-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name DDT (27 possible isomers)(137)
IUC Name 2,2-bis-(p-chlorophenyl)-l,1-trichloroethane
Structural Formula
Common Names Dichlorodiphenyl trichloroethane.ethane
dicophane, chlorophenothane
Molecular Wt. 354-5
Density (Condensed) 1.6
&
Melting Pt. 1Q8.5-109C Boiling Pt._
Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
'* 1 mm
1.9 X10"7mm
185
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Lower
Upper_
Upper_
Solubility
Cold Water 0.001 mq/l
^
Hot Water
Ethanol
Others: soluble in ketones, esters of the lower fatty acids, aromatic hydrocarbons, and
halogen derivatives of hydrocarbons^'>
Acid, Base Properties
Highly Reactive with
Compatible with actions of heat. Pure DDT does not decompose below 195 C, but the technical
material decomposes at about 100 c
12)
Shipped in fiber drums, bags, tins, and bottles.
ICC Classification
Coast Guard Classification
Comments Colorless crystals or white to slightly off white nowdpr. Technical DDT contains
approximately 70 percent of p.p'-DDT which is thp mn^t pffprtivp insecticide principal. Tn
application. DDT is formulated as dusts, concentrated emulsions, wettable powders, preparation
for fine-droplet spraying, and aerosols.
References (1) 1513
(2) 1617
53
-------
PROFILE REPORT
2,4-D (135)
1. GENERAL
Introduction
The discovery of the growth regulating properties of the chlorinated
phenoxyacetic acids in 1944 and their subsequent employment as herbicides
began the modern era of selective chemical weed control. These compounds
are selective to broad-leaved weeds in cereals and could be absorbed from
soil as pre-emergent herbicides. The growth regulating action is shared
by a group of hundreds of related molecules all derived from the same
parent substance, 2,4-dichlorophenoxyacetic acid or 2,4-D. In fact, to
permit the proper application and formulation of 2,4-D, the amine salts
and esters of the acid have been generally used instead of 2,4-D as such.
The chlorophenoxy groups of herbicides which includes 2,4-D, 2,4,5-T
(2,4,5-trichlorophenoxy acetic acid) and MCPA (2-methyl-4-chlorophenoxy
acetic acid) comprise approximately half the total domestic herbicide
market. The U. S. production figures for 2,4-D from the year 1960 to 1967
in thousands of pounds are:0449'1610
Annual U. S. Production (thousand Ib)
1960 1961 1962 1963 1964 1965 1966 1967
§> 361,315 43,392 42,977 46,312 539714 63,320 68,182 77,139
171ft
However, in 1970 only 43,576,000 Ib of 2,4-D were produced. The pro-
duction figures thus illustrate the gradual declining importance of 2,4-D
as a base material for herbicides.
55
-------
Manufacture
2,4-D is generally prepared by the condensation reaction of monochloro-
acetic acid and 2,4-dichlorophenol in an alkaline solution at atmospheric
pressure, 60 to 80 C, and a residence time of 6 to 8 hr in a jacketed stirred
reactor:1610
•*• Nad 4-
Large scale commercial facilities for the manufacture of technical
grade 2,4-D in the United States include the following1774' 1775' 1776s
1777, 1778, 1779, 1780.
Dow Chemical Company, Midland, Michigan
Rhodia Inc., Chipman Division, Portland, Oregon
Transvaal Inc., Jacksonville, Arkansas
The Transvaal plant was formerly operated by Hercules Inc.
Uses
The chlorophenoxy acids are active by contact and by translocation
from leaves to roots of perennial weeds and are used as pre-emergent appli-
cations to the soil for control of young seedlings. They are also effective
for aquatic weed control, for the elimination of unwanted vegetation, and
are selective against many broad-leaved annual weeds in cereal and grass
0509
crops.
In addition, 2,4-D and its derivatives have also found important uses
in related fields such as thinning of fruit, prevention of preharvest drop,
fruit setting, promotion of rooting and postharvest decay prevention.
-------
Sources and Types of Pesticide Wastes
The sources of pesticide wastes may include the following: (1)
pesticide manufacturers; (2) pesticide formulators; (3) pesticide whole-
salers; (4) professional applicators; (5) cooperage facilities that recon-
dition drum; (6) agricultural users; (7) government facilities that store,
transport, and use pesticides; (8) urban and suburban home and garden
users; (9) commercial and industrial processes including those from rug
and fabric treatment facilities manufacturing plants, hospitals, etc.
In general, pesticide wastes can be classified as either diluted or
concentrated wastes. Diluted pesticide wastes include those generated in
the waste waters of the manufacturers, formulators, agricultural runoffs,
and possibly spent caustic solutions used to clean empty pesticide con-
tainers. Concentrated pesticide wastes include any unused or contaminated
pesticides, pesticide materials left in containers after emptying, sludges
formed in treating waste water containing pesticides, sawdust or straw used
to soak up accidental pesticide spills.
Unlike most pesticides, 2,4-D is also used as an aquatic herbicide
and applied directly to lakes, rivers, irrigation waterways, and other
surface waters for weed control, thus posing a potential water pollution
problem. 2,4-D has been reported to persist for several months in lake
waters.1757
Chlorophenoxy pesticides appear as waste stream constituents in varied
forms and compositions. Typical waste streams containing chlorophenoxy
compounds are as follows:
Solvents including toluene and xylene containing 1 to 5 percent
2,4-D and/or 2,4,5-T
Organic waste containing 20 to 25 percent 2,4-D; 20 to 25 percent
2,6-D; 10 to 15 percent mono- and trichlorophenoxy acetic acids
Still bottoms containing 2,4-D, 2,6-D and chlorophenols.
Solid wastes containing 0.5 percent 2,4-D
57
-------
More detailed information relating to the forms and quantities of waste
chlorophenoxy compounds is presented in the volume titled Waste
Forms and Quantities.
Physical and Chemical Properties
The physical and chemical properties of 2,4-D are summarized in the
attached worksheet.
2. TOXICOLOGY
2,4-D is of moderate, acute toxicity to mammals. The acute oral and
dermal LDrn values to the rat have been reported to be 375 and 1500 mg/kg
1277
body weight respectively. Inhalation of 2,4-D dusts and sprays is
0449
relatively harmless, and percutaneous absorption is negligible.
Chronically 2,4-D is of low toxicity, ?.rid can be ingested b'y animals
and man in daily dosages approaching those which produce acute toxic
effects when given only once. Thus, the cumulative effects of 2,4-D are
minimal.
The American Conference of Governmental Industrial Hygienists 1971
n f)99£
recommended Threshold Limit Value (TLV) for 2,4-D in air is 10 mg/M .
The 48-hour Median Tolerance Limit (TL.) for 2,4-D established by the
Federal Water Pollution Control Administration for various types of fresh
water organisms in micrograms per liter are: P. Californica (stream
invertebrate), 1,800; Daphnia pulex (cladocerans), 3,200; Rainbow trout
(fish), 960; and Gammarus lacustris, 1,800. These .data are indicative of
the hazards to aquatic life associated with the use of 2,4-D.
58
-------
3. OTHER HAZARDS
As an organic acid, 2,4-D is corrosive and reacts with metals and
bases. When heated to decomposition, highly toxic fumes of hydrogen
chloride and other chlorinated products are emitted.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Although 2,4-D is only mildly toxic to humans, the use of rubber
gloves, goggles, and a respirator is recommended in its handling and
application. Storage of 2,4-D should be in a cool, dry, well-ventilated
area, away from acute fire hazards, and with proper warning signs posted.
No Department of Transportation shipping labels are required for 2,4-D,
0278
as the hazards in shipping 2,4-D are generally considered as minimum.
The National Agricultural Chemicals Association has established a
Pesticide Safety Team Network with Area Coordinators throughout the
country to provide nationwide 24-hour service. The network became opera-
tional on March 9, 1970 (with a central telephone number - [513] 916-4300)
and should be consulted in all cases of accidents, spills, leakage, fires,
and other types of disasters involving 2,4-D.
Disposal/Reuse
Contaminated or degraded 2,4-D could not be practically considered
for reprocessing. The safe disposal of 2,4-D is defined in terms of the
recommended provisional limits in the atmosphere and potable water source
and/or marine habitat. These recommended provisional limits are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
2,4-D 0.1 mg/M3 0.01 TLV
Contaminant in Basis for
Water and Soil Provisional Limit Recommendation
2,4-D 0.5 ppm (mg/1) Stokinger and
Woodward Method
59
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Pesticide Wastes
Option No. 1 - Adsorption with Powdered Activated Carbon.* The effec-
tiveness of powdered activated carbon on the removal of 2*4-0 from water has
been examined by Aly and Faus't, Sigworth, and Whitehouse. Aly
and Faust constructed adsorption isotherms for 2,4-D in accordance with the
Freundlich equation, from which the amount of activated carbon required
to reduce the 2,4-D concentration in water from 10 ppm to 1 ppm and 0.1 ppm
was calculated to be 85 mg/liter and 318 mg/liter respectively. Sigworth's
studies were conducted with initial 2,4-D concentrations of 1 and 6 ppm;
however, the results obtained were inconclusive because of the possibility
of employing inaccurate analytical procedures. Whitehouse investigated
the effects of pHs contact time, and carbon dosage on 2,4-D removal from
water, and showed that with an initial 2,4-D concentration of 100 ppm over
90 percent removal of 2,4-D could be achieved at pH values lower than 3.2
after one hour of mixing and a carbon dosage of 300 mg/liter. With a lower
2,4-D initial concentration of 10 ppm, a pH of 6, and one hour contact
time, 90 percent 2,4-D removal could be obtained with a carbon dosage of
120 mg/liter and 99 percent 2,4-D removal with a carbon dosage of 320 mg/
liter. Based on the results of the studies of Faust and Aly and Whitehouse,
the addition of powdered activated carbon to a liquid solution (preferably
at a lower pH) followed by stirring and filtration is an adequate method
for treating dilute 2,4-D wastes.
Option No. 2 - Adsorption with Granular Activated-Carbon Beds.* Al-
though the effectiveness of granular activated-carbon beds to remove 2,4-D
from water has not been discussed in the literature per se, Robeck et al
*The contaminated carbon could be regenerated in a multi-hearth furnace
under a controlled atmosphere at temperatures in excess of 1600 F, so that
the adsorbed impurities are voltalized and selectively oxidized from the
surface of the carbon.
-------
reported that following passage through the carbon columns, the concentration
of 2,4,5-T (which is simply 2,4-D with an additional aromated chlorine) in
0441
water was reduced from 3.6 ppb to 0.05 ppb. Treatment of waste water
containing a variety of pesticide wastes with granular activated-carbon
beds have been practiced by Fisons Pest Control Ltd. in England since 1955,
where over 99 percent removal of the pesticides are obtained. '
The treated effluent is diluted with river water before discharge to the
river, and the results of government biological surveys indicated no
effects of the discharge on the river. In the United States, both Rhodia
and Dow utilized granular activated-carbon beds in the treatment of their
2,4-D manufacture waste water. ' Activated-carbon bed adsorption
was also originally employed as the treatment procedure for the waste
water from 2,4-D manufacture at the Naugatuck Chemicals plant, Elmira,
Ontario, Canada, although the method was later abandoned due to the
high treatment cost associated with the removal of dichlorophenol at that
time (1951). Because of the adequate contact time provided and the fact
that it is a well established chemical engineering unit operation, adsorp-
tion with granular activated-carbon beds should be considered as one of
the most ^ju.s£a£4cu?y-j!iej^_dj_j^
Option No. 3 - Biological Degradation. The biological treatment of
2,4-D waste water has been investigated by Mills1630 and Sidwell.1781 Mills
reported that 2,4-D acid could be oxidized by bacterial action in the
laboratory, but his pilot plant work with trickling filter and activated
sludge systems were mainly concerned with the removal of dichlorophenol
from the 2,4-D manufacture waste water, and no data on the removal of
2,4-D were given. Si dwell described the Jacksonville, Arkansas project
on joint treatment of municipal waste water and 2,4-D manufacture waste
water from the Transvaal Inc. plant. Pretreatment of the industrial
effluent included processing through a crushed limestone filled neutrali-
zation ditch and an in-plant equilization pond, and a final pH adjustment
to 7.2 by automatic addition of slaked lime slurry in a continuous stirred
pit. The combined municipal-industrial waste water containing 2 to 4.2 mg/
liter phenoxy acids was then treated in an aerated lagoon and stabilization
pond system before discharge to the receiving stream. Although the
removal of chlorophenoxy acids by the lagoon and pond system ranged from
-------
only 49 to 80 percent, the stabilization pond effluent with typically 1.1
mg/liter chlorophenoxy acids was considered to be good quality, as sub-
stantiated by the results of the biological surveys of the upper receiving
stream conducted in December 1969 and December 1970. The continuous suc-
cessful operation of the aerated lagoon - stabilization pond system at
Jacksonville, Arkansas indicates that 2,4-D containing waste water when
combined with sewage could be adequately treated by biological methods.
_—-—^
Option No. 4 - Ion Exchange. The use of ion exchange columns to re-
move the sodium salt of 2,4-D from water has been examined by Aly and
1 c oc
Faust. The results of their studies showed that the sodium salt of
2,4-D when present in relatively high concentrations (120 mg/liter) could
be completely removed from water by strongly basic anion exchange resins,
and indicated that neutralization of 2,4-D to its sodium salt followed by
passage through ion-exchange columns is an adequate method for treating
dilute 2,4-D wastes.
Option No. 5 - Removal by Surface Active Agents. The removal of pes-
ticides from water by the use of surface active agents to produce a foam
0445
has been investigated by Whitehouse. Although 2,4-D was not included
in the study, the results with aldrin and dieldrin showed that up to 90
percent removal was attainable and demonstrated the value of the process
as a possible near future treatment method for other types of pesticides.
The other treatment methods for the removal of 2,4-D from water that
have been investigated include adsorption with clay, chemical coagulation,
and chemical oxidation. The works of Faust and Aly, Schwartz and
Whitehouse0445 all suggested that adsorption with clay was an unsatisfactory
method for removing 2,4-D from water. Faust and Aly ' examined the
effects of chemical oxidants on 2,4-D compounds and concluded that both
chlorine and potassium permanganate were ineffective in the removal of
2,4-D compounds from water. The laboratory studies of Faust and Aly
also showed that chemical coagulation with alum and ferric sulfate doses
up to 100 ppm were ineffective in removing 2,4-D. These processes are
therefore considered as inadequate methods for treating dilute 2,4-D
wastes.
-------
Concentrated Pesticide Wastes
Option No. 1 - Incineration. The complete and controlled high temper-
ature oxidation of 2,4-D in air or oxygen with adequate scrubbing and ash
disposal facilities offers the greatest immediate potential for the safe
disposal of pesticides. The research on incineration of pesticides con-
ducted by Kennedy et al at Mississippi State University has led to the
conclusion that 2,4-D approached complete combustion at temperatures as
low as 1,110 F and identified carbon monoxide, carbon dioxide, chlorine
and hydrogen chloride as the volatile products from burning of the 2,4-D
formulation at 1,650 pou06^»0053 jhe equilibrium product distributions
resulting from the thermal decomposition and combustion of 2,4-D at atmos-
pheric pressure and three temperatures, 2J90 F (1,200 C), 1,470 F (800 C),
930 F (500 C) have also been computed using the TRW Chemical Analysis
Program (Table 1). The results also indicate the possible formation of
hydrogen chloride, but that at higher air/fuel ratios, complete combustion
is approached and both methane and carbon monoxide are only present in
small quantities. It is expected that either a rotary kiln or liquid
combustor, depending upon the form of the waste, followed by secondary
combustion and aqueous or caustic scrubbing would be an acceptable disposal
method. Primary combustion should be carried out at a minimum of 1,500 F
for at least 0.5 seconds with secondary combustion at a minimum temperature
of 2,200 F for at least 1.0 second. The abatement problem may be simplified
by insuring against elemental chlorine formation through injection of steam
or methane into the combustion process. Incineration is also being con-
sidered by Rhodia, Inc., Portland, Oregon as a possible means of disposing
the solid and semi-solid wastes generated in 2,4-D manufacture. In
addition, combustion units designed for the disposal of chlorinated organic
wastes and capable of recovering chlorine in the form of usable hydrogen
chloride have been developed, and a 7,000 Ib/hr plant is now under con-
struction for E. I. du Pont de Nemours & Company in Victoria, Texas by
Union Carbide Corporation. Properly designed and operated incineration
is therefore considered as the best present and near future method for the
disposal of concentrated 2,4-D wastes.
63
-------
TABLE 1.
EQUILIBRIUM COMPOSITION OF 2, 4-D/AIR SYSTEM
(1 AtM PRESSURE) MOLE FRACTION, GAS PHASE*"1"
Wt %
Pesticide
100
70
50
20
Temp.
1200
800
500
1200
800
500
1200
800
500
1200
800
500
C
C
C
C
C
C
C
:C
C
C
C
C
CH4
2.329-4
3.522-3
4.171-2
1 .'002-4
1.520-3
1.832-2
-
6.T67-4
7.594-3
-
-
1 .045-3
CO
4.283-1
3.883-1
2.812-2
4.010-1
3.661-1
2.772-2
3.820-1
.3JS08-1
2.762-2
7.792-2
7.012-2
2.771-2
co2
1.574-4
2.151-2
1.982-1
1.380-4
1.912-2
1.925-1
1.253-4
1,756-2
1.911-1
1.560-1
1.638-1
1.9.24-1
H2
2.852-1
2.758-1
1.373-1
1.870-1
1.81-2-1
9,099-2
1.189-1
1.154-1
5.858-2
8.168-3
1.656-2
2.173-2
H20
2.530-4
1.400-2
1.870-1
1.585-4
8.671-3
1.222-1
1.000-4
5.292-3
7.836-2
4.322-2
3.543-2
2.916-2
KC1
2.859-1
2.967-1
4.077-1
1.875-1
1.930-1
2.499-1
1.192-1
1.220-1
1.522-1
5. 198- 2
5.199-2
5.300-2
HCN
-
2.671-4 2
2
2
2.772-4 3
3
4
6
6
6
Condensed
Phase Graphite
N2 Mol/ 100 G Feed
_
-
.238=1
,304-1
.983-1
.794-1
.883-1
.845-1
.621-1
.621-1
.750-1
2.575
2,667
3.297
1.472
1.558
2.213
0.554
0.633
1.293
-
-
0.056
*The data format used is an exponential form, i;;e. X.XX-Y is .equivalent to X.-XX10
Mole fractions less than 10 are indicated by -.
-------
Option No. 2 - Chemical Degradation. The use of chemical reagents to
decompose concentrated pesticide wastes to less toxic forms has also been
investigated by Kennedy et al. ' The Mississippi State work showed
that liquid ammonia and metallic sodium or lithium would completely decom-
pose 2,4-D, but the reagents are dangerous to use and the toxicity of the
degradation products are not known. The action of caustic alkalies would
only hydrolyze 2,4-D to the corresponding salts, and no further degradation
could be obtained. Based on these results and the superiority of inciner-
ation by comparison, chemical degradation could not be recommended as a
method for the disposal of concentrated 2,4-D wastes.
Option No. 3 - Application to Soil Surface. Research on the reduction
of 2,4-D waste process liquors into biologically inactive compounds by means
of application to and degradation in the soil surface has been conducted
at Alkali Lake in eastern Oregon under the direction of R. L. Goulding of
IJC.A ly^t;
Oregon State University since late 1969. ' The results of the
study to date suggested subsurface injection of 2,4-D as a useful, economic
approach to control airborne losses of the waste component, and indicated
clearly the apparent degradation of 294-D by soil microorganisms when
applied at the rate 250 Ib/acre equivalent of 2,4-D. Data derived from
samples taken from the actual test plots showed that the 2,4-D concentra-
tion in the soil layer subjected to subsurface injection has declined from
an initial 135 ppm to 30 ppm after a 480-day period. The Oregon State
work in progress thus provides strong support to the adequacy of the
soil surface application as a disposal method for concentrated 2,4-D
wastes.
Option No. 4 - Deep Well. Although 2,4-D is only sparingly soluble in
water, its persistence and stability in water and the potential contamination
of ground water make deep well at best a questionable method for the disposal
of 2,4-D. Incidents of ground water contamination that persisted for over
3 years leading to the damage of lawns, shrubs and crops, as a result of
the penetration of the 2,4-D waste water through permeable sediments after
0446
being discharged to rivers or lagoons have been reported. Deep well
-------
disposal of 2,4-D wastes is currently being practiced at Dow Chemical
•I 77D
Company, Midland, Michigan, but the method is not recommended by the
National Working Group on Pesticides, and should be considered only
under very special situations where hazards would be nonexistent.
The disposal of 2,4-D wastes in open pits, lagoons, unapproved land-
fill sites, and by on site burning or deep sea burial are not recommended
practices because of the obvious contributions to air and water pollution.
To summarize, the adequate methods for treating dilute 2,4-D wastes
are: (1) adsorption with powdered activated carbon; (2) adsorption with
granular activated-carbon beds; (3) biological degradation; and (4) ion
exchange.
The adequate methods for the disposal of concentrated 2,4-U wastes
are (1) incineration, and (2) soil surface application.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that disposal systems to handle both dilute and
concentrated 2,4-D will still be required at National Disposal Sites
located near formulators, users, and especially agriculture centers in
the near future. The dilute 2,4-L) wastes that will require treatment
include spent cleaning solutions for 2,4-D containers and any other 2,4-D
contaminated waste water. The concentrated 2,4-D wastes that will require
treatment include any surplus, contaminated, partially or fully degraded
pesticides.
The processes recommended for the treatment of dilute 2,4-D wastes at
National Disposal Sites are:
-------
Process
Activated-
Carbon Beds
Ion Exchange
Biological
Degradation
Order of Preference
First Choice
Second Choice
Third Choice
Remarks
Demonstrated technology on commercial
scale; also adequate for removal of
the sodium salt and esters of 2,4-D
and most other types of pesticides
from waste water.
Demonstrated technology; requires
neutralization to the sodium salt
first and not adequate for the
removal of the 2,4-D esters from
water.
Demonstrated technology on commercial
scale; requires dilution with muni-
cipal sewage before treatment in
aerated lagoons and stabilization
ponds.
The processes for the treatment of concentrated 2,4-D wastes at
National Disposal Sites are:
Process
Incineration
Soil Surface
Application
Order of Preference
First Choice
Second Choice
Remarks
Demonstrated technology; applicable to
the disposal of organic pesticide wastes;
possibility of recovering chlorine in
the form of usable hydrogen chloride.
Demonstrated technology; also applicable
to the disposal of other types of herbi-
cides that are degradable by soil micro-
organisms.
It should be noted that the activated-carbon bed and biological
degradation processes could also be employed in the treatment of other
types of dilute aryloxalkylcarboxylic acid wastes, such as 2,4S5-T and
MCPA wastes. To dispose of other types of concentrated arloxalkylcar-
boxylic acid wastes, because of the lack of supporting data on soil
surface application, incineration is the only recommended process.
-------
7. REFERENCES
0062. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr. Chemical
and thermal methods for disposal of pesticides. Residue Reviews,
29: 89-104, 1969.
0063. Kennedy, M. V., B. J. Stojanovic, and F, L. Shuman, Jr. Chemical
and thermal aspects of pesticide control. Journal of Environ-
mental Quality. 1 (1): 63-65, Jan. 1972.
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards, p.35-40,
Aug. 1971.
0278. Code of Federal Regulations. Title 49--transportation, parts 71
to 90. (Revised as of January 1, 1967). Washington, U.S.
Government Printing Office, 1967. 794p.
0441. Robeck, 6. G., K. A. Dostal, J. M. Cohen, and J. F. Kreissl.
Effectiveness of water treatment processes in pesticide removal.
Journal of American Water Works Association, 57(2): 181-199,
Feb. 1965.
Whitehouse, J. D. A study of the removal of pesticides from water.
Research Report No.8, Water Resources Institute, University of
Kentucky, Lexington, Kentucky, 1967. 175 p.
Faust, S.D., and 0. M. Aly. Water pollution by organic pesticides.
Journal of American Water Works Association. 56(3): 267-279,
Mar. 1964.
The Working Group on Pesticides. Ground disposal of pesticides:
the problem and criteria for guidelines. Washington, U.S.
Government Printing Office, 1970. 55 p.
Finkelstein, H., Comp. Air pollution aspects of pesticides.
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. 173 p.
0509. Metcalf, R. L. The chemistry and biology of pesticides, In_
pesticides in the environment, v.l part 1. Ed. by R. White-
Stevens. New York, Marcel Dekker, Inc., 1971. p.1-144.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. April 1, 1968.
Washington, Federal Water Pollution Control Administration.
234 p.
0445.
0446.
0448.
0449.
-------
0620. The Working Group on Pesticides. Information available on disposal
of surplus pesticides, empty containers and emergency situations.
Washington, U. S. Government Printing Office, 1970. 52 p.
0621. The Working Group on Pesticides. Summary of interim guidelines for
disposal of surplus or waste pesticides and pesticide containers.
Washington, U.S. Government Printing Office, 1970. 25 p.
1035. Lambden, A. E., and D. H. Sharp. Treatment of effluents from the
manufacture of weedkillers and pesticides. Manufacturing Chemist,
31: 198-201, May 1960.
1277. Bailey, J. B., and J. E. Swift. Pesticide information and safety
manual. Berkeley, California, University of California,
Agricultural Extension Service, 1968. 147 p.
1610. Pesticides: present and future. Chemical Engineering, 76 (8):
133-140, Apr. 7, 1969.
1618. Melnikov, W. N. Chemistry of the pesticides. New York, Springer-
Verlag, 1971. 480 p.
1630. Mills, R.E. Development of design criteria for biological treat-
ment of an industrial effluent containing 2,4-D waste water.
Proceedings; l4th Industrial Waste Conference, Purdue University,
Lafayette, Indiana, 1963. p.340-358.
1631. Sharp, D. H. The disposal of waste materials in the pesticide
industry. J_n_ Disposal of industrial waste materials: papers
to be read at the Conference at Sheffield University. 17th-19th
April, 1956. London, England, Society of Chemical Industry,
1956. p. 9-15.
1635. Sigworth, E. A. Identification and removal of herbicides and
pesticides. Journal of American Water Works Association, 57(8):
1016-1022, Aug. 1965.
1636. Aly, O.M., and S. D. Faust. Removal of 2,4-dichlorophenoxyacetic
derivatives from natural waters. Journal of American Water Works
Association. 57(2): 221-230, Feb. 1965.
1718. United States Tariff Commission. Synthetic organic chemicals:
United States production and sales, 1970. Washington, U.S.
Government Printing Office, 1972. 262 p.
1743. Halswitt, C., and J. A. Mraz. HC1 removed from chlorinated organic
waste. Chemical Engineering. 79 (11): 80-81, May 15, 1972.
1754. Goulding, R. L. Waste pesticide management annual progress report,
July 1, 1970 - April 12, 1971. Environmental Sciences Center,
Oregon State University, Corvallis, Oregon. 8 p.
69
-------
1755. Goulding, R. K., M. L. Montgomery, and W. S. Stanton. Waste
pesticide management interim progress report, 26 January, 1972.
Environmental Health Services Center, Oregon State University,
Con/all is, Oregon. 34 p.
1756. Schwartz, H. G. Adsorption of selected pesticides on activated
carbon and mineral surfaces. Environmental Science and Tech-
nology, 1(4): 332-337, Apr. 1967.
1757. Schwartz, H. G. Microbial degradation of pesticides in aqueous .
solutions. Journal of Hater Pollution Control Federation,
39(10): 1701-1714, Oct. 1967.
1774. Personal communication. A. Livingston, Blue Spruce Co. to C.C. Shin,
TRW Systems, May 25, 1972. 2,4-D manufacture.
1775. Personal communication. G. Lawrence, Diamond Shamrock Chemical Co.
to C. C. Shih, TRW Systems, May 26, 1972. 2,4-D manufacture.
1776. Personal communication. D. Robinson, Rhodia Inc., Chipman Division
to C. C. Shih, TRW Systems, May 25, 1972. 2,4-D manufacture
waste treatment.
1777. Personal communication. R. Gitschlag, Rhodia Inc., Chipman Division
to C. C. Shih, TRW Systems, May 25, 1972. 2,4-D manufacture
waste treatment.
1778. Personal communication. F. Chase, Dow Chemical Co., to C. C. Shih,
TRW Systems, May 26, 1972. 2,4-D manufacture waste treatment.
1779. Personal communication. W. Reynolds, Hercules Inc., to C. C. Shih,
TRW Systems, May 26, 1972. 2,4-D manufacture waste treatment.
1781. Sidwell, A. E. Biological treatment of chlorophenolic wastes.
Environmental Protection Agency, Water Quality Office, Water
Pollution Control Research Series 12130 EGK. Washington, U.S.
Government Printing Office,, June 1971. 177 p.
1789. Aly, O.M., and S. D. Faust. Studies on the removal of 2,4-D and
2,4-DCP from surface waters. Proceedings; 18th Industrial
Waste Conference, Purdue University, Lafayette, Indiana, 1963.
p.6-8.
70
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name 2.4-i) (135)
Structural Formula
IUC Name 2,4-Ui chlorophenoxyaceti c acid
Common Names
rr1
Molecular Wt. 221.05 Melting Pt. 13S-14Qr. Boiling Pt.
Density (Condensed) @ Density (gas) @
Vapor Pressure (recommended 55 C and 20 0
0.4 mm &
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 0.06% at 25C Hot Water Ethanol
Others: Highly soluble in ether, benzene, carbon tetrachloride, acetone, and tetra and
pentachloroethanes vt'
Acid, Base Properties A typical organic acid that readily forms sodium,
and ammonia salts.
Highly Reactive with
Compatible with
Shipped in fiber drums and bags.
ICC Classification Coast Guard Classification
Comments 2,4-D Is a white crystalline substance when pure and has practically no odor;
technical grade compound, however, smells more orlp^^ lii»»
References (1) 0509
(2) 1618
71
-------
PROFILE REPORTS ON
ORGANOPHOSPHORUS PESTICIDES
Methyl Parathion (274). Parathion (321), Demeton (491),
Guthion (495)
1. GENERAL
Introduction
The practical development of organophosphorus insecticides is largely
due to the original extensive work of G. Schrader beginning in 1937. Thou-
sands of organophosphorus compounds of many types have been evaluated for
insecticidal properties and the current commercially used compounds include
insecticides that are marketed in multimillion pound quantities. The num-
ber of highly toxic organophosphorus compounds is virtually limitless and
their suitability as insecticides depends on their physical and chemical
properties and how safely they may be employed. Of the four organophosphorus
insecticides included in this Profile Report: parathion and methyl parathion
represent the two most widely used broad spectrum organophosphorus insecti-
cides, demeton is one of the more successful plant systemic insecticides,
and Guthion is one of the most toxic organophosphorus insecticides with
prolonged activity.
Organophorphorus insecticides are among the fastest growing products
in the pesticide industry. The U.S. production figures for parathion and
methyl parathion from the year 1960 to 1967 are:0449'1610
Parathion
Methyl Parathion 1^94
Annual Production (Thousand Ib)
1960 1961 1962 1963 1964
7,434
11794
8,423 8,786 — — 12,768
18£27 16,156 15^99 18£40
1965
16,607
29; 11
1966
19,444
35,862
1967
11,361
33344
73
-------
Individual production figures for Guthion and demeton are not available, but
0449
based on the quantities used on crops, it is estimated that 4,142,000
Ib of Guthion and 377,000 Ib of demeton were manufactured in 1964. The four
organophosphorus insecticides investigated in this Profile Report accounted
for approximately 60 percent of the total organophosphorus insecticide
production in 1964.0449
Manufacture
Parathion and Methyl Parathlon. Both insecticides are manufactured from
sodium p-nitrophenolate; parathion by reacting 0,0-diethyl phosphorothio-
chloridate with the sodium compound, and methyl parathion from the reaction
1 f\ 1 ft
of the equivalent 0,0-dimethyl compound :
(R0)2 P Cl + NaO-/ V-NO? -» (R0}2 P -0-^ V--N0? + NaCl
This process is usually carried out in aqueous medium or in organic solvents
(chlorobenzene, xylene, aliphatic ketones). The phosphorothiochloridates
necessary for the synthesis of the parathions are prepared by reacting the
appropriate alcohol with phosphorus pentasulfide, followed by chlorination
1618
4 ROM + P2S5 -» 2(RO)2 PSH + H2$
2(RO) PSH + 3 C12 -» 2(RO)2 PCI + 2HC1 + $2C12
Large scale commercial facilities for the manufacture of parathion and
1592 1531
methyl parathion in the United States include the following ' :
Kerr-McGee Chemical Corporation, Hamiltion, Mississippi
Kerr-McGee Chemical Corporation, Los Angeles, California
Monsanto Chemical Company, Anniston, Alabama
Stauffer Chemical Company, Mount Pleasant, Tennessee
74
-------
Demeton. Demeton is produced by the reaction of 0,0-diethyl phosphoro-
thiochloridate with 2-hydroxydiethyl sulfide in the presence of sodium hydroixde
1 filfl
or carbonate of the alkali metals :
(C2H50)2 P Cl + HOCH2CH2 SCgHg + NaOH
f,
NaCl
Demeton contains approximately two parts of the thiono-isomer and one part
of the thiol-isomer, and the thiono-isomer compound obtained is partially
isomerized directly in the process of preparation.
Guthion. Guthion is produced by the reaction of the N-halomethyl
derivatives of azimidobenzoyl with salts of dimethyldithiosphosphoric
acid1618:
(QUO), a | 2 32 + NaBr
3 2 -»
When the methylbromo derivative is used, Guthion is obtained in almost
quantitative yield. The 4-oxo-3,4-dihydro-l,2-,3-benzotriazine necessary
for the synthesis can be prepared from the amide of anthranilic acid by
ifil ft
the action of sodium nitrite in acid medium :
+HN02 - N .: +2H2°
75
-------
Both demeton and Guthion are manufactured by Chemagro Corporation at
their Kansas City, Missouri facility.
Uses
The principal application areas of the four organophosphorus in-
secticides have been summarized by Van Wazer (Table 1).
Sources and Types of Pesticide Wastes
The sources of pesticide wastes may include the following :
(1) Pesticide manufactures; (2) pesticide formulators; (3) pesticide
wholesalers; (4) professional applicators; (5) cooperage facilities that
recondition drums; (6) agricultural users; (7) government facilities that
store, transport, and use pesticides; (8) urban and suburban home and home
garden users; (9) commercial and industrial processes including those from
rug and fabric treatment facilities manufacturing plants9 hospitals, etc.
In general, pesticide wastes can be classified as either diluted or
concentrated wastes. Diluted pesticide wastes include those generated in
the waste waters of the manufacturers, formulators, agricultural runoffs,
and possibly spent caustic solutions used to clean empty pesticide con-
tainers. Concentrated pesticide wastes include any unused or contaminated
pesticides, pesticide materials left in containers after emptying, sludges
formed in treating waste water containing pesticides, sawdust or straw used
to soak up accidental pesticide spills.
Organophosphorus pesticides appear as waste stream constituents
in varied forms and concentrations. Typical waste streams containing
organophosphorus pesticides are as follows:
Aqueous slurries containing 10 percent mixed Malathion •
and Parathion; 5 to 7 percent mixed intermediates;
3 to 4 percent carbaryls; 5 to 10 percent diatomoceous
earth; 3 to 5 percent organic solvents
-------
TABLE 1 162°
APPLICATION AREAS OF ORGANOPHOSPHORUS INSECTICIDES
Crops
Insecticides
Guthion
Methyl
Parathion
Parathion
Demeton
Cotton
X
X '
X
x •
Fruits,
Fruit, Deciduous
Citrus & Nuts
X
X X
X
Grasses Orna-
& Forage ments
X X
X X
Sugar
Small Cane
Potatoes Grains & Beets
X
XXX
X '
Soy Stored
Beans Crops Tobacco Vegetables
X
X
X X X
-------
Solid wastes containing 0.5 percent parathions
Process solution containing 10 percent demeton and Guthion.
Solid wastes containing 0.5 percent demeton and Guthion.
More detailed information relating to the forms and quantities of waste
organophosphorus pesticides is presented in the Appendix Volume titled
Waste Forms and Quantities.
Physical and Chemical Properties
The physical and chemical properties of the four organophosphorus
insecticides are included in the attached worksheets. Since demeton
contains a mixture of 0,0-diethyl 0-(and S-) ethyl-2-thioethyl phosphoro-
thioates, individual property worksheets for the thiono-isomer and the
thiol-isomer are also attached.
2. TOXICOLOGY
All the organophosphorus insecticides function by the common mechanism
of cholinesterase inhibition. The enzyme cholinesterase is an essential
constituent of the nervous system not only of the Insecta but also of all
higher animalss and when inhibited is no longer able to carry out its normal
function of rapid removal and destruction of the neurohormone acetylcholine
from the nervous synapse. As a result, acetycholine accumulates and disrupts
the normal functioning of the nervous system, giving rise to the typical
cholinergic systems associated with 0-P poisoning. In insects the poisoning
leads to hyperactivety, tremors, convulsions, paralysis, and death. In
higher animals, these cholinergic effects are translated into muscarinic
effects such as nausea, salivation9 lacrimation and myosis; nicotinic effects
such as muscular fasciculations, and central effects such as giddiness,
tremulousness, coma, and convulsions. The symptoms of poisoning are
usually rapid in onset, and death caused by respiratory failure can occur
within a few minutes to several hours following exposure. In cases of
oral ingestion death has been essentially instantaneous.
78
-------
The four organophosphorus insecticides included in this Profile Report
are all highly toxic and exhibit similar toxicity symptoms, although the
toxicity of methyl parathion for higher animals is somewhat lower and both
methyl parathion and Guthion penetrate the skin with greater difficulty than
parathion or demeton. All four organophosphorus insecticides can be absorbed
through the skin and excessive skin contact can lead to death. Special
precautions should be taken to prevent both skin contamination and inhalation.
The relative acute oral and dermal LD5Q values of the four organo-
phosphorus insecticides to the rat range from 2 to 14 mg/kg and 7 to 220
mg/kg and are representative of the hazards associated with the use of
specific insecticides (Table 2). Demeton contains both the thiol-isomer
and the thiono-isomer, and the thiol-isomer has been identified to be far
more toxic than the thiono-isomer; the respective acute oral LDKn values
1618
to the rat are 1.5 and 30 mg/kg. The American Conference of Governmental
Industrial Hygienists 1971 recommended Threshold Limit Values (TLV) for the
compounds in mg/M3 of air are0225:parathion, 0.1; methyl parathion, 0.2;
demeton, 0.1; Guthion (azinphosmethyl)0.2.
The 48-hour median tolerance limits (TLm) for the organophosphorus
insecticides for various types of fresh water organisms have been established
by the Federal Water Pollution Control Administration (Table 3). To provide
reasonably safe concentrations of these materials in receiving waters,
application factors of 1/100 should be used with these values. Another
comparision of the toxicity of the organophosphorus insecticides to fish
life are their 96-hour TL values for the bluegill sunfish in mg/liter:
1611
parathion, 0.095; methyl parathion, 1.9; Guthion, 0.0052. These data
indicate that Guthion is the most toxic of the organophosphorus insecticides
to fish life, and possibly to other forms of aquatic life.
Most of the organophosphorus insecticides do not accumulate in animal
tissues. However, Guthion has been found in fish several weeks after being
exposed in laboratory experiments to sub-lethal concentrations in water.
-------
TABLE 2
ACUTE ORAL AND DERMAL LD
50
VALUES
OF ORGANOPHOSPHORUS INSECTICIDES FOR WHITE RATS
1277
Insecticides
Pa rath ion
Methyl Parathion
Demeton
Guthion
Oral LD5f)
Males
13
14
6.2
13
(mg/kg)
Females
3.6
24
2.5
, 11
Dermal
Males
21
67
14
220
LD5Q (mg/kg)
Females
6.8
67
8.2
220
TABLE 3
48-HOUR TLm VALUES FROM STATIC BIOASSAY
(in micrograms per liter)
0536
Insecticides
Stream
Invertebrate
Species
Cladocerans Fish
TL_ TL
Species
m
Gammarus
TLm Lacustris
m Species m TLm
11 D. pulex 0.4 Bluegill 47 6
D. magna 4.8 Bluegill 8000
D. pulex 14 Bluegill 8181
8 D. magna 0.2 Rainbow t. 1U 0.3
Parathion
Methyl
Parathion
*
Demeton
Guthion
P.Californica
P.Californica
* This is listed as demelton in.the orginial table.
80
-------
3. OTHER HAZARDS
Parathion and metyl parathion are unstable to heat. Parathion should
not be heated above 100 Cs and methyl parathion may explode at 120 C. For
an adequate safety margin, methyl parathion should not be heated above
55 C. When heated to decomposition, all four organophosphorus in-
secticides emit highly toxic fumes of nitrogen oxides, phosphorus, and
sulfur compounds.
The fire hazards of organophosphorus insecticides are relatively slight
and are far outweighed by their health hazards. Parathion has a flash point
©
of about 120 C, and 80 percent methyl parathion in xylene has a flash point
of 46 C. The hazards from fires involving organophosphorus insecticides
have been investigated and it was concluded that: first, most of the
insecticide is destroyed by decomposition before it can evaporate; second,
over 90 percent of the evaporting insecticide is destroyed by the flames;
and third, the evaporating portion is considerably diluted by the time it
reaches anyone. When all these factors are considered, it is apparent
that a fire involving tons of organophosphorus insecticides may occur without
causing serious injury to anyone nearby.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, and Transportation
Great care should be exercised in handling the organophosphorus in-
secticides because of their high toxicity and the dangers of absorption
through the skin. The use of rubber glovess goggles, a respirator, and
other protective clothing is advisable. Any material spilled on the skin
should be immediately removed with plenty of water and soap. If clothing
has been contaminated, it should be removed as soon as possible and the
skin washed as above. Periodic examination of blood cholinesterase
levels is also of value in the early detection of over-exposure.
-------
Organophosphorus insecticides should be stored in well ventilated
areas in a separate building, away from any foodstuffs, feeds, or any other
material intended for consumption by humans or animals. In addition,
they should not be stored near sources of heat such as furnaces, heating
kettles, and steam lines. Ample warning signs should be posted in storage
areas.
Adequate procedures for the transportation of parathion and methyl
parathion have been established by the Department of Transportation.
Label requirements, as well as the maximum quantites permitted to be
shipped in one outside container, are also specified. Although shipping
regulations for demeton and Guthion are not specifically mentioned in
9
the reference, the same rules governing the transportation of the parathions
should also apply here.
The National Agricultural Chemicals Associations has established a
Pesticide Safety Team Network with Area Coordinators throughout the country
to provide nationwide 24-hour emergency service. The network became operational
on March 9, 1970 (with a central telephone number: [513] 916-4300) and
should be consulted in all cases of accidents, spills, leakage, fires, and
other types of disasters involving Organophosphorus insecticides.
Disposal/Reuse
Contaminated or degraded Organophosphorus insecticides could not be
practically considered for reprocessing. The safe disposal of the
insecticides is defined in terms of provisional limits in the atmosphere
and a potable water source and/or marine habitat. The provisional
limits are as follows:
-------
Contaminant Basis for
in Air Provisional Limits Recommendation
Parathion 0.001 mg/M3 0.01(TLV
Methyl Parathion 0.002 mg/M3 0.01 TLV
Demeton 0.001 mg/M3 0.01 TLV
Guthion 0.002 mg/M3 0.01 TLV
Contaminant Basis for
In Mater and Soil Provisional Limits Recommendation
Parathion 0.005 ppm (mg/1) Stokinger &
Woodward Method
Methyl Parathion 0.01 ppm (mq/1) Stokinger &
Woodward Method
Demeton 0.005 ppm (mg/1) Stokinger &
Woodward Method
Guthion 0.01 ppm (mg/1) Stokinger &
Woodward Method
The recommended criterion for release of the organophbsphorus
insecticides to the water environment is so low that none of these
insecticides (with the possible exception of methyl parathion) should
be applied directly in or near the marine habitat without danger of
causing damage. To meet the provisional limits, effluents from plants
treating waste water containing the organophosphorus insecticides must
normally be diluted in municipal sewers (with an approximate dilution
ratio of 10:1) or large creeks or holdings ponds before discharge to
lakes, rivers, or oceans.
The permissible criteria for the organophosphorus insecticides in
the surface water for public water suppl-ies, however, is much higher and
the limit established relative to parathion is expressed as 0.1 mg/liter
parathion equivalent. This equivalence is the ratio that a given
cholinergic insecticide has to parathion as unity in its cholinesterase
inhibiting properties.
These limits have been set with relation only to human intake directly from
a related domestic water supply and do not take into account the consequence
of higher and possible objectionable concentrations in fish available to be
eaten by man.
-------
5. EVALUATION OF CURRENT AND NEAR FUTURE DISPOSAL PROCESSES
Dilute Pesticide Wastes
Option No.1 - Adsorption with Powdered Activated Carbon. The effectiveness
of powdered activated carbon on the removal of parathion from water has
been reported by Robeck et al and Sigworth. Robeck et al investigated
initial parathion concentrations ranging from about 1 to 10 ppb and found
that over 99 percent of the parathion could be removed with powdered activated
carbon dosages of 5 to 20 ppm. Sigworth1s studies were conducted with higher
initial parathion concentrations of 10 ppm and concluded that 5 ppm carbon
dosages in a treatment plant could be expected to give 75 percent removal.,
whereas dosages of 10 ppm would accomplish 90 percent removal of most of
the pesticides in extensive use today. The necessary carbon dosage and
the associated degree of removal for methyl parathion, demeton, and
Guthion should be in the same range as those for parathion. Although the
addition of powdered activated carbon to a liquid solution followed by
stirring and filtration is not necessarily the best method when large quantities
of aqueous wastes have to be dealt with-, the procedure is indeed an adequate
and acceptable technique for treating dilute organophosphorus pesticide
wastes.
*
Option No.2 - Adsorption with Granular Activated-Carbon Beds. The
effectiveness of granular activated-carbon beds to remove parathion from
0441
water has also been investigated by Robeck et al. Following passage
through two carbon columns, it was found that the parathion concentration
in water was reduced from 11.4 ppb to 0.05 ppb. Treatment of waste water
containing a variety of pesticide wastes with granular activated-carbon
bed have been practiced by Fisons Pest Control Ltd., in England since
1955, where over 99 percent removal of the pesticides is obtained.
The treated effluent is diluted with river water before discharge to the
river, and the results of government biological surveys indicated no effects
*
The contaminated carbon may be regenerated in a multi-hearth furnace under
a controlled atmosphere at temperatures in excess of 1,600 F, so that the
adsorbed impurities are voltali zed and selectively oxidized from the surface
of the carbon.
-------
of the discharge on the river. Chemagro's organophosphorus pesticide
plant at Kansas City, Missouri, which also manufactures demeton and
Guthion, is at the present considering the installation of granular
activated-carbon beds for the treatment of waste water generated at the
plant. Because of the adequate contact time provided and the fact
that it is a well established chemical engineering unit operation,
adsorption with granular activated-carbon beds should be considered as
one of the most satisfactory methods for treating dilute organophosphorus
pesticide wastes.
Option No.3 - Alkaline Hydrolysis. All the four organophosphorus
insecticides considered in this Profile Report are readily hydrolyzed in
alkaline medium. Ketelaar reported the hydrolysis constants of parathion
and methyl parathion in alkaline solution at 15 C as 0.00215 and 0.0092
liter min mol~ , respectively. The actual reaction rate is
bimolecular and depends on the hydroxyl ion concentration in the solution.
The half life times for parathion and methyl parathion in a 1 N hydroxide
1 /-I o
solution are 32 min and 7.5 min respectively. According to Melnikov,
the time for 50 percent hydrolysis of the thiono-isomer of demetion at
20 C and pH 13 is 75 min and that of the thiol-isomer is 0.85 min. The
hydrolysis rate of Guthion in alkaline medium is not available directly,
1 fil ft
although Melnikov indicates at pH 5 50 percent of the Guthion is
hydrolyzed at 20 C in 240 days and that in alkaline solution Guthion
breaks down several times faster. From this information, it is apparent
that alkaline hydrolysis in a properly designed mixing tank with sufficient
residence time is an adequate process for treating dilute parathion,
methyl parathion, and demeton wastes. The Kerr-McGee Los Angeles Plant,
which manufactures parathion and methyl parathion, treats its waste
water by alkaline hydrolysis in a tank followed by a holding lagoon
1529
before discharge to the municipal sewer.
Option No.4 - Activated Sludge Treatment. Stutz and Coley and
Stutz1039 reported the biological treatment of waste water containing -
parathion and methyl parathion manufacturing wastes by the activated
sludge process at Monsanto's Anniston, Alabama plant. The processing
85
-------
steps for waste treatment involve chlorination, holding in a raw waste
lagoon, limestone neutralization, and pH adjustment with soda ash or
caustic before feeding to the activated sludge unit. Plant effluent
analysis indicates parathion concentrations less than 0.1 mg/liter, and
since the effluent is discharged into a relatively large creek (with an
approximate dilution ratio of 100:1) and then to a river, a factor of
safety for fish toxicity of at least 100:1 is provided. The biological
treatment of waste waters containing demeton and Guthion with an
aerated lagoon preceding the activated sludge unit has been investigated
by Lue-Hing and Brady on the pilot scale, and the system developed
was found to be totally effective for detoxification. As a result of the
successful study, a full scale design with a two-stage activated sludge
process has been proposed as the secondary waste water treatment unit at
Chemagro's Kansas City, Missouri organophosphorus pesticide manufacturing
facility. As of today, however, Chemagro is still conducting studies with
a 1/5 full scale aeration tank in its secondary waste water treatment
effort. With proper biological acclimation, the activated sludge
process preceded by the necessary primary waste treatment steps is an
adequate and satisfactory method for treating dilute organophosphorus
pesticide wastes.
Option No.5 - Removal by Surface Active Agents. The removal of
pesticides from water by the use of surface active agents to produce a
0445
foam has been investigated by Whitehouse. Although organophosphorus
pesticides were not included innthe study, the results with aldrin and
dieldrin showed that up to 90 percent removal was attainable and
demonstrated the value of the process as a possible treatment method
for other types of pesticides.
The other treatment processes for the removal of organophosphorus
insecticides from water that have been investigated include coagulation
followed by sand filtration, and chemical oxidation with chlorine, potassium
0441
permanganate, and ozone. Organophosphorus insecticides are not removed
by coagulation and filtration, and in the case of parathion, chemical
-------
oxidation will sometimes render the more toxic paraoxon as a product.
These processes are therefore considered as inadequate methods for
treating dilute organophosphorus pesticide wastes.
Concentrated Pesticide Wastes
Option No.l - Incineration. The complete and controlled high
temperature oxidation of organophosphorus insecticides in air or oxygen
with adequate scrubbing and ash disposal facilities offers the greatest
immediate potential for the safe disposal of these pesticides. The
research on incineration of pesticides conducted by Kennedy et al at
Mississippi State University has led to the conclusion that temperatures
at or nearvl ,800jF will be sufficient to degrade 99 percent or more of
most reagent-grade pesticides and commercial pesticidal formulations. '
It is expected that either a rotary kiln or liquid combustor,
depending upon the form of the waste, followed by secondary combustion
and scrubbing would be an acceptable disposal method. Primary combustion
should be carried out at a minimum of 1,500 F for at least 0.5 seconds
with secondary combustion at a minimum temperature of 2,200 F for at
least 1.0 second. The equilibrium product distributions resulting from
the thermal decomposition and combustion of parathion at atmospheric
pressure and three temperatures, 2,190 F (1,200 C), 1,470 F (800 C),
930 F (500 C), have been computed using the TRW Chemical Analysis Program
(Table 4), and the results indicate the possible formation of objectionable
&
combustion products such as hydrogen sulfide and phosphorus oxides. As
the same combustion products will be obtained in the incineration of the
other three organophosphorus insecticides, an adequate gas clean up
system must be installed to alleviate the air pollution problem. Monsanto's
Anniston, Alabama parathion and methyl parathion manufacturing facility
uses incineration to dispose of its semi-solid residue wastes, and has
proven that an aqueous scrubbing system followed by a mist eliminator is
effective in recovering 99.9 percent of the phosphorus pentoxide.
*
A higher air/fuel ratio will lead to the formation of sulfur dioxide
instead of hydrogen sulfide.
87
-------
TABLE 4
EQUILIBRIUM COMPOSITION OF PARATHION/AIR SYSTEM
(1 Atm Pressure) MOLE FRACTION, GAS PHASE**1"
Condensed
Wt. % Phase Graphite
Pest1c1dt Temp. CH^ CO COo H2 O HCN H=S N; P40£ Mol/IOOG Feed
100 1200 C 6.584-4 3.784-1 1.229-4 4.795-1 3.834-4 1.572-4 5.140-2 3.025-2 - 1.693
800 C 1.224-2 2.812-1 1.129-2 5.142-1 1.890-2 - 9.095-2 4.631-2 2.316-2 2.298
500 C 1.460-1 1.983-2 9.855-2 2.568-1 2.467-1 - 1.322-1 6.622-2 3.314-2 2.748
70 1200 C 3.384-4 3.693-1 1.171-4 3.438-1 2.683-4 3.417-4 3.538-2 1.993-1 - 0.740
800 C 5.736-3 2.937-1 1.230-2 3.520-1 1.351-2 - 6.082-2 2.446.1 1.564-2 1.199
500 C 6.884-2 2.170-2 1.181-1 1.764-1 1.854-1 - 8.288-2 3.254-1 2.081-2 1.800
50 1200 C 1.795-4 3.632-1 1.132-4 2.504-1 1.921-4 3.700-4 2.424-2 3.208-1 - 0.105
800 C 2.854-3 3.020-1 1.301-2 2.483-1 9.799-3 - 4.195-2 3.695-1 1.092-2 0.461
500 C 3.465-2 2.319-2 1.347-1 1.251-1 1.405-1 - 5.545-2 4.719-1 1.395-2 1.123
20 1200 C - 8.885-2 1.109-1 3.222-2 9.896-2 - 9.140-3 6.484-1 5.013-3
800 C - 6.655-2 1.342-1 4.287-2 7.917-2 - 1.913-2 6.521-1 5.042-3
500 C 5.524-3 2.581-2 1.669-1 4.995-2 6.245-2 - 2.017-2 6.637-1 5.132-3 0.022
~*SiialT amounts of CS2, COS, P2, P4, and $2 are also present at 1200 C.
The data format used is an exponential form, i.e.
t -4
Mole fractions less than 10 are Indicated by -.
-Y
The data format used is an exponential form, i.e., X.XX-Y is equivalent to X.XX 10
-------
The other major air pollutant of concern, sulfur dioxide, is undoubtedly
removed by the same system. Properly designed and operated incineration
is therefore considered as the best present and near future method for
the disposal of concentrated organophosphorus pesticide wastes.
Option No.2 - Chemical Degradation. The use of chemical reagents to
decompose concentrated pesticide wastes to less toxic forms has also been
investigated by Kennedy et ai.0062>0063 The Mississippi State work has shown
that: (1) sulfuric and nitric acids are not effective in destroying the
organophosphorus pesticide malathion; (2) sodium hydroxide from 2N.to 8N
concentration will break down malathion sufficiently to yield inorganic
phosphates; and (3) liquid ammonia and metallic sodium or lithium will
completely decompose malathion, but the reagents are dangerous to use
and the toxicity of the degradation products are not known. Based on the
results to date, treatment with sodium hydroxide is the only recommended
chemical method for the disposal of concentrated organophosphorus pesticide
wastes.
Option No.3 - Sanitary Landfill. Soil burial of organophosphorus
pesticide wastes, because of their relatively short persistence time in
D7f)fi DdRR
soil of one to three months, ' is a satisfactory means of disposal
provided the site is acceptable from a geologic and ground water hydrology
standpoint and has been approved as a sanitary landfill by appropriate
;ra1
0448
authorities. The practice of disposing large quantities of concentrated
pesticides at any one sanitary landfill site, however, is not recommended.
Option No.4 - Deep Hell. Although a properly planned, properly designed,
properly constructed, and properly operated deep well disposal installation
is an expensive investment, it may still be the only economic alternative
for pesticide manufacturers and large f emulators to dispose of large
volumes of pesticide wastes from productive operations, however, the
method is uneconomical for the occasional disposal of small volume pesticide
wastes. The solubility in water of the four organophosphorus insecticides
considered in this report are: parathion, 24 ppm; methyl paration, 50 ppm;
-------
demeton, 60 ppm; Guthion, 30 ppm. Because of the potential contamination
of ground water, deep well disposal of organophosphorus pesticide wastes
is not recommended by the National Working Group on Pesticides, and
the method should be considered only under very special situations where
hazards would be nonexistent.
The disposal of organophosphorus pesticide wastes in open pits,
lagoons, unapproved landfill sites, and by on-site burning or deep-sea
burial are not recommended practices because of the obvious contribu-
tions to air and water pollution.
To summarize, the adequate methods for treating dilute organophosphorus
insecticides are: (1) adsorption with powdered activated carbon; (2) adsorption
with activated-carbon beds; (3) alkaline hydrolysis (except for Guthion);
and (4) activated sludge treatment. The adequate methods for the disposal
of concentrated organophosphorus pesticide wastes are: (1) incineration;
(2) chemical degradation with 2N to 8N sodium hydroxide solution; and (3)
approved sanitary landfill.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that disposal systems to handle both dilute and con-
centrated organphosphorus pesticide wastes will be required at National
Disposal Sites located near pesticide manufacturers, formulators, and users
and especially agriculture centers. The dilute pesticide wastes that will
require treatment will include spent cleaning solutions for pesticide
containers and any other pesticide contaminated waste water. The con-
centrated pesticide wastes that will require treatment include any surplus,
contaminated, partially or fully degraded pesticides.
-------
The process recommended for the treatment of dilute organophosphorus
pesticide wastes at National Disposal Sites are:
Process Order of Preference Remarks
Activated-carbon Beds
Activated Sludge
Alkaline Hydrolysis
First choice
Second Choice
Third Choice
Demonstrated technology; also
adequate for removal of most
other types of pesticides from
waste water.
Demonstrated technology;
however„ other types of
pesticides in waste water
may be toxic to bacteria
specially acclimated for
treating organophosphorus
wastes.
Demonstrated technology; but
not applicable to pesticides
that are not readily hydrolyzed
in alkaline medium such as
Guthlon.
The only process recommended for treating concentrated organo-
phosphorus pesticide wastes at National Disposal Sites is incineration.
Both chemical degradation with strong alkaline solution and sanitary
landfill are not considered suitable for the disposal of lar*je volumes
of concentrated pesticide wastes.
It should be noted that the activated-carbon bed and the activated
sludge processes are also applicable to the treatment of other types of
dilute organophosphorus pesticide wastes, such as TEPP and malathion
wastes. To treat other types of concentrated organophosphorus pesticide
wastes, incineration is again the only recommended process.
-------
7. REFERENCES
0062. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr. Chemical
and thermal methods for disposal of pesticides. Residue Reviews,
29:89-104, 1969.
0063. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr. Chemical
and thermal aspects of pesticide disposal. Journal of Environmental
Quality, T(l):63-65. Jan. 1972.
0206. Lichtenstein, E. P. Persistence and degradation of pesticides in
the environment. J.n_ National Academy of Sciences—National
Research Council Publication No. 1402, 1966. p.221-229.
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards,
Aug. 1971. p. 35-40.
0315. Smith, W. M., and J. 0. Ledbetter. Hazards from fires involving
organophosphorus insecticides. American Industrial Hygiene
Association Journal, 32(7):468-474, July 1971.
0441. Robeck, G. G., K. A. Postal, J. M. Cohen, and J. F. Kreissl.
Effectiveness of water-treatment processes in pesticide removal.
Journal of American Water Works Association, 57(2):181-199, Feb. 1965.
0445. Whitehouse, J. D., A study of the removal of pesticides from water.
Research Report No. 8, Water Resources Institute, University of
Kentucky, Lexington, Kentucky, 1967. 175 p.
0448. The Working Group on Pesticides. Ground disposal of pesticides:
the problem and criteria for guidelines. Washington, L). S.
Government Printing Office, 1970. 62 p.
0449. Finkelstein, H. Preliminary air pollution survey of pesticides; a
literature review. Report No. NAPCA-APTD-69-44, PB 188-091. Silver
Springs, Maryland, Litton Systems., Inc., Oct. 1969. 169 p.
0509. Metcalf, R. L. The chemistry and biology of pesticides, In
Pesticides in the environment, v. 1. Part 1 and 2. Ed. by R. White-
Stevens. New York, Marcel Dekker, Inc., 1971. p. 1-144.
0536. Water Quality Criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. April 1, 1968.
Washington, Federal Water Pollution Control Administration. 234 p.
-------
REFERENCES (CONTINUED)
0620. The Working Group on Pesticides. Information available on disposal
of surplus pesticides, empty containers and emergency situations.
Washington, U. S. Government Printing Office, 1970. 52 p.
0621. The Working Group on Pesticides. Summary of interim guidelines for
disposal of surplus or waste pesticides and pesticide containers.
Washington, U. S. Government Printing Office, 1970. 25 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1035. Lambden, A. E., and D. H. Sharp. Treatment of effluents from the
manufacture of weedkillers and pesticides. Manufacturing Chemist,
31:198-201, May 1960.
1036. Lue-Hing, C., and S. D. Brady. Biological treatment of organic
phosphorus pesticide waste-waters. JTI^ Proceedings; 23rd Industrial
Waste Conference, Purdue University, 1968. p.1,166-1,177.
1037. Stutz, C. N. Treating parathion wastes. Chemical Engineering
Progress, 62(10):82-84, Oct. 1968.
1039. Coley, G., and C. N. Stutz. Treatment of parathion wastes and other
organics. Journal of the Water Pollution Control Federation,
38(8):1,345-1,349, Aug. 1966.
1277. Bailey, J. B., and J. E. Swift. Pesticide information and safety
manual. Berkeley, California, University of California,
Agricultural Extension Service, 1968. 147 p.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,643 p.
1529. Personal communication. S. Clift, Kerr-McGee Chemical Corporation,
to C. C. Shih, TRW Systems, Apr. 14, 1972.
1531. Personal communication. J. Bell, Monsanto Chemical Company, to
C. C. Shih, TRW Systems, Apr. 14, 1972.
1610. Pesticides: present and future. Chemical Engineering, 76(8):
133-140, Apr. 7, 1969.
1611. Weiss, C. M. Organic pesticides and water pollution. Public Works,
95 (12): 84-87, Dec. 1964.
93
-------
REFERENCES (CONTINUED)
1613. Ketelaar, J. A. Chemical studies on insecticides II-the hydrolysis
of 0 O'^dimethyl-and-dimethyl-0"-p-nitrophenyl thiophosphate
(parathion and dimethyl parathion (E605)). Recueil Travaux
Chemiques de Pays-Bas, 69: 649-658, 1950.
1615. National Agricultural Chemicals Association. Safety guide for
warehousing parathions. Washington, 1968. 19 p.
1617. Metcalf, R. L. Organic insecticides; their chemistry and mode of
action. New York, Interscience Publishers Inc., 1955. 392 p.
1618. Melnikov, W. N. Chemistry of the pesticides. New York,
Springer-Verlag, 1971. 480 p.
1619. Personal communication. L. Frisbie, Chemagro Corporation, to
C. C. Shih, TRW Systems, Apr. 19, 1972.
1620. Van Wazer, J. R. Phosphorus and its compounds, v. 2. New York,
Interscience Publishers, Inc., 1961. 1*100 p.
1631. Sharp, D. H. The disposal of waste materials in the pesticide
industry. I_n_ Disposal of industrial waste materials: papers
to be read at the Conference at Sheffield University.
17th-19th April, 1956. London, England, Society of Chemical
Industry, 1956. p. 9-15.
1635. Sigworth, E. A. Identification and removal of herbicides and
pesticides. Journal of American Water Works Association,
57(8):1,016-1,022, Aug. 1965.
94
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H. M. Nams Methyl Parathion (274]
IUC Nams 0D0-dim2thyl 0-n-nitronh
Common Mamas OnO-dimsthyl 0-4-nit
Molecular Ht. 263.21^
Density (Condensed) 1.358 @
Vapor Pressure (recommended 55 C
(2)
0.05 nun @ 109 C
Flash Point 46 cI^JLj,,,.^ a
Flanunability Limits in Air (wt %)
Explosive Limits in Air (wt. g)
• Solubility
Cold HaterSS mg/liter at 25 C
HAZARDOUS WASTES PROPERTIES
WORKSHEET
Structural Formula
enylphsophorothioate c
ronhenyH thi ophosphate (CH30)2 PO^\N02
Melting Pt. 36 Ct2) Boiling Pt. ?
20 C(2^ Density (gas) 9 '•
and 20 0
-5 (2)
0.97X10 3nun3 20 C 0
Autolgnition Temp.
Lower Upper j
Lower Upper
(2)
1 ; Hot Mater Ethanol !
Others: xylene
Acid, Base Properties
Highly Reactive with heat and may
explode at temperatures above 120 C
Compatible with
Shipped in one to ten gallon cans and 55 qallon steel drums
ICC Classification Poison B
Coast Guard Classification Poison B I
• Commant<; A white solid, commercial methvl parathion is a liquid j^msisting of 8Qt n*»thyl !'
parathion and 20% xvlene. Decomposes at tenneratures ahnvo ambient and roav develop sufficient
internal pressure to cause the container to ruotuire wiolentlw.
References (1) 0766 \
(2) 1618 ?
(3) 1615
95
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HAZARDOUS IdASTES PROPERTIES
WORKSHEET
H. H. Name p^thinn (321)
Structural Formula
IUC Name Q.O-diethyl O.p-nltrophenvlphosphorothioate
Common Names Ethyl Parathion. 0.0-diethyl 0-4-nitrophenvl
thiophosphate
(c2H5o)2 P o r j NOZ
Molecular Wt. 291.27^ Melting Pt. 6 C^ Boiling Pt. 375 C
Density (Condensed) 1.26 @ 25/4 C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
(L57 X10"5mm@ 20 C^_ 0.6 mm @ 157-162 C^ @
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Mater 24 mg/liter^2' Hot Water Ethanol soluble
Others: benzene, xvlene.phthalates. glycols, esters, hetones, toluene, chloroform,
"carbon tetrachloride, animal and vegetable oilsU )
Acid, Base Properties
Highly Reactive with heat, parathion should not be heated above 100 C and may explode
at higher temperatures
Compatible with
Shipped in one to ten gallon cans and 55 gallon steel drums
ICC Classification Poison B Coast Guard Classification Poison B
Consents Yellowish liquid. It emits highly toxic fumes of nitrogen oxides, phosphorus
and sulfur when heated to decomposition. :
References (1) 1492
(2) 1618
(3) 1615
96
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Kms Demeton (491)
000-diethyl 0-(and S-) ethyl-2-thioethyl Structural Formula
IUC Nam. phosphorothioates
Common Names Systox,, E-1059
PSO
Molecular Wt. 258.34^ Melting Pt. Boiling Pt._
Density (Condensed) 1.1183'2) @ Density (gas)
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Demeton (thiol-ismoeH (491)
Structural Formula
IUC Name Q.Q-diethvl S-2-(ethv1thio)-ethv1
Phosphorothfoate
Common Names Svstox (thiol-isomer)
0,0-diethyl S-2-ethyl mercaptoethyl
thiophosphate
SCH
2
Molecular Wt. 258.34^ Melting Pt. Boiling Pt._
Density (Condensed) 1.132^ @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
1 mm 9 128 C(2) 0.25 nn @100 C(3) 2.6 X10" mm 9 20
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water 0.02-0.2%^ Hot Water Ethanol_
Others: Highly soluble in most organic solvents
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification Poison B Coast Guard Classification
Comments Colorless oil
References (1) 1492
(2)
(3)
(2) 1617
1618
98
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Dematon (thiono-isomer)(491)
Structural Formula
IUC Name Q.Q-diethvl Q-? fethvlthioUethyl
phosphorothioate
Common Names Q.Q-diethyl 0-2-ethvl mercaptoethyl_
thionophosphate , systox Ithiono-isomer)
Molecular Wt. 258-34 Melting Pt. Boiling Pt.
Density (Condensed) 1.119^J 9 Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
1 mm @ 123 V2\ 2.5 X1Q"4 mm @ 20 C^3^ Q.4 nm @ Iflfi P.
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water 0.002-0.02%U) Hot Water Ethanol
Others: Highly soluble in organic solvents, including the petroleum hydrocarbons.
Acid, Base Properties
Highly Reactive with Isomerizes very readily to form the thiol-isomer
Compatible with_
Shipped in
ICC Classification Poison B Coast Guard Classification,
Comments A colorless liquid when pure
References (1) 1492
(2) 1617
(3) 1618
9,9
-------
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Guthion (49.5)
0,0 dimethyl S-(l ,2,3-benzotriazinyl-4-keto)-
IUC Name 3-methyl phosphorodithioate
Common Names Azinphosmethyl .
Structural Formula
Molecular Wt. 317.34
(1)
Density (Condensed)
Melting Pt. 73-74C
Density (gas)
(1)
Boiling Pt.
Vapor Pressure (recommended 55 C and 20 0
20 C^2)
2.2X10"7 mm
Flash Point
Autoignition Temp.
Upper_
Upper_
So'lubil ity
Cold Water 0.003 %
(2)
Hot Water
Ethanol soluble
(1)
Others: soluble in methanol, propylene glycol, xylene and other organic solvents
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in one to ten gallon cans and 55 gallon steel drums
ICC Classification Poison B
Comment*; A white solid/ '
and wettable powders for spraying in aqueous solutions.
• Coast Guard Classification
It is usually marketed In.tbe form of emulsive concentrates
References (1) 1492
(2) 1618
100
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PROFILE REPORT
Dinitro Cresol (162)
1. GENERAL
Introduction
Dinitro cresol (4,6-dinitro-o-cresol, DNOC) belongs to the class of
dinitrophenol compounds with a wide range of biocidal action and are useful
as insecticides, acaricides, herbicides, and fungicides. Potassium dinitro-
o-cresylate, marketed in Germany in 1892, was the first synthetic organic
insecticide. The compounds in use today are all derivatives of 4,6-dinitro-
2-alkylphenols and their salts or esters.
Current production of DNOC is only at the rate of 20,000 to 30,000
Ib/year, and indications are that it is being displaced more and more
by its homologs, and primarily by 2,4-dinitro-6-sec-butylphenol (DNBP,
dinoseb). DNBP has the advantages of being less explosive,
somewhat less toxic to man and domestic animals, and more effective in
controlling plant pests, plant diseases, and weeds. DNBP surpasses DNOC
almost three times in insecticidal and herbicidal effect, and because of
the lower dosage, the cost of treatment per unit of area is substantially
lower. Less of the DNBP compound remains on the plants, and the hazard in
using it is decreased. Although this Profile Report is principally
concerned with DNOC, the waste management techniques discussed will also
be generally applicable to DNBP.
Manufacture
DNOC is produced by the direct nitration of o-cresol with a nitrating
mixture at a low temperature, or in some cases, the o-cresol is first
sulfonated with concentrated sulfuric acid before the nitration.
Blue Spruce Company, Basking Ridge, New Jersey, is the only U.S.
manufacturer of technical grade ONOC.
101
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Uses
DNOC is used in agriculture to control plant pests and diseases, and
for the treatment of fruit trees before opening of the buds, either in the
form of emulsions with oils or more often in the form of aqueous solutions
of its salts. In the control of weeds DNOC is used exclusively in the
form of aqueous solutions of the salts, and good results are obtained in
1618
weed control in plantings of flax, grains, and some other crops.
Sources and Types of Pesticide Wastes
The sources of pesticide wastes may include the following :
(1) pesticide manufacturers; (2) pesticide formulators; (3) pesticide
wholesalers; (4) professional applicators; (5) cooperage facilities that
recondition drums; (6) agricultural users; (7) government facilities that
store, transport, and use pesticides; (8) urban and suburban home garden
users; (9) commercial and industrial processes including those from rug
and fabric treatment facilities manufacturing plants, hospitals, etc.
In general, pesticide wastes can be classified as either diluted or
concentrated wastes. Diluted pesticide wastes include those generated
in the waste waters of the manufacturers, formulators, agricultural runoffs,
and possibly spent caustic solutions used to clean empty pesticide con-
tainers. Concentrated pesticide wastes include any unused or contaminated
pesticides, pesticide materials left in containers after emptying, sludges
formed in treating waste water containing pesticides, sawdust or straw
used to soak up accidental pesticide spills.
Physical and Chemical Properties
The physical and chemical properties of DNOC are described in the
attached worksheet. •
102
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2. TOXICOLOGY
The dinitrophenols are biologically active because of their ability
to uncouple oxidative phosphorylation. As a result insects poisoned by
DNOC undergo pronounced increases in the rate of respiration, which may
reach 3 to 10 times normal, and they die from metabolic exhaustion because
of their inability to utilize the energy provided by respiration and
glycosis for the conversion of ortho-phosphate to high energy phosphate
bonds.0509
DNOC is also highly toxic to man and animals and a number of fatalities
have resulted from its use in medicine, industry, and agriculture. It is an
accumulative poison in man and is excreted very slowly. The symptoms of
poisoning include a feeling of warmth, excessive perspiration and thirst,
general debility and weariness, acute distress, collapse, and death followed
by almost instantaneous rigor. Opacity of the lens of the eye has been
produced in laboratory animals following chronic poisoning by DNOC and has
occurred occasionally in humans taking this compound for reducing purposes
in the past.1617
The acute oral and dermal LDcn values of DNOC to the rat are 30 and
5 1277
600 mg/kg body weight respectively. The chronic toxicity of DNOC has
also been extensively studied, and it was established that a DNOC concen-
tration of 100 ppm can be tolerated in the diet with no measurable
effects.0509'1617
The American Conference of Governmental Industrial Hygienists (ACGIH)
1971 recommended Threshold Limit Value (TLV) for DNOC in air is 0.2 mg/M3.0225
The 48-hr Median Tolerance Limits (TLm) for DNOC established by
the Federal Water Pollution Control Administration for various types of
fresh water organisms in micrograms per liter are : P. Californica
»
(stream invertebrate), 560; and Rainbow trout (fish), 210. These data
are indicative of the hazards to aquatic life associated with the use
of DNOC.
103
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3. OTHER HAZARDS
DNOC forms highly water soluble salts with caustic alkalies, ammonia,
and organic amines, and these salts, when in the dry state, explode readily
I c"l O
from shock or detonation.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling Transportation, and Storage
DNOC is highly toxic and is rapidly absorbed through the intact skin
when used in the form of oil solutions. Work with DNOC should be carried
out with the strict observance of necessary precautionary measures, and
the use of rubber gloves, goggles, a respirator, and other protective
clothing is advisable. Special care should be exercised in handling the
salts of DNOC because of their explosive nature.
DNOC should be stored in cool, dry, well ventilated places and away
from any area where the fire hazard may be acute. Outside or detached
storage is preferred. Proper warning signs should be posted in storage
areas.1616
DNOC is classified as a Class B poison by the Department of
Transportation and the rules governing its transportation are given in
the Code of Federal Regulations (CFR) Title 49--Transportation, Parts
71-90.0278
The National Agricultural Chemicals Association has established a
Pesticide Safety Team Network with Area Coordinators throughout the
country to provide nationwide 24-hr service. The network became
operational on March 9, 1970 (with a central telephone number
[513] 916-4300) and should be consulted in all cases of accidents,
spills, leakage, fires, and other types of disasters involving DNOC.
-------
Disposal/Reuse
Contaminated or degraded DNOC could not be practically considered
for reprocessing. The safe disposal of the pesticide is defined in terms
of the recommended provisional limits in the atmosphere and potable
water source and/or marine habitat. The recommended provisional limits
are as follows:
Contaminant and Basis for
Environment Provisional Limits Recommendation
DNOC in air 0.002 mg/M3 0.01 TLV
DNOC in water and soil 0.01 ppm(mg/l) Stokinger and
Woodward method.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Pesticide Wastes
Option No.l - Adsorption with Granular Activated-Carbon Beds. Treatment
of waste water containing DNOC with activated-carbon columns has been
practiced by Fisons Pest Control Ltd., in England since 1955s1035'1631
where over 99 percent removal of the pesticide is obtained. There are
six adsorption towers, each 7 ft 6 in. in diameter and 25 ft high overall,
capable of containing 7 to 10 tons of activated carbon. The activated
carbon employed is normally 10 to 20 B.S.S. mesh and the flow rate through
the towers normally 3S000 gal/hr, and the spent carbon is reactivated in
a conventional rotary furnace. The nominal concentrations of DNOC in the
plant effluent are 60 to 190 ppm before treatment and 0.1 to 0.6 ppm after
treatment. The treated effluent is diluted with river water before
additional treatment in trickling filters and an aeration system followed
by discharge to river. No further removal of DNOC from the waste water is
observed in the biological treatment stages, but the results of governmental
biological surveys indicated no effects of the discharge on the river thus
105
-------
indicating the adequacy of the activated-carbon treatment by itself.
Because of the proven capability and the fact that it is a well established
chemical engineering unit operating, adsorption with granual activated-
carbon beds should be considered as one of the most satisfactory methods
for treating dilute DNOC wastes.
Option No.2 - Adsorption with Powdered Activated Carbon. Although the
use of powdered activated carbon to remove DNOC from water has not been
investigated directly, the effectiveness of DNOC adsorption with granular
activated-carbon beds and the results of the related studies on powdered
activated carbon adsorption of other pesticides conducted by Robeck et al,
0441Sigworth,1635 and Whitehouse indicate that the addition of powdered
activated carbon to a liquid solution followed by stirring and filtration
is an adequate method for treating dilute DNOC wastes.
Option No.3 - Biological Degradation. Southern Dyestuff Company,
Charlotte, North Carolina, has demonstrated on the pilot plant scale
that waste waters containing nitrophenols could be successfully treated
1450
in an activated sludge unit, and is presently in the process of
installing a complete waste treatment facility including an activated
sludge unit, an aeration system, and a chlorination stage to handle their
manufacturing waste streams. In the opinion of Southern Dyestuff,
waste waters containing DNOC could also be adequately treated by the same
system.1805
Option No.4 - Eli Lilly Process. R.H.L. Howe of Eli Lilly and Company
has developed a patented process for removing nitrophenols and nitroanilines
from waste waters. The process consists of acidifying the waste stream
to a pH of less than about three, adding an absorbent material to take up
the colored components, adding a metallic oxide or hydroxide to adjust the
pH to more than about five and also to form a precipitate, and separating
the mixture into an effluent and a sludge or foam (scum). The resulted
effluent is free of nitrophenols and nitroanilines and can then be treated
1OQO 1974
by conventional techniques. According to Howe, s the process is
also applicable to the treatment of waste waters containing 100 ppm to a
-------
few weight percent DNOC, and the treated effluent would be non-toxic to
fish life and safe to any receiving sewer or water course.
Option No.5 - Light Catalyzed Chlorine Oxidation. The effect of ultraviolet
radiation on the rate and extent of chlorine oxidation of 2,4-dinitrophenol
0887 1804
has been briefly investigated by Meiners et al. ' The results with
initially 38 ppm 2,4-dinitrophenol (15 ppm total organic carbon) indicated
the rapid degradation of the compound (practically 100 percent elimination
in 8 min) and the fairly rapid decrease in the total organic carbon (53
percent in 10 min), and demonstrated the value of the process as a near
future treatment method for dilute DNOC wastes.
Concentrated Pesticide Wastes
Option No.l - Incineration. The complete and controlled high temperature
oxidation of DNOC in air or oxygen with adequate scrubbing and ash disposal
facilities offers the greatest immediate potential for the safe disposal
of the pesticide. The research on incineration of pesticides conducted by
Kennedy et al at Mississippi State University has led to the conclusion
that DNBP approached complete combustion at temperatures as low as 600 C
and identified carbon monoxide, carbon dioxide, and ammonia as the
volatile products from burning of the DNBP formulation at 900 C. '
Because of the similarity in chemical structure of DNBP and DNOC,
temperatures not far above 600 C should also be sufficient to degrade DNOC
and the same combustion products should be obtained. It is expected that
either a rotary kiln or liquid combustor, depending on the waste form, fol-
lowed by secondary combustion and scrubbing would be the best current and
near future method for the disposal of concentrated DNOC wastes. Again,
primary combustion should be carried out at a minimum of 1S500 F for at
least 0.5 second with secondary combustion at a minimum temperature of
2,200 F for at least 1.0 second.
Option No.2 - Chemical Degradation. The use of chemical reagents to
decompose concentrated pesticide wastes to less toxic forms has also
been investigated by Kennedy et al. ' The Mississippi State work showed
that: (1) DNBP was altered structurally by sodium hydroxide but the spectrum
-------
produced was not resolved; (2) 80 percent of the DNBP were decomposed when
treated with the sodium biphenyl reagent prepared by heating a mixture
of metallic sodium, anhydrous toluene, and the dimethyl ether of ethylene
glycol-, (3) 93.8 percent DNBP degradation were obtained when the pesticide
was treated with liquid ammonia and metallic sodium. Although liquid ammonia
and metallic sodium would probably also completely decompose DNOCS the reagent
is dangerous to use and the toxicity of the degradation products are not
known. Based on the results to date, chemical degradation could not be
recommended as a method for the disposal of concentrated DNOC wastes.
Option No.3 - Sanitary Landfill. Although data is not available on the
persistence of DNOC in soil, the pesticide readily forms water soluble
ammonium, sodium, potassium, and calcium salts and poses the problem of
potential ground and surface water pollution. Sanitary landfill should
therefore be considered only for the disposal of small quantities of DNOC
wastes, and only at approved sites that are acceptable from a geologic and
ground water hydrology standpoint.
Option No.4 - Deep Well. Although DNOC itself is only sparingly soluble
in water, the potential contamination of ground water by the water soluble
ammonium, potassium, sodium, and calcium salts of DNOC makes deep well,
at best, a questionable method for the disposal of DNOC. Deep well disposal
is not recommended by the National Working Group on Pesticides, and
should be considered only under special situations where hazards would be
nonexistent.
The disposal of DNOC wastes in open pits, lagoons, unapproved landfill
sites, and by onsite burnings or deep-sea burial are not recommended
practices because of the obvious contributions to air and water pollution.
To summarize, the adequate methods for treating dilute DNOC wastes are
either adsorption with granular activated-carbon beds or adsorption with
powdered activated carbon. The only adequate method for the disposal of
concentrated DNOC wastes is incineration. Based on the information to
date, activated sludge treatment, the Eli Lilly process, and light catalyzed
chlorine oxidation could all be considered only as possible near future
methods for treating dilute DNOC wastes.
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
DNOC and its homologs, because of their relatively high'toxicity and
widespread use and distribution as a pesticide in the farming communities,
are candidate waste stream constituents for National Disposal Site
treatment. The recommended unit operation for disposal of dilute
dinitrophenol waste is adsorption with activated carbon in either
powdered or granular form while the only operation judged adequate
for concentrated dinitrophenol waste disposal is controlled incineration.
It should be noted that both the activated carbon and incineration
processes are generally applicable to the disposal of most pesticides.
They are therefore expected to be utilized at National Disposal Sites
which handle pesticides and are located near agricultural centers and
pesticide manufacturers.
109
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7. REFERENCES
0
0062. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman9 Jr. Chemical
and thermal methods for disposal of pesticides. Residue Reviews,
29: 89-104, 1969.
0063. Kennedy, M. V.9 B. J. Stojanovic, and F. L. Shuman, Jr. Chemical
and thermal aspects of pesticide control. Journal of Environmental
Quality, 1 (1): 63-65, Jan. 1972.
0025. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0278. Code of Federal Regulations. Title 49—transporation, parts 71 to 90.
(Revised as of January 13 1967). Washington, U.S. Government
Printing Office, 1967. 794 p.
0441. Robeck, G. G., K. A. Dostal, J. M. Cohen, J. F. Kreissl. Effectiveness
of water treatment processes in pesticide removal. Journal of
American Water Works Associations, 57: 181-199, Feb. T9&T.~*~
0445. Whitehouse, J. D.s A Study of the removal of pesticides from water.
Research Report No. 8, Water Resources Institute, University of
Kentucky, Lexington, Kentucky, 1967. 175 p.
0448. The Working Group on Pesticides. Ground disposal of pesticides: the
problem and criteria for guidelines. Washington, U.S. Government
Printing Office, 1970. 55 p.
0509. Metcalf, R. L. The Chemistry and biology of pesticides, In pesticides
in the environment. V. 1 Part 1. Ed. by E. White-Stevens. New
York, Marcel Dekker, Inc., 1971. p. 1-144.
0534. Jones, H. R. Environmental control in the organic and petrochemical
industries. Park Ridge, New Jersey, Noyes Data Corporation, 1971.
257 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. April 1, 1968.
Washington, Federal Water Pollution Control Administration. 234 p.
0620. The Working Group on Pesticides. Information available on disposal
of surplus pesticides, empty containers and emergency situations.
Washington, U.S. Government Printing Office, 1970. 52 p.
0621. The Working Group on Pesticides. Summary of interim guidelines for
disposal of surplus or waste pesticides and pesticide containers.
Washington, U.S. Government Printing Office, 1970. 25 p.
-------
REFERENCES - CONTINUED
0887. Meiners, A. F., E. A. Lawler, M. E. Whitehead, and J. I. Morrison.
An investigation of light-catalyzed chlorine oxidation for
treatment of waste water. Robert A. Taft Water Research Center
Report No. TWRC-3. Washington, U.S. Government Printing Office.
1968. 128 p.
1035. Lambden, A. E., and D. H. Sharp. Treatment of effluents from the
manufacture of weedkillers and pesticides. Manufacturing Chemist.
31: 198-201, May 1960.
1277. Bailey, J. B., and J. E. Swift. Pesticide information and safety
manual. Berkeley, California, University of California, Agricultural
Extension Service, 1968. 147 p.
1433. Kirk-Othmer encyclopedia of chemical technology, 2d ed. v 11. New
York, Interscience Publishers, 1966. 899 p.
1450. Personal Communication. F. Huber, Southern Dyestuff Company to
W. Kendrick, TRW Systems, Apr. 26, 1972. Treatment of aqueous
waste streams containing dinitrophenol.
1616. National Agricultural Chemicals Association. Safety manual for
handling and warehousing Class B poison pesticides. Washington,
1969. 13 p.
1617. Metcalf, R. L. Organic insecticides—their chemistry and mode of
action. New York, Interscience Publishers Inc., 1955. 392 p.
1618. Melnikov, W. N. Chemistry of the pesticides. New York, Springer
Verlag, 1971. 480 p.
1631. Sharp, D. H. The disposal of waste materials in the pesticide
industry. Jj^ Disposal of industrial waste materials: paper to
be read at the Conference at Sheffield University. 17th-19th
April, 1956. London, England, Society of Chemical Industry,
1956. p. 9-15.
1635. Sigworth, E. A. Identification and removal of herbicides and
pesticides. Journal of American Water Work Association, 57
(8): 1016-1022. Aug. 1965.
1802. Personal communication. R. Howe, Eli Lilly and Company to C. C. Shih,
TRW Systems, June 5, 1972. Dinitrocresol removal from water.
1804. Personal communication. A. Meiners, Midwest Research Institute to
C. C. Shih, TRW Systems, June 5, 1972. Light-catalyzed chlorine
oxidation of dinitrophenols.
1805. Personal communication. F. Huber, Southern Dyestuff Company to
C. C. Shih, TRW Systems, June 5, 1972. Dinitrocresol waste
treatment.
ill
-------
REFERENCES - CONTINUED
1964. Personal communication. A. Livingston, Blue Spruce Company to
C. C. Shih, TRW Systems,, June 12, 1972. Dinitro cresol manufacture.
1974. Personal communication. R. Howe, Eli Lilly and Company to C. C. Shih,
TRW Systems, June 8, 1972. Dinitrocresol and nitrophenol waste
treatment.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Omitro Cresol (162)
IUC Name 2-4-dinitro-6-methvlphenol
Coimnon Names 4.6-dinitro-O-cresol, PNC. DNOC
Structural Formula
Molecular Wt. 198.1
Melting Pt. 86.4C
(2)
Boiling Pt..
Density (Condensed)
@
Density (gas)
Vapor Pressure (recommended 55 C and 20 0
5.2 X 10~5mm<8 25 C
(2)
Flash Point
Auto1gn1t1on Temp._
Flaranabllity Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
(?}
Cold Mater 0.0128%u;
Others:
Hot Water_
soluble in acetone and benzene
Ethanol 4.3* at 15 C
(3)
Acid, Base Properties DNOC is a pseudo acid and readily forms water soluble sodium,
potassium, calcium and ammonium saltsO)
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification
Poison B
Coast Guard Classification
Comments DNOC is a yellow crystalline substance in the pure <:tatp.
C
References (1) 509
(2} 1618
(2> 1433
(3)
113
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PROFILE REPORT
Cadmium Cyanide (84), Calcium Cyanide (91). Copper Cyanides (120).
Cuprous Cyanide (128), Cyanide (129), Lead Cyanide (239), Nickel
Cyanide (295). Potassium Cyanide (344). Silver Cyanide (370).
Sodium Cyanide (387). and Zinc Cyanide (457)
1. GENERAL
The cyanides listed above are included in a combined Profile Report
because they respond in similar fashion to disposal processes due to the
cyanide group present in each of the compounds.
Hydrocyanic acid (215), hydrogen cyanide (218), and mercuric cyanide
(254) are not included in this combined Profile Report, but are included
in separate reports because of the special disposal problems these
compounds present.
The majority of cyanide-containing waste streams are discharged
from the electroplating industry and include liquid, slurry, sludge, and
solid forms depending upon the degree of concentration. Rinse waters
from copper electroplatings for examples may be concentrated by passing
through evaporators. In this case, the waste may be a crystalline solid
containing 15 percent by weight copper in copper cyanide and sodium
cyanide salts (40 percent solids by weight) with traces of other metals.
A typical concentrated liquid waste from copper electroplating rinse
waters may contain 2 percent copper cyanide, 6 percent sodium cyanide„
sodium sulfonate, hydrocarbons and zinc phosphate in 83 percent water.
A characteristic concentrated liquid waste stream containing cyanide
wastes from zinc electroplating may be 0»8 percent cyanide 1n 1 percent sodium
hydroxide containing 3(300 ppm of zinc and 165 ppm nickel. A characteristic
115
-------
sludge may contain 20 percent sodium ferrocyanide with 2 percent zinc and
insolubles, and 50 percent water.
It is estimated that there are 21 ,323 9 600 Ib of cyanide wastes and
2,106,000 Ib of copper wastes generated in the electroplating industry
each year. The geographic distribution of these wastes is shown in
Volume 14S the volume titled, "Waste Forms and Quantities."
Calcium Cyanide
Pure calcium cyanide is known only in the laboratory. A crude
cyanide containing 48 to 50 percent cyanide expressed as sodium cyanide
is the only important calcium cyanide of commerce at the present time.
It is sold in the form of black or gray flakes, powder, or cast blocks
and is known as black cyanide or under trade names such as Aero Brand
cyanide, Cyanogas, and Aerocase 28. Physical/chemical properties are
summarized in the attached worksheet,
Calcium cyanide is prepared by a process in which calcium cyanamide
is caused to react with the carbon present in crude calcium cyanamide in
the presence of salt:
CaCN2 + C Ca(CN)2
The temperature for the reactions i ,OOOC, is attained through the use of
an electric furnace. The melt is quick-cooled on a flaking wheel, which
rapidly chills the product to prevent reversion to cyanamide. This product
is sold in the form of a dark gray flake or is melted and cast into molds
for sale as bricks.
The more important uses for black cyanide are as follows:
(1) Cyanidation of Gold and Silver from Ores - Metallic gold and silver
dissolve in cyanide solutions in the presence of oxygen to form
-------
the corresponding cyano complexes. The dissolved gold and silver
are reprecipitated with zinc dust as a sludge which is refined
to obtain pure gold, silver and the other metals present. The
zinc added is converted to zinc cyanide which in an alkaline
1158
solution, complexes as per the following reaction:
2 Zn (CN)2 + 4 OH" + [Zn(CN)4)]2 + [Zn(OH)4]2
(2) Depressor in Froth Flotation - Black cyanide in solution has the
property of rendering certain minerals less amenable to flotation
(it depresses zinc in lead-zinc ores, zinc and iron in complex
1 -i CQ
lead-zinc-iron ores, and iron in copper ores).
(3) Fumigation of Citrus Groves„ Greenhouses, etc.
(4) Commercial Production of Hydrogen Cyanide - Black cyanide is
acidified and the evolved hydrogen cyanide-water mixture is
concentrated by distillation.
(5) Manufacture of Ferrocyanides.
(6) Case Hardening of Steels - In case hardening (carburizing), a
high carbon surface layer is imported to a low carbon steel by
heating up to 1,600 F in a molten bath containing Ca(CN^» NaCl,
CaO, and carbon.1146
Cadmium Cyanide
Cadmium cyanide crystallizes as a colorless rhombic crystal. It may
be prepared in the laboratory by treating cadmium sulfate with an alkali
metal cyanide or by dissolving cadmium hydroxide in aqueous hydrocyanic
acid. Its main use is in the form of a complex in electroplating with
cadmium for rust protection. Because of high losses during purification,
cadmium cyanide is not prepared commercially in dry form, but usually as a
solution of sodium cyanocadmate, Na~[Cd(CN)9]. This is formed by dissolv-
1433
ing cadmium oxide in sodium cyanide solution.< Physical/chemical
properties are summarized in the attached worksheet.
117
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Copper Cyanides
Copper forms two cyanides„ cupric cyanide, CufCN)^, and cuprous
cyanide, CuCN. Cupric cyanide is a yellow powder which is unstable and
rapidly decomposes at ordinary temperatures giving off cyanogen and
forming 2 CuCN • Cu(CN).. 5 H20. Only the more stable cuprous compound is
an item of commerce9 and therefore, only this compound will be discussed
in this Profile Report.
When pure, cuprous cyanide is a white insoluble compound. Its
principal uses are in electroplating, medicines removal of oxygen from
molten metals (particularly copper), insecticides, underwater paint, and
organic nitrile separation. In solutions for electroplating of copper,
cuprous cyanide is placed in solution by formation of complex ions with
excess soluble cyanide.
1433
There are several methods for the preparation of cuprous cyanide.
In one method cupric sulfate solution is reacted simultaneously with
aqueous solutions of sodium hydroxide and sodium hydrogen sulfite to
reduce the cupric ions. A sodium cyanide solution is then added and the
cuprous cyanide precipitated, filtered, washed and air dried. Another
preparation method used today is to treat alkali cyanide solution with
cuprous chloride. Commercial preparation of cuprous chloride is accom-
plished by reducing cupric chloride with scrap copper in the presence of hot
sodium chloride brine.
Chemical/physical properties are summarized in the attached worksheet.
Lead Cyanide
Lead cyanide is a white crystalline material that is slightly soluble
in aqueous solutions of ammonium salts, ammonium hydroxide, hot nitric
acid, and alkali cyanides. It has been used to a small extent as an insec-
ticide and in electroplating for producing a smutty effect in green gold
deposits. It is not generally available commercially, but is best prepared
for use by slowly addingB with stirring, a cold solution of sodium cyanide
-------
and sodium hydroxide to lead acetate dissolved in cold water. The precipi-
tated lead cyanide is allowed to settle, washed and drieds if to be stored.
Physical/chemical properties are summarized in the attached worksheet.
Nickel Cyanide
Nickel cyanide is a light green powder that is present, either as the
tetrahydrate, Ni(CN)3 • 4 1^0, or as 2 Ni(CN)2 • 7 H20. It is hydroscopic
but at 200 C becomes anhydrous. It reacts with alkali and alkaline earth
cyanides to form soluble orange or yellow tetracyanonickelates. Nickel
cyanide is usually prepared by the action of an alkali metal cyanide on a
solution of a nickel salt.
Nickel cyanide is not used in electrodeposition of the metal, because
nickel cannot be deposited from an aqueous solution of the pure alkali
nickel cyanide complex. Nickel cyanide is added to plating baths for the
electroplating of other metals such as gold or silver to make harder
deposits, or in zinc-plating baths to enhance the brightness. It also is
used in small quantities as an anticorrosion agent. It reacts with
alkali metal and alkaline earth metal cyanides to form nickelocyanides.
Physical/chemical properties are summarized in the attached worksheet.
Potassium Cyanide
Potassium cyanide is a white, crystalline,, deliquescent solid that is
less subject to hydrolysis in aqueous solution than is sodium cyanide.
Potassium cyanide is made either by neutralization of potassium hydroxide
with hydrogen cyanide or by the Beilby process which utilizes the molten
carbonate. The overall reaction is as follows:
A
K2 C03 + 4C + 2NH3 -f 2KCN + SCO + 3H20
Potassium cyanide is often used in preference to sodium cyanide for
electroplating silver and copper. The reasons for this preference are:
(1) the potassium bath can be operated over a wide current-density
range; ' ;'' ' ''
119
-------
(2) a lower metal content is required for a comparable current-
density range and electrodeposit appearance;
(3) it has a greater tolerance to organic contaminants; and
(4) it permits higher carbonate concentrations. Potassium
cyanide also finds some use in mixtures with sodium cyanide for
nitriding steel.1146
Physical/chemical properties for potassium cyanide are summarized in
the attached worksheet.
Silver Cyanide
Silver cyanide, AgCN or Ag (CN) , is a white odorless powder that
X X
has a complex structure. Silver cyanide reacts with solutions of soluble
metal cyanides to form a very slightly dissociated complex union [Ag(CN)2].
This complex is formed in the cyanidation of silver ores and in electro-
plating. The complex is decomposed by alkaline sulfides with precipitation
of silver sulfide and by reaction with mineral acids with precipitation
11 co
of silver cyanide and liberation of hydrogen cyanide.
Silver cyanide is usually manufactured by adding an alkali metal
cyanide to a solution of silver nitrate according to the following
reaction:
Ag N03 + Na CN -> Ag CN 4- + Na N03
The principle use of silver cyanide is in electroplating.
The physical/chemical properties for silver cyanide are summarized in
the attached worksheet.
Sodium Cyanide
Sodium cyanide is a hardB white crystalline solid. At high tempera-
tures, it does not ignite in contact with air? this permits its use in high
temperature metal treatment. Its applications include metal treatment,
electroplating baths and synthesis of organic intermediates. Its use in
120
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extraction of low-grade gold, silver and molybdenum ores account for only
a small part of the total use.
Most sodium cyanide is manufactured either by the neutralization of
hydrogen cyanide with sodium hydroxide or by the Castner Process described
as follows:
1) Sodamide is formed from sodium and ammonia:
2NH3 + 2Na -»• 2Na NH£ + H2
2) Sodamide reacts with carbon at 350=400 C to form sodium cyanamide:
2 Na NH2 + C -»• Na£ CN2 + 2H£
3) At temperatures of about 700 Cs the sodium cyanamide reacts with
further quantities of carbon to form molten cyanide:
Na2 CN2 + C -> 2Na CN 1433
Physical/chemical properties for sodium cyanide are summarized in the
attached worksheet.
Zinc Cyanide
Zinc cyanide is a white solid. It is very stable when dry and can be
heated in the absence of air to 1000 C without decomposition. In the
presence of air it decomposes at 800 C. It dissolves easily in solutions
of soluble cyanides to form complexes such as:
K2[Zn(CN)4] and Na2 [Zn(CN)4] • 3H20
Zinc cyanide is prepared by a number of processes. One involves its prep-
aration from zinc oxideB sulfuric acid9 and sodium cyanide according to
the following equations:
ZnO + H2 S04+ Zn S04 + HgO
Zn S04 + 2NaCN+ Zn(CN)2+ + Na2 S04
It may also be prepared by treating a solution of zinc acetate with hydro-
gen cyanide. As a waste considerable zinc cyanides as Na9[Zn(CN)A]9 is
1433
formed in gold and silver ore processing with sodium cyanide.
-------
The principal uses for zine cyanide are in electroplating, and
occasionally in medicine. Its physical/chemical properties are summarized
in the attached worksheet.
2. TOXICOLOGY
Volatile cyanides resemble hydrocyanic acid physiologically, inhibiting
tissue oxidation and causing death through asphyxiation. The non-volatile
cyanide salts are of high toxicity systemically, if they are ingested. Care
should be taken to prevent the formation of hydrocyanic acid. Daily expo-
sure to cyanide solutions may cause a "cyanide" rash characterized by
itching, and by muscular, papular, and vesicular eruptions. Exposure to
small amounts of cyanide compounds over long periods of time may cause loss
of appetite, headache, weakness, nausea, dizziness and symptoms of the
upper respiratory track and eyes. The Threshold Limit Value (TLV) (ACGIH)
recommended is 5 milligrams per cubic meter of air.
The toxicity of the various metal ions that combine with the cyanide
ion has been extensively discussed in the report "Water Quality Criteria".
Even if the cyanide ion concentration is reduced to near zero, the concen-
tration of the metal ions remaining must be considered. Therefore, con-
centration limits have been established for the metallic ions in public
water supplies. The permissible and desirable limits for cyanide and
metal ions are summarized below.
Permissible Desirable
Constituent Criteria, mg/1 Criteria, mg/1
Cadmium 0.01 Absent
Copper 1.0 Virtually absent
Lead 0.05 Absent
Silver 0.05 Absent
Zinc 5 Virtually absent
Cyanide 0.20 Absent
-------
Aquatic Toxicity
A discussion not only of cyanide ion toxicity but of the toxicity
toward aquatic life of all the metal ions covered as cyanides in this
Profile Report is also included in the report "Water Quality Criteria".
The toxicity of cyanides towards aquatic Tife increases rapidly with a
rise in temperature. Fish can recover from short exposure to concentrations
of less than 1.0 mg/1 of cyanide ion if removed to water free of cyanides.
Fish appear to be able to convert cyanide to thiocyanate, an ion that is
not inhibitory to their respiratory enzymes. The complex cyanides formed
by the action of cyanide with zinc or cadmium salts are much more toxic than
sodium cyanide. However, the reaction between cyanide and nickel produces
a cyanide complex less toxic than sodium cyanide at high pH levels.
3. OTHER HAZARDS
Cyanides evolve hydrocyanic acid rather easily when acidified. HCN
is a flammable gas and is highly toxic. Carbon dioxide from the air is
sufficiently acid to liberate hydrocyanic acid from cyanide solutions.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Adequate procedures for safe handling and storage of cyanides as
1562
concentrated or dilute solutions are described in detail by Graham.
His book provides recommended procedures for building design, equipment
design, ventilation, employee safety, design of storage containers, and
material specifications. The U. S. Department of Transportation (DOT)
classification and shipping regulations for the various cyanides covered
by this Profile Report are summarized below:
Compound : Shipping Regulations
Cadmium Cyanide ; Cadmium cyanide is not normally prepared commercially
iii the dry form, but usually as a solution of sodium
cyanocadmates by dissolving cadmium oxide in sodium
•••"••• cyanide solutions. See "Sodium Cyanide".
-------
Compound
Calcium Cyanide
Cuprous Cyanide
Lead Cyanide
Nickel Cyanide
Potassium Cyanide
Silver Cyanide
Sodium Cyanide
Zinc Cyanide
Shipping Regulations
Calcium cyanide is shipped in steel drums as a
Class B poison. It must be protected from moisture
because it decomposes slowly. Also, it usually
contains calcium carbide which will liberate
acetylene upon contact with moisture.
Cuprous cyanide is usually packed in fiber drums in
wooden kegs. It is a toxic item and should carry
warning labels as recommended by the Manufacturing
Chemists Association. It may be shipped by freight
express or motor truck but is not mail able.
Lead cyanide is not usually manufactured on a large
scale. It is shipped under the same regulations as
cuprous cyanide.
Nickel cyanide is shipped as a Poison B under a
poison.label.
Potassium cyanide is shipped as a Poison B under a
poison label.
Silver cyanide is packed in cardboard tubes or in
fiber containers. It may be shipped by express but
is not mailable. It is a restricted item and must
carry a warning label similar to that recommended
by the Manufacturing Chemists Association.
Sodium cyanide is shipped in iron drums and smaller
containers packed in drums. Container cars can also
be used. Drums and packages are shipped under a
poison B label. Carload shipments carry a placard
labeled "Dangerous".
Zinc cyanide is shipped under the same regulations
as cuprous cyanide.
A definition of acceptable criteria for disposal of cyanide salts must
also take into account acceptable criteria for not only the release of
cyanide ion but also the release of the associated metallic constituents
into streams or sewage works. Most industrial states have laws regulating
the discharge of waste streams from metal processing works and plating
operations. Laws are being enacted that reduce the quantities of waste
that may be discharged, but in many cases there are not definite standards
for acceptable wastes. The severity of the waste nuisance varies with:
-------
0) Volume and toxicity of wastes produced (as metal ions
free of cyanide).
(2) Nature of receiving waters,
(3) Minimum flow of the natural streams, or
(4) The process used in the sewage plant.
l 'ifi?
Graham includes information (Table 1) which compares the
concentration of constituents in typical plating rinse wastes with
standards set by some states. Future laws will lower the range of
permissible concentrations.
The safe disposal of the metal cyanides is defined in terms of the
recommended provisional limits for the residual metal cyanides and the
disposal process product soluble metal ions in the atmosphere., in potable
water sources, and in marine habitats. These recommended provisional
limits are as follows:
Contaminant in
Air
Cadmium cyanide
Calciura cyanide
Copper cyanide
Lead cyanide
Nickel cyanide
Potassium cyanide
Silver cyanide
Sodium cyanide
Zinc cyanide
Contaminant in
Water and Soil
Cadmium cyanide
Calcium cyanide
Copper cyanide
Lead cyanide
Nickel cyanide
Potassium cyanide
Silver cyanide
Sodium cyanide
Zinc cyanide
Provisional Limit
0.002 mg/fT as Cd
0.05 mg/M3 as CN
0.01 mg/M3 as Cu
0.0015 mg/M3 as Pb
0.01 mg/M3 as Ni
0.05 mg/M3 as CN
0.0001 mg/M3 as Ag
0.05 mg/M3 as CN
0.05 mg/M3 as CN
Provisional Limit
0.01 mg/1 as .CN
0.01 mg/1 as CN
0.01 mg/1 as CN
0.01 mg/1 as CN
0.01 mg/1 as CN
0.01 mg/1 as CN
0.01 mg/1 as CN
0.01 mg/1 as CN
0.01 mg/1 as CN
Basis for Recommendation
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
Basis for Recommendation
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
Drinking Water Standard
125
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TABLE 1
CONCENTRATION OF CONSTITUENTS OF TYPICAL DILUTE PLATING
RINSE WASTES COMPARED WITH SOME STATE STANDARDS1562
Plating Wastes Range of Permissible Concentration,ppm
Constituent Concentration, ppm Effluent to Influent* to
(Avg) (Max) Streams In Streams Sewage Works
CN
Cu
Zn
Cd
Ni
Pb
PH
30
20
15
15
25
0
Varies
500 None to 0.5
100 1
50
50
200
30
Varies 6.5-9.5
None to 0.2
0.4
0.3 - 1.5
0.3
-
0.35
6.3 - 9
2
1 • * 3
-
-
1-3
0.1
5 - 6.5
* Influent after dilution and mixing with all other wastes.
126
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Much of the information in the literature on the volume and composition
of electroplating, metal treating, metal finishing wastes, and mining wastes
refers to the large or intermediate-size plants that do routine operations.
There are wide variations in both volume and composition from plant to
plant. This is because the waste streams from these plants are the product
of local plant conditions and practices such as dragout, rinsing techniques,
recovery methods employed, and the admixture of other waste streams. There
is little or no information on the volume and composition of wastes encoun-
078"?
tered in the smaller plating shops that do general plating."'00
Recovery and Conservation of Water and Cyanide
Any expedient that prevents the loss of chemicals or removes them from
the waste stream in reusable or resalable form may be considered as a
recovery operation. In recovery processes the metal ion can be recovered
as well as sodium cyanide. In some localities water is valuable and its
recovery may be economically attractive.
Evaporation Methods. The evaporation of collected plating rinses for
return to plating baths is an attractive process. Cyanide wastes have been
concentrated (by distillation of H20) to recover the metal and cyanide
values for reuse in the plating process. The distillate generated is used
as rinse water. In many cases the recovery of the cyanides by this tech-
nique is economically feasible when the values of the cyanides and water
1 *ifi?
are considered. When feasible, this method is recommended because
resources are conserved and landfill is not required for disposal.
Ion-Exchange Methods. Ion exchange has been successfully applied to
mixed wastes (chromium and cyanides) by the use of a duel bed process. In
this process the waste stream is first passed through a cationic exchanger
to absorb metals, help break up complex metal cyanides and generate free
hydrogen cyanide, and then through an anionic exchanger to absorb the
0783
liberated hydrogen cyanide. The concentration of cyanide in the waste
127
-------
stream must be below about 5 percent. Regeneration—the removal of
cyanides and metals from the resins--must be done periodically. The
is accomplished by passing sulfuric acid and/or sodium hydroxide through
the resins to redissolve the cyanides and metals. Regenerated solutions
are generally concentrated but still toxic. If they are to be discharged,
they require chemical treatment, but because they are concentrated treat-
ment may be carried out batchwise in small tanks. In many cases recovery
of the metals as cyanide is economically feasible.
Chemical Recovery Methods. Chemical recovery methods are not widely
used, except for precious metals. In plating, metal treating, or mining
the precious metals are nearly always recovered. Silver is plated from
1 *ifi?
cyanide solutions or precipitated by the addition of zinc dust.
Copper is precipitated from cyanide solutions by the addition of hydrazine.
Nickel and copper are precipitated at elevated temperatures at a pH above
3.5 by the addition of iron.0783
1112
Waste - Plus - Waste Method. George arid Cochran describe a method
for the recovery of six metal cyanides. Addition of an acid waste to an
alkaline cyanide waste was investigated for five different combinations of
cyanide wastes. At the optimum final pH values of the mixtures, the metal
cyanides were almost quantitatively precipitated. The pH was adjusted by
the addition of acid rinse water and lime. No evolution of hydrogen
cyanide was detected. The waste-plus-waste technique, though not in com-
mercial use, is attractive because no reagents for recovery are required
of the metal cyanides and the effluent may be treated to reduce residual
cyanide content via chlorination or electrolytic oxidation.
Cyanide Destruction
The chemical destruction of cyanides in liquid waste streams has
received a great deal of attention and numerous methods have been proposed.
Some of the more attractive methods are briefly discussed in the following
paragraphs. For dilute cyanide wastes, chlorination under alkaline condi-
tions is generally favored; too mich heat Is generated if the technique is
-------
used on concentrated wastes and undesirable and dangerous side-reactions
will take place unless the operation is carried out very slowly, or the
waste is first diluted. When considerable amounts of concentrated wastes
must be treated, e.g.9 from cyanide heat-treating, the wastes must be
diluted or another method for cyanide destruction such as electrolytic
oxidation must be used.
Chiorination. Oxidation of cyanides by the hypochlorite ion (which
may be furnished by either chlorine or sodium or calcium hypochlorite)
proceeds in three stages. '
CM" + H* + OC1" -* CNC1 + OH" (1)
CMC! + 20H" -> CNO" + Cl + H20 (2)
2CNO" + 30C1~ + H20 -> 2C02 + N£ + 3C1" + 20H" . (3)
Reaction (1) is very fast; reaction (2) is very slow below pH 9 unless
excess hypochlorite is presentj at pH 10 or higher it is rather rapid and
oxidation to the cyanate stage is complete in 5 minutes or less, provided
no nickel ion is present. If nickel is present,, reaction (2) is not com-
pleted in less than 30 minutes,, and then only if 20 percent excess reagent
is used. Reaction (3) is very slow above pH 9 requiring at least an hour,
and many hours if the pH is 11 or more. The best practice is to adjust the
pH to 8.5 and allow 1 hour reaction time. About 10 percent excess hypo-
chlorite should be useds or destruction of the cyanides will be incomplete.
The heavy metals present will be precipitated as hydroxides or carbonates
in total chlorination treatment. An exception is copper which will not be
precipitated in wastes containing copper and rochelle salts unless suffi-
cient calcium is also present as chloride or hydroxide„ so that the tartrate
will be precipitated as the calcium salts thus allowing precipitation of
copper. It has been shown that iron cyanide complexes are not destroyed
by chlorination and that a cyanide residual reappears on long standing
(100 hours).
-------
Total chlon'nation (i.e.9 to N2 and C02) does not lend itself readily
to continuous treatment processes because current control methods are not
adequate. If a packaged cyanide treatment system is employeds continuous
operation for oxidation to cyanate (1,000 times less toxic than cyanide) is
possible. A second system is required for oxidation of cyanatess with
appropriate holding time due to the slow reaction.
Kastone Process. DuPont has introduced a process which appeals
primarily to small plant operators using cyanide baths to plate zinc or
cadmium. This process oxidizes cyanides to cyanates and simultaneously
precipitates zinc or cadmium complexes by simple filtration. The Kastone
Process uses a proprietary peroxygen formulation that contains 41 percent
0484 0485
hydrogen peroxide with trace amounts of stabilizers. ij-T^~t^ jne cyanates,
though 1,000 times less toxic than cyanides, cannot be discharged into most
natural streams. Therefore, this process has only limited application.
/—
< Electrolytic Oxidation. Automatic electrolytic oxidation units are
marketed by Research Control, Inc., for complete decomposition of cyanide
ion content in waste streams. Some difficulties have been reported
with this unit for dilute solutions, but this problem has been circum-
vented by using a semi conductive bed in the cell. The bed serves as an
intermediate electrode that provides in effect more than a million anode
and cathode sites per cubic foot.
Radiation Decomposition. A patent has been issued for destroying
cyanides by gamma radiation which serves to rupture the CsN triple bond
and converts the cyanide ion into hai
is not in commercial use at present.
0287
and converts the cyanide ion into harmless by-products. This method
Conversion of Cyanides to Ferrocyanide by Ferrous Sulfate. The
formulation of less toxic cyanide complexes such as ferro and ferricyanides
has been used as a method for disposing of cyanide waste waters. This pro-
cess involves the use of iron salts to form complex compounds with the free
cyanide in the wastes. These cyanide complexes are precipitated and
removed as sludge. The major advantage of this treatment method is that
-------
it is relatively inexpensive where waste ferrous sulfate is available.
However, considerable quantities of sludge are formed, and the treated
solutions are strongly colored. There is also evidence that ferrocyanides
may decompose to free cyanide in the presence of sunlight. The
regeneration of cyanide can then contaminate the receiving stream.
Reaction with an Aldehyde. A patent has been issued for the removal
of cyanide from a waste stream by reaction with an excess of an aldehyde
1791
according to the following :
KCN + CH20 (aqueous) + H20 -»- HOCH2CN + KOH
CNCH2OH + KOH + H20 + HOCHgCOOK + NH3
It is claimed that nearly all cyanides, even stable complexes, are des-
troyed in this manner. However, though the reaction products are not toxic,
there is the problem of disposal of the organic compounds formed.
Ozonation. Ozonation is reported to be more economical and easier to
control than chlorination. Ozonation, however, oxidizes cyanides only to
the cyanate in accordance with the reaction given below.
3CN~ + 03 +3CNO"
I CCO
The oxidation of the cyanate is too slow to be practical.
Acidification. Waste acid solutions have been used to acidify cyanide
waste solution. Air is then passed through the solution and the liberated
hydrogen cyanide is discharged up a high stack or is passed through a
burner. This method is not recommended because of the danger involved.
Lagooning. Though the methods discussed above are available for
treating cyanide wastes, lagooning of cyanide wastes from small and medium
sized metal processing and plating operations is widely practiced. For
example, in the Los Angeles area commercial waste disposal companies col-
lect cyanide wastes and truck these wastes to a large abandoned rock quarry.
If precious metals, such as silver, are present, these are first removed
by salvage companies. :
131-
-------
The use of lagoons for cyanide wastes cannot be recommended because
the cyanides may some day leak into underground water supplies and the
wastes, if acidifieds will liberate hydrogen cyanide.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The oxidation of cyanides in alkaline solution by chlorine or hypo-
chlorites is an acceptable method for destroying cyanide. However,
because cyanide wastes are generated by a large number of metal treating
operators, some of whom are small., in some cases proper treatment is an
economic burden and not always complete. It is, therefore, recommended
that National Disposal Sites have the capability for treatment of cyanide
wastes by the use of the chlorination techniques.
Additional research is recommended to establish operations that will
permit recovery of the various metals, and either recovery or destruction
of the cyanide. A study is also recommended of the economics associated
with the various recovery methods proposed or now in use .
132
-------
7. REFERENCES
0287. Byron, R. F. Radiation decomposition of waste cyanide-solutions.
U. S. Patent 3,147,213.
0484. Martin, Jr., M. H. Kastone process. Washington, Environmental
Science and Technology, 5(6):496-497, June 1971.
0485. Zeroing in on plating wastes. Chemical Week, 107(25):54-55,
Dec. 16, 1970.
0536. Federal Water Pollution Control Administration, U. S. Department of
the Interior. Report on the committee on water quality criteria.
Apr. 1, 1968. 234 p.
0586. Eckenfelder, Jr., W. W. Industrial water pollution control.
McGraw-Hill Book Company, 1966.
0783. Battelle Memorial Institute. A state-of-the-art review of metal
finishing waste treatment. PB-203 207. Ohio, Nov. 1968. 88 p.
1111. Grune, W. N. Plating and cyanide waste literature review. Water
Pollution Control Federation Journal, 40(6):1,180-1,198, June 1968.
1112. George, L. C., and A. A. Cochran. Recovery of metals from electro-
plating wastes by the waste-plus-waste method. Technical Progress
Report 27. Pittsburgh9 Pennsylvania, Aug. 1970. 12 p.
1146. Camp, J. M., and C. B. Francis. Liquid carburizing. The Making,
Shaping and Treatment of Steel. U. S. Steel Company, 1961.
1158. Henglein, J. A. Chemical technology. Oxford, England, Pergamon
Press, 1969. 894 p.
1309. Harshaw Pollutronics. Improving todays environment for a better
tomorrow. Cleveland, Ohio, The Harshaw Chemical Company.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1562. Graham, H. K. Electroplating engineering handbook. 2d ed. Westwood,
New Jersey, Metals and Plastics Publications, Inc., 1962. 773 p.
1791. Morico, J. L. Process for the destruction of cyanide in waste
solutions. U. S. Patent No. 3,5059217. Apr. 7, 1970. 7 p.
133
-------
HAZARDOUS fc!ASTES PROPERTIES
WORKSHEET
H. M. Name Cadi urn Cyanide (84)
Structural Formula
IUC Name Cadi urn cyanide
Common Names
Cd(CN)
2
Molecular Wt. 164.45 Melting Pt. 7200 decomposes Boiling Pt.
Density (Condensed) 2.226 @ 20 C_ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
0 @ (
Flash Point Autolgnltion Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Mater 1-71 at 15 C Hot Water Ethanol si sol
Others: Alkali cyanide or hydroxide solutions
Acid, Base Properties
Highly Reactive with_
Compatible with Most metals
Shipped in_
ICC Classification Poison B < 200 Ib. Coast Guard Classification Poison B Label
Comments Usgd, jn bright copper electroplating-
Readily forms complex cyanides.
References (1) 1433
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Calcium cyanide (91) .
Structural Formula
IUC Name Calcium cyanide
Common Names "Black cyanide"
Molecular Wt. 92.12 Melting Pt. 1840 C Boiling Pt._
Density (Condensed) @ Density (gas) - @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point ^ Autoignition Temp.
Flammability Limits in Air (wt %) Lower - Upper_
Explosive Limits in Air (wt. %) Lower - Upper_
Solubility
Cold Hater Partial hydrolysis Hot Hater Ethanol_
Others:
Acid, Base Properties I" water becomes alkaline due to hydrolysis
Highly Reactive with weak acids to give HCN, decomposes in moist air. Solution alkaline.
Reacts with CQ? of air.
Compatible with
Shipped in 4 oz to 100 1b metal container
Poison label
ICC Classification Class B poison Coast Guard Classification
Coiranents Article of commerce contains 40-50% Ca(CN)?
References (1) 1433
135
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Copper cyanide (120)
Structural Formula
IUC Mama Cupric cyanide
Common Names
Cu(CN)
2
Molecular Wt. 115.61 Melting Pt. Decomposes Boiling Pt._
Density (Condensed) @ Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignitlon Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Hater Inso1 • Hot Water : Ethanol sol,
Others: Soluble in acids or. bases, sol in cyanide solution
Acid, Base Properties
Highly Reactive with Acid to give HCM. Not sjfcabie^can b& dried.
Compatible with_
Shipped in Glass bottles, special drums.
ICC Classification None. Coast Guard Classification,
Commen ts :
Not normally an item of commerce.
References (1) 1433
136
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Cuprous cyanide (128)
IUC Warns Cuprous cyantde
Common Names
Structural Formula
CuCN
89.56
Molecular Wt.
Density (Condensed) 2.92
Melting Pt
474 C
Boiling Pt.
G> 20
Density (gas)
Vapor Pressure (recommended 55 v and 20 0
Flash Point
Autolgnitlon Temp.
Flammabllity Limits in Air (wt %) Lower
Explosive Limits in Air (wt. X) Loaer
Solubility
Cold Hater
Insol
Hot Mater Insol
Upper_
Upper_
Ethanol
Others: Sol in NH^OH, alkali cyanide solutions
Acid, Base Properties None
Highly Reactive
Decomposed by HNO, and dil HC1.
Compatible with
Metals, glass
Shipped in 10Q-1b drums
ICC Classification None
Comments
Coast Guard Classification
References (1)
ias;
137
-------
HAZARDOUS WASTES PROPERTIES
hflRKSHEET
H. M. Name Lead cyanide (239)
IUC Name Lead cyanide
Structural Formula
Common Names
Pb(CN),
Molecular Wt.
Density (Condensed)
259.23
Melting Pt. decomp. Boiling Pt._
@ __ Density (gas) _ 9 _
Vapor Pressure (recommended 55 C and 20 Q)
Flash Point
Auto1gn1tion Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Mater slightly soluble Hot Water
Others: decomposes In arid;
Acid9 Base Properties
Ethanol
in NaCN solution
Highly Reactive with ac1ds
Compatible with_
Shipped in wooden kegs, fiber drums
ICC Classification none
Coast Guard Classification none
used in metallurgy
References (1) 1433
-------
HAZARDOUS WASTES PROPERTIES
KDRKSHEET
H. M. Name Nickel cyanide (295)
... , , • Structural Formula
IUC Wane Nickel cyanide
Common Names
Ni(CN)
2
Molecular Wt. -[82.81 _ Melting Pt. losses HgO @200 C Boiling Pt. decomposes
Density (Condensed) 146. a _ @_2Q_ _ C_ Density (gas) _ & __
Vapor Pressure (recommended 55 C and 20 C)
Flash Point _ - _ Autolgnition Temp. -
Flammability Limits in Air (wt %) Lower _ ; _ Upper
Explosive Limits in Air (wt. %) Lower _ - _ Upper
Solubility
Cold Water Insol. Hot Water Ethanol
Others: Slight sol, in dil acid.freely in alkali cyanide, ammonia and ammonium carbonate.
Acid, Base Properties
Highly Reactive with acids.
Compatible with_
Shipped jn Wooden kegs, glass bottles, fiber drums, paper sacks.
HPoison Label
ICC Classification Poison Label. Poison B<20Qlbcoast Guard Classification Poison B (2)
Comments Used in nickel plating. Commercial salt usually contains 20-25% water.
References (1) 1433
139
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name ^otessjurn cyanide (344)
IUC Mama Potassium cyanide
Common Names
Structural Formula
KCN
Molecular Ht.
65.11
Melting Pt. 634 c
Density (Condensed) ]-52 @ 20 _^ _ Density (gas)_
Boiling Pt..
Vapor Pressure (recommended 55 C and 20 Q
Flash Point
Auto1gnit1on Temp.
Flammabllity Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. 2) Lowsr_
Upper_
Upper_
Solubility
Cold Hater 33 qm/100 ml
Others:
C
Hot Water 50 gm/lQQ ml at TQQEthanolSO qm/100 ml
Acid, Base Properties Strongly alkaline in aqueous solution. pH of 0.1N
aq.soln. = 11.0
Highly Reactive with CO, in a1r9 acids, metal salts, oxidizers
Compatible with most metals at room temperature
Shipped in_
ICC Classification Poison B. Poison label
Article of commerce. 95% KCN
Coast Guard Classification Poison B,
Poison label
References (1) 1433
-------
m.^.^-.-A.-^^a'^J..!, .
HAZARDOUS MASTES PROPERTIES
t&RKSHEET
H. H. Mama Silver cyanide(370)
Structural Formula
IUC Kms Silver cyanide
Ccjmnon Wamss
Molecular felt. 133.90(1) Melting Pt. 320 C dec.(1) Boiling Pt._
Density (Condensed) 3.95 @ 20 C Density (gas) ?
Vapor Pressure (reconnietided 55 C and 20 (3
9 - © - C
Flash Point Auto1gn1t1on Jmp._
Flanonablllty Limits in Air (wt %) Lowar = Upper_
Explosive Limits in A1r (wt. %) Lo^sr = Upper_
Solubility
Cold Uater Insol. Hot Mater Insol. Ethanol Insol,
Others: Insol. dil. acids„ sol, in alkali cyanides
Acid, Base Properties
Highly Reactive with Darkens on exposure to air. HC1 releases to HCM.
Compatible with
Shipped in
Poison B
ICC Classification Poison B, Poison Label Coast Guard Classification Poison label
Comments.
References (1) 1433
141
-------
HA
H. H. Name Sodium cyanide (387)
IDC Name Sodium cyanide
Common Names
Molecular Ht. 49.02
ZARDOUS WASTES PROPERTIES
WJRKSHEET
Structural Formula
NaCN
Melting Pt. 560 C Boiling Pt. 1500 C
Density (Condensed) 1.60(cubic)g 20 C Density (gas) - 9
Vapor Pressure (recommended 55 C and
0.76 mmHg @ 800 C^
20 0
3.34 g 900 C ^ 36 mmHg @ 100 C^
Flash Point - Autolgnition Temp. -
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Solubility
Cold Water 32-8 gm/100 ml at
Lower - Upper
Lower - Upper
r(D
10 Hot Water 45 gm/100 ml at 34.7 tthanol si. sol.
Others: v- sol in lq- %
Acid,, Base Properties Strongly alkaline..
Highly Reactive with yhpn hpat-j>rf
reacts with molten NaCN. Is a aood
S Si ntroconrp nf fy^Arac nf Co r\v* U4 HArnmn^c-ar A 4 w»
redutijna substance. Reacts with acids to liheratP HPW
Compatible with most materials of construction.
Shipped in 25 Ib oackaoes. 100
ICC Classification Po1son C1ass B
ConraB»nt< Sold as 30% soln, 73-752,
,. 160. 200 Ib drums
Coast Guard Classification Poison Class B
96-98% briquettes „ qranular
References (1) 1433
142
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Zinc cyanide (457)
Structural Formula
IDC Name Zinc cyanide
Common Names
Zn(CN)
2
Molecular Wt. 117.42 Melting Pt. uPrnmp Ann r Boiling Pt._
Density (Condensed) @ Density (gas) @
Vapor Pressure (recommended 55 C and 20 Q)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 0.00058g/100g @18 C Hot Water Ethanol Insoluble
Others: Soluble in dilute mineral acids.
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification Poison B - Poison Label Coast Guard Classification Poison B
Commen ts „
References (1) 1433
143
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-6
3. Recipient's Accession No.
4. Title and subtitle Recommended Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume V, National
Disposal Site Candidate Waste Stream Constituent Profile
Reports - Pesticides and Cyanide Compounds
5. Report Date
Issuing date - Aug. 1973
6.
7. Amhorcsj R. s. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
G. I. Gruber, M. J. Santy, and C. C. Shih
8- Performing Organization Kept.
No- 21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089
12. Sponsoring Organization Name and Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Final
14.
15, Supplementary Notes
Volume V of 16 volumes.
16. Abstracts
This volume contains summary information and evaluation of waste management methods in
the form of Profile Reports for pesticides and inorganic cyanides. These Profile
Reports were prepared for either a particular hazardous waste stream'constituent or a
group of related constituents. Each Profile Report contains a discussion of the
general characteristics of the waste stream constituents, their toxicology and other
associated hazards, the definition of adequate management for the waste material, an
evaluation of the current waste management practices with regard to their adequacy, and
recommendation as to the most appropriate processing methods available and whether the
waste material should be considered as a candidate for National Disposal, Industrial
Disposal, or Municipal Disposal.
17. Key Words and Document Analysis. 17o. Descriptors
Pesticides
Inorganic Cyanide Compounds
National Disposal Site Candidate
Hazardous Wastes
17b. Identifiers/Open-Ended Terms
17C.COSATI Field/Group 06p.
. Q7C; 07E; ] -jg . -,
18. Availability Statement
Release to public.
- 144 -
19.. Security Class (This
Report)
UNCLASSIFIED
~...^-~-...~-~.. ... ~-
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
150
22. Price
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