * j * u
solvents and water washes.
*
DuPont at Deepwater, New Jersey; Ethyl Corporation at Baton Rouge,
Louisiana and Houston, Texas; Houston Chemical at Beaumont, Texas;
Nalco Chemical at Houston, Texas.
94
-------
Five leading printing ink manufacturers* currently account for about
2617
85 percent of the total U.S. production. Information obtained from
contacting these manufacturers and a waste disposal firm handling printing
ink production wastes, the Pollution Control Corporation of America
(PCCA),2617'2618'2619 showed that the lead containing wastes generated
from each plant ranged from 250 to 10,000 gal. per month. The only defi-
nitive quantity information, however, was the figures supplied by PCCA
indicating that 7,200 gal. of aqueous wastes containing an average of
1 percent lead were generated per month from a printing ink manufacturer
2618
with 30 million Ib per year production capacity. On this basis, the
waste generation factor was calculated to be 290 Ib of lead per million
pound of printing ink produced, and the corresponding total lead loss
from the printing ink industry was estimated to be 21,000 Ib per year.
The geographical distribution of these lead wastes was computed according
to the production capacity of the printing ink manufacturing facilities
in each region of the United States as classified by the Bureau of
Census (Table 1).
* These five manufacturers are: (1) Tenneco Chemicals Inc., Cal Ink Division;
(2) Inmont Corporation; (3) Sun Chemical Corporation; (4) Cities Service
Company, Levey Division; and (5) Sinclair and Valentine Printing Inks.
f The Pollution Control Corporation of America has 13 plants across the
United States to handle industrial wastes.
95
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REFERENCES
0469. The Hazardous Wastes Working Group of the Governor's Task Force on
Solid Waste Management. Selected problems of hazardous waste
management in California. Sacramento, California, Jan. 1970.
39 p.
1508. Andres, D. R, and L. A. Barch. California solid waste planning
study-hazardous waste disposal survey 1971. California State
Department'of Public Health, Jan. 1972. 69 p.
2617. Personal communication. C. Higby, Tenneco Chemicals Inc., Cal Ink
Division, Berkely, California to S. S. Kwong, TRW Systems, Nov. 17,
1972. Lead wastes from printing ink.
2618. Personal communication. D. Ryan, Pollution Control Corp. of America,
Lemont, Illinois, to S. S. Kwong, TRW Systems, Nov. 21, 1972.
Lead wastes from printing ink.
2619. Personal communication. W. Fanning, Sinclair and Valentine Printing
Ink, Santa Fe Springs, California, to S. S. Kwong, TRW Systems,
Nov. 18, 1972. Lead wastes from printing ink.
96
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WASTES OF SOLUBLE COPPER COMPOUNDS
The major sources of soluble copper wastes generated in the United
States are the electroplating industry, the printed circuit industry,
spent copper catalysts from the chemical industry, copper pickle
liquors, and the textile industry. The soluble copper wastes are of
particular concern because of their high degree of toxicity to aquatic
organisms.
Copper wastes from the electroplating industry come from several
sources, but the most important of these is the rinse water. A typical
waste stream has soluble copper concentrations in the range 50 to
10,000 ppm, alkaline concentrations from 1 to 20 percent as sodium
hydroxide, along with some cyanides, chromium, nickel, and lead. It
is estimated that there are 2.1 million Ib of copper lost in the waste.
streams from the electroplating industry each year. The geographical
distribution of these wastes was calculated on the basis of the
distribution of "value added by manufacture" dollar amounts for
finished,metal products in the United States (Table 1). A more
complete discussion of the copper wastes from the electroplating
industry can be found in the report "Wastes from the Electroplating
Industry".
Copper wastes from the printed circuit industry are generated
mainly in the etching process where the copper not comprising the
circuit is chemically removed from the circuit board. It is estimated
that 456,000 Ib of copper wastes (as copper) are generated each year
in this industry.
The chemical industry generates a significant quantity of copper
wastes each year.by discarding spent copper catalysts. Based on the
information supplied by industry sources, 600,000 Ib of copper wastes
(as copper) are generated annually from spent copper catalysts.
97
-------
TABLE 1
COPPER WASTES (AS COPPER) GENERATED BY U.S. INDUSTRY
OD
Sources
II
III
Bureau of Census Regions
IV V
VI
VII
VIII
IX
6.35 x 105 8.52 x 105 1.16 x 105
39.12 x 105 2.22 x 105 0.87 x 105
Total
Annual Waste Production (Ib/yr)
. Electroplating 2.75 x 106 5.99 x 105 6.78 x 105 0.95 x 105 1.03xl05 0.48 x 105 0.76 x 105
Printed . A A . * & *
Circuit 8.71 x 10 16.05 x 10* 7.80 x 10* 1.55 x 10 2.38 x 10* 0.26 x 10* 0.86 x 10*
Spent
Catalysts 2.22 x 104 15.75 x 104 13.66 x 104 2.90 x 104 9.56 x 104 5.74 x 104 7.71 x 104
Pickling of , 5 ,
Copper 15.00 x 10° 14.77 x 10° 23.92 x 10° 4.03 x 10° 8.58 x 10° 6.63 x 10° 2.54 x 10°
Textile
Industry
0.15 x 105 2.17 x 105 21.06 x 105
0.49 x 104 7.51 x 104 45.61 x 104
1.55 x 104 0.91 x 104 60.00 x 104
2.74 x 105 5.79 x 105 84.00 x 105
1.76 x 105 60.00 x 105
-------
Copper wastes are generated from the acid pickling of copper largely
as a result of dragout of liquor from the pickling vats and the dumping
of the vats when the acid strength is depleted. It is estimated that
copper wastes (in the form of a liquid) from the pickling of copper
amount to 8,400,000 Ib of copper annually.
Copper wastes from the textile industry are generated in the dyeing
and finishing of cotton yarns. It is estimated that copper wastes (in
the form of a liquid) from the textile industry amount to 5,975,000 Ib
of copper annually. .
Detailed discussions of the general assumptions used in the computa-
tion of the quantities information and the forms and composition of the
waste streams from the printed circuit industry, spent copper catalysts,
pickling of copper, and the textile industry are included in the
following sections of this report.
Copper Wastes From the Printed Circuit Industry
Approximately 15,000,000 Ib of copper foil were produced in 1971 for
use in the printed circuit industry. Since 5 percent of this is exported,
approximately 14,250,000 Ib of copper foil is supplied to five major
laminators in the United States who apply the copper to laminated circuit
boards. The boards, with the layer of copper affixed, are then sent to
the printed circuit plants. At these plants, the board is etched and
becomes the finished printed circuit.2601'2607
Copper wastes from circuitry manufacture are generated largely as
a result of the etching process in which the excess copper is removed
from the circuit board. After the board has been etched, the remaining
copper (which comprises the circuit) is sometimes electroplated with a
finishing coat of copper. There is some copper loss in the electro-
plating operation, but it is small compared to the loss of copper in the
etching process.
99
-------
The composition of the concentrated liquid waste generated in the'
etching process is dependent upon the type of etchant used and the type
of acid solution used for cleaning. Ferric chloride is the major etchant
material, but cuprous chloride, ammoniacal chlorite, ammonium persulphate,
and chrome/sulfuric solutions are also used. The acids used for cleaning
are hydrochloric, fluorbboric, concentrated sulfuric, acetic and citric
acids.
The waste is generally characterized by a high concentration (1,000
to 50,000 ppm) of soluble copper. A typical waste may contain ferric
chloride solutions having soluble copper contents of 3,000 to 50,000 ppm,
lead and nickel in the range of 10 to 50 ppm, and hydrochloric acid
concentrations of 15 to 30 percent.*
The plant manager of a major printed circuit plant in the Los Angeles
area (Cinch Graphic) supplied a waste generation factor of 3.2 percent for
the printed circuit industry and indicated that this is a representative
factor within the Industry. Since 14.25 million Ib of copper foil is
used by the printed circuit industry each year, 3.2 percent of this figure
gives 456,000 Ib of water soluble copper waste (as copper) generated per
year by this industry.
The 456,000 Ib of copper waste were distributed geographically on
the basis of the distribution of "value added by manufacture" dollar
amounts for electrical supplies produced in the United States and by
Bureau of Census regions (Table 1).
Copper Wastes from Spent Copper Catalysts
It is estimated that there are over 300 tons of copper waste (as
copper) generated annually by the chemical industry from spent catalysts.
This figure was supplied by industrial contacts that are in the business
of buying spent catalysts and reselling it to other companies that recover
the metal content. Industry sources indicated that the 300 ton per
*Rollins Environmental Services data.
1OO
-------
year figure is probably conservative.
It is impossible to relate the amount of copper waste to the
quantity of copper used in the production of copper catalysts each
year. This is due to the fact that many producers of copper catalysts
enter into secrecy agreements with both suppliers of copper and the
companies that they supply.
The composition of the sludge that comprises the spent copper
catalyst depends upon the type of copper catalyst used and the particular
segment of the chemical industry utilizing it. A typical waste may
contain 27 percent cuprous-cupric chloride tar in 65 percent mixed
organics (from the production of aniline).*
The geographical distribution of the 600,000 Ib of copper waste
was computed on the basis of the distribution of "value added by
manufacturer" dollar amounts for the chemical industry and by Bureau
of Census regions (Table 1).
Copper Wastes From the Pickling of Copper
The treatment of copper in an acid bath, known as pickling,
removes oxide from the metal surface and produces a bright sheet
stripped down to bare metal and suitable for finishing operations.
Both sulfuric and hydrochloric acid are used in the industry.
Regardless of which acid is used, the disposal of spent pickle
liquor is a serious problem which has still not been satisfactorily
0285
solved for the metal finishing industry at reasonable cost.
Pickling may be done either batchwise or as a continuous operation.
Usually the acid is prepared at about 5 to 15 percent strength, depending
on the work to be processed in the pickle tank and the type of acid used
for pickling. As the acid worses on the oxide surface, there is a gradual
buildup of copper compounds (largely copper sulfate when sulfuric acid 1s
used) in the pickle bath and a depletion of the free acid strength. When
*Rollins Environmental Services data.
101
-------
the copper content reaches a level which begins to slow the pickling
operation, the bath is either dumped or reprocessed. In some pickling
operations the acid is continually withdrawn for disposal or reprocessing
in order to maintain uniform pickling conditions for all the copper passing
through the operation.
The copper leaving the pickle vat will drag out some of the liquor
with it and carry this liquor into the subsequent rinsing and neutralizing
operation. The loss of the spent pickle liquor (spent liquor plus acid
mixture) by dragout varies, but it can run as high as 20 percent of the acid
used.0286
In some cases the dragout of liquor from the pickling vat may be so
great that the copper contamination level in the pickle vat never reaches
an objectionable level. The strength of the vat is then controlled entirely
by makeup of fresh acid and water to bring the acid to its proper dilution.
The discharge from the pickling area generally includes spent strong
pickle liquor and acidic rinse water which must be neutralized before it
can be discharged.
A typical spent pickle liquor may contain 0.5 percent copper sulfate
with 0.2 percent stannous sulfate in 4 percent sulfuric acid with traces
of sodium phosphate-borax.*
A. consultant specializing in the treatment of copper pickling liquor
wastes (of Lancy Laboratories) stated that between 0.1 and 0.2 percent of
2611
the copper is lost during the pickling operation. An average loss
factor of 0.15 percent was used to estimate the total amount of copper
waste generated from the pickling of copper in,the United States. Since
Q
5.6 x 10 Ib of copper metal (including new refined and secondary copper)
is processed in the United States each year, 0.15 percent of this figure
gives 8,400,000 Ib of copper waste generated from the pickling of copper
annually. In this calculation, it was assumed that all of the copper
used in the United States is eventually pickled.
*Rollins Environmental Services data.
102
-------
Industry sources also Indicated that a large pickling mill may lose
9fil 1
up to 800 Ib of copper per day through dragout and rinsing operations.
Since there are about ten large pickling mills In the United States, the
loss from the mills alone accounts for 2,400,000 Ib per year of the copper
waste from pickling. The other 6,000,000 Ib per year of copper waste can
easily be accounted for by the countless small shops in the country that
pickle copper.
The 8,400,000 Ib of copper wastes were distributed geographically
on the basis of the distribution of "value added by manufacture" dollar
amounts for the nonferrous metal rolling and drawing industry in the
United States and by the Bureau of Census regions (Table 1).
Copper Wastes from the Textile Industry
Copper wastes from the textile industry are generated mainly 1n the
dyeing and finishing of cotton cloth.
There are varied methods of dyeing cotton and many types of dyes are
used. Small volumes of cloth are dyed on jigs—which are small, tapered
tanks with the large surface area at the top. Larger volumes of cloth are
usually dyed in a continuous dyeing range, which consists of a number of
boxes through which the cloth passes to be dyed, oxidized, dried and finished.
Two of the most important dyes are direct.dyes and aniline black dyes.
Direct dyes (water soluble) are applied with or without heat directly
to cotton with salt (10 to 60 percent) and sodium carbonate (1 to 5 percent).
Some chemicals, such as copper sulfate (others are acetic acid and formaldehyde)
may be used occasionally to modify the shade or fastness.
103
-------
Aniline black dye is an insoluble pigment produced by the oxidation
of aniline. The cloth is passed through a dye bath typically consisting
of 90 Ib of aniline hydrochloride, 35 Ib of sodium chlorate, and 13 Ib
of copper sulphate in 100 gal. of water. After impregnation, the cloth
is passed over stream-heated rollers to develop the black pigment.
Soaping and washing complete the operation. Since the dye bath is costly,
it is seldom dumped.
It is important to note that dye wastes are extremely variable in
contaminating matter. It is common, in aniline dyeing, to discharge 15,000
to 23,000 gal. of waste per 1,000 Ib of cotton processed. In direct dyeing
1185
there are 1,700 to 6,400 gal. of waste per 1,000 Ib of cotton processed.
All of the contaminants in dye waste come from the chemicals added to the
dye baths.
The finishing operation imparts a smooth appearance and certain rigidity
to the cloth. The. cotton is often waterproofed, fire-proofed, or mildew-
proofed. Copper wastes may be generated in the mildew proofing bperation
where copper ammonium fluoride and copper ammonium carbonate are the
1 ceo
chemical agents used.
A typical dye waste from the textile industry may contain 900 ppm
copper and 100 ppm chromium in a neutral aqueous mixture with coal tar dyes
containing 400 ppm phenols (97% water).*
It is estimated that the textile industry generates 6,000,000 Ib of
copper wastes (as copper) annually. This number was obtained from the
Booz-Allen data and confirmed by industry sources to be in the right
order of magnitude. This is not an unreasonable amount of copper waste
in light of the fact that the textile industry had a wastewater effluent
I -IOC
of 128 billion gallons in 1971. "oa
*Rollins Environmental Services data
104
-------
The 6,000,000 Ib of copper wastes were distributed geographically
on the basis of the distribution of "value added by manufacturer" dollar
amounts for cotton finishing plants 1n the United States and by Bureau
of Census Regions (Table 1).
105
-------
REFERENCES
0085. Industrial waste profiles No. 4 - textile mill products. Report
prepared by the Federal Water Pollution Control Administration.
Sept. 1967. 133 p.
0285. Lund, H. F. Industrial pollution control handbook. McGraw-Hill
Company, New York. 1971. 1,000 p.
0783. A state-of-the-art review of metal finishing waste treatment.
Technical Report, Battelle Memorial Institute. Nov. 1968. 53 p.
1185. State-of-the-art of textile waste treatment. Report prepared for
the Environmental Protection Agency by the Department of Textiles
of Clemson University under Grant No. 12090 ECS. Feb. 1971. 350 p.
1662. Shreve, N. R. Chemical process industries. McGraw-Hill Company,
New York, 1967. 900 p.
2601. Personal communication. B. Yoder, Yates Industries, to D. Dal Porto,
TRW Systems, Dec. 7, 1972. Amount of copper used in printed
circuit industry.
2603. Personal communication. B. Trees, Metal Finishing Suppliers Association,
to D. Dal Porto, TRW Systems, Dec. 7, 1972. Wastes from electro-
plating industry.
2606. Personal communications. G. Calpakis, Parkans International, to
D. Dal Porto, TRW Systems, Dec. 20, 1972. Copper wastes from
spent catalysts.
2607. Personal communications. F. Gorman, Cinch Graphic, to D. Dal Porto,
TRW Systems, Dec. 5, 1972. Copper wastes from printed circuit
industry.
2611. Personal communication, C. Forbes, Lancy Laboratories, to D. Dal Porto,
TRW Systems, Jan. 2, 1973. Copper wastes from the pickling of
copper.
1O6
-------
WASTES OF SELENIUM AND SELENIUM COMPOUNDS
Selenium is not found in significant quantities as wastes. The only
major source of selenium waste that has been identified is in the manufacture
and reconditioning of xerox drums (Table 1), and this is discussed in the
following section of this report.
Selenium is combined with cadmium and sulfur as cadmium sulfoselenide
and used in cadmium red and cadmium orange pigments. The ratio of cadmium
to selenium in a typical light red shade is 5 to 1, while in a maroon red
shade it is 3 to 1. Cadmium orange is normally a mixture of the cadmium
red and cadmium yellow pigments. About 51,000 Ib of selenium are used
in these cadmium pigments each year. Because of the relatively low volume
usage of selenium in paints and allied products, only an estimated 370 Ib
of selenium are lost in the waste solvent-based paint sludges from paint
manufacture each year, and. an additional 2,600 Ib as paint residue left in
used paint containers (Table 1). A more complete discussion of the selenium
paint wastes can be found in the report "Toxic Paint Wastes".
Selenium Wastes from the Manufacture
of Duplicating Machines
Amorphous selenium, a super-cooled state of liquid selenium, has found
extensive use as a coating on metal cylinders in the field of xerography
where low electrical conductivity is essential. The low conductivity of
selenium permits the development step to be carried out before the electro-
static image is destroyed by electrical conduction through the plate.
The manufacture of selenium plates and drums is generally of a single
basic design. The substrate is made of meticulously cleaned, oxidized
aluminum in sheet or drum form, onto which high purity amorphous selenium
is vacuum plated. About 4 Ib of selenium are required per 100 square ft
107
-------
TABLE 1
WASTES OF SELENIUM AND SELENIUM COMPOUNDS
o
00
Source and I II
Material
Waste Paint
Sludge
Selenium 10 80
Sludge 0.92 x 106 8.12 x 106
Paint Residue
Selenium 150 470
Old Paint 13 x 106 41 x 106
Xerox Drum
Manufacture
Selenium - 450
Solid waste - 7 x 105
4
Acid waste - 5 x 10
Bureau of Census Regions
III - " IV V VI VII VIII IX Total
Annual Waste Production (Ib/year)
115 25 30 20 25 5 60 370
11. 32,x 106 2.40 x 106 3.16 x 106 1.76xl06 2.74 x 106 0.44 x 106 5.97 x 106 36.83 x 106
510 190 390 160 240 110 340 2,560
44 x 105 16 x 106 34 x 106 14 x 106 21 x 106 9 x 106 29 x 106 221 x 106
450
7 x 105
5 x 104
-------
of cylinder surface, and approximately 158 tons of selenium were used in
xerography in 191
0.002 in. thick.
2309
xerography in 1969. Xerox drums normally contain selenium coatings
In addition to selenium, arsenic is used as an alloying element to
control color sensitivity and selenium crystallization in xerographic
photoreceptors. The use of arsenic varies from 5,000 to 20,000 Ib per
year, depending on the type of alloy produced and the production levels
required. Projected purchase of arsenic in 1973 is about 13,000 Ib.
Replacement of the selenium coating on xerox drums may be necessary
2309
after reproducing 30,000 to 500,000 copies. The usual practice is to
remove the worn out cylinder from the copying machine and return it to
the factory for reconditioning. During the reconditioning process, coatings
from the spent xerox drums are removed through heat stripping and mechani-
cal chipping (lathe) operations, and the selenium and arsenic are reclaimed
from the alloy chips through further reprocessing. The records at
Xerox showed that for the past three years (1970 to 1972), 93 percent of
all the xerox drums coated at the Joseph C. Wilson Center for Technology
in Webster, New York* were shipped to the United States or Canada and 90
percent were returned for reclamation and recycle. Overseas shipments
from the Wilson Center, however, are not normally returned.
Detailed information on the types, quantities, forms and composition
of the selenium and arsenic-bearing wastes generated during the manufacture
and reconditioning of xerox drums was provided by the Xerox Corporation
(Table 2).2 This information indicated that about 700,000 Ib of solid
wastes containing 300 to 400 Ib of arsenic and selenium are generated
each year, principally from the following sources: (1) polishing of pre-
viously stripped aluminum xerox drums; (2) air and water filtration systems
from alloying arsenic in selenium; and (3) coating room laminar flow
filters, shipping containers for arsenic and selenium, and toner residues
from xerographic developer reclaim. Of the selenium and arsenic found in
*The selenium and arsenic coated drums are manufactured and recon-
ditioned exclusively at Xerox's Webster, New York facility.
109
-------
TABLE 2.
ARSENIC AND SELENIUM WASTES FROM
THE MANUFACTURE OF XEROX DRUMS
Se
Waste Cone.,
ppm
Dry buffing wastes -
Rotoclone sludge
Spent buffing wheels
Caustic mask* 1
Developer reclaim
Vacuum pump 6
oil filters
Selenium bags
Arsenic bottles
Hi -Flo filters 90
Coating room 150
filters
Hi -Cap filter 90
Absolute filter 4
Demineralizer 4
resin
160
200
150
,800
300
,000
200
0
,000-1
,000
,000-1
,000
,000
As
Cone.
ppm
40
50
50
1,200
60
20
0
• 500
00,000
50,000
00,000
2,000
30,000
Major
Component
Cotton
Cotton
Steel (55%)
Caustic soda
solution
Toner
Organic fiber
Polyethylene
Polyethylene
Glass fiber
Glass fiber
Polymer fiber
Paper fiber &
aluminum foil
1 ami nate
Resin
Minor
Component
Aluminum,
fatty acid
Aluminum,
fatty acid
Cotton
—
Mineral oil
—
—
Steel .tricresyl-
phosphate
Steel
~ —
—
Physical
Characteristics
Fine fibers
Fine fibers in water
Cotton cloth on steel
drum 40 Ib each
Liquid and sludge
Powder
Large pieces
Film
Quart bottles
Fiber blanket with metal
frame
Typical home furnace
filter
Large, low density
Paper and aluminum foil
Granules
Annual
Volume
Ib.
240,000
220,000
200,000
50,000
20,000
1,800
300
1,000
100
1,000
100
200
700
*Liquid waste
-------
TABLE 2. (CONTINUED)
ARSENIC AND SELENIUM WASTES FROM
THE MANUFACTURE OF XEROX DRUMS
Waste
Shotter water
filters
Heat strip oven
f i 1 ters
Nitric acid
cleaner*
Sand— As/Se
mixture
Degreaser filters
Post-coat buff dry
waste dust
Post-coat buff
filter bags
Post-coat buff
degreaser filters
Se
Cone. ,
ppm
3,000
20,000
11,000
50,000
450
150
500
100
As
Cone . ,
ppm
2,000
—
6,000
250
50
100
300
60
Major Minor
Component Component
Polymer fiber
Polymer fiber
Acid solution
Sand
Organic wool Trichlor-
fibers ethyl ene
j,X_l_
Cotton Cr
i i X
Cotton Cr
Organic fiber Cr
Physical
Characteristics
Large pieces
Large pieces
Liquid
Coarse powder
Large units
Fibrous powder
Cloth
Large pieces
Annual
Vol ume
Ib.
400
600
800
1,000
2,000
500
150
2,000
*Liquid waste
-------
the solid wastes, there is usually more selenium present than arsenic
(Table 2), and approximately 25 percent of the selenium is combined with
arsenic chemically, (e.g., arsenic triselenide), with the remaining
2667
selenium containing less than 1 percent arsenic in them.
Some liquid wastes are also generated through chemical solution
operations for the removal of arsenic and selenium alloys from production
hardware and tools. The total liquid waste amounts to 50,000 Ib or 100
barrels a year, consisting primarily of caustic solutions. The
arsenic and selenium components in these wastes are for the most part
complex anions that are not identified at this time.
Because of the air pollution control systems (absolute filters, oil
traps, etc.) installed at the manufacturing facility, only small quantities
of arsenic and selenium are discharged to the atmosphere. The total
discharged has been reported to be less than 20 Ib of arsenic and selenium
per year.
All of the arsenic and selenium-bearing solid and liquid wastes from
Xerox are presently being shipped to the Nuclear Engineering Company in
Sheffield, Illinois for disposal.2674
112
-------
REFERENCES
2309. Davis, W.E. National inventory and sources and emissions (barium,
boron, copper, selenium, and zinc 1969) — selenium (section IV).
Report prepared by Davis (W.E.) and Associates, Leawood, Kansas
for the Environmental Protection Agency under Contract No.
68-02-0100. Washington, U.S. Government Printing Office, Apr.
1972. 57 p.
2667. Personal communication. J. Hall, Xerox Corporation, to C. C. Shih,
TRW Systems, Nov. 16, 1972.
2674. Personal communication. R. R. Bouley, Xerox Corporation, to
C. C. Shih, TRW Systems, Feb. 22, 1973.
113
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WASTES OF BORON HYDRIDES
The boron hydrides (boranes) are compounds of boron and hydrogen. Of
the various borane compounds, only diborane, pentaborane, and decaborane are
of any commercial significance. There is currently one producer of boranes
2020
in the United States, the Gallery Chemical Company, Gallery, Pennsylvania,
and diborane and decaborane are the only boranes manufactured at present.
Diborane Wastes
There is essentially no toxic waste generated in the production of
diborane. The annual production of diborane was estimated at less than
200 Ib, which is used almost exclusively for defect doping in the manufacture
of semiconductors. Three major gas suppliers, Air Products and Chemicals
Inc., the Linde Division, Union Carbide Corporation, and Matheson Gas
Products, buy 10 mole percent diborane mixed^with either argon, nitrogen,
or hydrogen, and further dilute it to diborane concentrations from 10 ppm
to 1,000 ppm (but most typically 100 ppm), and resell it to the semiconductor
manufacturers. In the gas dilution process, diborane wastes are generated
in the form of residual gas remaining in the manifolds after mixing is
complete.
Air Products and Chemicals Inc. mixes diborane with H,, N0 or argon
2017
in three locations in the United States - Emmaus, Pennsylvania, Long
Beach, California, and Houston, Texas. The Emmaus, Pennsylvania
3
facility runs about 0.1 ft every six months to a storage cylinder, which
has been filling for six years and is currently half full. The Long Beach,
California facility handles approximately 10 Ib/yr of the 10 mole percent
mixture. They occasionally vent "a few cc of the mixture" to the atmosphere
with no monitoring or control. The Houston facility operates similarly to
the Long Beach facility.
©
The Linde Division of the Union Carbide Corporation mixes diborane in
five locations - East Chicago, Indiana; Houston, Texas; Keaseby, New Jersey;
2018
Linden, [Jew Jersey; and Torrance, California. The Torrance, California
115
-------
facility uses approximately 60 Ib/yr of the 10 mole percent mixture. After
dilution there are usually a residue of 500 cc.
Matheson Gas Products mixes diborane in three locations - Cucamonga,
California,2011 Newark, California,2010 and East Rutherford, New Jersey.
The quantity of residual gas waste generated from these operations is not
known.
Based on the information obtained, the quantity of diborane waste
generated is less than 0.2 cu ft per plant each year. Since the residual
gas wastes normally have a diborane concentration of 100 ppm, the diborane
contained in these wastes is less than 1.54 x 10" lb per plant each year.
These diborane wastes are distributed geographically according to the
locations of the gas mixing facilities (Table 1).
Pentaborane Wastes
Pentaborane has been used for research in rocket fuels but is no longer
being manufactured. There is, however, a stockpile of approximately 200,000
lb of pentaborane in storage at Edwards Air Force Base, California, in the
Mojave Desert. Current consumption of pentaborane in the manufacture of
the high temperature elastomer, Pentasil, amounts to only 50 to 75 lb per
year, and no pentaborane containing waste is generated in this application.
Decaborane Wastes
The only decaborane waste identified is the several lb of toxic solid
wastes generated each year in its production process. Aside from a small
amount of decaborane used in classified research in solid propel 1 ants, 40
to 70 Ib per year are used by the 01 in Corporation, New Haven, Connecticut,
2008
in the manufacture of Dexsil, a patented high temperature elastomer.
-------
TABLE 1
WASTES OF BORON HYDRIDES
Bureau of Census Regions
Material I II III IV V VI VII VIII IX Total
Annual Waste Production (Ib/year)
Diborane - 6.0 x 10"6 1.5 x 10"6 - - - 3.0 x 10"6 - 6.0 x 10"6 16.5 x 10"6
Decaborane - <10 - - - - -
-------
REFERENCES
2008. Personal communication. R. Finch, Olin Research Center, to M. Appel,
TRW Systems, June 1972. Decaborane.
2010. Personal communication. L. Fluer, Matheson Gas Products, to M. Appel,
TRW Systems, June 1972. Diborane.
2011. Personal communication. Mr. Wilson, Matheson Gas Products, to
M. Appel, TRW Systems. June 1972. Diborane.
2015. Personal communication. J. Nahan, Air Products and Chemicals, Inc.,
to M. Appel, TRW Systems, June 1972. Diborane,
2017. Personal communication. B. Brown, Air Products and Chemicals, Inc.,
to M. Appel, TRW Systems. June 1972. Diborane.
2018. Personal communication. L. Chambers, Linde Division, Union Carbide
Corporation, to M. Appel, TRW Systems. June 1972. Diborane.
118
-------
WASTES OF CHROMIUM COMPOUNDS.
The principal sources of chromium wastes in solid, semi-solid, or
concentrated liquid form have been identified as: (1) dragout and rinse
water from the metal finishing industry; (2) filter residue from sodium
dichromate manufacture; (3) waste sludges from paint manufacture; (4) paint
residue left in used paint containers; and (5) surplus chemicals under the
custody of Department of Defense. In addition, significant amounts of
chromium compounds in highly diluted forms (ppm level) are also lost through
the waste waters from the textile industry, the leather tanning industry,
and from the blowdown of cooling towers.
t
The chromium wastes from the metal finishing industry, the sodium
dichromate manufacture, the textile industry, the leather tanning industry,
and the blowdown of cooling towers are discussed in detail in individual
sections of this report. Also included in later sections are brief dis-
cussions of the ammonium dichromate wastes from photo-engraving and
potassium chromate and dichromate wastes.
The major chromium containing pigments include chrome green, chrome
oxide green, chrome yellow, chrome orange, zinc yellow, and molybdate
orange. With the exception of chrome oxide green (Cr^O.,), all the other °
chromium pigments contain chromium in the hexavalent state and are
normally only used in solvent-based paints. Chromium wastes are generated
from paint manufacture in the form of waste paint sludges as a result of
kettle washings and equipment cleanup. The typical solvent-based waste
paint sludge is characterized by the following composition: 27.5 percent
pigments, 25.0 percent binders, and 47.5 percent organic solvents. The
-\>
typical water-based waste paint sludge, however, contains 15 percent pigments,
20 percent binders, and 65 percent water. It is estimated that a total of
140,000 Ib of chromium are lost through 37 million Ib of solvent-based waste
paint sludges each year; and a total of 10,000 Ib of chromium lost through
26 million Ib of water-based waste paint sludges each year. The geographical
distribution of these paint manufacturing wastes are calculated on the basis
of the regional distribution of "value added by manufacture" dollars amounts
119
-------
for paints and allied products in the United States (Table 1). A more
complete discussion of the sources and constituents of the chromium wastes
from paint manufacture and the assumptions used in the computation of the
total quantity of the wastes generated can be found in the report, "Toxic
Paint Wastes."
The paint residues left in used paint containers discarded in
municipal dumps constitute another source of chromium paint waste. It
is estimated that approximately 1 million Ib of chromium are lost through
these paint residues each year. The geographical distribution of the paint
residue wastes was calculated on the basis of the population distribution
in the United States (Table 1). Again, a more complete discussion of
the paint residue wastes can be found in the report "Toxic Paint Wastes".
Chromium compounds under the custody of Department of Defense and
awaiting disposal include 34,243 Ib of anhydrous sodium chromate, 3,040
Ib of potassium dichromate, 2,030 Ib of chromium trioxide, and smaller
quantities of potassium chromate and sodium dichromate dihydrate dis-
tributed throughout the United States (Table 1). All these surplus
chromium compounds were probably originally acquired for metal treatment
and plating purposes.
Chromium Wastes from the Metal Finishing Industry
In the metal finishing industry, hexavalent chromium compounds are
formulated for use as cleaning agents, oxidizing agents, surface prepa-
ration agents as well as the chemicals used to electroplate the decorative
chrome surface. The wastes are generated from the extensive washing of
the metal parts as well as spills, tank leakages, etc. Many of these
metal treatment tanks became exhausted and have to be periodically
drained.
120
-------
TABLE 1
WASTES OF CHROMIUM COMPOUNDS
Source &
Material
II
III !V V VI VII
Vinual Waste Production (Ib/year) _
VIII
IX
Total
Chromium Waste
from Metal
Finishing as
7.99 x 106 17.41 x 106 19.70 x 106 2.76 x 106 2.99 x 106 1.39xl06 2.21 x 106 0.44 x 106 6.31 x 106 61.20xl06
Chromium Waste
from Sodium
Dichromate
Production
. as Cr-O
Solvent-Based
Paint Sludge
Chromium
SIudge
Water-Based
Paint Sludge
Chromium
Sludge
Paint Residue
Chromium
Old Paint
2.0 x 10°
11.0 x 10°
5.0 x 10°
18.0 x 10°
3,000 30,000 42,000 9,000 12,000 7,000 10,000 2,000 22,000 137,000
0.92 x 106 «.12 x 106 11.32X106 2.40 x 106 3.16 x 106 1.76xl06 2.74 x 106 0.44 x 106 5.97 x 106 36.83x10
240 2,160 3,010 640 840 470 730 120 1,590 9,800
0.65 x 106 5.74 x 106 7.99 x 106 1.70x106 2.23 x 106 1.24xl06 1.93xl06 0.31 x 106 4.21 x 106 26.00 x 106
0.56 x 105 1.78 x 105 1.92 x 105 0.72 x 105 1.46 x 105 0.61 x 105 0.92 x 105 0.40 x 105 1.27 x 105 9.63 x 105
13 x 106 41 x 106
44 x 10U
16 x 10U
34 x 106 -14 x 106 21 x 106 9 x 106
29 x 106 221 x 106
Chromium Waste
from Dyeing of
Wool as
2.89 x 105 1.08 x 105. 0.15 x 105
2.96 x 105 0.37 x 105
0.15 x 105 7.60 x 105
-------
TABLE 1 - CONTINUED
WASTE OF CHROMIUM COMPOUNDS
Bureau of Census Regions
Source & i n III IV V VI VII VIII IX Total
Material
Annual Waste Production (Ib/year)
Chromium Waste R K K a & • a K c A
from Leather 4.85x10° 3.30x10° 5.29x10° 0.32x10 1.20x10° 0.63x10° 0.06x10° - 0.35x10° 16.0x10°
Tanning as
Cr
Chromium Waste fifififiCKKfififi
from Cooling 0.93x10° 2.94x10° 3.18x10° 1.19x10° 5.38x10° 2.23x10° 3.39x10° 0.66x10 2.10x10° 22.0x10°
Tower Slowdown
as Na2Cr207
Chromium Waste
from Photo-
Engaving as 230 740 790 320 590 250 380 160 520 4,000
(NH4)2Cr04
Total Potassium cccccccc-c c
Chromate/Dichromate 2.76x10 6.14x10 6.87x10 1.19x10 2.60x10 1.10x10 1.68x10 0.33 x 103 2.53x10 25.20 x 103
Waste as ICCr-O,
Stored Waste (Ib)
Cr03 .... 1>0io - - 800 220 2,030
Na2Cr04 300 33,943 34,243
K2Cr20? .... 4o 3,000 - - - 3,040
Na2Cr2072H20 - - - - 520 - - - - 520
K2Cr04 - - - 120 - - 20 140
-------
The composition of the chromium wastes from the metal finishing
industry varies widely with the type of metals being processed, the metals
being plated, the design of the equipment, and other important factors.
The levels of chromium normally vary from a few ppm to a few percent of
the total waste stream. Wastes from metal finishing may include many
other metals such as copper, zinc, cadmium, and nickel. Likely to be
included in the stream are grease, oils, acids, organic additives and
cleaning agents. Information on the forms and composition of typical chromium
containing metal finishing waste streams from various industry sources has
been provided by Rollins Environmental Services and is summarized here (Table 2),
Discussion with various experts in the metal finishing industry has
resulted in the conclusion that only 15 percent of all chromium compounds
used in metal finishing ever end up as part of the finished product. '
1472
The sodium dichromate consumption for metal treatment and plating
amounts to 72 million Ib per year, and the 85 percent of the chromium
compounds discharged by the metal finishing industry amounts to 62 million
Ib per year when calculated as sodium dichromate. The geographical
distribution of these chromium wastes was calculated on the basis of the
regional distribution of "value added by manufacture" dollar amounts for
the metal finishing industry in the United States and by Bureau of Census
regions (Table 1).
Chromium Waste from Sodium Dichromate Manufacture
The chromite or chrome-ironstone ore is the raw material for sodium
dichromate manufacture and contains principally ferrous chromite,
(FeO • Cr^CL), plus small amounts of aluminum, silicon, and magnesium
oxides. In sodium dichromate manufacture, sodium chromate is first
obtained by calcining a mixture of chromite ore, limestone, and soda
ash, and is then reacted with sulfuric acid to yield the dichromate.
* The chromium wastes occur in forms other than the dichromate, including
trivalent chromium salts, chromic acid, and chromates (Table 2).
123
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TABLE 2
TYPICAL METAL FINISHING WASTE STREAMS CONTAINING CHROMIUM
Waste Description
Form
Source:
Industry/Process
3000 ppm of a mixture of chromium, 20% aluminum sulfate Liquid
and 35% sulfuric acid (trace of copper, nickel, lead)
12.5% chromic acid - dichromate in 10% to 30% sulfuric Liquid
acid with 5000 to 120,000 ppm chromium (85% as Cr+3)
with 100-1000 ppm lead, copper and iron
Dilute chromic acid solution containing chromium +3 at Liquid
100-200 ppm and chromium +6 at 2000 to 4000 ppm with
traces of organics (combined wash waters).
Partially neutralized aqueous plating waste containing Liquid
5-10% zinc chromate, and 5-10% zinc phosphate contaminated
with various organic oils.
Solutions of chromates and dichromates in sulfuric acid Liquid
(6-12%) containing 5000-170,000 ppm chromium with copper,
lead and traces of organics.
0.1-0.5% chromium, 100-400 ppm copper, 100-600 ppm nickel Liquid
in 5-10% aqueous hydrofluoric-hydrochloric acid.
1 to 20% chromium in solids concentrations of 10-80% from Sludge
settling and/or dewatering processes. Includes copper in
varying amounts with varying amounts of inert filter aids.
100-1000 ppm chromium as alkaline cyanide solutions (6-20%) Liquid
with copper in varying amounts with possible traces of
organics, nickel, lead and zinc.
5-6% chromic acid in water solution with 1% iron Liquid
9% chromic acid in 13% aqueous sulfuric acid Liquid
0.1-1% sodium or potassium dichromate in water, usually Liquid
sulfuric acid present in a 1-15% concentration
Aluminum anodizing
bath with drag out
Metal finishing
Metal plating
Zinc plating
Formation of protective and
decorative coatings (metals)
Plating preparation (metal)
Chemical process (plating
operations, manufacturing,
metallurgical)
Metal plating (formation of
protective and decorative
coatings)
(1) Metal Plating
(2) Shipbuilding
Metal finishing and plating
1) Metal Finishing
2) Shipbuilding
(3) Plating
-------
The production process involves initially grounding the chromite ore
to a fine powder (150 to 200 mesh) in ball mills, followed by blending of
the raw material with soda ash, limestone and sufficient filter residue
(from further along in the process) in a rotary mixer, and calcination of
the mixture at high temperatures 2,000 F in a rotary kiln. After a 4-hr
retention time, the roast from the kiln is sent directly to leaching tanks
or thickeners, where the soluble chromate is dissolved in hot water and
concentrated. The underflow from the last tray in the thickener is fil-
tered, and the leached residue is dried in rotary dryers. A portion of
the filter residue is recycled to the kiln feed where it serves to keep
the reacting mass in a relatively dry condition, but the rest has to be
disposed of as wastes.* The waste from this filtration process is in the
form of a gangue residue, and contains approximately 4 percent trivalent
chromium as CrJ). (dry weight basis), along with various amounts of iron,
2591
aluminum, calcium, and magnesium salts.
The chrome ore processing industry is represented by some rather old
plants as well as a large new facility. The waste quantity information
received covers one plant of older technology, and one plant which recently
came on-stream. 9l»zb This information provided a chromium waste
generation factor of 34 Ib Cr^O., per ton or sodium dichromate product for
the new plant, and a waste generation factor of 210 Ib Cr90- per ton of
C *3
product for the old plant. Based on the production capacity of the sodium
dichromate plants and using the higher waste generation factor for the
other old plants, it was estimated that a total of approximately 18 million
Ib of waste chromium, as Cr^O.,, are generated each year from ore processing.
This represents an estimated average waste generation factor of 130 Ib
Cr^O., per ton of sodium dichromate product, a value that is in sharp dis-
agreement with Booz-Allen's estimate of 1 Ib Cr waste per ton of product.
The raw material requirement for the production of sodium dichromate, as
given by Faith et al,1501 is 1.1 Ib chromite ore (50% Cr203) per Ib of
sodium dichromate dihydrate produced. Mass balance calculations showed
Because of the presence of iron, aluminum, silicon, and magnesium in
the chromite ore, recycling of the total quantity of filter residue
to the kiln would lead to the buildup of these undesirable impurities.
125
-------
that this is equivalent to a waste generation factor of 90 Ib Cr203 per
ton of sodium dichromate product, thus indicating that the waste quantity
information provided by the industrial contacts is a more reasonable
estimate.
The geographical distribution of the chromium wastes from sodium
dichromate production was calculated on the basis of the production capacity
and locations of the sodium dichromate plants in each U. S. Bureau of Census
region (Table 1).
Chromium Wastes from the Textile Industry
Chromium wastes from textile processing result mainly from the
chrome mordant dyeing of wool for garments and carpeting. In the past,
chromate oxidizers were used for the sulfur dyeing of cotton products,
but this practice is expected to be discontinued under environmental
pressures.
Estimates of chromium consumption and waste generation in the wool -
textile industry were obtained through contacts with various textile
trade organizations. The American Dye Manufacturers Institute estimated
that approximately 25 percent of all wool processed in the United States
is chrome dyed, and indicated that about 1 Ib of chromium is consumed
pcoq
per hundred Ib of wool dyed. Representatives of the Northern Textile
Association (NTI), on the other hand, felt that the portion of wool
subjected to chrome mordant dyeing is closer to 35 or 40 percent of the
2590
total. NTI has also indicated that the 40 percent figure is believed to
be more accurate and this was used in the calculation of the total.waste
quantity. Based on the figure that 190 million Ib of wool were processed
in 1971, this total has been estimated to be 760,000 Ib per year as
sodium dichromate.
126
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The chrome mordant dye wastes usually occur in highly diluted forms
(1-100 ppm Cr) in combined waste streams from the many other processes
used in textile mills, and the chromium present may either be in the
trivalent or hexavalent state.
The geographical distribution of these chrome mordant dye wastes was
calculated on the basis of the regional distribution of "value added by
manufacture" dollar amounts for the wool weaving and finishing industry
and by Bureau of Census regions (Table 1). The chromium wastes from the
textile mills are found mostly in the Census regions I, II and V, while
the remaining regions contribute only an insignificant proportion of the
total waste load.
Chromium Waste from Leather Tanning
The basic chromic sulfates are produced in large quantities for use
in the leather tanning industry, and are incorporated in various proprie-
tary 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 dichromate solution with either an organic
material or sulfur dioxide. The organic reduction using crude molasses,
corn sugar, and sometimes even sawdust is the older and more widely used
method. Sulfur dioxide, when used, performs the dual role of reducing
agent and, upon oxidation, of furnishing the required sulfate. If sugar
is used, sulfuric acid must be added.
The leather industry creates very large volumes of chromic sulfate
wastes in aqueous solutions from the chrome tanning and subsequent
washing of the hides. Hide tanning essentially consists of removing
organic matter from the hides, and this organic matter, if allowed to
build up in the chrome tanning solutions, would interfere with the
tanning process. The tanning solutions are therefore normally dumped
after being used once or possibly twice.
127
-------
Approximately 32 million hides (cattle hide equivalent) were tanned
in 1960. Hide tanning volume is believed to have remained constant.
About 70 percent of all U.S. leather is used for upper leather on shoes,
and virtually all of this is chrome tanned. A study on the treatment of
chrome tanning wastes indicates that 1,800 Ib of chromium is dis-
1187
charged for every 2,500 hides. The estimate of 16 million Ib of
chromium waste is in reasonable agreement with the Booz-Allen figures.
In addition, the figures agree, within a factor of two, with the waste
generation factor estimated by Stanley Consultants (when a hide weight of
40 Ib is assumed).0513 Very little waste stream segregation is per-
formed in the tanning industry and the 2-12 ppm trivalent chrome concen-
tration in the diverse mixture of brines, fat, acids and large amounts of
rinse water constitute a fairly typical waste stream. The geographical
distribution of these wastes was calculated on the basis of the regional
distribution of "value added by manufacture" dollar amounts for the
leather tanning and finishing industry and by Bureau of Census regions
(Table 1).
Chromium Wastes from Cooling Tower Slowdown
Chromium compounds are added to cooling water as fungicides, slimv
cides and anti-corrosion agents. Accurate figures or even general
estimates on the amounts of chromium compounds discharged from cooling
towers and similar equipment are difficult to obtain for the following
reasons:
(1) The large number and diversity of cooling and water
circulating equipment;
(2) The wide variation in applications for this type of
equipment;
(3) The diversity of proprietary water treatment additives
which might contain chromium.
128
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Discussions with the Cooling Tower Institute (CTI) revealed that on
the basis of a survey by the Institute, 6.5 million Ib of sodium chromate
(Na^CrO.) were used per year for the operation of 856 cooling towers. CTI
had no estimate of the total number of cooling towers in the United States,
although it was indicated that half of the requirement for cooling towers
lies in the southern United States.2262
The total chromium loss from cooling tower blowdown is assumed to be
equal to the total sodium dichromate demand for anti-corrosion purposes,
at 22 million Ib per year. The total quantity of blowdown, i.e., cooling
water removed to prevent mineral buildup in cooling systems, is in the
multiple millions of gal. per year. Cooling tower blowdown normally contains
10 to 30 ppm of hexavalent chromium.
The geographical distribution of the chromium losses from cooling
tower blowdown was calculated on the basis that 50 percent of the total
waste load was contributed by the Bureau .of Census regions V, VI, and
VII, while the remaining 50 percent was distributed according to the
population in each Census region (Table 1).
Chromium Wastes from the Photographic Industry
Chromium wastes from the photographic industry are generated in the
gravure and leather press plate making operations. The industry purchases
only the ammonium chromates and appears to be the only consumer of these
low volume chromate salts. Chromate solutions at about 4 to 5 percent
are used to sensitize and polymerize gelatin coatings over copper plates
when exposed to light coming through a photo negative. Unexposed chromate
coated gelatins are then washed away in water streams thereby exposing
portions of the plate for etching. Chromates occur as wastes from washing
the plates as well as from the chromate tanks which require dumping at 4
to 6 month intervals. An average size tank or tray contains 5 to 10 gal.
of the solution. These tanks are normally emptied down a sink without
any processing. An estimated 500 such plants are performing this type
of operation across the nation, and the total quantity of ammonium
dichromate discharged amounts to approximately 4,000 Ib per year2235'2250
129
-------
The geographical distribution of these ammonium dichromate wastes
was calculated on the basis of the population distribution in the United
States (Table 1).
Wastes of Hexavalent Chromium Salts of Potassium
The potassium chromium compounds can be expected to replace the usual
sodium compounds in specific cases where the change in cation improves the
process in question. Use of the potassium compounds can occur in nearly
every process where the sodium compound is used but it is more expensive
and this restricts the usage. The potassium salt consumption and waste
2250
amounts represent 3 percent of the sodium salt volume. The total waste
load, calculated as potassium dichromate, amounts to 2.5 million Tb per
year. The geographical distribution of the potassium chromate/dichromate
wastes was assumed to be the same as the geographical distribution of the
sum total sodium chromate/dichromate wastes from the metal finishing and
textile industries and cooling tower blowdown (Table 1).
130
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REFERENCES
0087. Cost of clean water, v. 3. Industrial Waste Profiles No. 7, Leather
Tanning and Finishing. Washington, Federal Water Control Adminis-
tration, 1967. 59 p.
0513. Effluent requirements for the leather tanning and finishing industry.
Preliminary report prepared by Stanley Consultants, Inc., Mascatine,
Iowa, for the Water Quality Office, Environmental Protection Agency
under Contract No. 68-01-0024, Sept. 1971. 97 p.
1187. Activated sludge treatment of chrome tanney wastes. A. C. Lawrence
Leather Co., Water Pollution Control Research Series, Report No.
121. Federal Water Pollution Control Administration. Grant
No. WPRD 133-01-68, Sept. 1969. 176 p.
1471. Personal communication. James Zebers, Industrial Pump and Filter
Corp., to J. F. Clausen, TRW Systems, March 21, 1972.
1472. Personal communication. Allen Olsen, Parker Co., to J. F., Clausen,
TRW Systems, March 21, 1972.
1501. Faith, W. L.t D. B. Keyes, and R. L. Clark, Industrial Chemicals,
3d ed. New York, John Wiley and Sons, Inc., 1965. 852 p.
1506. Sodium bichromate. j£ chemical profiles, New York, Schnell
Publishing Co., 1969.
2235. Personal communication. R. McCann, Platemakers Education and Research
Institute, to J. F. Clausen, TRW Systems, Mar. 17, 1972.
2250. Personal communication. R. Banner, Diamond Shamrock Corporation, to
J. F. Clausen, TRW Systems, Aug. 21, 1972.
2583. Personal communication. E. Myers, American Dye Manufacturers Institute,
to J. F. Clausen, TRW Systems, Nov. 28, 1972.
2584. Personal communication. J. Mercy, Wool Manufacturers Council, to
J. F. Clausen, TRW Systems, Dec. 4, 1972.
2590. Personal communication. J. A. Stewart, Northern Textile Association,
to J. F. Clausen, TRW Systems, Dec. 12, 1972.
2591. Personal communication. D. Jones, PPG Industries, to J. F. Clausen,
TRW Systems, Nov. 13, 1972.
2673. Personal communication. S. Lant, Diamond Shamrock Chemical Company,
to J. F. Clausen, TRW Systems, Dec. 11, 1972.
131
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WASTES OF INORGANIC CYANIDES
The principal source of cyanide wastes is the electroplating industry
where cyanide compounds are used extensively to make up the plating baths.
Waste streams from the electroplating industry contain varying amounts of
cyanides ranging from 0.5 to 20 percent, normally in an alkaline solution
along with cadmium, copper, zinc, nickel, and chromium compounds. It is
estimated that 21 million Ib of cyanides are discharged through electro-
plating wastes each year. The geographical distribution of these electro-
plating wastes was calculated on the basis of the distribution of "value
added by manufacture" dollar amounts for finished metal products in the
United States (Table 1). A detailed discussion of the cyanide wastes from
the electroplating industry can be found in the report "Wastes from the
Electroplating Industry".
The less toxic ferrocyanide is a component of the iron blue and the
chrome green pigments. Cyanide wastes are generated in paint manufacture
as a result of the kettle washings and equipment cleanup, and are found in
the solvent-based waste paint sludges, which typically contain 27.5 percent
pigments, 25.0 percent binders, and 47.5 percent organic solvents.
Approximately 45,000 Ib of cyanides are lost through the 37 million Ib of
solvent-based waste paint sludges generated each year. The geographical
distribution of these waste paint sludges was calculated on the basis of
the regional distribution of "value added by manufacture" dollar amounts
for paints and allied products in the United States (Table 1). A more
complete discussion of the cyanide wastes from paint manufacture and the
assumptions used in the computation of the waste quantities can be found
in the report "Toxic Paint Wastes".
The paint residues left in used paint containers constitute another
source of cyanide waste. It is estimated that 310,000 Ib of cyanides are
lost through these paint residues each year. The geographical distribution
of these paint reside wastes was calculated on the basis of the population
distribution in the United States (Table 1). Again, a more complete
133
-------
discussion of the paint residue wastes can be found in the report "Toxic
Paint Wastes".
>
Cyanide compounds in Department of Defense storage facilities awaiting
disposal include sodium, calcium, copper, potassium and silver cyanides,
and potassium ferrocyanide and ferricyanide (Table 1), but amount to less
than 2,000 Ib total. With the exception of calcium cyanide, which has been
used as a rodentcide, all the other surplus cyanide compounds were acquired
for plating purposes.
134
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TABLE 1
WASTES OF INORGANIC CYANIDES
Bureau of Census Regions
Source and I II III IV V VI VII VIII
Material
Annual Waste Production (Ib/year)
Cyanides from 2.78 x 106 6.07 x 106 6.86 x 106 0.96 x 106 1.04 x 106 0.49 x 106 0.77 x 106 0.15 x 106
electroplating
Paint Sludge
Cyanides 1,100 9,900 13,800 2,900 3,850 2,150 3,350 550
Sludge 0.92 x 106 8.12 x 106 11.32 x 106 2.40 x 106 3.16 x 106 1.76xl06 2.74 x 106 0.44 x 106
Paint Residue cc c c cccc
Cyanides 0.18 x 103 0.57 x 10s 0.62 x 10s 0.23 x 10b 0.47 x 105 0.20 x 10s 0.30 x 10s 0.13 x 10s
£t Old Paint 13 x 106 41 x 106 44 x 106 16 x 106 34 x 106 14 x 106 21 x 106 9 x 106
Cl Stored Wastes (Ib)
Sodium
Cyanide -1,400 - - - - - 16
Calcium
Cyanide - - - - - .180
Copper
Cyanide - 100 ... . - - 32
Potassium
Cyanide - - -- 2- --
Silver
Cyanide - - - - - - - 16
Potassium
Ferri cyanide - - _ _ ' 4 - --
Potassium
Ferrocyanide - - - - - 12
IX Total
2.20 x 106 21.32 x 106
7,300 44,900
5.97 x 106 36.83 x 106
0.41 x 105 3.11 x 105
29 x 106 221 x 106
1,416
25 205
132
2
10 26
4
12
-------
WASTES OF HYDROFLUORIC AND FLUOBORIC ACIDS
i
Hydrofluoric and fluoboric acids are the two fluorine containing
hazardous chemicals more commonly found in industrial waste streams that
require specialized handling and disposal. The principal sources of hy-
drofluoric acid waste* are the spent pickling solutions and the rinse
water from the stainless steel pickling process, whereas the principal
source of fluoboric acid waste is the rinse water from metal plating.
Hydrofluoric and fluoboric acid wastes from these sources are discussed
in the following sections of this report.
Hydrofluoric Acid Waste from Stainless Steel Pickling
Steel pickling is the process of chemically removing the oxides and
scales formed on the surface of the steel products in the rolling operations,
It is usually done between the hot working and cold working phases of the
operation. Solutions of inorganic acids are normally used as the pickling
solutions. Generally, sulfuric acid or hydrochloric acid is used to pickle
carbon steel and solutions of two or three acids, including hydrofluoric
acid, are used to pickle stainless steel.
The wastes from the stainless steel pickling come from two sources:
(1) the spent pickling solutions containing the concentrated acids and
iron salts; and (2) the rinse water from the pickling operation containing
dilute acids and iron salts. A typical spent pickling solution may contain
7 percent hydrofluoric acid, 10 percent sulfuric acid, 4 percent iron salts,
and traces of other metals such as chromium, nickel, cobalt, etc.f
Information provided by industrial sources indicated that for a manu-
facturing facility producing 20 tons of stainless steel per day, 200 to
*0ther than the extremely dilute hydrofluoric acid discharges from
the fertilizer industry.
Rollins Environmental Services data.
137
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300 gal. of pickling waste containing 1.5 percent hydrofluoric acid are
generated. On this basis, the waste effluent is estimated to be 140
Ib per ton of stainless steel pickled and the hydrofluoric acid loss is
approximately 2 Ib per ton of stainless steel product. For a total U.S.
stainless steel production of 1.4 million tons per year, the total
pickling wastes amount to 196 million Ib per year, with a corresponding
hydrofluoric acid loss of 2.8 million Ib per year. The geographical
distribution of these pickling wastes was determined on the basis of the
production capacities and locations of stainless steel producing facilities
(Table 1).
Fluoboric Acid Waste from Metal Plating
In metal plating, fluoborate baths are sometimes used, particularly
for the plating of lead, tin, and their alloys. The main source of waste
comes from the liquid entrainment dragged out by the plating products
which are subsequently rinsed with water. The aqueous waste effluent
thus generated may contain 1 to 2 percent fluoboric acid, 5 percent hydro-
chloric acid, 2 percent carbon black.* Information provided by industrial
sources indicated that the total U.S. consumption of fluoborate baths is
an estimated 10,000 gal. per year. Since the fluoborate baths contain,
on the average, 21 to 22 oz of fluoborate per gal., the total net fluo-
borate waste is about 13,800 Ib per year. As the waste effluent contains
an average of 1.5 percent of fluoboric acid, the total fluorine waste
effluent amounts to 460 tons per year. The geographical distribution of
these wastes was determined on the basis of the distribution of "value
added by manufacture" dollar amounts for finished metal products and ac-
cording to Bureau of Census regions (Table 1).
* t
' Rollins Environmental Services data.
138
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TABLE 1
WASTES OF HYDROFLUORIC AND FLUOBORIC ACIDS
Source and Bureau of Census Regions
Material I II III IV V VI VII VIII IX Total
Annual Waste Production (Ib/year)
Stainless steel
pickling, hydro- fi , - fi
fluoric acid loss - 1.96 x 10b 0.84 x 10b - - - - - 2.8 x 10°
Metal plating and
finishing fluo- 33 3 3 3 3 3 3 3 3
boric acid loss 1.8 x 10J 3.9 x 10J 4.5 x 1(T 0.6 x 10° 0.7 x 10J 0.3 x 10J 0.5 x 10° 0.1 x 10J 1.4 x 10J 13.8 x 10J
-------
REFERENCES
2624. Personal communication. P. Haines, Allegheny Ludlum Steel, Dunkirk,
New York, to S. S. Kwong, TRW Systems, Dec. 18, 1972.
2625. Personal communication. E. Taishoff, American Iron and Steel
Institute, to S. S. Kwong, TRW Systems, Dec. 13, 1972.
2626. Personal communication. E. Parhan, Relwood Circuit, Inc., to
S. S. Kwong, TRW Systems, Dec. 15, 1972.
140
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WASTES OF SPECIFIC ORGANIC CHEMICALS
The determination of the waste forms and quantities of five hazardous
organic chemicals has been included in this study. These five hazardous
organic chemicals are: acrolein, chloropicrin, dimethyl sulfate, penta-
chlorophenol, and polychlorinated biphenyls (PCBs). The basis for selecting
these particular five organic chemicals are their degree of toxicity, the
probability of their presence in significant quantities as solid, semi-
solid, or concentrated liquid wastes, and the complexity of the treatment
that is required in their disposal/recovery.
Of the five hazardous organic chemicals investigated, the polychlor-
inated biphenyls are the only compound(s) actually found in sizable volumes
as wastes. The PCB wastes as well as the wastes of the other four organic
chemicals are discussed in individual sections of this report.
Acrolein Wastes
Acrolein is a volatile and highly toxic liquid that is produced in
the United States by essentially two manufacturers located in the New
2fi2Q
Orleans area. y><-vj\j It ^ preparec| almost entirely as an intermediate
product or as a starting material for captive in-house applications and
only very small quantities of the chemical are being sold commercially.
In the production of acrylic acid by vapor phase, for example, the cata-
lytic oxidation of propylene is a two-step reaction with acrolein as the
intermediate product.
Since acrolein is flammable, highly irritating, and toxic, extreme care
is exercised in its production process to minimize losses to the atmosphere
OCpQ 9C3f)
or through the plant waste streams. ' The exact quantity of acro-
lein wastes generated at the two manufacturing plants has not been disclosed,
but is believed to be of very low volume and further investigations are not
merited.
141
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Chloropicrin Wastes
Chloropicrin is a slightly oily liquid prepared from nitromethane.
The product is recovered from the reaction mixture by distillation. The
waste effluent from the production process is a clear aqueous solution,
typically containing less than 0.01 percent of Chloropicrin with 3 percent
2631
sodium hydroxide and 20 percent sodium chloride. One major producer
of Chloropicrin, Sobin Chemical, mixes the waste effluent with brine so-
lution and sends it to their chlorine plant (in same location) as a feed,
forming a closed loop with no direct waste discharge from the Chloropicrin
manufacturing plant.
There are currently four major Chloropicrin manufacturers in the
United States2627'2628'2631: Sobin Chemical, Niklor Chemical Company,
Dow Chemical Company, and International Minerals and Chemicals Corporation
(IMC). Information provided by Niklor Chemical indicated that a total of
approximately 600,000 gal. of waste containing less than 0.01 percent Chlo-
ropicrin is discharged into the Los Angeles County sewage disposal system
p/r qi
per year. Based on a production capacity of 600 tons per year and a
0.01 percent Chloropicrin concentration in the aqueous waste stream, the
Chloropicrin loss at Niklor Chemical was estimated to be 0.04 percent of
the Chloropicrin production. Assuming the same waste generation factor
for the Dow and IMC plants, and negligible Chloropicrin loss at the Sobin
plant, the total Chloropicrin loss in the United States through plant
waste water amounts to only 1,700 Ib per year. These Chloropicrin wastes
were distributed geographically according to the locations and production
capacities of the Chloropicrin plants in each Bureau of Census region
(Table 1).
Dimethyl Sulfate Wastes
Dimethyl sulfate is produced almost exclusively by Du Pont. It is
prepared in a liquid phase reaction between oleum and dimethyl ether, and
the product is separated from the reaction liquid by distillation as the
overhead product. The bottom product is recycled back to the reactor and
142
-------
eventually, a viscous, dark brown liquid residue is formed in the bottom
of the distillation column. This liquid residue is the major source of di-
2623
methyl sulfate waste. The composition of this waste stream is not known,
pcpo
but is believed to contain much less than 1 percent dimethyl sulfate.
Du Pont has two plants producing dimethyl sulfate, one in West Virginia
and one in New Jersey. Each plant generates approximately 4,000 gal. of
pcpo
the liquid residue waste per year. On this basis, the total waste
stream was calculated to be about 120,000 Ib per year. As this liquid
waste contains much less than 1 percent dimethyl sulfate, the assumption
of 0.1 percent dimethyl sulfate concentration indicates that the total di-
methyl sulfate loss is about 120 Ib per year. These dimethyl sulfate
wastes were assumed to be equally distributed in the states of West Virginia
and New Jersey (Table 1).
Pentachlorophenol Wastes
pcpi
Pentachlorophenol is supplied by essentially four major producers.
The loss of Pentachlorophenol through plant waste streams during the
manufacturing process is very small. According to one major producer,
only 100 Ib per year of pentachlorophenol are lost in the waste water
?fi?n
for an annual pentachlorophenol production of 4 to 5 million Ib. The
total U. S. production of pentachlorophenol is about 20 million Ib per.
year. Based on a waste generation factor of 20 Ib pentachlorophenol loss
per million pound product, the total pentachlorophenol loss in the United
States amounts to only 400 Ib per year. These pentachlorophenol wastes
were distributed geographically according to the locations and production
capacities of pentachlorophenol plants in each Bureau of Census region
(Table 1).
A major application of pentachlorophenol is for termite and mold
controls on lumber products in wood and construction industries. For
wood preserving, the products are treated with 5 to 10 percent solution
of pentachlorophenol in organic solvent under pressure. Pentachlorophenol
is absorbed into the wood products. After the wood treating process, the
products are subject to vacuum to remove any remaining, unabsorbed liquid
entrainment. The whole wood treating operation is carried out in a
143
-------
TABLE 1
WASTES OF HAZARDOUS ORGANIC CHEMICALS
Source and Bureau of Census Regions
Material I II III IV V VI VII VIII IX Total
Annual Waste Production (Ib/year) . .
Acrolein wastes ---------
Chloropicrin
production
wastes, as
Chloropicrin - - 1,100 ----- 600 1,700
Dimethyl sulfate
production wastes,-
as dimethyl
sulfate 60 - - 60 - - - - 120
Pentachlorophenol , '
production wastes,
as pentachloro-
phenol - 200 100 - - - 100 400
PCB wastes, as PCB 0.98 x 106 3.10 x 106 3.35 x 106 1.25 x 106 2.55 x 106 1.06 x 106 1.61 x 106 0.69 x 106 2.21 x 106 16.80 x 106
-------
closed system, so that there is practically no pentachlorophenol loss in
?6??
the process.
Wastes of Polychlorinated Biphenyls
Polychlorinated biphenyls (PCBs) are a family of organic chemicals
varying in physical state from mobile oily liquids to fine white crystals
and hard transparent resins.* PCBs were first identified as potential
food contaminants in 1966 and since that time have been found throughout
the global environment. Because of the similarity of PCBs to the chlor-
inated hydrocarbon pesticides such as DDT in terms of toxicity effects,
persistence and wide dispersal in the environment, and tendency to ac-
cumulate in food chains, the release of PCBs into the environment has
caused growing concern in recent years.
In the United States, PCBs have been manufactured by a single producer,
the Monsanto Company, and marketed under the trade name "Aroclor". Be-
cause of the findings of the impact of PCBs on the environment, Monsanto
has restricted sales of Aroclors based on consideration of either the
possibility of contamination of food products or its inability to control
or monitor possible PCB losses. In November 1971, Monsanto released figures
for U. S. domestic sales of Aroclors during the period 1963 to 1970 ac-
2fil ^
cording to category of use and grade of Aroclor (Table 2). These
figures indicate that prior to Monsanto's voluntary reduction of sales in
September 1970, approximately 60 percent of the sales were for closed-
system electrical and heat transfer uses, 25 percent for plasticizer ap-
plications, 10 percent for hydraulic fluids and lubricants, and less than
5 percent for miscellaneous applications such as surface coatings, adhesives,
printing inks, and pesticide extenders. The fraction of sales for use in
confined systems, primarily as dielectric fluids for transformers and
*There are about 210 possible PCB compounds, about 50 of which are
produced commercially and usually exist as mixtures. The commercial
mixtures are sold under the trade name Aroclor and are distinguished by
numbers—the first two digits 12 specify polychlorinated biphenyls and
the last two digits the approximate percentage of chlorine in the mixture.
The more highly chlorinated PCBs are more persistent, whereas the less
chlorinated ones are more toxic.
143
-------
TABLE 2
PCB MANUFACTURING AND SALES DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO.
1957 THROUGH 1971
(Thousands of Pounds)
U.S. production*
Domestic sales
Domestic sales by category
Heat transfer
Hydraul i cs/1 ubri cants
Misc. industrial
Transformer
Capacitor ,
Plasticizer applications
Petroleum additives
Domestic sales by PCB grade
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260 °
Aroclor 1262
Aroclor 1268
1957
32,299
_
1,612
704
12,955
17,028
-
—
23
196
18,222
1,779
4,461
7,587
31
1958
26,061
_
1,549
755
5,719
14,099
3,939
—
16,
113
10,444
2,559
6,691
5,982
184
72
1959
31,310
_
2,685
1,569
5,984
16,499
4,573
-
254
240
13,598
3,384
6,754
6.619
359
102
1960
37,919
35,214
_
2,523
1,559
7,921
16,967
6,244
—
103
155
18,196
2,827
6,088
7,330
326
189
1961
36,515
37,538
_
4,110
2,114
6,281
15,935
9,098
—
94
241
19,827
4,023
6,294
6,540
361
158
1962
38,353
38,043
157
3,915
1,681
7,984
15,382
8,924
—
140
224
20,654
3,463
6,325
6,595
432
210
*Production amounts prior to 1960 are not available.
Amounts for plasticizer applications prior to 1958 are not available.
-------
TABLE 2 - CONTINUED
PCB MANUFACTURING AND SALES DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO.
1957 THROUGH 1971
(Thousands of Pounds) . ,
1963
U.S. production
Domestic sales
U.S. export sales
Domestic sales
by category
Heat transfer
Hydraulics/lubricants
Misc. industrial
Transformer
Capacitor
Plasticizer applications
Petroleum additives
Domestic sales by
PCB grade
Aroclor 1221 .
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Aroclor 1262
Aroclor 1268
44
38
3
3
1
7
15
9
18
5
5
7
,734
,132
,647
582
,945
,528
,290
,606
,181
-
361
13
,510
,013
,911
,626
414
284
1964
50,833
44,869
4,096
929
4,374
1,692
7,997
19,540
10,337
-
596
13
23,571
5,238
6,280
8,535
446
190
1965
60,480
51,796
4,234
1,237
4,616
1,841
8,657
23,749
11,696
-
369
. 7
31,533
5,565
7,737
5,831
558
196
1966
65,849
59,078
6,852
1,766
4,258
1,779
8,910
28,884
13,481
-
528
16
39,557
5,015
7,035
5,875
768
284
1967
75,309
62,466
8,124
2,262
4,643
1,426
11,071
29,703
13,361
-
442
25
43,055
4,704
6,696
6,417
840
287
1968
82,854
65,116
11,231
2,529
5,765
1,283
11,585
29,550
14,404
-
136
90
44,853
4,894
8,891
5,252
720
280
1969
76,387
67,194
10,624
3,050
8,039
1,079
12,105
25,022
16,460
1,439
507
273
45,401
5,650
9,822
4,439
712
300
1970
85,054
73,061
J3.651
3,958
7,403
1,627
13,828
26,708
19,537
-
1,476
260
48,588
4,073
12,421
4,890
1,023
330
1971
40,471
37,635
9,876
3,480
1,643
578
11,528
17,305
3,102
-
1,600
211
21 ,000
261
5,800
1,750
-
-
1972
25-30,000
25-30,000
?
.
_
_
25-30,000
25-30,000
_
-
300
300
4,000
. _
6,000
600
-
-
-------
capacitors, has increased to approximately 90 percent in 1971 and 100 per-
cent in 1972. To meet the problem of scrap disposal, Monsanto has set up
a disposal system with a capacity of 10 million Ib per year for their
customers. Within a year of announcement of the service, 500,000 Ib of
waste PCBs had accumulated at the disposal site, where it is held in
pCOQ
storage, pending the completion of the incinerator.
Solid, semi-solid, and concentrated liquid,PCB wastes are generated
as equipment or products containing these materials are replaced and dis-
carded. Although the current application of PCBs has been limited prin-
cipally to electric equipment and utilities, PCB wastes continue to be
generated from applications which were previously acceptable. Information
on the forms and composition of some typical PCB waste streams was provided
by Rollins Environmental Services and is summarized in this report (Table 3)
Estimates on the PCB losses by disposal into incinerators, dumps,
and landfills were made on the basis of the useful service life of PCBs
in transformers, capacitors, plasticizers, and heat exchangers. The gen-
eral assumptions employed were those as suggested by Nisbet and Sarofim
(1) only 10 percent of the PCB sales for transformer fluid is
to replace oil that is scraped and the remaining 90 percent
is for new units as transformers are fairly permanent in-
stallations;
(2) a useful life of approximately 10 years for capacitors and
heat exchangers, thus the rate of disposal of PCBs from
these applications is equal to the corresponding sales
volume 10 years ago;
(3) a useful life of one year for plastic objects and a rate
of disposal of plasticizers into dumps equal to 90 percent
of the sales, the residual 10 percent is accounted for by
the rate of vaporization of plasticizers.
Calculations based on the assumptions stated above indicate that
8,400 tons of PCBs ended up in incinerators, dumps and landfills in 1972.
These PCB wastes were distributed geographically according to the population
148
-------
TABLE 3
EXAMPLES OF PCB WASTES
Waste Description
Physical
Form
Waste Source
90 percent polychlorinated biphenyls; Liquid
10 percent alpha methyl styrene.
Spent dielectric fluid of the arochlor- Liquid
inerteen type; essentially 100 percent
polychlorinated biphenyls and their
breakdown products.
Heat transfer oil containing 20 percent Liquid
polychlorinated biphenyls, 80 percent
lube oil.
Spent dielectric fluid of the askarel- Liquid
pyranol type containing 50 percent or
more polychlorinated biphenyls, 30-40
percent chlorinated diphenyl ether;
breakdown products and water.
10 to 90 percent polychlorinated bi- Liquid
phenyls (PCB) with diphenyl and
diphenyl oxide (heat exchanger dis-
placement).
5 to 99 percent PCB (containing chlorine Liquid
in the range of 20 to 60%) mixed with
solvents, oils, water and dirt (elec-
trical capacitors).
2 to 10 percent PCB by weight in Liquid and
capacitors including shell and Solid
impregnated membranes.
Rags and filter aid contaminated with Solid
various compounds of PCB (spills and
filtering).
Chemical
Utilities, power
equipment manu-
facture; utilities
service
Chemical
Utilities service
Rubber
Utilities; power
equipment
Utilities; power
equipment
Utilities; power
equipment
149
-------
20,000
18,000
a:
UJ
a.
G 16,000
o
Z°
O 14,000
CO
u
a.
12,000
10,000
8,000
1969 1971 1973 1975 1977 1979 1981
1983 1985
Figure 1. PCB wastes requiring disposal per year.
-------
distribution in the United States (Table 1). The same set of assumptions
was also used to estimate the total quantity of PCB wastes requiring
disposal per year for the period 1969 to 1982 (summarized here in Figure 1)
The results of the computations indicate that after Monsanto restricted
its PCB sales and PCB application as plasticizers was discontinued, the
PCB wastes generated per year dropped sharply from 19,000 tons in 1970 to
10,800 tons in 1971. However, because of the large increases in PCB sales
as dielectric fluid for capacitors during 1963 to 1970, the PCB wastes
generated per year will increase again to a high of 16,600 tons in 1977
and 1978, remain relatively unchanged till 1980,. and thereafter decrease
to approximately 10,000 tons from 1982 on.
151
-------
REFERENCES
2615. Inter-departmental Task Force on PCBs. Polychlorinated biphenyls and
the environment. Washington, U.S. Government Printing Office,
1972. 192 p.
2620. Personal communication. W. Wetzel, Reinhold Chemicals, Inc., to
S. S. Kwong, TRW Systems, Dec. 18, 1972.
2621. Personal communication. W. B. Papageorge, Monsanto Company, to
S. S. Kwong, TRW Systems, Dec. 7, 1972.
2622. Personal communication. W. H. Rogers, J. H. Baxter & Company, to
S. S. Kwong, TRW Systems, Dec. 21, 1972.
2623. Personal communication. Mr. Mclaughlin, E. I. Du Pont de Nemours &
Company, to S. S. Kwong, TRW Systems, Nov. 30, 1972.
2627. Personal communication. P. DeAngelis, Sobin Chemical, to S. S. Kwong,
TRW Systems, Dec. 7, 1972.
2628. Personal communication. E. El kins, Dow Chemical Company, to S. S.
Kwong, TRW Systems, Dec. 15, 1972.
2629. Personal communication. E. D. Southard, Union Carbide Corporation,
to S. S. Kwong, TRW Systems, Dec. 18, 1972.
2630. Personal communication. R. Tess, Shell Chemical Company, to S. S.
Kwong, TRW Systems, Nov. 29, 1972.
2631. Personal communication. J. M. Wilhelm, Niklor Chemical Company, to
S. S. Kwong, TRW Systems, Jan. 12, 1973.
2638. Nisbet, J. C. T., and A. F. Sarofim. Rates and routes of transport
of PCBs in the environment. Environmental Health Perspectives,
1:21-38, Apr. 1972.
152
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EXPLOSIVE, PROPELLANT AND CHEMICAL WARFARE MATERIEL
Obsolete conventional and chemical ammunition, and explosive wastes
constitute a high volume, high hazard disposal problem. A large portion of
these wastes must be treated by special techniques at National Disposal Sites
under civilian or military cognizance, to minimize or eliminate danger to the
public and impact upon the environment.
Almost all explosive, propellant, and chemical warfare materiel wastes
may be divided into two major categories, based on origin:
(1) Obsolete and surplus ammunition and ordnance materiel scheduled
for disposal by the Armed Services;
(2) Wastes generated in the manufacture of explosives, military and
commercial explosive devices, and other ordnance items.
The hazardous materials contained in explosive, propellant and chemical
warfare materiel wastes have been subdivided for convenience, because of the
large number involved, into seven classes. The seven classes, and typical
hazardous materials representative of the classes, are:
(1) Initiating Agents and Primers—Mercury Fulminate, Lead Azide, Lead
Styphnate, DDNP, Tetrazene, Copper Acetylide, DPEHN.
(2) Propel!ants. Nitrocel 1 ulose Based—Smoke!ess gunpowder, nitro-
cellulose, Gelatinized nitrocellulose, rocket propellant (double-
base), ballistite, pyrocellulose, composition D-2, nitroglycerin,
(3) Propellants. Composite/Other—Rocket propellant TP-H-1011, Rocket
propellent TP-H-1016, Rocket Propellant ANB-3066, Ammonium
Perchlorate, Chlorine Trifluoride, IRFNA, Perchloryl Fluoride.
(4) High Explosives—Ammonium Picrate, Glycol Dinitrate, Picric Acid,
PETN, TNT, Dynamite, Composition A, Composition B, Composition B2,
Composition C, RDX, HMX, Tetryl, Pentolite, Cavity Hot Melt,
Plastic Explosive.
153
-------
(5) Pyrotechnics and Incendiaries—White Phosphorus, Red Phosphorus,
Napalm, NP (Thickened Gasoline, with Napalm), PTI (Incendiary
Mixture), Magnesium Powder, Thermite, SGF2 (Fog, Oil, Smoke
Mixture).
(6) Riot Control Agents—Chloracetophenone Tear Gas (CN), Tear Gas
Irritant (CS), CBC (Brombenzylcyanide), CN-DM (Burning Mixture of
CN and DM), CNS (Chloracetophenone and Chlorpicrin), DA (Diphenyl
chloroarsine), DM (Adamsite, diphenylaminochloroarsine).
(7) Chemical Warfare Agents—GB. VX, Lewisite, Sulfur Mustard (H, HD),
Nitrogen Mustards.
Obsolete Munitions
Obsolete and surplus conventional ammunition and ordnance material
scheduled for disposal by the Armed Services have been inventoried for
each Department of Defense facility in the United States as of July 28,
1972 by the Joint AMC/NMC/AFLC/AFSC Commanders Panel on Disposal Ashore
pcoc
of Ammunition. The inventory indicates the number of rounds and gross
weight of each Federal Stock Catalog item of ammunition or ordnance mater-
ial at each facility. There are 39 such facilities, located in 24 states
(Table 1). With the assistance of Navy-furnished information on the haz-
ardous materials contained in the individual ammunition items, ' a
state-by-state inventory of the quantities of each of the hazardous material
classes used as fill and the associated quantities of obsolete ammunition
was compiled by TRW (Table 2). The inventory represents the quantities in
hazardous obsolete conventional ordnance device stockpiles scheduled for
disposal as of July 28, 1972 for the U.S. Army, and conventional obsolete
ordnance device stockpiles scheduled for disposal by the U.S. Navy as of
November 30, 1972. The inventory does not include data on the quantities
and locations of obsolete and surplus lethal chemical agents or ordnance
devices containing lethal chemical agents. Such information is not avail-
able, to the level of detail presented here (Table 2),
The obsolete conventional ordnance devices scheduled for disposal
encompass virtually the entire range of conventional munitions—from minute
fuze components, weighing fractions of an ounce, to 280 mm artillery pro-
jectiles over 600 Ib in weight. The number of individual rounds and components
of obsolete munition are in the tens of millions. The numbers of types of
154
-------
TABLE 1
DEPARTMENT OF DEFENSE FACILITY STORAGE POINTS
FOR OBSOLETE CONVENTIONAL AMMUNITION
State
Facility
Alabama
Arizona
California
Colorado
Florida
Georgia
Hawaii
Illinois
Indiana
Kentucky
Maryland
Nevada
New Jersey
New Mexico
New York
North Carolina
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
Texas
Utah
Virginia
Washington
Anneston (A)
Navajo (A)
Sierra (A), Alameda (N), North Island (N), El Toro (N),
Miramar (N), Moffett Field (N), Concord (N), Seal Beach (N)
Pueblo (A)
Jacksonville (N), Key West (N), Cecil Field (N)
Brunswick (N)
Oahu (N)
Savanna (A)
Crane (N)
Lexington (A)
Indian Head (N)
Hawthorne (N)
Earle (N)
Fort Wingate (A)
Seneca (A)
Cherry Point (N)
McAlester (N)
Umatilla (A)
Letterkenny (A)
Quonset Point (N)
Charlestown (N), Beaufort (N)
Red River (A), Corpus Christi (N)
Tooele (A)
Norfolk (N), Virginia Beach (N), Yorktown (N), Oceana (N),
St. Juliens Creek Annex (N)
Bangor (N), Keyport Bangor Annex (N)
(A; = Army
(N) = Navy or Marine
155
-------
en
TABLE 2
OBSOLETE CONVENTIONAL MUNITIONS
HAZARDOUS MATERIAL CONTENTS AND GROSS WEIGHT DISTRIBUTION BY STATE -
SCHEDULED FOR DISPOSAL BY THE DEPARTMENT OF DEFENSE* 2586,2594,2668,2669
.Hiaoama
Col orado
Florida
Georgia
Hawa i i
naWd 1 i
Tl 1 i nnic
1111 IIU 1 o
Indiana
Kentucky
Maryland
Nevada
New Jersey
New York
North Carol i na
Oklahoma
Urecjon
Pennsylvania
Rhode Island
Sou th Ca ro 1 i nc
i exas
Utah
U Ldlt
Virginia
Washington
Continental
United States
pelght of Explosive
(D (2)
900 539,664
23,608 1,327,982
2,210 962,052
1 812
4,151 265,317
47,856 1,059,183
16^790 6,086,532
1,921 855,000
17 15,617
93,670 3,964,246
6,454 207,706
6,786 1,238,392
5,000
35,654 13,997,459
4,396 1,937,082
11,398 3,459,496
1,143 177,665
7,936 407,675
1,099 478,181
,' Incendiary", Pyrotechnic and
Ag
(3J
159
49
15
117
49
394
32,002 399,348 176
2,022 447,479 7
305,014 37,821,828
966
Code: (1) Initiating Agents and Primers;
(5) Pyrotechnics and Incendiaries;
ent Fill, in Ib
(4) (5)
1,118,677 6,802
621,303 128,819
317,692
397 38
l l
1,879,438 63,179
752,641
6,678,784 416,618
302,314
20,304
12,824,056 774,514
524,258
735,751
2,808 21
6,479,680 911,987
1,353,290
2,485,059
34
314,027 94,331
113,149 433
129,238
658,333 178,545
1,463,890 7,915
38,775,092 2,942,303"
Riot Control •->.
(6)
15,666
2,595
81
104
186
37,971
7,610
440
952
946,944
113
4,795
176
1,017,633
(2) Propellants, nitrocellulose
(6) Riot Control Agents
TOTAL
1 ,681 ,709
2,104,466
1,282,035
1,248
1 j
2,212,238
1,859,410
13,198,925
1,197,206
35,938
17,664,213
738,907
1 ,980,929
7,829
21,426,126
4,241,712
5,955,953
34
587,279
529,193
608,518
1,273,199
1,921,489
80,862,836
based; (3) f
Weight of- Obs'olete 'Munitions Containing Each
(1)
3,446,600
9,423,300
8,403,000
1,400
157,000
19,157,800
7,916,100
6,243,200
35
4,060,300
699,400
2,490,000
12.500
35,121,200
16,642,400
28,515,800
79,700
3,632,200
4,037,400
395,600
52,300
Fill
Category, in Ib
(2) (3) - - (4)
3,727,600
10,948,700 1
8,403,000
6,700
1,535,800 4
19,114,200
22,694,000 30
6,243,200
25,200
15,330,300 7
957,800
6,588,600
54,440,200 786
16,642,400
24,423,000
713,100
3,674,200
4,037,400
1,701,800 2
2,797,000
150,487,300 204,004,200 834
ropellan'ts
composite/other;
3,095,600
,200 9,882,600
9,073,800
2,600
,700 3,172,000
19,192,600
,000 20,581,392 7
6,385,000
37,600
,600 25,049,800 2
900 1,612,200
3,247,200
5,200
,000 46,565,400 34
17,107,000
29,202,000
232 864,400
3,468,200
4,037,400
,600 1.967.JOO
800 2,874,100
,000 207,405,500 46
(4) High explosives
(5)
564,600
358,300
111
26
195,200
,340,700
81
,443,000
660,500
31
,482,800
79
217,700
130,135
349,^00
40,200
,783,200
(6)
32,400
12,100
200
1,500
320
82,800
63,000
1,200
1,300
2,486,000
226
9,200
360
2,690,600
TrtTAI
1 U 1 ML
6,812,800
13,002,000
9,073.800
19,300
26
4,954,200
20,288,600
36,722,200
6,554,000
63,300
48,369,400
2,686.700
7,363,800
19,100
69,542,500
19,128,400
30,267,000
81
1,752,100
3,674,300
4,037,400
4,782,500
6,310,700
301,237,344
Will not agree with sum of weights of obsolete munitions containing the individual fill categories because of redundancies due to multiple
fills in many ordnance items.
Y S. Army - as of July 28, 1972; U. S. Navy - as of November 30, 1972
-------
individual rounds and components stored for disposal are in the tens of
thousands—over 1,100 Federal Stock Numbers in California alone. There are
approximately 301,000,000 Ib of obsolete conventional ammunition, containing
almost 81,000,000 Ib of explosive or otherwise hazardous materials. The
detailed information presented on the quantities and locations of these
hazardous wastes was developed by the Joint Logistics Commanders Panel, to
scope the problem as first step in accomplishing the objective of developing
"a joint plan for disposal ashore of ammunition by ecologically acceptable
pcoc
means, due to the restrictions on deep water dumping."
Prior reports have indicated a portion of the surplus chemical munitions
stored at U. S. Army facilities (3,071 tons of Mustard; 2,085 tons of GB;
l fi?^
and 2,700 tons of Phosgene). The organophosphorus chemical warfare
agents (GB and VX, the "nerve gases") are contained in artillery shells,
rocket warheads, bombs, mines and sprayers (see Table 1, page 239, Volume
VII of this report). Mustard is contained in a similar array of stored
munitions (Table 3). The major materials resulting from the destruction
of the lethal chemical warfare agents scheduled for disposal over the next
t
10 years amount to some 70,000 tons of calcium and sodium chloride, sulfate,
sulfite, fluoride, carbonate and phosphate, and sodium methylisopropyl-
1 TV)
phosphonate, at nine locations (Table 4).
The explosive-contaminated inert wastes generated by ordnance device
manufacture are almost always contaminated packaging materials—paper, plaster,
cardboard fiberboard and wood.
Hazardous wastes generated in the manufacture of explosives, military
and commercial explosive devices, and other ordnance devices are in excess
of 48,000,000 Ib, annually (Table 5). Of this total, close to 23,000,000
Ib are explosive scrap. The data for explosive contaminated inert wastes
is incomplete, and the estimate for such hazardous wastes (25,506,000 Ib)
represents only a portion of the total. Data for hazardous wastes produced
by Government Owned, Contractor Operated (GOCO) plants under U. S. Army
9COT
cognizance was obtained directly from the Army. Data on the explosive
0
waste output of the contractor operated plants under Atomic Energy Commission
direction, was furnished by Mason and Hanger Silas Mason Co. Inc.,
157
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TABLE 3
SOME U. S. MUNITIONS CONTAINING MUSTARD
958
OD
" Ammunition
Shells
M60° Cartridge
M2/M2A1 Cartridge
M2/M2A1 Cartridge
MHO Projectile
Ml 04 Projectile
. £W ;
Agent
HD
HD
HT
HD
HD
Delivery Device
105mm howitzer
4.2 in mortar
4.2 in mortar
155mm howitzer
155mm howitzer
Ammunition
Wt/lbs '
43
25
25
99
95
CW Agent
Wt/lbs
3.0
6.0
5.8
9.7
11.7
Explosive
Wt/lbs
0.3
0.7
0.7
0.8
0.8
Propellent
Wt/lbs
2.75
0.4
0.4
None
None
-------
TABLE 4
JAGES FRC
WARFARE AGENTS'
ESTIMATED SALT TONNAGES FROM DISPOSAL OF LETHAL CHEMICAL
.1732
Site Estimated Salt Tonnage*
Edgewood Arsenal, Maryland 3,400
Pine Bluff Arsenal, Arkansas ' 7,800
Rocky Mountain Arsenal, Colorado 13,000*
Tooele Army Depot, Utah 25,000
Umatilla Army Depot, Oregon 7,300
Anneston Army Depot, Louisiana 5,700
Pueblo Army Depot, Colorado 3,900
Newport Army Ammunition Plant, Indiana 3,000
Lexington Blue-Grass Army Depot, Kentucky 900
Total 70,000
*Mixtures of calcium chloride, sulfate, sulfite, fluoride, carbonate
and phosphate.
. 0958
4,350 tons from disposal of GB; 7,900 tons from disposal of mustard,
comprised of mixtures of sodium chloride, sulfate, sulfite, fluoride, car-
bonate, phosphate, and methylisopropylphosphonate.
159
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TABLE 5.
EXPLOSIVE MANUFACTURING WASTES ?/ulfl ?dqfi ?rqfi
POUNDS PER YEAR SOLID WASTES* DISCHARGED—BY STATE^0'^? 2297 1623
2637,
State
Alabama
Arzona
Arkansas
California
Colorado
Connecticut
Illinois
Indiana
Iowa
Kansas
Louisiana
Massachusetts
Minnesota
Missouri
Nebraska
New Jersey
New Mexico
New York
Ohio
Pennsylvania
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Total
Initiating Agents Propel 1 ants, .nitro- Propellants High Explosives
& Primers cellulose based Composite/Other
Scrap Contain. Scrap Contam. Scrap Contain. Scrap Contam.
Explosives Inert Explosives Inert Explosives Inert Explosives Inert
1,800 700 22,000
3,700
4,100 1.400 1,043,000 218,000 2,900
10 1.800 3,700
132,000 3,898,000
132,000 3,700 133,000
1,819,000
138,000 3,614,000 1,877,000 3,979,000 138,000
37,000 1,643,000
22,000
21 ,900
219,000 222..000
219,000 60,200 219,000
1,100 237,000 365,000 365,000 7,300
25,800 10,300 126,000
200 400 20,500
600 200 11.800
500 152,000 51.300
10 1,419,000
110,000
148,000 76,000 713,000 115,000 3,700
10 2,871.0004,344,000 3,012,000
192,000
11,000
141,000 730,000
304,000 4,018,000 6,046,000 8,824,000 1,756,000 333,000 13,810,000
73,000
1,095,000
862,000
3.614,000
72,300
60,200
50,000
300
577,000
243,000
44,000
91 ,300
4,636,000
274,000
11,692,000
Pyrotechnics & Total
Incendiaries
Scrap Contain. Scrap Contam
Explosives Inert Explosives Inert
24,000
3,700
548,000 639,000 548,000
6,800 1.057.000
3,700
11,000 11,000
4,030,000 1
269,000
1,819,000
11.207,000 2
1,680,000
22.000
21 ,900
1,200 . 442,000
438,000
373,000
152,000
1,500 22,000
12,400
52,000
1,419,000
14,600 - 125,000
200,000 1,065,000
5,883,000 8
192,000
11,000
783,000 639,000 22,699,000 25
74,000
-
639,000
219,000
1,800
,095,000
862,000
,153,000
72,000
120,000
592,000
60,000
400
500
729,000
243,000
44,000
282,000
,980,000
274,000
,506,000
. All haz.
Wastes
98,000
3,700
1,187,000
1,276,000
5,500
11,000
5,125,000
269,000
2,681.000
13,360,000
1,680,000
22,000
21 ,900
513,000
558,000
975,000
212.000
23,000
13,000
781 ,000
1,662,000
169,000
1,347,000
14,863,000
466,000
11,000
871,000
48,205,000
*Excluding explosive wastes discharged as solute or suspensoid in facility outfalls.
-------
indicated a current annual scrap explosive generation rate of 598,000 Ib
per year, and an estimate of 230,000 Ib per year of contaminated inert.
Direct information from several of the Air Force contractors was used in
projecting an annual hazardous waste output of 2,313,000 Ib (1,904,000 Ib
of scrap propel 1 ant and 409,000 Ib of contaminated inert waste).2596'2496'2448
I COO
Other than partial data presented in an earlier report, there was no data
directly available from non-military explosives and commercial explosive
device manufacturers. An estimate was made, accordingly, of scrap explosives
generated by this segment of the industry, using Bureau of the Census employee
population figures, Bureau of Mines explosives production data for 1971,
in-house knowledge of type of explosive produced at various locations, and
"Waste Factors" of 0.3 percent for all explosives other than initiating
agents. For initiating agents, a waste factor of 0.1 percent was used.
161
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REFERENCES
0958. tidgewood Arsenal, Department of the Army. Transportable disposal
system. Edgewood Arsenal, Maryland, EASP 200-11, July 1971. 297 p.
1287. Bureau of Mines Staff. Mineral facts and problems. U.S. Bureau of
Mine's, Washington. Bulletin 650, 1970. 1291 p.
1623. Booz-Allen Applied Research Inc. A study of hazardous waste materials,
hazardous effects and disposal methods, Vol. I. Draft Report.
Washington, Jan. 12, 1972. Baarinc Report No. 9075-003-001.
1732. Johnson, H. J., Personal communication to R. S. OttingerB TRW Systems,
from H. S. Johnson. May 9, 1972. Re: letter from W. P. Junkln,
Edgewood Arsenal.
2297. Booz-Allen Applied Research Inc. Final Report; A study of hazardous
waste materials, hazardous effects and disposal methods, Vol. I,
Washington. June 30, 1972. 9075-003-001. 109 p.
2448. Hollerman, E. Response to request for information on waste propellents,
Personal communication to G. I. Gruber, TRW Systemss from Aerojet
Solid Propulsion Co., Sacramento, California. Oct. 17, 1972.
2496. Personal communication to G. I. Gruber, TRW Systems on hazardous
waste quantity projections - explosives and propel!ants.
2586. Joint AMC/NMC/AFLC/AFSC Commanders panel on disposal ashore of
ammunition. JLC CONUS Inventory by location of obsolete conventional
munitions as of July 28, 1972. Mechanicsburg, Pennsylvania. U. S.
Navy Ships Parts Control Center.
2594. Department of the Navy. Navy transportation safety handbook, NAVORD
Op. 2165, V. 2, pt 1 and 2. Department of the Navy, Naval Ordnance
Systems Command, Oct. 1, 1971.
2596. Rochford, E. M. Disposal of propellant and ingredient waste. Personal
communication to G. I. Gruber, TRW Systems from Hercules Inc.,
Magna, Utah. Dec. 27, 1972.
2632. Honea, F. I. and J. E. Wichmann. Disposal of waste or excess high
explosives; progress report, January - March 1971. Mason and Hanger,
Silas Mason Co., Amarillo, Texas, MHSMP-71-27. 26 p.
2637. Fauroat, C. W. Personal communication to H. Johnson from Picatlnny
Arsenal, 13 Dec. 1972. Response to request for information concerning
categories of solid waste generated at AAP's and summary of solid
wastes1.
2668. U. S. Navy ships parts control center. Magnetic tape S.N. 24820, Data
for NAVORD OP 2165 Navy transportation safety handbook.
2669. U. S. Navy ships parts control center. Magnetic tape S.N. 78664.
Ownership code 2 assets.
162
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RADIOACTIVE WASTES
The radioactive wastes created and stored by the AEC were documented
in the preceding study performed by Booz-Allen Applied Research. The wastes
stored by commercial firms in Agreement State sites were not included in the
data provided by the AEC. Early in 1973 the Kentucky State Department of
Public Health with the support of the Office of Radiation Programs, the
Office of Research and Monitoring and the Office of Solid Waste Management
Programs of EPA undertook a program to transcribe their records of the
radioactive wastes stored at the Maxey Flats site onto computer compatible
media. These data are particularly important since the Maxey Flats site
is estimated to receive forty-five percent of all non-AEC stored wastes.
However, these data have not been reviewed or analyzed to any significant
degree at the present time (August 1973). Therefore, no quantitative data
are presented.
163
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-n
3. Recipient's Accession No.
4. Title and Subtitle
Recommended Methods of Reduction, Neutralization, Recovery, or
Disposal of Hazardous Waste. Volume XIV, Summary of Waste
Origins, Forms, and Quantities
5. Report Date
Issuing date - Aug. 1973
6.
7. Author(s) R. $. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
G. I. Gruber, M. J. Santv. and C. C. Shih
8. Performing Organization Kept.
N°- 21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089
12. Sponsoring Organization Name and Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
Volume XIV of 16 volumes.
16. Abstracts
This volume provides information on the origins, forms, and quantities of 13 groups of
hazardous waste stream constituents, including pesticides, mercury and mercury com-
pounds, arsenic and arsenic compounds, cadmium and cadmium compounds, lead compounds,
soluble copper compounds, selenium and selenium compounds, boron hydrides, chromium
compounds, inorganic cyanides, hydrofluoric and fluoboric acids, specific organic
chemicals, explosive propellant and chemical warfare materiel and radioactive material.
Separate reports on paint wastes and wastes from battery manufacture and the electro-
plating industry are also presented.
17. Key Words and Document Analysis. 17o. Descriptors
Waste Origins
Waste Forms ^
Waste Quantities
Industrial Wastes
17b. Identifiers /Open-Ended Terms
I7c. COSATI Field/croup 06F; QSJ. 07B; Q7C; 07E; T3B; 13H; 19A; 19B
18. Availability Statement
Release to public.
- 164 -
19.. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
170
22. Price
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