EPA-440/9-76-018
BENZIDINE: WASTEWATER TREATMENT TECHNOLOGY
prepared by
THOMAS M. KEINATH, Ph.D.
for1
CRITERIA AND STANDARDS DIVISION
OFFICE OF WATER PLANNING AND STANDARDS
ENVIRONMENTAL PROTECTION AGENCY
%
June 1976
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PREFACE
Although many chemicals have been shown to induce cancer in
laboratory animals, only a few have been positively identified
as human carcinogens. Benzidine and its salts, without
question, are carcinogenic to humans.
Carcinogenic hazards to man may result from various types
of exposure associated with water. The presence of carcinogens
in drinking water, recreational water bodies, food processing
waters, or fisheries all are potential sources of human
exposure. Ample reason exists, therefore, to believe that the
presence of benzidine in the aquatic environment poses a threat
to man and the environment.
To secure information relative to (1) che occurrence of
benzidine in the v/astewaters of synthetic organic chemical
manufacturing facilities, (2) the occurrence of benzidine in
the wastewaters of benzi di ne-b ased dye users, (3) prospects for
no aqueous discharge, (4) applicable wastewater treatment
technology and (5) to establish the effect of benzidine on
publicly owned wastewater treatment facilities, the
Environmental Protection Agency contracted Dr. T.H. Keinath to
provide appropriate evidentiary material. Such material was
gathered, in part, through a questional're survey and through
personal visits to the Buffalo Dye Plant of Allied Chemical
Corporation, GAF Corporation, Fabricolor, Inc., Clyde Fabrics,
Inc., S. B. Foot Tanning Company, and Peninsular Paper Company.
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TABLE OF CONTENTS
TABLE OF CONTENTS 11
LIST OF FIGURES 1v
LIST OF TABLES 1v
PREFACE v1
I. EXECUTIVE SUMMARY 1
II. CHARACTERIZATION OF THE BEMZIDINE-BASED DYE
MANUFACTURING INDUSTRY 4
BENZIDINE'MANUFACTURE 4
WASTEWATER SOURCES AND HANDLING PROCEDURES 5
Allied Chemical Corporation • 5
Benzidine Sulfate Production 5
Dye Production 5
GAF Corporation 6
Benzidine Hydrochloride Production ..... 6
Dye Production 6
Fabrlcolor, Inc 6
Housekeeping Practices 7
WASTEWATER VOLUMES AND CHARACTERISTICS 7
Allied Chemical Corporation . 7
GAF Corporation 11
Fabrlcolor, Inc. 13
Literature Cited 14
III. BENZIDINE: WASTEWATER TREATMENT TECHNOLOGY 15
TREATMENT TECHNOLOGY ALTERNATIVES 15
OXIDATION WITH NITROUS ACID 15
Chemical Reactions 15
Waste Collection Systems. ..... . . 16
Allied Chemical Corporation . 16
GAF Corporation 18
Nitrous Acid Treatment Process .... 18
Allied Chemical Corporation 18
GAF Corporation ...20
Nitrous Acid Treatment Process Performance .... 20
Nitrous Add Treatment Costs 22
Allied Chemical Corporation 22
GAF Corporation . 23
Comments 23
OXIDATION WITH OZONE 25
Results of Laboratory Studies 25
Projected Process Costs .... 27
ADSORPTION WITH GRANULAR ACTIVATED CARBON 28
Process Design Parameters 28
Process Configuration and Operation 33
Process Costs . . . 35
Concerns of the Benzidine Task Force of SOCMA ... 38
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Page
ADSORPTION USING POLYMERIC ADSORBENTS 39
BIODEGRADATION USING THE ACTIVATED SLUDGE PROCESS .... 40
OTHER POTENTIAL TREATMENT METHODS . 45
NO AQUEOUS DISCHARGE 46
SUMMARY . • . . 46
LITERATURE CITED 49
IV. DISCHARGE OF BENZIDINE TO PUBLICLY OWNED TREATMENT WORKS . . 51
DISCHARGE LOCATIONS . . . 51
PRETREATMENT SYSTEMS 51
Allied Chemical Corporation 51
GAF Corporation 60
OCCURRENCE OF BENZIDINE IN POTW'S 60
EFFECTS OF BENZIDINE ON PUBLICLY OWNED TREATMENT WORKS ... 62
EFFLUENT LIMITATIONS FOR INDUSTRIAL DISCHARGES 63
Allied Chemical Corporation . . 63
GAF Corporation 65
Fabricolor, Inc 66
LITERATURE CITED 67
V. FEASIBLE TECHNOLOGIES FOR BENZIDINE TREATMENT .68
VI. CONTROL OF WASTEWATER DISCHARGES OF BENZIDINE-BASED
DYE APPLICATORS 71
ANALYSIS OF MASS BALANCE APPROACH . 72
Site Visit Surveys 72
Textile . . 72
Leather 74
Paper 77
Questional're Survey 80
Paper . . 80
Textile 83
Leather ........ 83
Analytical Surveys 85
Paper 85
Leather ........ 85
Textiles 87
POTENTIAL REDUCTION PROBLEMS 87
SUMMARY 90
LITERATURE CITED 91
VII. APPENDICES
A. INDUSTRIAL HYGIENE & ENVIRONMENTAL CONTROL EMPLOYED
BY THE BUFFALO DYE PLANT 92
B. CHLORAMINE T PROCEDURE FOR BENZIDINE DETECTABILITY
LIMITS 105
C. MASS BALANCE QUESTIONAIRE SURVEY 107
D. CORRESPONDENCE OF GAF & ALLIED CHEMICAL CORPORATION
TO CLIENTS REGARDING OXIDATIVE/REDUCTIVE
STRIPPING PROCEDURES 115
111
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LIST OF FIGURES
Page
III-l PROCESS FLOW SHEET FOR ACID NITRITE DECOMPOSITION
OF BENZIDINE 17
111-2 BENZIDINE DECONTAMINATION AT GAF 19
II1-3 ADSORPTION ISOTHERMS FOR ODD, DDT, ODE AND BENZIDINE . . 30
II1-4 ADSORPTION ISOTHERMS FOR AROCHLOR 1242, AROCHLOR
1254, AND BENZIDINE 31
IV-1 BUFFALO DYE PLANT PRETREATMENT FACILITY 53
IV-2 BUFFALO DYE PLANT PRETREATMENT PLANT SLUDGE BENZIDINE
CONCENTRATIONS 58
IV-3 SCHEMATIC FLOW DIAGRAM FOR GAF'S PRETREATMENT SYSTEM . . 61
LIST OF TABLES
Page
II-l BENZIDINE* CONTAINED IN DYE MOTHER LIQUORS ...... 9
I1-2 BENZIDINE IN COMBINED WASTEWATERS OF ALLIED'S BUFFALO
DYE PLANT 10
III-l BENZIDINE* CONTAINED IN NITROUS ACID TREATED WATERS . . 21
HI-2 TOXIC OR REFRACTORY INDUSTRIAL WASTEWATER TREATMENT
GRANULAR CARBON INSTALLATIONS (ON-SITE REACTIVATION) . . 36
III-3 TOXIC OR REFRACTORY INDUSTRIAL WASTEWATER TREATMENT
GRANULAR CARBON INSTALLATIONS (CENTRAL REACTIVATION) . . 37
III-4 COMPARISON OF POTENTIAL TREATMENT METHODS 48
IV-1 BENZIDINE IN PRETREATEO WASTEWATERS OF THE BUFFALO
DYE PLANT 55
IV-2 PHENOL IN PRETREATED WASTEWATERS OF THE BUFFALO DYE
PLANT 59
IV-3 PROPOSED EFFLUENT LIMITATIONS FOR INDUSTRIAL DISCHARGES
INTO SEWERS OPERATED BY THE BUFFALO SEWER AUTHORITY ... 64
1Y
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LIST OF TABLES (cont.)
Page
VI-1 CALCULATED MAXIMUM POSSIBLE BENZIDINE CONCENTRATIONS
IN THE WASTEWATERS OF CLYDE FABRICS, INC 73
VI-2 BENZIDINE CONCENTRATIONS IN EXHAUSTED DYE LIQUORS
AT CLYDE FABRICS, INC 75
VI-3 CALCULATED MAXIMUM POSSIBLE BENZIDINE CONCENTRATION
IN THE WASTEWATERS OF PENINSULAR PAPER CO 78
VI-4 BENZIDINE DISCHARGED BY FOUR PAPER MANUFACTURERS:
MASS BALANCE APPROACH 81
VI-5 SUMMARY OF MASS BALANCE APPROACH FOR PAPER, TEXTILE,
AND LEATHER MANUFACTURERS 82
VI-6 BENZIDINE DISCHARGED BY THREE TEXTILE GOODS MANUFACTURERS:
MASS BALANCE APPROACH 84
VI-7 BENZIDINE DISCHARGED BY TWO LEATHER MANUFACTURERS:
MASS BALANCE APPROACH . 86
VI—8 USE OF REDUCING AGENTS BY BENZIDINE-BASED DYE
APPLICATORS 89
V
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SECTION I
EXECUTIVE SUMMARY
At the time of this writing three manufacturers (GAF, Fabricolor, Inc.,
and Allied Chemical Corporation) produce benzidine-based dyes. Allied
Chemical Corporation, however, has announced that it will cease production
of such dyes by August 1976. Currently, 1.2 million pounds of benzi-
dine is used in the production of such dyes annually. The Benzidine Task
Force of SOCMA has estimated the number of benzidine-based dye applicators
at 1200 to 1500.
Housekeeping measures available to the various benzidine manufacturers
are adequate to prevent the discharge of benzidine directly to process
sewer lines.
Few, if any, process or in-plant changes would result in major benefits
with respect to the discharge of benzidine to the waste stream.
Benzidine can be effectively oxidized using the nitrous acid oxidation
procedure to end products such as phenol ics. Costs for thi'j process
were 3.86 and 12.3 cents per pound of product (benzidine) or $69.34 and
$46.53 per 1000 gallons of wastewater treated at GAF and Allied Chemical
Corporation, respectively. The difference in costs is r!ue to the use
of a filtering operation at Allied Chemical Corporation. This technology
can be implemented within one year.
Use of ozone for the degradation of benzidine in wastewaters appears
to be effective in reducing the concentration to the 1 to 10 ppb level.
Considerable additional research and several years are required to fully
evaluate the utility of this process. Projected process costs appear
excessively high.
Benzidine can be effectively removed from solution to the 1 to 10 ppb
level using the adsorption on granular activated carton procedure. This
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technology could probably be implemented within two years after requisite
pilot-scale studies have been conducted.
Benzidine at concentrations in excess of 1 ppm is not biologically de-
graded by the activated sludge process. At the 50 ppb level benzidine
is biodegradable. The vast majority (90+%) of benzidine that is removed
is biologically degraded while only small quantities (<10/0 are incor-
porated into the sludge mass.
Publically owned wastewater treatment facilities employing the activated
sludge process would not be adversely affected if the concentration of
benzidine in its influent were maintained at levels less than 1 ppm.
If pretreatment of the wastewater of a benzidine and/or direct dye man-
ufacturing facility was required, it could be accomplished using either
the nitrous acid oxidation or activated carbon adsorption methods.
The nitrous acid oxidation procedure for benzidine is the only technology
currently employed.
Concentrations of benzidine in the wastewater of a selected dye applicator
that represented a "heavy benzidine-based dye use" textile industry situation
averaged 13.32 ppb as calculated by the mass balance approach. Actual
analyses for benzidine performed on the exhausted dye liquors averaged
3.5 ppb. Similar mass balance analyses conducted for "heavy benzidine-
based dye use" leather and paper manufacturing concerns showed calculated
residual benzidine concentrations of 0.25 and 8.5 ppb, respectively.
A questional"re survey of three additional textile manufacturers showed
that average concentrations of benzidine that could have been present
in the wastewater (as calculated by the mass balance approach) ranged
from 0.15 to 0.414 pptt. A similar mass balance survey of two leather
and five paper manufacturing concerns showed average benzidine concent-
rations that ranged from 0.27 to 0.73 ppb and 0.0045 to 3.19 ppb, respect-
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3
ively. Corresponding maximum possible benzidine
concentrations for the textile, leather, and paper
manufacturing concerns surveyed ranged from 0.15 to 0.68
ppb, 0.76 to 1.29 ppb, and 0.02 to 3.19 ppb, respectively.
(13) A tabular summary of treatment technology alternatives has
been included as Table II-6.
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SECTION II
CHARACTERIZATION OF TEE BENZIDINE-BASED DYE MANUFACTURING INDUSTRY
BENZIDINE MANUFACTURE
Production of benzidine-based dyes in the United States is limited to three
manufacturing concerns: (1) Allied Chemical Corporation; (2) GAF Corporation;
and (3) Fabricolor, Inc. At the Buffalo Dye Plant of Allied Chemical Corporation
the benzidine-based dyestuffs are produced as follpws: (1) nitrobenzene, the
basic raw material, is charged to a closed reactor, where it is reduced to azox-
ybenzene by caustic in methanol; (2) the azoxybenzene is then transferred to a
second vessel where it is mixed with zinc, a solvent, and caustic, resulting in
its further reduction of hydrazobenzene; (3) the hydrazobenzene is subsequently
transferred to a third reactor where its rearrangement to benzidine sulfate oc-
curs upon the addition of sulfuric acid; (4) the benzidine sulfate is recovered
as a slurry after salting by pressure filtration; (5) the benzidine sulfate
slurry is then transferred to a closed tetrazotization reactor where acid and
sodium nitrite are added; and (6) the benzidine tetrazo is coupled with various
chemical constituents to form the dye. It is noteworthy that all transfers be-
tween reaction vessels are made through enclosed piping.
Neither GAF Corporation nor Fabricolor, Inc. produce hydrazobenzene as both
purchase the material from Lakeway Chemical Company of Muskegon, Michigan. At
GAF's Rensselaer Plant the hydrazobenzene is charged to a closed reactor and
is subsequently rearranged to benzidine hydrochloride upon the addition of water
and muriatic acid. The benzidine hydrochloride is subsequently transferred to
a closed tetrazotization chamber through enclosed piping. Upon tetrazotization
the tetrazo is coupled with various chemicals to form the dye.
At Fabricolor, Inc. of Paterson, New Jersey the hydrazo is reacted to form
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-5-
benzidine tetrazo which is subsequently filtered and clarified by a closed delivery
plate and frame filter press. The tetrazo is then coupled with various chemicals
to form the dyestuff.
WASTEWATER SOURCES AND HANDLING PROCEDURES
Due to the known carcinogenicity of benzidine, extraordinary care has been
taken in its manufacture in order to reduce its potential contact with workers.
As a result, the manufacturing environment has been severely controlled; a con-
dition which is reflected in relatively careful wastewater handling procedures.
Allied Chemical Corporation
Benzidine Sulfate Production ... Because the entire benzidine sulfate pro-
duction process is enclosed, possible direct discharge of the material is extremely
remote. Only the washdown waters from the slurry and salting tanks, the discharge
from the pressure filters, the air pollution control scrubber blow-down, the worker
clothing laundry wastes, and the floor washdown waters would likely contain ben-
zidine. These waters are collected either in a decontamination reaction vessel
or in a sump. All floor washings, furthermore, are directed to the sump. The
waters collected there are subsequently transferred to the decontamination vessel
for treatment by the nitrous acid oxidation procedure. Virtually no opportunity
exists for the discharge, either accidental or otherwise, of untreated benzidine
sulfate to the process sewer.
Dye Production ... After tetrazotization the tetrazo is coupled with various
chemicals in enclosed reactors to fo:Tn the dye. Although the dye product is
certified to contain no more than 20 ppm of benzidine, it is usually assayed in
the 10 to 13 ppm range. Since complete chemical conversion is not achieved in
the dye production reaction, trace quantities of benzidine would also likely be
contained in the dye mother liquors that are discharged from the dye filter
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presses to the process sewer. Dye production waste mother liquors and equipment
and operations area v/ash waters are not treated by the nitrous acid procedure
prior to discharge to the process sewer.
GAF Corporation
Benzidine Hydrochloride Production ... Since benzidine is not salted-out
and is not pressure filtered at GAF, no opportunity for the discharge of benzidine
from those unit processes exists. Only the air pollution control scrubber blow-
down, the worker shower wastes, and the floor washdown waters could possibly con-
tain benzidine. These waters are collected in a sump which also serves as a de-
contamination reaction vessel. The waters collected there are subsequently sub-
jected to decontamination by the nitrous acid oxidation procedure.
Dye Production ... As in the case of Allied Chemical Company, trace benzidine
concentrations are likely contained in the dye production wastewaters at GAF.
At GAF, however, only the waste dye mother liquors are not treated by the nitrous
acid procedure prior to discharge to the process sewer.
Fabvicolor, Inc.
The primary source of benzidine which could potentially be discharged to
the process sewer of Fabricolor, Inc. is the discharge of the filter.press which
is employed to filter and clarify the benzidine tetrazo. After filtering a batch
of the tetrazo, the material is transferred via a closed system to a coupling vessel.
After transfer, the filter press is washed with water while closed. The washings
are also transferred to the coupling vessel. Subsequently a bleach solution is
introduced to the filter press. This decontamination solution is then discharged
to the process sewer. The press is then opened and the solid residue is removed
and transported to a landfill.
The benzidine-based dye mother liquors constitute a secondary source of ben-
zidine that could be discharged to the process sewer at Fabricolor, Inc. Like
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the other two manufacturers of benzidine-based dyes, Fabricolor discharges the
mother liquors directly to the process sewer.
At Fabricolor, Inc. no provision has been made for the treatment of floor
washdown and air scrubber waters. It is noteworthy, furthermore, that Fabricolor,
Inc. has no worker showers which cotild potentially be a source of benzidine that
could be discharged into the wastewater stream.
Housekeeping Practices
Due to the long-term recognition of the carcinogenicity of benzidine and
the recent implementation of the Occupational Safety and Health Act, the house-
keeping practices employed by benzidine sulfate (chloride) manufacturers are
extremely stringent. (As an example, Allied Chemical Corporation's operating,
maintenance, and control practices related to the industrial hygiene program for
benzidine have been include as Appendix A.) Accordingly, one can conclude with
relative assurance that no in-plant or production process changes would result
in major benefits with respect to the discharge of benzidine to the wastewater
stream.
WASTEWATER VOLUi-ES AND CHARACTERISTICS
Allied Chemical Corporation
At Allied Chemical Company's manufacturing facility approximately 2.64 million
gallons (22 million pounds) of wastewater is discharged annually due to the pro-
duction of benzidine at a production level of one million pounds expressedas
benzidine sulfate. This represents approximately seven to eight-tenths of one-
percent of the total wastewater flow (370 million gallons). One analysis for
benzidine has been conducted on the benzidine production process wastewaters
prior to decontamination by the nitrous acid oxidation procedure. This analysis
showed a concentration of benzidine of 963 ppm. Allied produces approximately
4.4 million pounds of benzidine-based dyes annually.
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Benzidine concentration levels contained in the dye production wastewaters
at Allied's Buffalo Dye Plant have been recorded in Table II-l for fourteen dye
mother liquor samples obtained from the dye filter press exhausts during 1974.
Half of the fourteen samples showed less than detectable levels of benzidine while
the others showed levels that ranged from 30 to 115 ppb.
If one assumed that those samples that contained less than detectable levels
actually contained 10 ppb, then an average concentration of benzidine of 33.7
ppb can be calculated for the data presented. Assuming an average daily dye pro-
duction of 16,200 pounds and an average mother liquor discharge of 84,000 pounds,
one can estimate an expected average daily mass discharge of benzidine of approx-
-3
imately 2.8 x 10 pounds in the dye production wastewaters.
As noted earlier, the discharge from the nitrous acid treatment process
is sewered and thence diluted with other manufacturing wastewaters at the Buffalo
Dye Plant which contain, in addition to the usual dye and pigment manufacture
wastes, wastewaters from solutions used to clean equipment, wastes from dye inter-
mediate manufacture and from the manufacture of organic specialties such as dimethyl
aniline, diethyl aniline, resin chemicals and special acid anhydrides. The de-
tectability limit for benzidine in the diluted matrix is 2 - 5 ppb using the chlor-
amine-T procedure.
Results of analyses performed on the combined wastewater flow from Allied's
Buffalo Dye Plant during the period which extends from 24 March to 31 May 1974
have been summarized in Table I1-2. All analyses were performed on 24-hour com-
posite samples collected at 0800 hours at the influent to the pretreatment works.
During the period of analysis, benzidine was manufactured at approximately rated
capacity and the nitrous acid treatment performance was deemed to be operating
at best attainable efficiency. It is noteworthy, however, that on 31 March 1974
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TABLE II-l
Benzidine* Contained in Dye Mother Liquors
Date
Dye Type
Lbs. Dye
Lbs. Waste
Benzidine
Per Batch
Per Batch
Cone, (ppb)
3-21-74
Erie Fast Red FD
1150
18,000
64
3-26-74
Erie Catchine 3G
1300
16,000
<10
3-27-74
Erie Black GXOO
16,600
73,000
<10
3-28-74
Milling Scarlet
1000
15,000
<10
3-28-74
Erie Orange 2R
1730
13,000
50
3-28-74
Erie Brown 3GN
8600
34,000
<10
4-25-74
Erie Green GPD
2500
68,000
63
5-16-74
Erie Scarlet B
700
10,000
115
7-29-74
Erie Black GXOO
16,600
73,000
30
7-30-74
Erie Black GXOO
16,600
73,000
<10
7-31-74
Erie Black GXOO
16,600
73,000
30
8-1-74
Erie Black GXOO
16,600
73,000
<10
8-2-74
Erie Black GXOO
16,600
73,000
<10
8-8-74
Lanamid Golden Brown
1800
-
50
* Level of Detectability = 10 ppb.
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IV-
TABLE I1-2
Benzidine in Combined Wastewaters of Allied's Buffalo Dye Plant
Date
WW/Flow
(105 lbs/day)
Benzidine Cone,
(ppb)
Benzidine Loading
(lbs/day)
3-24-74
10.4
110
1.1
3-28-74
12.9
30
0.3
4-1 -74
11.5
650
5.2
4-5-74
10.9
190
2.2
4-9-74
12.7
*
-
4-13-74
10.1
80
0.8
4-17-74
12.9
30
0.4
4-21-74
10.8
70
0.8
4-25-74
13.0
100
0.1
4-29-74
13.1
120
0.2
5-3-74
11.2
50
O.b
5-7-74
10.1
*
-
5-11-74
13.6
10
0.2
5-19-74
8.7
*
-
5-27-74
8.4
20
0.2
5-31-74
11.1
50
0.5
Note: * indicates a concentration < 2-5 ppb
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-11-
approxirnately one to two pounds of benzidine were washed directly
to the process sewer system when the Vallez filter in Building 54
developed a leak. This was reflected in high loadings .on 1 &
2 April.
The data shown in Table II-2 was analyzed statistically {11 - 3) in
two ways; including (llode 1) each of the 16 data points assuming
that the three samples that showed less than detectable
concentration had concentrations of 5.0 ppb, and excluding (Mode
2) those values which fall outside the high 99% confidence limit
the analysis showed the following were loadings in pounds per day
The date point for 1 April (a high value which is attributable to
a preventable occurrence).
Mode 1 Mode 2
Average 0.80' 0. 38
Std. Deviation 1.30 0. 33
High 95% Conf. 1.49 0.57
High 99% Conf. 1.75 0.65
Comparison of the total average daily quantity of benzidine
discharged in the combined wastewater stream (0.38 pounds) with
the sum of the daily contribution of benzidine from the two
primary sources (0.0036) shows tl.at 99 percent of the benzidine
that appears in the combined wastewater flow cannot be accounted
for through an analysis of the point source contributions (dye
manufacture wastes and nitrous acid treated effluents). The most
plausible explanation for this anomaly is that benzidine-based
dyes or other benzidine derivatives are reduced in-situ to
benzidine 1n the process sewers.
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-12"
GAF Corporati on
Because GAF does not filter benzidine dihydrochlorlde, only
the air pollution control scrubber blow-down, worker shower
wastes, floor v/ashdown waters and dye mother liquors are
ultimately discharged from the benzidine-based dye manufacturing
building. The volume of discharge from the first three sources
is approximately 78,000 gallons (650,000 pounds) annually. This
represents approximately 7.8 thousanths of one-percent of the
total wastewater flow (1 billion gallons) or 18.5 thousanths of
one-percent of the process water flow (421 million qaHons) at
the Rensselaer Plant, No analyses for benzidine have been
conducted on the process wastewaters prior to decontamination by
the nitrous acid oxidation procedure. GAF annually produces
140,000 pounds of benzidine and 1.2 million pounds of benzidine-
based dyes.
Benzidine concentration levels contained in the discharge
from the building in which the benzidine and benzidine-based dyes
are produced (600,000 gallons per day average flow) were
determined to be less than detectable (detectabi1ity limit = 5
ppb) in 45 of 52 daily composite samples. This corresponds to
mass discharges of less than 0.025 pounds per day.
Concentrations of benzidine in the remaining seven samples ranged
from 12 to 134 ppb and averaged 50 ppb.
Results of 84 of 89 analyses for benzidine performed on
composite samples of the combined wastewater flow from the GAF
plant at Rensselaer showed concentration levels less than the
level of detectabi1ity (1.0 ppb). This corresponds to mass
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-13-
discharges of less than 0.037 pounds per day from the Rensselaer facility. Of
the five that contained detectable benzidine, three had concentrations less than
5 ppb, one had a concentration of 26 ppb, and the other a concentration of 42
ppb.
Fabricator, Inc.
Total wastewater flows at Fabricolor, Inc. average approximately 15.5 million
gallons (129 million pounds) annually which derives from an average daily flow
rate of 50,000 gallons/day over a 6-day work-v/eek. Fabricolor produces benzidine
dyes batchwise, one batch per day, two days per week. Manufacturing effluents
associated with the production of a batch include 360 gallons (3000 pounds) of
aqueous wastes from the filter press wash and 6950 gallons (58,000 pounds) of
filtrate water. Analyses performed for Fabricolor, Inc. by International Hydronics,
Inc. on a grab sample of these waste streams showed concentrations of benzidine
of 16 and 72 ppb, respectively, as determined by the Chloramine T procedure.
Moreover, the air scrubber blow-down which contributes 180 gallons (1500 pounds)
of water per batch was assayed at 24 ppb of benzidine. The total discharge of
benzidine on days during which benzidine-based dyes were manufactured was thus
calculated to be 4.26 x 10~3 pounds per day. If averaged over the total daily
discharge, a concentration level of 10.2 ppb of benzidine could be anticipated.
Results of analyses performed on a 24-hour composite sample of the total
process wastewater stream are as follows:
pH
Turbidity
Total Solids
Suspended Solids
Volatile Solids
Volatile Suspended Solids
COD
B0D5
T0C
Cobalt
Copper
Chromium, hexavalent
Chromium, trivalent
2.9
1700 JTU
14,656 ppm
124 ppm
1031 ppm
87 ppm
1000 ppm
175 ppm
309 ppm
0.4 ppm
1.83 ppm
0.01 ppm
0.12 ppm
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Fabricolor annually produces 60,000 pounds of benzidine and
0,5 million pounds of benzidine-based dyes.
Literature Cited
II - 1 Leter to A. W. Breidenbach, EPA, June 1, 1976 by A. J. von
Frank, Corporati on Director, Pollution Control, Allied Chemical
Corporation concerning questions posed by EPA.
i I - 2 Letter to A. I/. Breidenbach, EPA, June 1 , 1976 by M. A. Brodwell ,
Production Manager, Rensselaer,, II. Y., GAF Corporation, concerning
questions posed by EPA.
II - 3 K.A. Brown lee, Industrial Experimentation, (Mew York, New York,
Chemical Publishing Conpany, Inc. 1953)
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SECTION III
BENZIDINE: WASTEWATER TREATMENT TECHNOLOGY
TREATMENT TECHNOLOGY ALTERNATIVES
Development of treatment technology for the destruction or removal of ben-
zidine from wastewaters has occurred only recently, certainly not more than a
decade ago. Various treatment procedures that have been proposed as potentially
feasible methods include destruction using ionizing (gamma) radiation, oxidation
using ozone, hydrogen peroxide, or nitrous acid, adsorption on granular activated
carbon, and biodegradation using the activated sludge process. Neither the ion-
izing radiation npr the oxidation procedure using hydrogen peroxide have, to the
knowledge of the author, been evaluated directly using the carcinogen, benzidine.
Only the oxidation procedure using nitrous acid has been implemented at plant
scale by two of the three benzidine dye manufacturers (Allied Chemical Corpora-
tion & GAF Corporation) ani for treating benzidine manufacture wastewater.
OXIDATION WITH NITROUS ACID
Chemioal Reactions
Reaction of benzidine with excess nitrous acid in a strong acid'medium yields
the benzidine tetrazonium salt. The reaction has been observed by Dien (III-l)
to be practically quantitative. Further, little or no benzidine can be detected
in the completed reaction mass. The benzidine tetrazonium salt, however, is
not stable. It has been noted by Dien to decompose slowly and spontaneously
at ambient temperatures and very readily at higher temperatures. The decomposi-
tion products in acidic medium Include phenyl phenol, diphenyl dlchloride, di-
hydroxybiphenyl, and hydroxychlorobiphenyl as major constituents and phenol and
bi phenyl phenol ap minor constituents. No benzidine and no polychlorinated
-------
-16-
biphenyls other than dichlorobiphenyl can be detected in the acid decomposed pro-
duct.
In an alkali medium, the benzidine tetrazonium salt also decomposes with
the evolution of nitrogen gas. The product is a highly colored material which
probably is an azo compound which is formed when the decomposed phenolic product
acts as a coupler and reacts with the tetrazonium salt. Under oxidizing conditions,
these azo compounds as well as the benzidine tetrazonium salt can be expected
to degrade to di-pheno quinone. Only under strong or catalytic reducing condi-
tions would the possibility exist, that these azo compounds could revert back
to benzidine itself.
A process schematic diagram has been provided by the Task Force on Benzidine
of the Synthetic Organic Chemicals Manufacturing Association (SOCMA). The dia-
gram has been labeled as Figure III-l and has been included herein.
Waste Collection Systems
Allied Chemical Corporation ... The nitrous acid treatment method has been
implemented at the Buffalo Dye Plant of Allied Chemical Corporation. At that
location (see Figure III-l) the filtrate and/or wastes from the Vallez filter
flow directly into the rubber lined, agitated, 3000 gallon treatment reactor.
Drainage from the product sampling box is directed into the holding tank which
feeds the treatment reactor. Drainage from the process scrubber is routed
directly to the treatment reactor. All other process wastes including the dis-
charges of the locker room shower and laundry washing machine are directed from
the floor drains to the double sump on the first floor of Building 54. These
wastes are subsequently pumped from the sump via pumps to the holding tank.
One pump is employed as the primary pump while the other serves as a spare being
activated by a hi/gh level switch in the sump.
-------
r—
—1
1CF
TO Sfcvslfc*
FIGURE III-l
Process Flow Sheet For
Acid Nitrite Decomposition of Benzidine
-------
-18-
GAF Corporation ... Also using the nitrous acid oxidation procedure GAF
discharges all floor washings, shower and change room discharges, and the blow-
down of the caustic scrubber into a 5000 gallon catch tank. A schematic dia-
gram of the system is shown in Figure II1-2. When approximately 3000 gallons
of wastewater has been collected (ca. 2 weeks elapsed time) the nitrous acid
oxidation process is initiated. After treatment, the contents of the catch tank
are discharged to the process sewer.
Nitrous Acid Treatment Process
Allied Chemical Corporation ... When approximately 2500 gallons of process
and wash-down wastewaters have been collected in the treatment reactor the fol-
lowing bat-ch treatment procedure is initiated (refer to Figure III-l):
(1) Fill H2S04 measuring tank (3-MT-18).
(2) Mix 208 NaN02 solution in 3-PAT-l.
(3) Transfer filtrate from Vallez pressure filter (PF-2) to RAT-8
along with the first wash from PF-2 to RAT-8 to total volume
of 2F0G gallons (20,850 pounds).
(«0 Circulate the contents of RAT-8 through the cooler (C-28)
using a pump (1 CP-54) until the temperature of the con-
tents of RAT-8 has been reduced to 10° C.
(5) Add H2SO4 from 3-MT-18 to RAT-8 as necessary to hold contents
of RAT-8 acid to Congo Red indicator paper (pH a 2.0).
(6) Slowly transfer the 20 percent sodium nitrite solution from
3-PAT-l to RAT-8. Sample and check with starch-iodide at
15-minute intervals. When the test shows the presence of
nitrite after 30 minutes, the contents of RAT-8 are drained
to the process waste treatment sewer, where it undergoes
dilution and further treatment (pretreatment) which consists
of equllization, neutralization, and clarification prior to
discharge to the municipal sewer.
(7) The above procedure is repeated for the balance of the washes
from PF-2.
(8) The above procedure Is repeated for the treatment of accumu-
lated liquids from drains which collect in PHT-1 after trans-
ferring contents of PHT-1 to RAT-8.
-------
FIGURE III-2
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-------
-20-
Tandem air-operated valves are used on the inlet and drain lines of the
treatment reactor. Air piping to these valves is arranged such that both are
operated by a single cock. In this manner the inlet valve is closed when the
drain valve is open and visa versa. This system prevents the introduction of
untreated effluent to the treatment reactor while the drain valve is open.
The treatment system is rated at five charges per day. Currently approx-
imately three batches are processed per day.
GAF Corporation ... Essentially the same procedure is employed by the GAF
Corporation with the exception that muriatic acid is used in place of sulfuric
acid. Also, the temperature is reduced to 10°C using ice rather than a cooler.
In all other respects the chemical treatment procedure is identical.
'Although the batch treatment process at GAF could accommodate three to five
charges per day, at current production levels only one batch of 3000 gallons is
treated bi-weekly.
Nitrous Acid Treatment Process Performance
Allied Chemical Corporation has conducted analyses for benzidine on samples
of wastewaters treated using the nitrous acid oxidation procedure. Results of
such analyses have been tabulated in Table III-l. Of the eleven samples analyzed,
nine showed concentrations less than the detectable level (10 ppb; refer to Ap-
pendix B) while two showed concentrations of 190 and 218 ppb.
If one were to assume that the average concentration of benzidine in the
nitrous acid treated matrix was 10 ppb, then one would expect that approximately
8 x 10~4 pounds of benzidine would be discharged daily along with an average
of 9700 gallons of nitrous acid treated effluent at the Buffalo Dye Plant.
GAF has also conducted analyses on the nitrous acid treated effluent. Be-
cause the procedure they used for the ch1oram1ne-T method for benzidine lacked
sensitivity (detectabillty limit of 10 to 20 ppb), all of their results showed
-------
TABLE II1-1
Benzidine* Contained In Nitrous Acid Treated Wastes
Type of
Benzidine
Date
WW Treated
PH
Cone, (ppb)
8-21-74
Filter Press Filtrate
2.2
190
8-30-74
Filter Press Filtrate
1.5
<10
8-30-74
Filter Press Filtrate
1.5
<10
8-30-74
Filter Press Filtrate
1.6
<10
8-30-74
Filter Press Mash Water
1.5
<10
9-1-74
Filter Press Filtrate
2.1
218
9-3-74
Filter Press Wash Mater
1.6
<10
9-1-74
Filter Press Wash Water
4.2
<10
9-1-74
Filter Press Wash Water
4.0
<10
9-5-74
Filter Press Wash Water
2.4
<10
9-7-74
Filter Press Wash Water
1.9
<10
* Level of Detectab111ty » 10 ppb.
-------
-22-
non-detectable levels of benzidine. Nonetheless, their results partially, but
not conclusively, confirmed the results obtained by Allied.
As above, If one were to assume that the concentration of benzidine in the
nitrous acid treated matrix v/as 10 ppb, then one would expect that approximately
2.5 x 10"® pounds of benzidine would be discharged daily with an average of 300
gallons of nitrous acid treated effluent at GAF's Rennsselaer Plant.
Nitrous A aid Treatment Costs
Allied Chemical Coryovation ... Capital construction and operation and main-
tenance costs have been estimated for the nitrous acid oxidation method by the
Benzidine Task Force of SOCMA. The capital costs (1959 index) have been de-
tailed as follows for the Buffalo Dye Plant:
Cost ($)
Description of Element
Material
Labor
Nitrite Dissolution & Distribution System
5400
4300
Acid Distribution Piping
3000
3500
pH and Sample Controls at RAT-8
1200
1200
Acid Sump Pump (CP-52 and Piping to PHT-1)
5200
2800
Holding Tank (PHT-1)
2300
1400
Pump (CP-54) for Circulation
6000
3800
Graphite Cooler (C-28)
15,500
5000
Sewer Revisions
400
800
Decontamination
-
300
Construction Overhead
15,000
-
Engineering
13,600
-
Totals
67,600
23,100
TOTAL CAPITAL COSTS
$90,700
-------
-23-
Moreover, it has been estimated that the annual costs for O&M are $108,000
(II1-4). Assuming that the capital is amortized at 10 percent over a 10-year
period, then the annual capital costs are calculated to be $14,745. The total
annual costs then are $122,745 for the system which has been installed at the
Buffalo Dye Plant of the Allied Chemcial Corporation.
A total of one million pounds of benzidine sulfate expressed as benzidine
is produced by Allied Chemical Corporation annually. Associated with this level
of production, a total of 2,637,900 gallons of wastewater is produced annually.
Expressing the cost of using the nitrous acid process to oxidize the benzidine
in the wastewater on a unit cost basis one determines that the cost per 1000
gallons of wastewater treated is $46.53 while the cost expressed on a per pound
of product (benzidine sulfate) basis is equivalent to 12.3 cents.
GAF Corporation ... A complete breakout of the capital cost elements assoc-
iated with the construction of the nitrous acid treatment process at the Renss-
elaer plant is not available. Nonetheless, the total capital cost of the system
was estimated at $3000 (1965 index) and the operating cost was estimated at ap-
proximately $5000 per annum (III-3). Assuming that the capital is amortized at
10 percent over a 10-year period, then the annual capital costs are calculated
to*be $409. The total annual costs for the system which has been Installed by
GAF Corporation then are $5409.
Since GAF's annual discharge is 78,000 gallons, the unit costs for the nit-
rous acid treatment system 1s $69.34 per 1000 gallons of wastewater treated.
Expressed on a per pound of product (benzidine; 140,000 pounds annual) basis
the cost 1s equivalent to 3.86 cents.
Comenta ... Although the unit costs on a per 1000 gallon basis appear high
1n contrast to cost f/lgures for the treatment of other Industrial wastewaters,
the total annual costs are not prohibitive for Allied Chemical Corporation and
-------
-24-
GAF Corporation. The unit costs are high primarily because extensive v/ater con-
servation measures are practiced by these two manufacturers.
The unit costs on a per pound of product basis incurred by Allied are higher
by a factor of 3.6 than those incurred by GAF. This is due to the fact that
Allied's Buffalo Dye Plant uses a Vallez filter to filter the benzidine sulfate
whereas GAF uses no such filter. The filtering operation is the source of the
majority cf the benzidine production process wastewater which averages 2.64
gallons per pound of benzidine produced at the Buffalo Dye Plant. In contrast,
GAF uses approximately 0.5 gallons of water per pound of product.
-------
-25-
OXIDATION WITH OZONE
Studies pertaining to the use of ozone for the purpose of oxidizing benzidine
to innocuous end products have been confined to the laboratory to date. Three
such laboratory bench-scale studies were conducted either by or under contract
to Allied Chemical Corporation and have been reported by the Benzidine Task Force
of SOCMA. (II1-5)
Results of Laboratory Studies
The first of the three batch studies was conducted using a distilled water
matrix spiked with 117 ppm benzidine. Using a glass bubbler system through
which ozone was applied at the rate of 0.605 liters per minute to four liters
of the sample, the following results were obtained:
Time
(min.)
Ozone Absorbed
(ppm)
% Ozone
Absorbed
Residual Benzidine
(ppm)
0
0
0
117
3
51
38.3
103
6
80
30.2
63
12
115
21.9
19
18
1
24
170
15.9
0.09
36
219
13.9
O'.Ol
Qualitatively it was noted that originally the solution was clear, then turned
to a light brown color, then to dark brown, then to a yellow color, and finally
to a faint yellow. From the data, it was concluded that ozone effectively oxid-
ized benzidine and its intermediates.
Subsequently, a study was conducted using benzidine spiked samples of the
effluent of the Pretreatment Works of Allied's Buffalo Dye Plant. One sample was
analyzed as a blank 'while four samples were ozonated for various periods to
residual ozone concentration levels of 240, 495, 715, and 950 ppm. These were
-------
-26-
subsequently subjected to analysis. Results of this study are tabulated as:
Parameter Ozone Concentration (ppm)
0
248
295
715
950
Benzidine (ppb)
207
1
1
-
-
COD (ppm)
514
-
375
356
336
TOC (ppm)
313
290
201
140
166
Oil & Grease (ppm)
3.4
2.4
0.8
.0.6
0.4
NH3 (ppm)
27
23
24
24
26
SS (ppm)
25
52
71
85
116
PH
8.0
6.4
5.2
5.4
5.5
Co': or
2000
200
40
40
40
One can observe that ozone very effectively oxidized benzidine and reduced the
concentration of several other parameters. It is noteworthy, furthermore, that
the pH decreased for higher ozone dosages. This is likely due to the fact that
ozone attacks double bonds in organic compounds and usually forms different
organic acids because of the oxygen replacement of the.carbon-carbon double
bond.
Although the preliminary laboratory studies were positive regarding the
oxidation of benzidine, it is important to point out that many important questions
remain unanswered. For example: (1) what effect do other organics normally
found in the wastewater have on the ozone dosage requirements and on the kinetics
of oxidation? (2) what are the by-products of the oxidation? These, as well
as several other unknowns, must be elucidated before the technical feasibility
of employing ozone for the oxidation of benzidine can truly be established.
-------
-27-
At this time, ozonation cannot be regarded as a viable treatment alternative
for benzidine due to an inadequate data base.
Projected Process Costs
Based on the preliminary laboratory studies, order-of-magnitude process
cost projections have been made (III-5). Assuming that ozone would have to be
applied at a dosage of 500 ppm to achieve the desired reductions in benzidine
in the effluent of Allied's Buffalo Dye Plant, the daily ozone requirement is
projected c.t 25,000 pounds. This would require a capital expenditure for ozona-
tion equipment of approximately 3.8 million dollars. The installed cost would
logically be twice the equipment cost.
Annual operating expenses for maintaining such an ozonation system have
been estimated (II1-5) as follows:
Electrical Power @ $Q.02/kwh
$ 890,000
Oxygen @ $0.025/1b.
365,000
Depreciation @ 10% of capital
750,000
Maintenance @ 5% of capital
350,000
Taxes, insurance, etc. @ 1.5% of capital
100,000
Labor (1 man/shift)
40,000
TOTAL
$2,495,000
While these projections give an order-of-magnitude estimate of the costs
which would be incurred, realistic cost estimates could only be made after
extensive laboratory-and pilot-scale studies have been conducted. These would
unequivocably establish the ozone consumption requirements. Such studies would
likely require a one to three-year study period. They could potentially show
an ozone consumption rate of one-quarter to twice that used for the cost analysis
given above. Obviously* this could dramatically affect the costs for implementing
the ozonation process; either upward or downward.
-------
-28-
ADSORPTION WITH GRANULAR ACTIVATED CARBON
Although the adsorption process was known in ancient times, it was not
until the 20th century that powdered carbon was used on a large scale for the
removal of taste-and-odor-causing constituents from potable waters. Subsequent
development of granular activated carbons during the 1930's led to the expanded
use of active carbon; for sugar decolorization, solvent recovery, and liquid
and gas purification during the late 1940's. As part of the Advanced Waste
Treatment Program (19601s) of the Federal Water Pollution Control Administration
(FWPCA) the adsorption process was shown to be technically sound and economically
attractive for the removal of refractory and toxic dissolved organics from waste-
waters .
As early as 1951 evidence exists in the literature relative to the. removal
of certain toxicants and carcinogens from solution using activated carbons
(III-6, II1-7, & II1-8). The first experimental data which showed that benzidine
itself could be effectively removed from wastewaters using granular activated
carbon was provided by Sterbacek, Tausk, and Trca (III-9). Recently, Hager and
Rizzo (111-10) conducted a broad spectrum adsorption isotherm study on many
organic toxicants and concluded that the compounds selected could prbbably be
effectively removed from water by adsorption. In all cases preliminary evid-
ence indicated that the adsorption process could potentially be employed to
treat a wastewater to the extent that it would meet the EPA effluent objectives
for toxic chemicals studied.
"Process Design Parameters
Design of any adsorption system requires specification both of adsorption
equilibria and kinetics. A laboratory adsorption Isotherm testing procedure
(adsorption equilibria} 1s a reliable technique to ascertain the technical
feasibility of treatment using granular activated carbon. This testing procedure
-------
-29-
specifically estimates:
(1) The probable effluent levels of contaminant concentration
obtainable by adsorption treatment.
(2) The weight of contaminant that will be adsorbed by the ad-
sorbent at the contaminant concentrations studied.
A cursory, three-point adsorption isotherm conducted by the Benzidine Task
Force of SOCMA (II1-11) using Filtrasorb 300 (a product of Calgon Corp.) showed
adsorption capacities for benzidine of 7.1, 4.22, and 2.19 percent by weight
for equilibrium aqueous-phase concentrations of benzidine of 14,900, 900, and
10 micrograms per liter, respectively. This data has been plotted in Figures
111-3 and III-4 along with comparable data reported by Hager and Rizzo (111-10)
for DDD, uDT, DDE, and two isomers of the PCB family. Generally, the data shows
that benzidine adsorbed better than the five other toxicants. Only for the higher
solution-phase concentrations (greater than 10 micrograms per liter) did DDD and
Arochlor 1242 (a PCB isomer) adsorb better than benzidine. Based on the isotherm
data presented, it appears that adsorption on granular activated carbon is a
technically feasible process for removing benzidine from wastewaters. It should
be cautioned, however, that the data base is extremely sketchy.
Two additional considerations relating to the isotherms are worthy of men-
tion. First, because of the limitations of the Chloramine-T procedure for ben-
zidine, residual solution concentrations of less than 5 ppb cannot be determined.
Consequently, the isotherm for benzidine was extrapolated (dashed line) for
concentrations less than 5 ppb. Based on the Isotherms presented by Hager and
Rizzo (I11-10) and a thorough knowledge of the adsorption process, the actual
benzidine isotherm in this range of concentrations (1 to 5 ppb) would be ex-
pected to closely approximate that which was extrapolated.
-------
i'u.3 ' m m Kxziom
fllTERED
iCq
ft£TB?£D SAMPLE
i£? filtered
BENZIDINE
Contaminant Cr>» ^7T—
c°ncentraiion (p . 0
(Ports Per a„,on)
f
o>
0
1
-------
PIGUHE III—4
ADSORPTION ISOTHERMS FOR AROCHLOR 1242, AROCKLOR 1254, AND BENZIDINE
%Weight Pickup
1.0
0.1
0.01
BENZIDINE
AROCHLOR 1242,
AROCHLOR1254
FILTERED
FILTERED
—>
Co
I I I MINI I I I i mil i I I Mini
0.1 1.0 lO.O 100.0
Contaminant Concentration (Parts Per Billion)
-------
-32-
Secondly, the solubility of benzidine sulfate is approximately 80 mg/1
(III-ll). Consequently, if benzidine sulfate were present in the wastewater
at concentrations in excess of that level, then the excess could readily be
removed through diatomaceous earth (DE) filtration. In such cases a DE fil-
tration system would preceed the activated carbon contactor.
Specification of the kinetics or rates of adsorption cannot usually be ac-
hieved in the laboratory. Determination of the contact time required (for gran-
ular carbon beds) to effect desired reductions in benzidine concentration on
a wastewater would usually be performed in small pilot carbon beds under dynamic
hydraulic flow conditions. This is a well-established procedure which serves
to determine the number of contactors, the activated carbon inventory, and the
actual contact time required for a prototype installation. Whereas the isotherm
data serves to establish the technical feasibility of the adsorption process*
pilot-scale information is required to establish the economic feasibility of
employing the adsorption process for any specific application. No pilot-scale
studies have to date been conducted on a wastewater which contains benzidine.
Consequently, prototype process economics cannot be directly established, but
can only be indirectly approximated through analysis of the economics of existing
adsorption installations.
Requisite pilot-scale studies and more comprehensive isotherm studies
could logically be completed during a one-year study period. Upon completion
of such a study, the adsorption technology could likely be implemented within
one to two years. It is imperative to note, however, that such studies must
be completed before management decisions regarding the adsorption process can
be made.
-------
-33-
Process Configuration and Operation
An adsorption installation which could be employed for removing benzidine
from wastewaters would likely consist of the following process, elements: (1)
a diatamaceous earth filtration system; (2) a series of activated carbon cont-
actors; (3) a carbon reactivation furnace; and (4) a carbon-water transport
system. As was indicated above, a DE filtration system would be installed if
benzidine sulfate were present in the wastewater at concentrations in excess
of 80 mg/1, the solubility limit. This unit process would be installed in
advance of the carbon contactor in the process stream. It would serve to remove
any particulate benzidine sulfate from the waste stream allowing only the sol-
uble benzidine to pass on to the carbon contactors. It was shown earlier that
the soluble benzidine can probably be removed from the waste stream through
adsorption on granular activated carbon.
The adsorbers contain the granular activated carbon beds through which
the wastewater flows. They can be designed either for pressure or gravity flow
to achieve the desired contact time of the water with the carbon. Flow rates
usually are under 10 gallons per minute per square foot of carbon bed surface
area. Contact times for industrial wastewater mixtures usually are in excess
of 60 minutes — approximately twice the time employed for the purification
of domestic or municipal wastewaters.
All carbon contactors are usually fitted with well-designed water distri-
bution-underdrain systems to ensure efficient backwashing of the bed as well
as even distribution of the influent wastewater over the entire cross-section
of the bed. Established filtration design practices are usually employed in
the design of carbon adsorption contactors. It is to be noted, however, that
carbon beds must periodically be removed via a water slurry „.id that special
provisions must be made for the removal and transport of the carbon such that
-------
-34-
the procedure is not a hazard to workers.
Carbon beds are normally in excess of 10 feet in depth and usually are of
one of five basic configurations: (1) moving beds; (2) beds in series; (3)
beds in parallel; (4) expanded beds; and (5) packed beds. The type of config-
uration selected depends on a number of variables including the total water flow,
concentration of suspended solids, and degree of contaminant reduction desired.
Although the final design of any system must be predicated on dynamic pilot-scale
studies, it i. anticipated that a packed-beds-in-series configuration would
prove most effective for removing benzidine from wastewaters.
Thermal oxidation is employed to reactivata the exhausted carbon for re-
use. Further, multiple hearth furnaces or rotary kilns are employed for react-
ivation of the exhausted carbon. The size of the thermal reactivation equip-
ment is based on the exhaustion rate; i.e., the weight of carbon exhausted per
thousand gallons of wastewater treated and the weight of the contai.iinant on
the carbon. Excess capacity is always designed into the thermal reactivation
unit to allow for variances in carbon use rate due to changes in wastewater
flow and organic loading.
The exhausted granular activated carbon is heated to 1600 to 1800°F to
effect volatilization and oxidation of the adsorbed organic contaminants. Oxygen
in the furnace is normally controlled at less than 1 percent to effect selective
oxidation of contaminants over the carbon itself. A 5 percent loss of activated
carbon is an acceptable bench mark upon which granular carbon system economics
may be based. Moreover, in the case in which benzidine is removed from waste-
water, the reactivation equipment must include an afterburner and an air scrubber
to eliminate the possibility of discharging benzidine to the atmosphere.
Granular carbon is transported between the adsorbers and the reactivation
equipment by water slurry. Various pumping designs can be employed including
-------
-35-
centrifugal and diaphram pumps as well as movement using either hydraulic or
pneumatic pressure. The transport system is generally enclosed and normally
includes flush ports and wide radius bends. Approximately one to three pounds
of carbon can be transported per gallon of water used, depending on distance
and elevation considerations.
Process Costs
As was indicated above, process costs for the removal of benzidine from
wastewaters by adsorption using granular activated carbon cannot be directly
established because no continuous-flow, pilot-scale studies have been conducted.
Nonetheless, process costs can indirectly be approximated based on previous
experience with actual, full-scale industrial installations. Tables III-2
and III-3 summarize data from industrial granular activated carbon systems which
are purifying wastewaters that contain toxic or biologically refractive materials.
Table III-2was prepared for those installations which include on-site thermal
reactivation, while Table 111-3 summarizes data from installations where the
carbon is transported to central reactivation facilities. Both tables were
compiled by Hager and Rizzo (111-10).
The waste volumes treated annually have been shown for each installation
In Tables III-2 and 111-3. These vary considerably because of the point of
application at each plant. In certain cases, the total plant effluent is treated
-- in others, only specific waste streams are treated by adsorption.
The latter point of application normally is beneficial from a total cost view-
point as the quantity of contaminated water is usually less (smaller treatment
system required) and the contaminant concentrations are usually higher (greater
utilization of the carbon prior to reactivation).
Comparision of Table III-2 and II1-3 shows similar costs per 1000 gallons
regardless of whether the carbon is reactivated on-site or is reactivated off-
-------
TABLE ITI-2
TOXIC OR REFRACTORY INDUSTRIAL WASTEWATER TREATMENT
GRANULAR CARBON INSTALLATIONS (ON-SITE REACTIVATION)
(Partial Listing)
TOXIC OR REFRACTORY TYPE OF THERMAL CAPITAL COSTS* DIRECT OPERATING COSTS
PLANT FLOW CONTAMINANTS ON-SITE REACTIVATION ($000) 1000 GALLONS**
MILLION AVERAGE EFFLUENT
GAL/YEAR INFLUENT OBJECTIVE
6
10,000
•ng/1 TOC
400 mg/1
TOC
Multiple Hearth
350
$20
b20
180
370 mg/1
phenolics
10 mg/1
phenolics
Multiple He?.rth
1,300
2
c
70
300 mg/1
phenolics
1 mg/1
phenolics
Kiln
450
1
D**
50
100 mg/1
phenolics
1 mg/1
phenolics
Multiple Hearth
300
4
E
550
Color
Color
removal
Kiln
—
—
F
1100
Color
Color
removal
Multiple Hearth
—
* » Includes engineering, construction, adsorption system and reactivation equipment
** = Direct operating costs and do not -include depreciation or cost of capital invested.
-------
PLANT
A*
B*
C*
D
E*
F*
H
FLOW
MILLION GALLONS
PER YEAR
128
18
183
11
26
84
55
55
TABLE III-3
TOXIC OR REFRACTORY INDUSTRIAL WASTEWATER TREATMENT
GRANULAR CARBON INSTALLATIONS (CENTRAL REACTIVATION)
TOXIC OR REFRACTORY
CONTAMINANTS
AVERAGE
INFLUENT
Phenolics
TOC
Fhenolics
TOC
10 mg/1
250 mg/1
40 mg/1
300 mg/1
Phenolics 100 mg/1
TOC 600 mg/1
TOC
TOC
Color
TOC
900#/Day
275 mg/1
800 mg/1
Phenolics 1700 mg/1
TOC 3000 mg/1
TOC 1000 mg/1
EFFLUENT
C3JECTIVE
0.1 mg/1
0.1 mg/1
0.1 rr.g/l
60#/Day
Specific
Toxicity
Tests
Color
Removal
0.1 mg/1
Specific
Toxicity
Tests
* = Filtration Treatment also
** = Includes: Capital, Maintenance, Insurance & Utilities
TOTAL ANNUAL COSTS S/000 GALLONS
ADSORPTION CARBON
TREATMENT** REACTIVATION*** TOTAL
0.85
4.00
0.35
3.50
4.35
1.50
1.00
2.00
0.80
2.10
0.80
3.45
2.45
0.25
2.00
9.00
I.65
6.10
1.15
6.95
6.80
1.75
3.00
II.00
*** = Includes: Reactivation Capital, Transportation, Reactivation Utilities & Make-Up Carbon
-------
-38-
site on a service basis. While the total annual costs appear to be similar, ap-
preciably less initial investment of capital is required at each treatment site
if the reactivation system can be obviated by a reactivation service.
Total annual costs shown in Table II1-2 are seen to range from $1 to $20
per 1000 gallons. For removing benzidine from the wastewaters of direct dye
manufactures it is expected that the cost of activated carbon treatment would
likely fall in the range of $10 to $20 per 1000 gallons of wastewater treated.
Concerns of the Benzidine Task Force of SOCMA
The Benzidine Task Force of SOCMA has made known (III-ll) several concerns
relative to the use of granular activated carbon for the removal of benzidine
from wastewater. Those concerns led to their decision to recommend that this
technique not be employed. One concern relates to an assumed exposure hazard of
carbon which is saturated with benzidine at the 1 to 2 percent level (weight
basis). In this regard 1t is important to recognize that only approximately
0.1 percent of the total surface area of granular activated carbon is at the
exterior of the carbon granule. Clearly, 99.9 percent of the total surface area
is on the inside of the carbon particle in pores of less than one micron in dia-
meter. Obviously, therefore, the majority of the available surface area for
adsorption could not possibly come Into direct contact with humans.
If one were to assume that a batch of granular activated carbon were sat-
urated with benzidine at the 1 to 2% by weight level, then less than 0.001 to
0.002% by weight concentration would exist at the exterior surfaces of a carbon
granule where the benzidine could potentially come into physical contact with
humans. Of course, this is two orders of magnitude less 1n concentration than
the 0.1% level defined by OSHA regulations. Furthermore, it must be remembered
that exhausted activated carbon is always transported as a water slurry in pipe-
-------
-39-
lines, tanks, etc., and, therefore, never is physically in contact with treat-
ment system operators or other personnel.
The second concern voiced by the Benzidine Task Force related to the poten-
tial for discharging benzidine to the atmosphere from a thermal reactivation
furnace. Such furnaces are always fitted with an afterburner and an air scrubber
to prevent such discharges. These have heretofore been operated on a failsafe
basis. Accordingly, one can only conclude that this potential problem can
clearly be contained using standard operating procedures and proven technology.
ADSORPTION USING POLYMERIC ADSORBENTS
During recent years considerable bench and pilot-scale research has been
directed toward the application of polymeric adsorbents for the removal of
color and other refractory organics from industrial wastewaters. Rohm and
Haas' Amerlite XAD-4 is an example of such an adsorbent.
To the knowledge of the writer no substantive bench, pilot-scale, or proto-
type evidence has been obtained regarding the use of polymeric adsorbents for
the removal of benzidine from wastewaters. Consequently the technical and econ-
omic feasibility of employing such adsorbents for decontaminating wastewaters
that contain benzidine cannot be established at this time.
Extensive bench-and pilot-scale studies must be conducted before one can
make intelligent judgements regarding the feasibility of using polymeric adsor-
bents. Requisite studies could logically be completed during a one-year study
period. If, upon completion of such a study, this technology were found to be
technically and economically feasible, it could likely be implemented within
one to two years.
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-40-
BIODEGRADATION USING THE ACTIVATED SLUDGE PBOCESS
A thorough search of the biological literature showed that the earliest
studies ori the biodegradation of benzidine using activated sludge were conducted
by Malaney, et.al. (111-12) and Lutin et.al. (111-13) These studies were con-
ducted during the mid-1950's using Warburg respirometers which contained samples
of activated sludge obtained from three different wastewater treatment facili-
ties. The studies that were conducted using sludge concentrations of 2500
and 5000 ppm (mixed liquor suspended solids) and benzidine concentrations of
500 ppm uniformly showed that benzidine was inhibitory or toxic to each of the
three sludges employed. The researchers concluded, further, that the removal
of benzidine by biooxidation in an activated sludge aeration tank would be in-
significant and that the sludges showed no appreciable ability to acclimate to
the oxidation of benzidine. They allowed, however, that benzidine might be
removed either partially or completely by adsorption onto the sludge mass.
Another experimental study (nr-T4) conducted during the last quarter of
1973 by Ryckman/Edgerley/Tomlinson & Associates, Inc. (RETA) was commissioned
by the Hazardous and Toxic Substance Regulation Office of the Environmental
Protection Agency. This study also was conducted using Warburg respirometers
and two different types of sludges: an aniline acclimated sludge and a munic-
ipal wastewater treatment plant sludge. Concentrations of 2500 ppm (MLSS)
activated sludge were employed in the respirometer. The sludge samples were
spiked with two different concentration levels of benzidine; 1 and 5 ppm.
Results of the RETA studies showed that benzidine appeared to be slightly
inhibitory to both the acclimated aniline and non-acclimated municipal sludges
based on oxygen utilization measurements. Nonetheless, both of the sludges
showed rather large uptakes of the benzidine during the 12-hour studies. For the
case in which a concentration of 1 ppm of benzidine was introduced to the res-
-------
-41-
pircmeter flasks, 78 and 60 percent uptakes were noted for the acclimated and
non-acclimated sludges, respectively. When the benzidine concentration was
initiated at 5 ppm, uptakes of 64 and 50 percent were observed. The investi-
gators hypothesized that an adsorption mechanism (adsorption on the biological
floe) was involved in removing the benzidine. Although this hypothesis was sub-
sequently tested by RETA, no conclusive proof was obtained to either support or
reject an adsorption mechanism. It is noteworthy, further, that RETA suggested
that while the biological activity appeared to be retarded for benzidine concen-
trations of 1 and 5 ppm, bio-degradation of benzidine may actually occur at lower
concentrations.
Another Warburg respirometer study was conducted by International Hydronics
Corporation under contract to Allied Chemical Corporation (111-15). In essence,
these studies v/ere identical to those conducted by RETA: they were conducted
(1) with two different kinds of sludges (aniline acclimated and conventional
municipal); and (2) with 2000 to 2500 mg/1 MLSS. These studies showed that the
activated sludge which was aniline acclimated metabolized benzidine more rapidly
than did the unacclimated sludge. Moreover, results of the study indicated
that concentrations of benzidine in excess of 60 ppm were inhibitory to both
types of sludges. The results agree well with those of RETA.
Three recent continuous-flow studies were conducted by International Hyd-
ronics Corporation under contract to Allied Chemical Corporation and were supplied
to the writer by the Benzidine Task Force of S0CMA (111-15, 111-16 and 111-17).
The first study was conducted using a continuous-flow, bench-scale activated
sludge treatment system which contained an activated sludge at a concentration
of 3000 mg/1 (MLSS) or 1500 mg/1 (MLVSS). The system was operated at a hydraulic
flow rate of 7.2 liters per day, a hydraulic residence time of 8 hours, and a
process loading intensity (F/M) of 0.31 mg BOD/mg MLVSS-day. Benzidine was
introduced to the primary sewage effluent feed at a concentration of 0.1 mg/1,
-------
-42-
(100 ppb).
Results of this one-week study showed that the benzidine clearly was not
inhibitory to the biomass as BOD reductions averaged better than 92 percent.
The benzidine itself, however, passed through the system essentially untouched.
Unfortunately, the study was not continued beyond the one-week period to deter-
mine whether or not the sludge would acclimate to the benzidine in the feed and
ultimately biologically degrade it. An acclimation period of two months is
often required to attain steady-state biodegradation conditions.
The second study also was conducted using a continuous-flow two-liter,
bench-scale activated sludge system that contained an aniline acclimated acti-
vated sludge at a concentration of 1500 mg/1 (MLSS). Acclimation was achieved
by introducing aniline to the feed of the activated sludge system — first
at 10 ppm for a one-week period and subsequently by increasing the concentration
by 10 ppm increments over a four-week period to a final feed concentration of
50 ppm. Thereafter, benzidine was introduced to the feed at a concentration
of approximately 45 ppb while the aniline concentration was maintained at the
50 ppm feed level. The system was operated at a hydraulic flow rate of 7.5
to 9 liters per day, a hydraulic residence time of 5 hours, and a process loading
intensity (F/M) of approximately 0.25 mg BOD/MG MLSS-day.
During the study removal of organics averaged 66.6 and 87.4 percent for
COD and BOD, respectively. BOD residuals in the effluent of the two-liter
reactor averaged 12.5 mg/1. Throughout this period concentrations of benzidine
in the effluent averaged 1.83 ppb while the influent concentrations averaged
41.9 ppb for a removal efficiency of 96.11 percent. Of the benzidine that was
removed from the aqueous medium, 9.29£ was removed by adsorption onto the sludge
mass, while 90.71% was biologically metabolized or oxidized. It was reported.,
furthermore, that the system performed well throughout the nine-week period
-------
-43-
of study and that no sludge bulking was observed.
A third study was conducted exactly as the second except that an unacclimated
municipal sludge was employed for system start-up. During the two-week study
removal of organics averaged 82.1 and 89.6 percent for COD and BOD, respectively.
COD residuals averaged 28.2 ppm and the average effluent levels for BOD were
9.4 ppm. Throughout the period of study the concentration of benzidine in the
effluent averaged 2.02 ppb while the influent concentrations averaged 41.7 ppb
for a removal efficiency of 95.1 percent. As for the previous study, the quan-
tity of benzidine adsorbed onto the sludge floe was less than 10 percent of the
total quantity removed from the aqueous medium.
No acclimatization period was required for this third study. The sludge
apparently immediately biologically metabolized or oxidized the benzidine when
fed at the 40 ppb level.
To summarize this sub-section on biodegradation, it can be stated with
reasonable certainty that benzidine is toxic to non-acclimated sludges at con-
centrations of 500 mg/1, is slightly inhibitory at concentrations of 1-5 mg/1
and is clearly non-toxic at concentrations of 0.1 mg/1. Moreover, recent studies
have shown (1) that benzidine is biodegradable at the 0.045 ppm level acclimated
and unacclimated biological sludges and (2) that the vast majority of benzidine
that is removed (go%) is biologically degraded while only trace quantities
(10%) are incorporated in the sludge mass.
One can conclude, therefore, that benzidine manufacturing wastewaters
that have been treated using the nitrous acid oxidation procedure could be
discharged directly into an activated sludge wastewater treatment system and
that the majority (ca. 90%) of the benzidine that is introduced would be removed by
bio-oxidation. A comprehensive research program, however, would be required
to establish the proper set of process operating parameters that would yield
-------
-44-
optimal performance of the biological system. It can be further concluded that
benzidine would not adversely affect municipal biological wastewater treatment
systems. One would expect that the majority (ca. 90%)' of benzidine introduced
to a publicly -owned system would be biologically degraded and that less than
detectable quantities (1 ppb) would be incorporated in the waste sludge.
Moreover, it can be concluded that wastewaters derived from the
manufacture of benzidine-based dyes could be discharged directly to
a bio-oxidation treatment system. Since the concentration of
benzidine in the dye mother liquor is usually less than 10 ppb.
The majority of benzidine as introduced would be removed by bio-
logical degradation. However, the application of biological
treatment may require PH adjustment and possibly nutrient
addition if sufficient other wastes were not available within a
plant to mix with the dye production mother liquor.
-------
-45-
OTHER POTENTIAL TREAT14ENT METHODS
Both Case and Ketchen (II1-18) and Mytelka and Manganelli (111-19, 111-20)
reasoned that, in the presence of oxygen, irradiation of large organic molecules
in aqueous solution can result in the oxidation and fragmentation of the mole-
cules. Case and Ketchen (111-18) demonstrated that gamma radiation was effective
for the removal of color and the carbonaceous content of many dyes and other
organic components in textile mill effluents, but that a large variation existed
in the radiation dose required. Similarly, Mytelka and Manganelli (111-19, 111-20}
concluded that when an aqueous solution of the dye Direct Red 79 was subjected
to cobalt-60 ionizing radiation, the chemical oxygen demand, total organic carbon
concentration, dye concentration, and color of the suspension decreased and that
the waste became more amenable to biological oxidation. It is noteworthy, how-
ever, that neither of these two studies were conducted using either benzidine
or benzidine-based dyes and that no direct evidence that supports the technical
feasibility of employing gamma irradiation for the degradation of benzidine
currently exists..
Although it is believed that hydrogen peroxide could directly oxidize the
benzidine molecule, to the knowledge of the author, no studies have been cond-
ucted that demonstrate the technical feasibility of the proposed procedure.
This method as well as the gamma irradiation method should be explored to eval-
uate the technical feasibility of applying these techniques for the complete
destruction of benzidine in aqueous solution. If either of these were shown,
through experimental study, to be feasible alternatives for the oxidation of
benzidine in wastewaters, it would need to be thoroughly investigated and dev-
eloped prior to actual application. In the case of hydrogen peroxide it is be-
lieved that a study period of 3 to 5 years would be required to develop this
technology to the point of engineering reality. This R&D period would likely
-------
-46-
extend to 5 to 7 years in the case of ionizina radiation.
fiQ AQUEOUS DISCHARGE
The direct dye m<\nufacturing industry has not yet achieved a
"no aqueous discharge" management status. If the wastewaters
were treated using the granular activated carbon adsorption pro-
cedure, however, they likely could be reclaimed and recycled
directly to the processing operation to achieve a no discharge
condition. Conversely, if the nitrous acid procedure were
employed for oxidation of the benzidine in the wastewater, then
a no discharge condition could probably only be achieved only
through multiple-effect evaporation and subsequent disposal
of the resultant solids. Costs for such a reclamation system
would probably approach $100 per 1000 gallons of wastewater
treated (25 cents per pound of benzidine produced). A1ternatively,
multiple-effect evaporation could potentially, by itself, provide
a no discharge management status.
SUMMARY
Of the potential treatment technologies that are available
for the removal of benzidine from process wastewaters, only the
nitrous acid oxidation method has been implemented at the plant
scale (Allied Chemical Corporation and 6AF Corporation) and shown
to be effective for the concentrated benzidine manufacturing
wastes. It is to be noted that this process was employed only
for the treatment of benzidine manufacturing wastewaters. Residual
levels of benzidine in the nitrous acid treated effluent usually
were found to be less than 10 ppb.
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-47-
Berizi di ne-based dye rianuf acturi rig wastewaters can be treated
relatively inexpensively by the bio-degradation process. Due
to biological toxicity, however, this process probably cannot
be employed for the direct treatment of benzidine manufacture
wastewaters prior to a pretreatnent step such as the nitrous
acid oxidation process.
Allied Chemical Corporation, Fabricolor, Inc. and GAF
Corporation discharge their wastewaters to municipal biological
wastewater treatment systems. The final product wastewate rs,
after biological treatment, should show no detectable benzidine.
Jlo other benzidine treatment technologies have been implemented
at the plant-scale; in fact, none.have been evaluated beyond the
bench-scale. Consequently, plant-scale process efficiencies and
costs have not been established for any of the processes consid-
ered other than the nitrous acid oxidation process. A tabular
comparison of the potential treatment methods has been given in
Table 111-4.
The fact that the ranges for actual or projected process costs
given in Table III-4 are broad is due to the fact that benzidine
production methods vary considerably with respect to the quantity
of process wastewaters generated. If the wastewater volumes pro-
duced are high, then the associated costs are also respectively
higher.
-------
Wl-'V
COMPARISON OF POTENTIAL TREATMENT METHODS
Type of
T reatment
Level of Development
and/or Application
Effectiveness
Cost
tfi product
Benzidine Manufacturing l-.'astewaters
Oxidation with
Nitrous Acid
(Pretreatment Only)
Oxidation
with Ozone
Adsorption onto
Activated Carbon
Adsorption onto
Polymeric Adsorbent
Full Scale
Bench-Scale
(Preliminary Only)
Bench-Scale
(Preliminary Only)
Hone
10 ppb
1-10 ppb (proj.)
1-10 ppb (proj.
1-10 ppb (proj.)
2-12 (actual)
100-500 (proj.)
1-10 (proj.)
Unknown
'No Di scharge/Evapora-
ti on
None
N/A
2/
25 (proj.)
B. Benzidine-based dye flanufacturing Wastewaters
Biodegradation Bench-Scale
(Secondary Treatment
Only)
toxic for inf.
conc. = 10 ppm
1-10 ppb for inf.
conc.sl ppm
0.02 per poundaqe
(proj.) 1/
j/ Footnote: For treatment of dye mother liquors; (basis 0.40/thousand gal.)
\f Includes pretreated benzidine manufacturing wastes
-------
-49-
LITERATURE CITED
III-l Dien, C. K. "Reaction of Benzidine with Nitrous Acid." Report dated
4/30/74.
II1-2 Ferber, K. H., Statement made at a meeting held on 3 May 1974 in the
office? of the EPA Administrator. Meeting was attended by represent-
atives of the Hazardous and Toxic Substance Regulation Office of EPA
and members of the Benzidine Task Force of SOCMA.
III-3 Bradwell, W. A. Site visit notes taken on 8 October 1975.
III-4 Reiter, W. M., Personal communication on 12 June 1974 (Corporate Assist-
ant Director, Air. & Water Pollution Control, Allied Chemical Corp.)
II1-5 Anon., "Waste Treatment with Ozone" Benzidine Task Force, SOCMA, 5
June 1975.
III-6 Waarden, M. van der "Adsorption of Aromatic Hydrocarbons in Nonaromatic
Media on Carbon Black" J. Colloid Sci. 6, 443-9 (1951).
II1-7 Falk. H. L., and P. E. Steiner, "The Adsorption of 3,4-benzopyrene and
Pyrene by Carbon Blacks." Cancer Research 12* 40-3 (1952).
III-8 Hellstrom, N. "Comparative Adsorption Experiments. I. Some Hydrocarbons
in Ethyl Alcohol and in Heptane with Some Different Kinds of Carbons."
Svensk. Kem. Tid. 64, 263-70 (1952).
II1-9 Sterbacek, Z., P. Tausk, and J. Trca, "Purification of Wastewaters from
Dye Intermediates." Chem. Prmysl. 7, 127-30 (1957).
III-10 Hager, D. 6., and J. L. Rizzo, "Removal of Toxic Organics from Waste-
water by Adsorption with Granular Activated Carbon." Presented at the
Technology Transfer Session on Treatment of Toxic Chemicals, EPA,
Atlanta, Georgia 19 April 1974.
III-U Collins, R. "Removal of Water-Borne Benzidine by Activated Carbon."
Benzidine Task Force, SOCMA, 13 February 1974.
111-12 Malaney, G. W,, P. A. Lutin, J. J. Cibulka, and L. H. Hickerson, "Re-
sistance of Carcinogenic Organic Compounds to Oxidation by Activated
Sludge." Jour. Water Poll. Control Fed., 39, 2020 (1967).
111-13 Lutin, P. A., J. J. Cibulka, and G. W. Malaney, "Oxidation of Selected
Carcinogenic Compounds by Activated Sludge." Proc. 2lst Ind. Waste
Conf., Purdue Univ. (1966).
III-14 RETA, Inc. "Fate of Benzidine in the Aquatic Environment: A Scoping
Stiidy" A Report to the EPA: Contract #68-01-2226 dated 9 January
1974.
111-15 MacArthur, J. A. "Biological Treatability of Benzidine" Benzidine
Task Force, SOCMA, 17 October 1975.
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-50-
111-16 MacArthur, J. A. "Treatability of Benzidine Waste by Activated Sludge"
Benzidine Task Force, SOCMA, 15 March 1974.
111-17 MacArthur, J. A. "Biological Degradation of Benzidine." Benzidine
Task Force, SOCMA, 25 April 1975 and 28 July 1975.
III-18 Case, F. N., and E. E. Ketchen, "Study of Gamma Induced Low Temperature
Oxidation of Textile Effluents" Environmental Protection Technology
Series No. EPA-R2-73-260, Environmental Protection Agency, Washington,
DC (1973).
111-19 Mytelka, A. I., and R.*Manganelli, "Energy Induced Changes in an Azo
Dyestuff Waste" Jour. Water Poll. Control Fed., 40, 260 (1968).
111-20 Mytelka, A. I., arid R. Manganelli, "Radiation Treatment of an Indus-
trial Waste." Proo. 22nd Ind. Waste ConfPurdue Univ. (1967).
-------
SECTIOU IV
DISCHARGE OF BENZIDINE TO PUBLICLY OWNED TREAT14ENT WORKS
DISCHARGE LOCATIONS
Each of the three berizidirie-based dye manufacturers discharges its wastewaters
to a regional sewer authority. Allied Chemical Corporation discharges its waste-
waters after pretreatment to the Buffalo Sewer Authority v/hich operates a primary
treatment works on Bird Island. By 1977 this is to be expanded to a secondary
activated sludge system which will discharge to the Niagara River.
GAF Corporation discharges its wastewaters to the Rensselaer County Sewer
District No. 1. The district is currently in the process of placing on-line
a conventional activated sludge system which has provisions for chlorination
and sludge treatment by the Zimpro wet oxidation process. Construction was to
have been completed by 17 November 1975 and the system was to have been
entirely operational by 2 January 1976. GAF has also constructed
pretreatment facilities in association with Wlnthrop. Laboratories.
The discharge of Rensselaer Sewer District plant is to the Hudson
River.
Process and sanitary effluents of Fabricolor, Inc. are combined and flow
into a sewer system (Passaic Valley Sewer Authority) which parallels but does
not enter the Passaic River in the vicinity of Paterson, Mew Jersey. The municipal
system combines with other municipality discharges along a sewer line route to
the north shore of Newark-Bay where all the wastewater receives primary treatment
and then is piped across the bay to an outfall below water level in the Hudson
Riv^r in the lower portion of Upper New York Bay.
PRETREATMENT SYSTEMS
Allied Chemioal Corporation .... As indicated above, all process wastewaters
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from Allied's Buffalo Dye Plant are collected and combined in a process waste
sewer system. This, of course, includes the discharge of the nitrous acid treat-
ment system. The sewer discharges into a pretreatment system which consists of
equilization, neutralization and clarification of the aqueous stream. A schematic
flow diagram is shown in Figure IV-1. A brief description of each of the unit
processes follows:
Collection » Process wastes are collected from the various
manufacturing areas and discharged to the pretreatment plant
via three wet wells equipped with*three pumps. Screens are
provided to protect the pumps from debris. In normal oper-
ation, one pump operates continuously. The other pumps serve
as standbys providing reserve capacity for peak flows. These
are activated by high level switches in the wet wells. The
pumps raise the wastewater from the wet wells through a :
Parshall flume to equilization basins.
Equilization — Two earthen-dike lagoons, lined with clay,
operate in parallel to receive the process effluent and pro-
vide capacity to equilize variations in flow and concentration
of pollutants. Each lagoon has a nominal capacity of one
million gallons and is provided with a perforated air header
throughout its entire length. Low pressure air (10 psig)
is introduced into these headers to provide gentle mixing
of the lagoon's contents to prevent sedimentation of sus-
pended solids.
Neutralization — Neutralization of the process wastewaters
is achieved by adding a lime slurry (10 - 12% Ca(OH)p) to '
either or both of two agitated reactors of 10,000 gallon
capacity. The pH of the effluent has a variation of 8.0+
0.5.
Clarification — Neutralized waste process water flows to
the reaction well of a solids-contact clarifier by gravity
where it is contacted with previously precipitated solids.
A polyelectroyte flocculant is added to aid in floe formation.
The clarifier has a hydraulic residence time of two to six
hours depending on flow rates. Clarifier overflows are sub-
sequently discharged to the City of Buffalo Sewer Authority.
Thickening — Sludge settled in the clarifier (1 - 2% solids)
is continuously pumped to a conventional thickener where the
solids content is increased to 3 to 5%. The overflow from
the thickener is returned to the neutralization reactors.
The solids residence time in the thickener varies according
to flow and sludge production rates. Generally the resid-
ence time varies between one to two weeks.
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-53-
PROCESS
FLOW
WET
WELL
sample point
Total equil vol,
« 1.5 MG
FLUME
EQUILIZATION
EQUILIZATION
FILTRATE
OVERFLOW
NEUTRALIZATION
SLUDGE
CENTRIFUGE
THICKENER
CLARIFICATION
sample point
BUFFALO SEWER AUTHORITY
FIGURE IV-1
BUFFALO DYE PLANT PRETREATMENT FACILITY
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-54-
Dewatering -- Thickened sludge is pumped to one of two centri-
fuges where final dewatering is accomplished (20% solids).
Polyelectrolytes are added in this operation to improve process
efficiency. Dewatered sludge is collected and disposed of
in sanitary la-ndfill sites approved by State and County Agen-
cies. The centrate is returned to the neutralization reactors.
Analyses for benzidine were performed on the clarifier over-flow prior to
discharge to the Buffalo Sewer Authority during the period which extends from
20 March to 3 June 1974. These have been tabulated in Table IV-1.. All anal-
yses were performed on 24-hour composite samples collected at 0800 hours. In
addition to a leak in the Vallez filter which occurred on 31'March 1974 and was
noted earlier, an incompletely reacted dye batch of "Big Black" containing
benzidine was sewered in Building 125. This was reflected in high, loadings
°n 11 and 13 May.
The data shown in Table IV-1, as before, was analyzed statistically in
two ways: -- including (Mode 1) each of the 75 data points assuming
that the 18 samples that showed Tess than the detectable concentration
had concentration of 5 ppb; those values which fell outside the
99% confidence limit. The analysis showed the following for load-
ings per day: Mode 1 Mode 2
Average 0.51 0.38
Std. Deviation 0.76 0.27
High 95% Conf. 2.0 0.9
High 99% Conf. 2.5 1.2
can conclude, therefore, that benzidine loadings to the Buffalo Sewer Auth-
0!"ity of less than 0.41 pounds per day can be achieved at the 99
^rcent confidence level if leaks and batch discharges are either
61- . 1
'innnated or accounted for through suitable treatment provision^.
Average daily loadings of 0.33 pounds should be achievable when
th
nitrous acid treatment method is employed for benzidine manu-
f
Qcture wastes and the total wastewater stream is pretreated
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-55-
TABLE IV-1
Benzidine in Pretreated Wastewaters of the Buffalo Dye Plant
Date
AWW/Flow
{10° lbs/day)
Benzidine Cone.
(PPb)
Benzidine Loading
(lbs/day)
3-20-74
12.0
40
0.5
3-21-74
13.2
30
0.4
3-22-74
13.9
20
0.2
3-23-74
12.9
30
0.4
3-24-74
10.4
40
0.4
3-25-74
11.9
*
3-25-74
13.4
10
0.1
3-27-74
12.5
70
0.9
3-28-74
12.9
60
0.7
3-29-74
11.4
50
0.6'
3-30-74
10.7
30
0.3
3-31-74
8.7
30
0.3
4-1-74
11.5
140
1.1
4-2-74
14.3
120
1.5
4-3-74
11.9
-
4-4-74
12.9
40
0.5
4-5-74
10.9
80
0.9
4-6-74
9.2
40
0.4
4-7-74
7.2
120
0.9
4-8-74
11.7
40
0.5
4-9-74
12.7
50
0.7
4-10-74
14.3
30
0.4
4-11-74
15.4
50
0.8
4-12-74
15.3
*
.
4-13-74
10.1
40
0.4
4-14-74
9.0
40
0.4
4-15-74
9.6
*
-
4-16-74
12.7
*
4-17-74
12.9
*
4-18-74
13.1
*
m
4-19-74
13.1
*
-
4-20-74
12.8
4-21-74
10.8
10
0.1
4-22-74
8.3
20
0*2
4-23-74
12.5
60
0.7
4-24-74
12.4
30
0.4
4-25-74
13.0
60
0.8
4-26-74
12.3
*
4-27-74
11.4
*
4-28-74
9.0
*
m
4-29-74
13.1
*
«•
4-30-74
7.2
40.
0.3
5-1-74
10.6
60
0.7
Mote: * indicates a concentration4.2 - 5 ppb
-------
-56-
TABLE IV-1 (coot.)
Date
WW/Flow
(10° lbs/day)
Benzidine Cone,
(ppb)
Benzidine Loading
(lbs/day)
5-2-74
12.8
40
0.5
5-3-74
11.2
20
0.2
5-4-74
10.4
20
0.2
5-5-74
7.5
50
0.4
5-6-74
8.6
100
0.8
5-7-74
10.1
70
0.7
5-8-74
11.8
*
..
5-9-74
13.7
*
-
5-10-74
13.9
40
0.6
5-11-74
13.6
150
2.0
5-12-74
6.1
140
0.9
5-13-74
6.9
610
4.2
5-14-74
13.4
170
2.2
5-15-74
13.6
50
0.7
5-16-74
13.5
*
-
5-17-74
14.5
20
0.3
5-18-74
15.5
310
4.7
5-19-74
8.7
10
0.1
5-20-74
12.4
80
1.0
5-21-74
13.4
20
0.3
5-22-74
13.5
*
*•
5-23-74
12.9
40
0.5
5-24-74
12.8
30
0.3
5-25-74
8.9
10
0.1
5-26-74
8.4
20
0.2
5-27-74
8.4
40
0.3
5-28-74
7.7
~
5-29-74
11.4
*
•J*
5-30-74
11.3
30
0.3
5-31-74
11.1
50
0.5
6-1-74
11.8
90
1.1
6-2-74
9.1
80
0.7
6-3-74
1G»2
60
0.6
Note: * indicates a concentration - 5 ppb
-------
-57-
as described.
Analyses for benzidine were also performed on the centrifuged sludge which
is disposed of in sanitary landfill sites approved by the New York State Depart-
ment of Environmental Conservation and appropriate county agencies. Results
of the analyses are presented in Figure IV-2 for the period extending from 20
March through 15 December 1974.
Qualitatively, one can observe that the benzidine content of the sludge
varied greatly throughout the period of study. Initially (March through June
1974) the benzidine concentration ranged from 3 to 12 ppm. Since June 1974,
the benzidine content of the precipitated neutralization sludge increased
dramatically to 700 ppm - subsequently dropping to levels of 50 ppm by December
of 1974.
Sludge quantities generated vary widely depending upon the quality of the
process waste effluent among other factors. From January 1974 through April
1975 an average of 23.33 tons of dry solids were produced per week although the
solids production ranged from zero to 70 tons per week.
Attempts to conduct a mass balance on benzidine for the Pretreatment Works
of Allied's Buffalo Dye Plant have been unsuccessful. This is primarily due to
the fact that a considerable, but unknov/n, quantity of solids have accumulated
in the equilization lagoons.
Discharges of phenol from the Pretreatment Works to the Buffalo Sewer Auth-»
ority were monitored during a 14-day period beginning 19 October 1974. Data
for this period is presented in Table IV-2. All analyses'were performed on 24-
hour composite samples using the 4-amino anti-pyrene method. The majority of
the phenol loading is attributed to the process wastes from the manufacture of
methyl violet (II1-3).
-------
RATIONS
SLUDGE
^2 BUFFALO DYE
PRETRE
irrn
F.fo ^ ^ oj vo cvjcn^DKj
rvi ' — C\J — —¦ r\ i — /, i
C\J
c\J
— coTnoj (X)<£>roorv-roorv-,s:
c\j eg ~ c\j f\J — (\i
\!: rn
;v jvj: *
-J j | j h I * l-i »• • I
J.i'.,
j-l !
•itrirr: :[:£:!:!
I lit I I i » ? »
p.. r
-T :. a
_U • i.lL'-u
oc
o.
<
>-
d
=5
O
ta
ZD
a.
LU
CO
o
o
o
UJ
o
c*.- io rsj Gi
c\! evi
I
cn
CO
I
-------
-59-
TABLE IV-2
Phenol in Pretreated Wastewaters of the Buffalo Dye Plant
R Phenol Cone. Phenol Loading
Date (10 lbs/day) (ppm) (lbs/day)
10-19-74
12.4
1.61
20
10-20-74
12.3
1.49
18
10-21-74
13.4
0.56
8
10-22-74
13.0
2.83
37
10-23-74
14.1
1.01
14
10-24-74
14.6
0.63
9
10-25-74
14.5
1.88
27
10-26-74
14.0
1.23
17
10-27-74
11.9
0.49
6
10-28-74
13.0
0.17
2
10-29-74
12.0
2.30
28
10-30-74
13.7
2.98
41
10-31-74
14.7
3.95
58
11-1-74
14.8
2.24
33
-------
-fiO-
GAF Corporation .... As noted previously, GAF Corporation is currently
nearing the completion of a pretreatment facility. The facility is to be jointly
owned and operated by GAF and Winthrop Laboratories, a subsidiary of Sterling
Drug Company. A schematic flow diagram for this system which was placed
on-line in January 1976 is shown in Figure IV-3. A brief description of each
of the unit processes as provided by the design engineer follows:
Collection and Pumping — The pumping station vrill be located
at the junction of the GAF and Winthrop outfall .sewers. From
that point the waste flows are pumped up to the equalization
basins. The pumping arrangement for the combined GAF and
Winthrop flow will consist of four dry pit-type, horizontal
centrifugal pumps, each with a maximum capacity of 1800 gpm.
Preceding the pumping station, a metering chamber will be
provided to seperately meter and sample the GAF and Winthrop
discharges. The flow data will be transmitted to indicating,
recording, and totalizing meters located in the pumping station.
Composite samples of the wastes will be analyzed for pH, BOD
and suspended solids. This data will be used to proportion
charges at both the pretreatment and secondary treatment plants.
Grit Chambers — To prevent grit from depositing in the equili-
za.tian. basins.,., two grit chambers will be provided. Each chamber
task. will. ?iiid-proc.f ed. and-brick. line.d.r The.qr,tt and heavy .
settleable solids will be cleaned manually by alternately taking
each tank out of service.
Equilization Basins — To ease the problems normally encountered
in neutralizing industrial wastes, the raw wastes, after being
degritted, will pass through two clay-lined equilization basins.
The purpose of the basins is to level out flow variations and
rapid changes in pH and other characteristics of the wastes.
The wastes will be discharged uniformly from each basin and will
be mixed by use of Tow pressure air jets.
Neutralization — Following the equilization basin, lime or caustic
will be mixed with the wastewater stream in a series of three rapid
mixers until the pH of the wastewater has been elevated into the
range of 5.5 to 8.5. Three mixing chambers will be provided to
introduce the neutralizing agent into the waste ^tream. Each cham-
ber will have a detention time of five minutes.
OCCURRENCE OF BENZIDINE IN POTW'S
Analyses (IV-1, IV-2) for benzidine in samples collected from the primary
sedimentation effluent of the Buffalo Sewer Authority's treatment works on Bird
-------
-61-
figure iv-3
SCHEHWIC FUN DIA6RAH FOR GAPS PRETREATMENT SYSTEM
I 11
II
1
r^' .
I i»x J
e KT*
I au
SYNf.aOLS
•mv »-*<»-• w*«
AUIM w«l
** 'rutrxjk. Ut4
(" •
n i!
mi
M
.'V
-I T
t \
i aH
\
wnf^ w«i
Tft»» ««%n
/.«.
*"1»l
POLLUTION tCAtCWtll FWjCCI
GAF CO" Md1 W^INIV LADCRtfORICS
AlHRWn M*l
moccss now ouauii
wasM ioir *mu «yjc»'u
FIGURE 19
*"Z^Th«
i.+ ^
-------
-62-
Island showed concentrations at the level of detectability (0.2 to 0.5 ppb).
It is to be noted that these wastewaters were not subjected to biological oxid-
ation. Through dilution (ca. 100-fold) and possible degradation in the trans-
port system the benzidine concentrations were diminished to the level of de-
tectability.
EFFECTS OF BENZIDINE ON PUBLICLY OWNED TREATMENT WORKS
Based on the results of the biodegradation studies cited in the previous
section (III), it is clear that any municipal biological (activated sludge or
trickling filter) wastewater treatment system would not encounter operational
difficulties of benzidine were present in the influent at concentrations less
than 1 ppm. The biological studies showed, furthermore, that when benzidine
is Introduced to an activated sludge system at the 50 ppb level, approximately
95 percent of the benzidine is biologically degraded.
When the nitrous acid oxidation procedure is employed for the decontamina-
tion of benzidine manufacture wastewaters, the concentration of benzidine in
the combined wastewaters of the manufacturing facility is generally less
than 50 ppb. It is readily apparent, therefore, that any benzidine introduced
to publicly owned treatment works would be biodegraded even if the benzidine
wastewaters would be directly introduced to the biological treatment reactor
without dilution. Accordingly, one can conclude that benzidine in the wastewaters
of publicly owned treatment works would be degraded and would have no effect
on the operation of such works. Residual concentration of benzidine in the ef-
fluent of such treatment works should always be less thai) the level of detectab-
ility (0.2 ppb).
Because municipal biological sludges are usually artaerobically digested
(a biological process), it is important also to consider the potential adverse
effects that benzidine would have on thi,s process since small quantities of ben-
-------
-63-
zidine adsorb on the aerobic sludge mass. Unfortunately, no process performance
information is available in this regard. Nonetheless, because less than 10 per-
cent of the benzidine introduced to an activated sludge system (50 ppb level)
is actually incorporated in the sludge and because such low levels of benzidine
have no effect on aerobic biological activity, one can opine with reasonable cer-
tainty that the occurrence of benzidine in municipal wastewaters would not affect
the operational performance of anaerobic digesters.
In the case of benzidine*and benzidine-based dye manufacturers, one should
also consider the effects of the possible incorporation of benzidine-bases dyes
into an activated sludge mass which ultimately is anaerobically digested. The
reducing environment found in an anaerobic digester may serve to reduce the dyes
to the precurser, benzidine. Although no direct evidence is available to support
or refute this hypothesis, some indirect evidence has been gathered by Flege
(IV-3). His research showed that certain non-benzidine based dyes which are
usually used for dyeing synthetic fibers were broken down coring anaerobic di-
gestion to form the intermediates that originally were used for synthesizing
the dyestuff. Some of these intermediates were Identified as being carcinogenic.
This latter evidence, however, is very circumstantial and should not, therefore,
be construed as being indicative of what would occur in the case of benzidine-
based dyes. Even if such reduction of benzidine-based 'dyes would occur, the
concentrations would likely be sufficiently low so as not to be a problem.
EFFLUENT LIMITATIONS FOR INDUSTRIAL DISCHARGES
Allied Chemical Corporation .... Currently, no effluent limitations exist
for industrial discharges into sewers operated by the Buffalo Sewer Authority.
Such limitations have, however, been proposed. These have been tabulated in
Table IV-3. No reference ijS made to benzidine, benzidine-based dyes, or any
other specific organic materials other than phenol.
-------
i-64-
TABLE IV-3
PROPOSED EFFLUENT LIMITATIONS FOR INDUSTRIAL DISCHARGES
INTO SEWERS OPERATED BY
THE BUFFALO SEWER AUTHORITY
PARAMETERS PROPOSED LIMITS
Suspended Solids
BOD
C0D5
TOC
Oil & Grease
Ammonia as N
Phenol
Mercury
Arsenic
Chlorides
Dissolved Solids
Total Phosphates
Cyanide
Sulfates
PH
Silver
Aluminum
Boron
Barium
Calcium
Cadmium
Chromium
Copper
Iron
Manganese
Nickel
Lead
Antimony
Tin
Zinc
Surcharge over 250 mg/1
Surcharge over 250 mg/1
No determination
No determination
50 mg/1
No limit
0.1 mg/1
0.1 mg/1
0.1 mg/1
10,000 mg/1
10,000 mg/1
Surcharge over 5 mg/1
Complex 0.8 mg/1
Free 0.1 mg/1
500 mg/1 as NapSOy,
5.5 - 9.5 *
0.1 mg/1
No decision
1.0 mg/1
2.0 mg/1
No limit
0.2 mg/1
Total 2.0 mg/1
Trivalent 1.9 mg/1
Hexavalent 0.1 mg/1
0.4 mg/1
No limit
2.0 mg/1
2.0 mg/1
0.1 mg/1
No decision
No limit
0.6 mg/1
-------
-65-
GAF Corporation Effluent limitations imposed on GAF Corporation require
the construction of pretreatment facilities such that the effluent discharged
from the facilities shall be "transportable, treatable arid in compliance with
the following requirements:
(1) The effluent shall be equilized and neutralized with lime to a
pH range between 5.5 and 8.5.
(2) The effluent may contain a variety of insoluble materials illus-
trated by the following examples:
aluminum hydroxide
barium sulfate
calcium carbonate
calcium fluoride
calcium molybdate
calcium phosphate
calcium tunastate
chromium hydroxide
charcoal
cobalt hydroxide
copper hydroxide
filter aid
insoluble organigs
iron hydroxide
"lead hydroxide
manganese hydroxide
waste sludge
nickel hydroxide
zinc hydroxide
(3) The effluent may contain a wide variety of inorganic ions as it
luatrated by the following examples:
borate
calcium
ammonium
bromide
nitrate
phosphate
nitrite
potassium
magnesium
manganese
molybdate
chloride
fluoride
iodide
sodium
sulfate
sulfide
sulfite
thiosulfate
tungstate
(4) The effluent may contain soluble organic molecules in great variety
as illustrated by the following examples:
acetate
acetic acid
aceto nitrite
acetone
benzene
butyric acid
dime thyIformamide
formaldehyde
isopropyl alcohol
isopropyl acetate
methyl alcohol
oxalic add
para-cresol
phenol
-------
-66-
Dowtherm A
ether
ethyl alcohol
ethylene dichloride
¦ghthalates
tartaric acid
tetrahydroforam
toluene
(5) The most evident biologically resistant material in the effluent
is color. J$ormally> this will contribute a color of 4000 ABBA units
to a volume of 4^500,000 gallons."
It is noteworthy that again no reference is made to benzidine or ben
zidine-based dyes.
TPabricolorJ Inc. .... No pretreatment requirements have been imposed on
Fabricolor, Inc. by the Passaic Valley Sewer Authority.
-------
-67-
LITERATUES CITED
IV-1 Anon. "Survey of the Buffalo Sewer Authority Effluent for the Presence
of Benzidine" Great Lakes Laboratory, State University College of
Buffalo, 25 July 1975.
IV-2 Czarnecki, A. 0. "Buffalo Dye Plant Benzidine Study: Benzidine Loadings,
at the BSA Outfall to the Niagara River" Internal Memorandum of the
Buffalo Dye Plant, August 1975.
IV-3 Flege, R. K., "Determination, Evaluation and Abatement of Color in
Textile Plant Effluents." Completion Report, OWRR Project #B-012~GA,
Georgia Institute of Technology, Atlanta, GA (1968).
-------
SECT I or! V
FEASIBLE TECHNOLOGIES FOR BENZIDINE TREATMENT
The nitrous acid oxidation treatment procedure as described in
Section III of this report and applied by GAF Corporation and Allied
Chemical Corporation is the only treatment technology that, at
this time, can be considered to be feasible as a treatment method
for benzidine. The following justifications are given:
(1) None of the other treatment processes considered in Section
III can be judged feasible at this time because they have not
been tested or evaluated beyond the bench-scale in the labora-
tory. Circumstantial field evidence would indicate, however,
triat the biocleyradation process is feasible for treating
benzidine wastewaters containing less than 1 ppm benzidine.
(2) Although b1odegradatlon was shown to be effective, 1t can be
employed only as a secondary treatment process for benzidine
manufacturing wastewater because acceptable process efficien-
cies can be obtained only for influent benzidine concentra-
tions less than 1 ppm. For benzidine-based dye manufacturing
wastewaters, however, the biodegradation process can be
employed as a primary treatment method.
(3) The nitrous acid treatment technology can be employed as a
pretreatment method which preceeds a blodegradation system.
0
(4) Treatment efficiencies obtained through nitrous acid oxidation
at the Allled's Buffalo Dye Plant are such that the concentra-
tion of benzidine 1n the combined wastewaters prior to neutral-
ization averaged 47 ppl while the mass discharged was 0.38
pounds per day./ After neutralization and prior to discharge
to the Buffalo Sewer Authority collection sewer, the concen-
tration averaged 35 ppb and the mass discharged was 0.33
pounds of benzidine sulfate per day.
-------
-69-
(5) In the case of Allied Chemical Corporation as well as at
GAF and Fabricolor, Inc. (the only existing producers of
benzidine), the pretreated wastewaters are discharged to
municipal sewers. At the Buffalo wastewater treatment plant
no benzidine (<1 ppb) can be detected in the wastwater
matrix (refer to Section IV). Moreover, at such dilute levels
benzidine would have no effect v.hatsoever on the operation of
publicly owned treatment works (refer to Section IV).
(6) Pretreatment of benzidine manufacture wastewaters which
would be discharged by new sources to publicly owned treat-
ment works could also be achieved by the nitrous acid oxi-
dation procedure. Treatment efficiencies would likely equal
or exceed those obtained at Allied's Buffalo Dye Plant.
(7) If a new benzidine manufacturing facility were installed at
a location where the wastewater would be discharged directly
to a receiving watercourse, the nitrous acid oxidation pro-
cedure would also be suitable for the treatment of benzidine
production wastewaters. Assuming treatment efficiencies
equal to those obtained by Allied Chemical Corporation,
benzidine concentrations in the wastewater discharge would
likely be less than 25 ppb.
In the event that the effluent standards for benzidine
were to be set at a level lower than the 10 to 50 ppb range,
then additional treatment would be required as an add-on for
new facilities discharging directly to a watercourse. As
demonstrated i/n Section III, such additional treatment could
be achieved biologically. Discharge concentrations of
benzidine after oxidation with nitrous acid and subsequent
biodegradation would be expected to be in the 1 to 5 ppb
range.
-------
-70-
(8) The nitrous acid treatment technology can be readily im-
plemented within one year of the date of promulgation of
standards.
(9) Costs associated with treating wastewaters containing benct-
dine ranged from 2 to 12 cents per pound of product. The
cost varied due to different production methodologies.
Although only the nitrous acid treatment process has been installed
^8>*etofore and is feasible at this time, the adsorption technologies
Activated carbon and polymeric adsorbents) should further be explored
researched to evaluate their potential for application to new
^fect dischargers.
-------
SECTION VI
CONTROL OF WASTEWATER DISCHARGES OF BENZIDINE-BASED DYE APPLICATORS
Benzidine-based dyes are used principally in three industrial areas:
paper, leather, and textiles. According to the latest Tariff Commission Data
available, the market for benzidine dyes in 1973 was approximately 30 million
pounds. Of this total market approximately 40 percent of the total volume
is consumed in the manufacture of paper, 25 percent by the textile industry,
15 percent for leather production, and the remaining 20 percent in various
other industries. The dyestuff comprises approximately 1, 2-3, and 4-6 per-
cent of the finished weight of paper, textile goods, and leather products,
respectively, for which it is used.
Because approximately 2 to 20 ppm of benzidine is contained in the direct
dyes as they are used by the dye applicators, the possibility exists that the
dye applicators themselves could potentially cause pollution simply by dischar-
ging the benzidine that entered their processing system as an impurity. In
this regard the Benzidine Task Force of the Synthetic Organic Chemicals Manu-
facturing Association has recommended the use of a mass balance monitoring
analysis in lieu of a chemical analysis to ascertain that dye applicators meet
EPA guidelines. It is noteworthy that the mass or materials balance approach
1s routinely employed by the chemical engineering profession.
The "mass balance" monitoring approach requires the use only of inventory
records: i.e., knowing how many pounds of benzidine-based dyes were used during
a particular time period and knowing the total quantity of water discharged from
the plant during the same time period, one can calculate the maximum concentra-
tion 'of benzidine that could possibly be present in the wastewater assuming that
20 ppm of benzidine is present 'in the dye and that all of it is discharged
Into the wastewater. The "mass balance" or inventory monitoring approach is
-------
more economical than an analytical monitoring approach which would require
routine sampling and analysis and the acquisition of relatively sophisticated
analytical instrumentation.
To evaluate the efficacy of using the mass balance approach as proposed
by SOCMA, three types of scoping surveys were conducted. The first consisted
of site visits to three industrial firms that represented the paper, textile,
and leather industries. The second involved a questionaire that was forwarded
to five manufacturers of paper, leather and textile goods. The final survey
consisted of an analytical survey of benzidine contained in the wastewaters
of industries 1n the three industrial categories.
ANALYSIS OF MASS BALANCE APPROACH
Textile: Clyde Fabrics. Inc.... Clyde Fabrics, Inc. of Newton, North
Carolina manufacturers and dyes fab/ic for the construction of work gloves.
Benzldine-based dyes comprise approximately 80 percent of its entire dye usage.
Consequently, a survey of benzidine levels which occur 1n the wastewater dis-
charges of this particular industry could truly be classified as a "heavy use"
situation.
If one were to assume that the concentration of benzidine in the benzldine-
based dyes used by Clyde Fabrics, Inc. 1s 20 ppm as the maximum level certified
by the dye manufacturer, then one can calculate the maximum concentration of
benzidine that could be present 1n/the wastewater by the mass balance analysis.
Such calculations were conducted for data obtained for the month of June 1975.
The calculations which have been tabulated in Table VI-1 show calculated maximum
possible benzidine concentrations 1n the exhausted dye liquors ranging from
6.63 to 17.66 ppb with an average of 13.32 ppb and a median value of 13.07
ppb. The average calculated total mass discharge of benzidine 1s 0.0101 pounds
per day.
-------
-73-
TABLE VI-1
CALCULATED MAXIMUM POSSIBLE BENZIDINE CONCENTRATIONS
IN THE WASTEWATERS OF CLYDE FABRICS, INC.
Dye Usage
Water Usage
Benzidine
Date
(pounds)
(lOOD's gallons)
(ppb)
6-2-75
602.2
99
14.59
6-3-75
424.15
84
12.11
6-4-75
545.15
100
13.07
6-5-75
418.7
80
12.55
6-6-75
586.5
93
15.12
6-7-75
259.7
44
14/15
6-9-75
444.83
109
9.79
6-10-75
427.06
81
12.64
6-11-75
706.43
102
16.61
6-12-75
516.78
86
14.41
6-13-75
368.3
50
17.66
6-16-75
619.55
111
13.38
6-17-75
548.65
104
12.65
6-18-75
574.95
117
11.78
6-19-75
731.3
103
17.03
6-20-75
431.8
69
15.01
6-23-75
828.45
128
15.52
6-24-75
512.06
115
10.68
6-25-75
588.96
113
12.50
6-26-75
320.7
116
6.63
6-27-75
202.9
41
11.87
Average
507.58
92,619
13.32
-------
-74-
Even though a mass balance calculation should be conducted assuming that
all of the benzidine in benzidine-based dyes is discharged with the exhausted
dye liquors, one must recognize that some of the benzidine is actually trans-
ferred to the product. Such transfer of benzidine to the product has been es-
timated at 25 to 50 percent of the total benzidine present (VI-1). To eval-
uate this estimate of benzidine transfer, exhausted dye liquor of Clyde Fabrics,
Inc. were analyzed during July 1975. The results obtained have been tabulated
in Table VI-2. Based on these results (which are not directly comparable with
the data of Table VI-1 due to different period of analysis) one can estimate
that approximately 75 percent of the benzidine was transferred to the cloth.
Assuming that the benzidine which is discharged by Clyde Fabrics» Inc.
to the City of Newton, North Carolina wastewater collection system is conserv-
ative (i.e., not degraded), the concentration of benzidine in the influent
to the Newton wastewater treatment plant is calculated to be either 0.822 or
0.21,6 ppb depending on whether the concentration of benzidine in the discharge
of Clyde Fabrics, Inc. averages 13.32 or 3.5 ppb, respectively.
At Newton, North Carolina the wastewater treatment system consists of
(1) screening and grit removal, (2) primary clarification, (3) biological trick-
ling filtration, (4) secondary clarification, and (5) chlorination. Samples
of wastewater collected at the influent to the chlorine contact chamber and
analyzed for benzidine (VI-2) showed concentrations less than the level of
detectability (0.2 ppb).
Leather*: S. B. Foot Tanning Company .... S. B. Foot Tanning Company of
Red Wing, Minnesota processes and dyes beef hides for ultimate sale to the shoe
manufacturing industry. The company is a medium sized tanner, tanning approx-
imately 6500 to 6800 sides per day.
The calculated mass balance benzidine concentration that could be present
In the dye house blow-down wastewaters is 0.38 ppb (basis: 20 ppm benzidine
-------
-75-
TABLE VI-2
BENZIDINE CONCENTRATIONS IN EXHAUSTED DYE LIQUORS
AT CLYDE FABRICS, INC.
Sample Benzidine Cone.
Date Source (ppb)
7-17-75 Machine #1 3.1
7-17-75 Machine #2 4.2
7-17-75 Machine #3 2.2
7-22-75 Machine #2 4.5
Average
3.5
-------
-76-
in dye). Upon dilution with other process wastewaters the concentration is
reduced to 0.25 ppb. The average calculated total mass discharge of benzidine
is 0.0144 pounds per day.
S. B. Foot Tanning Company operates its own wastewater treatment plant
which consists of two primary clarifiers, a four million gallon aerated lagoon,
two secondary clarifiers, and a chlorine contact chamber. The treatment system
has a 4.4 day hydraulic detention time at the current 6.9 MGD wastewater flow
rate. An EPA demonstration grant was awarded to S. B. Foot Tanning Co. to
demonstrate the performance of their treatment system as BPCTCA. The project
terminated late in 1974. The final report is currently in review and is, there-
fore, not yet available.
Although the concentration of benzidine in the wastewater is at the level
of detectability, -one major potential problem must be addressed at the S. B.
Foot Tanning Company. That 1s, fn the tanning operation the possible reduction
of benzldine-based dyes to the parent material, benzidine, exists. This 1s
due to the fact that large quantities of sulfides (2000 lbs. NaHS and 1000 lbs.
Na£S) are used per day 1n the dehairing operation. Even though 35 percent of
the sulfides are recovered for recycle, the concentration of sulfides in the
Influent to the wastewater treatment facility is approximately 200 ppm. Since
the wastewaters are not segregated, a rather high potential exists for the
reduction of benzidine-based dyes.
To evaluate the potential 'magnitude of this problem a "likely" situation
can be calculated. The production manager of S. B. Foot Tanning Company esti-
mated (VI-3) that approximately one-quarter of one percent of the dyes used
are not exhausted and are thus discharged to the sewer. Assuming that all
of the unreacted benzldine-based dyes would be reduced 1n the sewer to benzidine,
one can estimate that the concentration of benzidine 1n the wastewater would be
raised by 15.86 ppb assuming that approximately 50 percent of the dye molecule
-------
-77-
1s benzidine on a weight basis. While it appears that the potential problem
is not a major consequence, the actual magnitude of the problem must be defined
through analysis of the wastewaters at S. B. Foot Tanning Company and at other
leather processing plants where similar reducing conditions could occur.
Paper: Peninsular Paper Company Peninsular Paper Company of Ypsilanti,
Michigan produces paper stock that is employed primarily for report covers, photo-
mounts, etc. Although this company is considered to be small by industry standards,
it is considered to be a high volume user of Direct Black 38, the only benzldine-
based dye it uses in Its manufacturing operations. Consequently, this dye
applicator can be classified as a "heavy use" situation.
Assuming that the Direct Black 38 used by Peninsular Paper Company con-
tains 20 ppm of benzidine, one can calculate the maximum concentration of ben-
zidine that could be present in their wastewater. Such calculations were con-
ducted for the accounting period which extended from 23 June through 27 July
1975. The calculations which have been tabulated in Table VI-3 show that Direct
Black 38 was used only on Fridays. The calculated maximum possible benzidine
concentrations in the exhausted pulping liquors ranged from 1.01 to 8.54 and
averaged 4.582 ppb on the days when the benzidine-based dye was used. The aver-
age calculated total mass discharge of benzidine Is 0.0128 pounds per day.
The dye was applied at a level of 1.8 percent of the finished weight of paper
produced.
Peninsular Paper Company occasionally strips the Direct Black 38 dye
from paper which has been recycled. In the past this was achieved either by
the reductive stripping method using hydrosulfite or by oxidative stripping
using hypochlorite. Because reductive stripping did not yield the desired result,
Peninsular Paper Co. now strips only oxidatlvely.
The wastewaters discharged by Peninsular Paper Co. are transported to the
City of Ypsilanti wastewater treatment plant through its gravity flow sewer
-------
-73-
TABLE VI-3
CALCULATED MAXIMUM POSSIBLE BENZIDINE CONCENTRATION
IN THE WASTEWATERS OF PENINSULAR PAPER CO.
Dye Usage Water Usage Benzidine Cone.
Date (pounds) (1000's gallons) (ppb)
6-23-75
0
764.8
0.0
6-24-75
0
329.0
0.0
6-25-75
0
332.8
0.0
6-26-75
0
335.8
0.0
6-27-65
625
324.8
4.61
6-30-75
0
417.6
0.0
7-1-75
0
269.8
0.0
7-2-75
0
305.2
0.0
7-3-75
575
225.8
6.11
7-7-75
0
397.6
0.0
7-8-75
0
234.4
0.0
7-9-75
0
262.8
0.0
7-11-75
750
680.0
2.64
7-14-75
0
360.4
0.0
7-15-75
0
301.0
0.0
7-16-75
0
324.6
0.0
7-17-75
0
253.4
0.0
7-18-75
150
357.0
1.01
7-21-75
0
538.8
0.0
7-22-75
0
282.6
0.0
7-23-75
0
267.4
0.0
7-24-75
0
358.0
0.0
7-25-75
1100
308.6
8.54
-------
-79-
network. The plant is a conventional activated sludge biological treatment
facility with primary and secondary clarification and anaerobic sludge diges-
tion. The City of Ypsilanti limits Peninsular's discharge only with respect
to the volumetric flow. No requirements regarding the discharge of any specific
pollutants have been imposed.
-------
-80-
Questionaire Survey
To futher evaluate the utility of the mass balance approach for monitoring
the wastewaters of benzidine-based dye applicators a questionaire was forwarded
to five industries in each of the three industrial categories; paper, textile,
and leather. Names and addresses of the 15 industries contacted by telephone
and subsequently by letter were supplied by the Benzidine Task Force of the
Synthetic Organic Chemicals Manufacturing Association. The questionaire,
questionaire information sheet, and supporting documentation have been appended
as Appendix C.
Taper .... Five paper manufacturing concerns were asked: (1) to identify
that month of the 1974 through 1975 calendar year period during which the firm
used the greatest quantity of benzidine-based dyes; (2) to record the quantity
of benzidine-based dyes used each day during that month; and (3) to record the
quantity of water discharged daily for the same period. All of the five indus-
tries contacted responded. Because one of the industries (#3) recycles and
reuses its wastewater, the data supplied by it cannot be used for evaluation
of the mass balance approach. Nonetheless, this industry (#3) used benzidine-
based dyes only one day during the month data base period. On that day a total
of 315 pounds of dye were used.
A compilation of the data supplied by the four other paper manufacturers
1s presented in Table VI-4. The table Includes data regarding the discharge
concentration and total discharge mass of benzidine on a dally basis assuming
that the benzidine-based dyes contain 20 ppm benzidine as an impurity and that
all of the free benzidine in the dye 1s discharged with the wastewater.
The data has been summarized in Table VI-5. The four manufacturers surveyed
used benzidine-based dyes on 19, 30, 18, and 2 days during their respective
"heavy use" one-month data base period. Average calculated concentrations of
benzidine that could have been present in the wastewater were 0.0213, 0.4893,
-------
-81-
TABLE VI-4
BENZIDINE DISCHARGED BY FOUR PAPER MANUFACTURERS: MASS BALANCE APPROACH
Day Industry #1
Cone. Disch. Mass
Cppb) (10"3#/day)
Industry #2 Industry #3
Cone. Disch. Mass Cone"! Disch. Mass
Cppb) (10-3#/day) (PPb) (10"3#/day)
Industry H
Cone. Discb. Mass
(ppb) (10-3#/day)
1
2
3
4
5
6
7
8
9
10
11
12
13
U
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
0.0006
0.06
0.23
0.60
0.0008
0.20
3.19
8.00
0.0
0.0
0.56
1.82
0.0016
0.40
0.0
0.0
0.0
0.0
0.47
1.24
0.0015
0.40
0.0
0.0
0.04
4.2
0.44
1.14
0.0014
0.40
0.0
0.0
0.04
4.2
0.34
1.06
0.0018
0.40
0.0
0.0
0.0
0.0
0.14
0.50
0.0
0.0 '
0.0
0.0
0.0
0.0
1.95
6.42
0.0
0.0
0.0
0.0
0.0014
0.14
1.11
3.36
0.0
0.0
0.0
0.0
0.0006
0.06
0.40
1.24
0.0
0.0
0.0
0.0
0.0
0.0
0.28
0.94
0.0
0.0
0.0
0.0
0.0014
0.14
0.22
0.72
0.0
0.0
0.0
0.0
0.0008
0.08
0.76
1.82
0.0016
0.40
0.0
0.0
0.0014
0.14
0.32
0.96
0.0072
1.68
0.0
0.0
0.0021
0.20
0.45
1.44
0.0214
5.32
0.0
0.0
0.0
0.0
0.66
2.24
0.0196
4.78
0.0
0.0
0.0014
0.14
0.32
0.84
0.0107
2.82
3.19
8.00
0.132
12.8
0.52
1.44
0.0016
0.40
0.0
0.0
0.173
17.0
0.81
2.30
0.0017
0.40
0.0
0.0
0.0
0.0
1.13
3.24
0.0
0.0
0.0
0.0
0.0015
0.14
0.38
1.02
0.0
0.0
0.0
0.0
0.0014
0.14
0.41
1.50
0.0
0.0
0.0
0.0
0.0014
0.14
0.34
1.26
0.0
0.0
0.0
0.0
"0.0
0.0
0.22
0.82
0.0
0.0
0.0
0.0
0.0
0.0
0.16
0.44
0.0
0.0
0,0
0.0
0.0
0.0
0.59
1.60
0.0015
0.40
0.0
0.0
0.0
0.0
0.38
1.30
0.0015
0.40
0.0
0.0
0.0
0.0
0.24
0.94
0.0016
0.40
0.0
0.0
0.0014
0.14
0.38
1.24
0.0015
0.40
0.0
0.0
0.0015
0.14
0.22
0.62
0.0017
0.40
0.0
0.0
0.0014
0.14
0.25
0.94
0.0016
0.40
0.0
0.0
0.0,
0.0015
0.14
-
-
-
-
0.0
-------
-82-
TABLE VI-5
SUMMARY OF MASS BALANCE APPROACH
FOR PAPER, TEXTILE, AND LEATHER MANUFACTURERS
Industry #
# days B
# days B
Avg. B
Avg. B
Max. B
Max. B
used
not used
Cone.
Discharged
Cone.
Discharged
(ppb)
(10"3#/day)
(ppb)
(10"3#/day;
PAPER
1
19
12
0.0213
2.11
0.1730
17.0
2
39
0
0.4893
1.50
1.9500
6.42
4
18
12
0.0045
1.11
0.0214
5.32
5
2
29
3.1900
8.00
3.1900
8.00
TEXTILE
6
20
10
0.2560
1.79
0.3600
2.38
7
7
24
0.1500
0.52
0.1500
0.52
9
20
10
0.41^0
2.16
0.6800
3.40
LEATHER
12
20
8
0.7305
4.51
1.2900
6.69
14
26
5
0.2738
0.54
0.76
0.98
SSSgs: (1) B designates benzidine
(2) Average values reported are for days during which benzidine
based dyes were used by the industry.
-------
-83-
0.0045 and 3.1900 ppb for Industries #1, #2, M, and #5, respectively. Cor-
responding calculated average total mass discharges of benzidine were 0.00211,
0.0015, 0.00111, and 0.008 pounds per day. Similarly, maximum possible concen-
trations of benzidine were calculated as 0.1730, 1.95, 0.0214, and 3.19 ppb for
Industries #1, #2, #4, and #5, respectively, while the maximum total mass dis-
charges were determined to be 0.017, 0.00642, 0.00532, and 0.008 pounds per
day. By v/ay of comparison, Peninsular Paper Co. showed an average calculated
concentration of benzidine of 4.582 ppb and a maximum calculated concentration
of 8.54 ppb.
Textile .... Five textile manufacturers were contacted and asked to supply
Information analogous to that supplied by the paper manufacturers. Of the five,
three responded. The data obtained has been compliled in Table VI-6. This
data has also been summarized in Table VI-^.
The three manufacturers surveyed used benzidine-based dyes on 20, 7, and
20 days during the one-month data base period. Average calculated concentra-
tions of benzidine that could have been present in the wastewater were 0.256,
0.15, and 0.414 ppb for Industries #6, #7, and #9, respectively. Corresponding
calculated average total dally mass discharges of benzidine were o.00179, 0.00052,
and 0.00216 pounds. Similarly, maximum possible concentrations of benzidine
were calculated as 0.36, 0.15, and 0.68 ppb for Industries #6, #7, and #9, res-
i
pectively while the maximum possible total mass discharges were determined to
be 0.00238, 0.00052, and 0.0034 pounds per day. By way of comparison, Clyde
Fabrics, Inc. showed an average calculated concentration of benzidine of 13.32
ppb and a maximum possible calculated concentration of 17.66 ppb.
Leather .... As before, five leather tanners were asked to supply Information
that could be employed to evaluate the mass balance monitoring approach. Of
the five, two responded, two Indicated a desire to respond but did not, and
one was unwilling to cooperate 1n the survey. The data obtained for the two
-------
T
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20^
21
22
23
24
25
26
27
28
29
30
31
-84-
TABLE VI-6
BENZIDINE DISCHARGED BY THREE TEXTILE GOODS MANUFACTURERS:
MASS BALANCE APPROACH
Industry #6
Cone. Discharge Mass
(ppb) (10-3 #/day)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.36
2.24
0.31
2.24
0.33
2.24
0.36
2.24
0.35
2.24
0.0
0.0
¦0.0
0.0
0.12
1.4
0.21
1.4
0.21
1.4
0.21
1.4
0.26
1.4
0.0
0.0
0.0
0.0
0.17
1.14
0.14
1.14
0.16
1.14
0.16
1.14
0.22
1.14
0.0
0.0
0.0
0.0
0.35
2.38
0.30
2.38'
0.27
2.38
0.31
2.38
0.32
2.38
Industry #7
Cone. Discharge Mass
(ppb) CIO"3 #/day)
0.15
0.52
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.15
0.52
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.15
0.52
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.15
0.52
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.15
0.52
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.15
0.52
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.15
0.52
Industry #9
Cone. Discharge Mass
(ppb) (10-3 #/day)
0.0
0.0
0.0
0.0
0.41
2.04
0.32
1.62
0.60
3.00
0.48
2.42
0.58
2.90
0.0
0.0
0.0
0.0
0.13
0.66
0.68
3.4
0.38
1.76
0.27
1.34
0.42
2.10
0.0
0.0
0.0
0.0
0.50
2.52
0.57
2.84
0.55
2.76
0.60
3.00
0.10
0.50
0.0
0.0
0.0
0.0
0.33
1.66
0.51
2.56
0.42
2.10
0.40
2.00
0.39
1.96
0.0
0.0
0.0
0.0
-------
who responded has been compiled in Table VI-7 and summarized in Table VI-5.
The two manufacturers surveyed used benzidine-based dyes on 20 and 26 days
during the one-month data base period. Average calculated concentrations of ben-
zidine that could have been present in the wastewater were 0.7305 and 0.2738
ppb for Industries #12 and #14, respectively. Corresponding calculated average
total daily mass discharges of benzidine were 0.00451 and 0.00054 pounds. Like-
wise, maximum possible concentrations of benzidine that could have occurred during
the period were determined to be 1.29 and 0.76 ppb for Industries #12 and #14,
respectively* while the maximum possible total mass discharges were calculated
to be 0.00669 and 0.00098 pounds per day. Again, by way of comparison, S. B.
Foot Tanning Company showed an average calculated concentration of benzidine
of 0.25 ppb.
Analytical Surveys
To provide additional data regarding the possibility of the discharge of
benzidine by dye applicators at relatively high levels, the Benzidine Task
Force of S0CMA conducted an analytical survey (VI-4) on the wastewaters of a
plant which is representative of each of the three industrial categories. These
analytical surveys are summarized in the following paragraphs.
Paper .... During the period in which a twenty-four hour composite sample
Was collected at a paper industry, one of four processing lines was using the
benzidine-based dye, Direct Black 38. The other three lines were using non-
benzidine based colors. Prior to discharge the plant's wastewater was chlor-
inated and was clarified using the coagulants aluminum sulfate and lime. Ap-
proximately half of the six million gallon per day effluent stream was recycled
back to the processing lines after treatment. Analysis of the sample which was
taken after the wastewater treatment system showed that no benzidine was detect-
able using the Chlortnaine-T procedure (detectable limit is 10 ppb).
Leather .... Two plants that are representative of the leather Industry
-------
-86-
TABLE VI-7
BENZIDINE DISCHARGED BY TWO LEATHER MANUFACTURERS: MASS BALANCE APPROACH
Day
Cone,
(ppb)
Industry ii 12
Discharge Mass
(10-3 #/day)
Cone,
(ppb)
Industry #14
Discharge Mass
(10-3 #/day)
1
0.0
0.0
0.20
2
0.0
0.0
0.25
3
0.44
2.89
0.76
4
0.64
4.18
0.16
5
0.40
2.79
0.0
6
0.46
3.00
0.40
7
0.49
3.27
0.29
8
0.0
0.0
0.26
9
0.0
0.0
0.24
10
0.88
5.42
0.41
11
0.13
0.86
0.04
12
0.86
5.09
0.0
13
1.08
6.69
0.0
14
0.63
3.48
0.03
15
0.0
0.0
0.26
16
0.0
0.0
0.10
17
0.93
5.88
0.28
18
0.42
2.9A
0.24
19
0.72
4.88
0.0
20
0.82
5.88
0.05
21
1.14
5.30
0.16
22
0.0
0.0
0.51
23
.0.0.
0.0
(L28
24
0.73
3.26
0.37
25
0.80
5.72
0.13
26
0.80
5.48
0.0
27
0*95
6.16
0.23
28
1.29
6.10
0.31
29
•
-
0.46
30
0.39
31
•
•»
0.31
0.38
0.50
0.76
0.32
0.0
0.82
0.60
0.48
0.50
0.76
0.08
0.0
0.0
0.08
0.46
0.32
0.64
0.48
0.0
0.10
0.38
0.98
0.66
0.80
0.30
0.0
0.58
0.68
0.94
0.80
0.58
-------
-87-
were sampled. The discharge from one of the plants totaled approximately one
million gallons per day and received no treatment other than simple clarification
prior to discharge to a municipal sewerage system. At the time when the com-
posite sample was collected, the benzidine-based dyes Direct Blue 6, Direct Black
38, Direct Red 37, Direct Green 1, Direct Green 6, Direct Blue 2, and Acid
Red 85 were being used in the leather processing system. The Chloramine-T
procedure again showed no detectable benzidine (less than 10 ppb).
In the ether leather processing plant that was sampled the benzidine-based
dyes that were used at the time of sampling included Direct Black 38, Erie
Brown 3GN, Erie Catechine 3G, and Erie Scarlet B. Other dyeings using Buffalo
Black NBR, a non-benzidine-based dye, were being made at the same time. The
plant's discharge of 200,000 gallons per day was treated by primary sedimentation
and the extended aeration process prior to discharge. As before, analyses of
the composited sample showed no detectable benzidine.
Textiles .... A textile mill whose primary product was upholstery also
was surveyed. During the sampling period the benzidine-based dye used was Erie
Black GXR. Other dyeings made during the sampling period included the dyes
Niagara Blue 2B, Erie Yellow Y, Erie Green MT, and Solantine Brown BRL, This
mill's effluent (700,000 gallons per day) was discharged directly Into a mun-
icipal sewerage system. Grab samples of the final effluent which were taken on
two-hour intervals and were composited over a 24-hour period showed no detectable
traces of benzidine using the Chloramine-T procedure (less than 10 ppb).
potential reduction problems
If strong reducing conditions exist, benzidine-based dyes may be reduced
to the parent compound,.benzidine. Generally, two possibilities for such re-
duction exist in the plants of dye applicators.
(1) Paper, leather, and textile producers commonly strip dyes from
product materials that did not meet quality control standards.
-------
-88-
These materials are then recycled for reprocessing. Such
stripping operations can be accomplished either oxldatlvely
or reductively.
(2) Reducing materials such as hydrosulfite may be used in textile,
paper, or leather processing operations that are not associated
with dye application itself. The dehairing operation at S. B.
Foot Tanning Company, mentioned earlier, is an example of such
an operation. If the reducing agents are discharged to the
process sewer where they may combine and mix with exhausted
dye liquors, then the break-down of benzidine-based dyes in
the dye liquors to benzidine could occur.
The Benzidine Task Force of SOCMA has attemped to eliminate the first of
the two potential problems by Instructing their respective clients to strip
oxidatively and not reductively. Copies of such Instructive notifications that
are being transmitted by Allied Chemical Company and GAF Corporation have been
Included as Appendix D.
Of the five paper, three textile, and two leather manufacturers that
responded to the questionalre survey, two Indicated that they did dtrlp benzidine-
based dyes reductively. All others did not. One, a paper manufacturer, strip
such dyes seven days per month at the rate of 10,000 pounds per day. The other,
a carpet manufacturer, indicated that an average of one beck bond of carpet
per month would be stripped. This requires approximately 80 pounds zinc formald-
ehyde sulfoxylate.
No similar efforts have to the knowledge of the writer been made to date
to eliminate the second possibility. To establish the potential magnitude of
the problem all survey respondents were queried regarding their use of reducing
•gents. Their responses have been tabulated in Table VI-8. In general, the
dally quantity of reducing agents used by any of the respondents Is substantially
'ess than that used by the S. B. Foot Tanning Company. Nonetheless, because
-------
-89-
TABLE VI-8
USE OF REDUCING AGENTS BY BENZIDINE-BA5ED DYE APPLICATORS
Industry
ID §
Use
(Yes/No)
Avg. Monthly
Usage
(pounds)
Maximum
Daily Usage
(pounds)
Reason
For Use
PAPER
1
Yes
975
190
pulp brightener
2
Yes
875
125
neutralizer
3
No
-
-
-
4
Yes
1000
35
chlorine reduction
5
No
m
-
-
TEXTILE
6
Yes
8000
600
clear dyes
7
Yes
1214
270
strip tint
9
Yes
250
20
clean equipment
LEATHER
12
14
No
No
-------
-90-
no actual data regarding the 1n-situ production of benzidine is currently avail-
able, this potential pathway should be extensively investigated to ensure that
excess concentrations of benzidine do not result from the reduction of benzldine-
based dyes that are contained in the exhausted dye liquors.
SUMMARY
Based on the data presented above, it appears that the mass balance monitoring
approach could be entirely satisfactory for use by dye applicators. If this
procedure is adopted, however, it is imperative to show either that benzidine-
based dyes are not reduced to benzidine under the reducing conditions that
might be encountered in the wastewaters of dye applicators or, if reduction
does indeed occur, that the maximum possible benzidine concentration meets the
discharge limits. Otherwise, a chemical analytical procedure would be the
only alternative.
It 1s Important to note also that most dye applicators either own and operate
a biological wastewater treatment system (aerated lagoon or extended air activated
sludge) or discharge Into a municipally owned one. Since it has been demonstrated
that biological treatment will remove approximately 90 percent of benzidine 1n
Wastewater 1f the Influent concentration 1s less than 50 ppb, the concentrations
of benzidine discharged to the environment by dye applicators would, therefore,
be expected to be extremely small. In essence, the bio-treatment systems would
provide an added margin of safety.
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-yi-
LITEBATURE CITED
VI-1 K. H. Ferber, Trip Report, 7-29-75
VI-2 W. M. Reiter, Trip Report, 7-29-75
VI-3 D. Waite, Trip Report, 8-5-75.
VI-4 Anon. "Survey of Benzidine in Effluents from Dye Users"
Benzidine Task Force, SOCMA, July 1974.
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APPENDIX
A
INDUSTRIAL HYGIENE & ENVIRONMENTAL CONTROI
EMPLOYED BY THE
BUFFALO DYE PLANT
-------
-93-
INDlJfiTRIATi HYGIK'IK f.- I'MVIUOMMENT AT< CONTROL
The operating, maintenance, and control practices
related to the industrial hygiene program for benzidine are
set forth in the SCD Industrial Hygiene Guideline Mo. 4.
The purpose of the guideline is to assure no retrogression
in standards or procedures which are designed to guarantee
safe working conditions.
Safe exposure levels in the manufacture of benzidine
depend on a few basic factors:
1. Manufacture and use only of aqueous benzidine sulfate
slurry which eliminates both dust and vapcr and permits
mass transfer v/ithin a closed system until entirely
converted to benzidine tetrazo.
2. Filtration, washing & disrharge of the benzidine sulfate
by means of a closed Valle' filter which can be decon-
taminated before periodic replacement of screens or
other maintenance.
3. Wet decontamination of any and all items of equipment
by operating personnel before maintenance application.
4. Establishment of control standards for air, clothing,
equipment, and building based on best past performance
with periodic revision toward tighter control.
5. Education and training of foremen and workers in the
nature of the hazard and the necessity for adherence
to rules and yood housekeeping.
6. Insistence on good housekeeping backed up by periodic
self-inspections as well as periodic management
inspections.
7. Seeking and locating the cause of excursions in
environmental levels of benzidine, followed by cor-
rective measures.
8. Well-engineered ventilation.
The proof of effectiveness of the above measures
can be demonstrated only over time. As pointed out, there
nave been no tumors among workers exposed only in the last
19 years.
K. II. Ferbor
5/30/75
KlIF: dmw
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-94-
ALTilKD C1JKMICAT. CDRl'OltATT.OM
si'jsciAVJ'Y c:;ii::;rCA),.7. ui.vision
industrial uvGi cuidklink wo .
ISSUED: JUNK 14, 1974
1. Subject: Benzidine Sulfate
2. Background Information:
Benzidine and its salts have long been recognizee! as a
human bladder carci:vigcn. The cases which have occurred
among Buffalo Dye L3. :rtt. workers all involve exposure to the
early process and op "ations. These operations were carried
out in open process' equipment, and included hand cleaning
of plate and frame *" ¦ '.cr presses, molten phase separations
of benzidine base, d< filiation and flaking with high dust
and sublimate level::. Kew manufacturing facilities, a
catalytic reduction process, elimination of all base opera-
tions and institution of a variety of process and administrative
controls have drastically reduced exposure levels. Mo new
cases have occurred among those workers whose only exposure
has been to the latest process and equipment commissioned
in 1955. The nature of the risk is such, however, that
exposure must be maintained at the lowest practicable limit
through the promulgation and enforcement of administrative,
engineering and processing controls, and industrial hygiene
practices.
It is the purpose-o£ this guideline to assemble the
existing rules, procedures, policies and controls for re.ady
reference nr.d guidance as well as to furnish a point of
departure for future improvements.
In Sfcpteuber 1972 , representatives of KIOSII inspected
the benzidine and benzidine tetrato plantr. and followed with
a report on their findings and recommendations which were
promptly implemented. For the )iiost part, these recommendations
have been included in this guideline.
In Dc-icoi.ibcr 1972, c.t Allied's request, Dr. Ralph G. Smith
of the University of Michigan examined the benzidine plant
and related health controls and made additional recommendations
which wore implemented and have also been included in this
guideline.
On May 3, 107 3, OSUA promulgated an emergency temporary
ntnmlnrd on certain carcinogens, including benzidno ..sulfate.
The Buffalo byo Plan,t promptly developed an action plan to
bring thrt production mid use Jvuilitios info compliance with
the standard. Thia p.lan will bc» fulJy executed Inilowing
installation at certain ncccsriary equipment in 1374.
-------
au/ikh ciu:;jtcat. coppoiwion
si'hciai.ty ciii:rvccA[.r» division -95-
indumtkial ];vg;[j::jij cuiwaiNi: no. if-
ISUUKD: ,IutI 4 . IT/4 Page 2
2. Background Information: (Cont'd.)
On December 5, 1973, Mr. Margolies of the Industrial
Hygiene Division of the N. Y. State Department of Labor
inspected the benzidine facilities and found our handling
of the occupational health aspects to be satisfactory.
On February 11, 1974, following deliberations by a
standard advisory committee, public hearings and written
testimony, 05IIA issued permanent occupational and health
standards for carcinogens including benzidine sulfate.
A copy of the pertinent sections is attached as a part of
this guideline (Appendix F).
On December 27 , 1973 (Fed. Reg. 3_8 (247) 35-388-35395,
Part II), the Environmental Protection Agency published
Proposed Toxic Pollutant Effluent Standards covering nine
pollutants, including benzidine and its salts. Public
hearings are scheduled for April 1974. Various studies
of the fate cf benzidine in the environment have .boon init-
iated by Allied to assist the EPA in the development of a
safe and practicable standard. The Synthetic Organic
Chemicals Manufacturers Association (SOCMA) is representing
industry at the forthcoming hearings.
In 1973, The International Labour office .issued
Report VII (2) on Control and Prevention of Occupational
Cancer. The proposed conclusions have boon given serious
consideration and these guidelines are in accord with the
principles set forth in the report.
3. Policy:
.1 The regulations of OSIIA as set forth, in the Federal
Register of Jan. 29, 1974, Vol.39, No. 20 Part III
pp 3756-3797 shall be followed in all respects unless
exceptions on variances thereto have been obtained
through Allied Legal.
.2 No individual (worker, supervisor or visitor) is to bo
knowingly exposed to benzidine or its salts at concen-
tration:1; or under conditions that are not in conformance
with these guidelines.
.3 The number of workers assigned to the maintenance of
benzidine sulfate and to the manufacture of equipment
i»t>wl liner, used in the benzidine process be kept
ii« low as practicable. Rotation of personnel into
ami out of the Ix:nv;iUine assignments shall no't bo
permitted.
-------
SPiiCiAr/i'Y ci:i.mu:a),c divi:;j.om -96-
IMDtiUTRIAL KYGIMNL: GUUWUNE U'O. /.<
ISSU1JP; Jlim; 14, 1D7'1 Payo 3
3. Policy. (Cont'd;)
.4 Within the limitation of contractual agreements,
older replacements' are to be selected over younger
men in order to limit the potential induction period.
.5 Maintenance or construction tradesmen are to work
only on decontaminated equipment.
.6 A preventive maintenance schedule should be developed
and executed based on past experience and engineering
calculations,
.7 Unanticipated maintenance on processing equipment or
hygiene accessories shall be given high priority of
attention.
.8 It shall be a condition of employment that benzidine,
workers conform to all rules and procedures, including
personal hygiene and protective measures.
.9 The working atmosphere, equipment and building surfaces
shall be regularly* monitored and minimum standards shall
be developed" and applied. Failures to moot the standards
shall prompt immediate investigation and corrective action,
.10 Biological monitoring shall be carried out and results
made available to the workers involved. Abnormal readings
shall result in prompt medical evaluation and appropriate
further diagnosis and therapy. Each'tort result shall be
filed in the respective individual's permanent jr-edical
record file.
.11 Benzidine or its salts shall bo manufactured, handled
and consumed in bulk quantities only at the Buffalo Dye
Plant. Laboratory quantities may bo furnished to
Divisional or Corporate Research upon request of a
section manager.
.12 All location medical case records shall bo maintained in
readily retrievable form for at leant 20 years or the
lifetime of the employee or retires, whichever io the
longer period.
.13 Effluents "containing'benzidine shall bo monitored and
a standard established for maximum discharge to city r. ewers
which will represent b
-------
AMJ.Ki) n:i:::rc,v. coloration -97-
SlMiCIAM'Y 'CliJif-UCAi.j DIVISION
INDUSTRIAI. 11 *•'n 1 amtfjLINJi HO. //-
ISSUED; JU'H' L'' t 1:it by individuals
r.hall bo maintained as a permanent x*ecorcl of tho FaJoty
Department:.
•7 Operating personnel uhall decontaminate equipment,
container.'! and solid wan Los before maintenances, application
or removal. Decontaminated surfaces are those- that
contain than 0.02 my/i»" of benzidine (calr:. as
bane) according to Standard Testing Kethod SiJ* 125 Kuppl.
or its rquivalont. Cases o" doubt should bo referred
to the r.ujporintendent of Safety.
-------
AJ.UKU L'JIJ-.M I ('AI. Cf)l:!'Oi:AT.l(Jtl QR
Ki'i-'.c.'iAf.rv cih:m.icai,:; oivjwion
LKDU.'-.TJIXAL liVCUKM!-: GUT.DKLINIS NO.
if>r.UL'D: 'H'-iJ-: .14, I'>7 4 Page 5
4. Guidelines: {Cont'd.)
.8 All workers and supervisors assigned to benzidine manu-
facture, maintenance or use shall be informed of the
nature of the hazard and required precautions as pre-
scribed in this guideline and in local rules and pro-
cedures. These coir.munications shall be made a matter
of record by the Safety Department.
.9 A special "street and work" locker room shall bo used
in liidcj. 54 to assure that potentially contaminated
clothing will not be worn or taken from the manufacturing
area. Rules and procedures shall be posted.
.10 Hourly personnel assigned to operate or maintain the
benzidine sulfate process in Eldg. 54, the transfer
of slurry to Bldg, 115 or the conversion to benzidine
tetrazo shall wear only freshly laundered work clothing
each day. Glover? shall be replaced on a daily basis.
Shoes, hats and bootees shall be replaced in accordance
with current practice and agreements, except as other-
wise determined by the Foreman and the Safety Department.
.11 Eating in the operating area of Bldg. 54 or in consuming
arear is not permitted. Smelting is allowed only at
designated times in specified areas. Food may be eaten
on3y in the Street side of the Street and Work Locker
room. Rules shall be posted.
.12 Employees v/ho are scheduled for the first time,for regular
assignment to actual operations or actual maintenance i"n
lSldg. 54 or on the Benzidine Tetrazo process in Bldg. 115
vail meet with the Technical Manager or his designated
• representative, prior to the commencement of work, to
discurr. the procedures necessary t:o protect themselves
from er.posuru to benzidine sulfate slurry. The Company
will make every effort to minimize replacement of personnel
in these areas in order to maintain at the lowest po."?;iblo
level the cumulative number of individuals assigned.
.13 Jinch operating and maintenance workman assigned regularly
or on a special basis to either the benzidine nulfato or
benzidine tetrazo processus in required to take a uhowcr
at the end of his shift.
-------
iicr.cfai.ty idi vi.:;j:om -99.
IllDUSTUIAl, IIVGlIiKi: CUl'DMLIIIU NO.
ISSUED: .1UH15 IA , 1974 4
Page 6
Guidoli.net;: (Cont'd.)
.14 Soiled clothing from benzidine operations or maintenance
shall be laundered separately from rccjular plant laundry
following a written decontamination, procedure provided by
the Plant Technical Dept. Periodic, random samples shall
be taken of both soiled and freshly laundered clothing
to ascertain the degree of contamination, if any, and the
efficiency of the laundering operation u.<;ing Std. Testing
Method SP 125 Suop IV CSee Appendix D) or equivalent.
.15 1hese individuals judged by the Safety Dept. to have been
significantly exposed in the past, shall be listed and
requested to have cystoscopic examinations at intervals
recommended by thoir chosen urologist. This list shall
distinguish, between those having at least one positive
diagnosis and those who have had only negative diagnoses,
personnel whose only exposure to the benzidine sulfate or
benzidine tcurazo processes has been subsequent to
Jan. 1, 1959, will not be required to have'cystoscopic
examinations an a condition of the job assignment.
Cystoscopic examination at Company expense v/il.l be
optional, however, at whatever frequency is recommended
by the selected urologist.
.1G At least once every six. months and at such shorter
intervals as may be recommended by the employee's
urologist, Papanicolaou urinalysis shall be carried out
on each present or former employee or retiree regularly
assigned for more than one month to benzidine operations
or maintenance. Corporate records of tiie results shall
be maintained by the Medical Dept. and made available to
the tested individual. Other may have access to the
records only on a "need to know" basis. In the event that
urinalyses disclose the possibility Of neoplastic changes,
the individual concerned will be so advised and requested
to undergo cystoscopic examination including an intravenous
pyologram. The recommendation of the urologist will deter-
mine whether said individual will then bo "1 istod" {4.15
itbnve) or continue under the urinalysis; protocol.
Urinalyses for benvsidj.no using .'ltd. Testing Method PP-1SM
Rev. (See Appendix K) shall be performed semi-annually
on currently assigned operating and roxitine maintenance
workers using samples collected at the end of the work
-------
-100-
ALLIKl) CUl'MlCAb (JOkl'OKATH)N
sriicialvv cijismical:; division
INDUSTRIAL HYGIKI!]^ GUI DHL IN 12 NO.
ISSUED: JUNE 14, 3.074 Pacjo 7
4. Guidelines; (Cont'd.)
.17 The atmosphere in both manufacturing and use areas shall
be sampled at critical working locations at least, semi-
monthly and analyzed for benzidine con Lent by Std. Testing
Method SP-152 Rev. 1 (See /ippendix C) . Unless superseded
by more stringent OSIIA standards, a single test result
in excess of .000060 rag/m-1 (60 nanograms/m^) or a mean of
ten consecutive results in excess of .000050 rog/m^
(50 ng/m^) shall be cause for immediate investigation
as to probable cause and required corrective action in
Bldg. 54. In the consuming areas the single test standard
shall be .000125 mg/m (125 ng/m^) pending accumulation
of sufficient data to evaluate best performance.
.18 Sludge from the Buffalo Dye Plant waste water treatment
plant shall be analyzed at least weekly for benzidine
content according to. St'd. Testing Method "o. 187 Rev. 3
(See Appendix L). Standard should be based on best past
performance (95Z upper quality control point) and test
results above such standard should invoke immediate
investigation and corrective action.
.19 A 24-hour average sample of the discharge of treated
waste water to Buffalo City Sewers shall be taken at
least weekly and analyzed by Std. Testing Method Mo.
SP 222 Rev. (See Appendix 11) . Standard should be. based
on best past performance (95v. upper quality control point)
and test results above such standard should invoke prompt
investigation and corrective action.
.20 The equipment, accessories, vent ducts, linos, walls and
floors of the manufacturing and use areas shall be
sampled at least monthly and analyzed for benzidine
content by Std. 'iVsting Method ;;p-l2.r> Suppl. I Kev. or
SP-125 Suppl. II" Rev. (See Appendices HI & 1)2) Any
result in excess of 0.10 mcj/r,» shall bo cause for
immediate decontamination of the surface in question
until repent tests indicate n level below 0.02 r.uj/ja*.
High results for any item should activate a suvvoy of
other areas to assure that the contamination is not
widespread.
.21 Periodic wipe tests shall bo made of hats, shoes *
goggles, gloves, glove boxes, lookers and other
accessories with which workers may bo in 'regular contact.
STM UP 125 Suppl. I Kev., Suppl. 13 Kev. and {Suppl. J II
are applicable. (Hoc Appondice.n U.l, P.2 nnd K) Standards
should bo baaed on bent past performance (95?. upper
quality control point) and tost renults in excess of
r.ueh standard should .invoke immediate investigation and
correuuivc action.
-------
Ai.i.i ::n cukmicaij c:oKrojIUriK 14 , 1974 payc 8
4. Guidelines: (Cont'd.)
.22 No items of equipment shall be removed from their
locations for replacement or repair until the surfaces
have been tested and found to have less than 0/02 mg/m2
of benzidine.
.23 Separate "street and work" locker rooms shall be provided
for "clean" or street, clothing and for "current use" or
work clothing, including work shoes. The 'lockers shall
be separated by a shower room. Rules for use of the
locker rooms and showers shall be posted.
.24 Benzidine workers shall change to clean clothes and
wash hands, face, neck & arias before leaving the manu-
facturing building or regulated area for lunch or other
reason.
.25 Whenever a major spill, emergency equipment cleanout or
unusual maintenance job involves risk of abnormal
exposure to benzidine sulfate, the workers at risk shall
be monitored for urinary benzidine before and after their
work period. The method'shall be at leant as sensitive
as Standard Testing Method SP-19/i. Any result in oxcess
of .025 rng/1 of benzidine in urine is considered excessive
and steps must be taken, to reduce potential exposure
before work is resumed or* repeated in kind.
.26 During production operations, including.transfer of benzidine
sulfate, the entire P»ldg. 54 (except "street" locker room)
shall be designated as the regulated area subject to OS1IA
regulations. When that portion of the process .involving
the formation, treatment and transfer of benzidine sulfate
is not in operation, the regulated area shall not normally
change except for unusual planned maintenance or construction
on the building or op vessels not containing benzidine sulfate
during which such temporary activity, the regulated area u>ay
bo considered to be limited to the closed vessels and accessory
equipment providing the work area has boon tested ana found
to ba passable vs. standards described .in these guidelines.
.27 Inflowing building nir shall be. filtered and fi.ll-.crs
Maintained in satisfactory working condition. The incoming
air after filtration shall not exceed 0.HOC03 0 of
cjuinonizable amines as benzidine, building and equipment
exhaust air shall be colJeeted and cleaned by wot scrubbing.
The exit air sha.1.1 not exceed 0. 000020 of benzidine
or such stricter standard as may be inipo'ied by a regulatory
iiyoncy. The scrubber shall be equipped with 'signals or
alarms to indicate that fans are running and adequate
differential pressure being maintained at all tii.uis whiJe
the process is operating.
-------
ALT.] Ill) CliKM I C.'Ali CUKI'UKat.lu.:
si'KCiAii'i'V ci;i;;iiCAi.L-. Division
INDUSTRIAL IIYGIJiiili CUIDKLIHK
ISSUED: JUI.'K M, .1.97/]'
-102-
NO ,Li
Pago 9
4. Guidolines: (Cont'd.)
.28 A self-inspection checklist should be prepared and used
at least monthly by the Operating Dept. to guide self-
inspections of both producing and consuming areas. In
addition, a thorough and comprehensive inspection should
bo conducted at least twice each year by a special panel
of technical personnel. This inspection should include
the entire transfer iine. Recommended corrective measures
should receive high priority of attention.
.29 l't is important to maintain a high standard of psycho-
logical factors which contribute to good manufacturing
practice, enthusiasm and morale. Adequate and well-
maintained lighting, clean and frequently painted equip-
ment and*-service lines, labeled lines, regularly cleaned
windows ar.d adequate storage facilities arc examples
cf the factors in cruestion.
.30 Laboratory operations involving benzidine sulfate shall
be confined to hoods in accord with OSiiA regulations
and specifications. Unused portions of samples should
be returned to the operating department or chemically
destroyed within one month. Temporary storage should
be in scaled & labeled containers kept inside of a hood.
Laboratory workers shall wash face, neck, hands & arms
after completion of the hood operations.
.31 Any problems associated with the application of these
guidelines should bo brought to the immediate attention
of the appropriate local department head or pla-r.t manager.
5. Appendices :
A. pp 40 f. 41 of Threshold Limit Values with Intended Changes
for 1S73 - /iCGIII.
Bl. STH-SP 125 Suppl. I Rev. (3/13/72)
JJ2. STM-SP 125 fluppl. II Iiev. (5/1C/74)
C. STM-SP 152 Rev. (5/9/74)
D. STM 125 Sxipitl. IV (1/29/74)
E. STM-SP-194 Rev. (4/20/73)
l?. Of»l»A Sl'.ttiHwinl for Covci nociona (I-'ed. Reg, 39 (20) 3756-
3760, 3779-CI, 3797 (1/29/74).
-------
ALLTKH C!!!:n.rCAT, CORPORATION _iq3_
KPKCIALTY CllKH t CAl.S IJ1VIK1 Oil
INDUSTRIAL IIYGlli:.'/: GUIUilLIHE NO. &
ISSUED: JllHK 34, 1974 Page 10
5* Appendices; (Cont'd.)
G. EPA Proposed Toxic Pollutant Effluent Standard (Fed. Reg.
3£ (2/57) 3528S-353S1 (12/27/73) )
II. STM SP-222 Rev. (1/15/74)
J. Tech. PvGport File i'o. 134: Decontamination of Beiv/.idj.nc
Filtrates and Kashas, R. A. Mazur (5/2/74)
K. STM SP-125 Supol. Ill (11/15/73)
L. STM SP-187 Rev. 3 (6/15/72)
G. Selected Literature References;
.1 Forbor, K. H. "Industrial Bladder Cancer" A Progress
Report and Soma .Unanswered Questions".
J. Nat'l. Cane. Inst. £3 (1) 245-248 (1969).
.2 Goldv/atcr, L. J. Rosso, A. J. & Kleinfeld, M., "Bladder
Tumors in a Coal Tar Dvc Plant" - Arch. Environ.
Health 11, 814-317 (1965).
.3 Gadian, V. , "Industrial Cancer" Fourth Symposium on
Chemical Process Hazards v.-j.ch rpccial Rtuercnces to Plant
Design - The Institution of Chemical Engineers - Worth
Western Branch - Uruist. , Manchester April C, 1971.
.4 British Ministry of Labour - Statutory Instruments 1967
No.-879 - The Carcinogenic Substances Regulations 1967.
.5 Chester Eoatty Research Institute, Royal Cancer Hospital
London, Unglan*;: "precautions for Laboratory V'orkcrK
who handle Carcinogenic Aromatic Amines". April 1966.
.6 Scott, ?. S. & KilliflmS, M. ll. C. - "The control of
Industrial 31r..;r:er Tumours". Brit. J. Industrial Med.
14, 150-163 (1?57).
.7 Int'l /Vjoncy for Research on Cnncor-Monograph on the
Kvaluation of Carcinogenic Rial;-of Chcnicnla to rtau
Vol. 1 IttO ist:.
•8 Int'l Labour Office - Control and Prevention of
Occupational C.-.r.ccr - Report VII (2) - ILO Conference -
58th iicysion 1973..
-------
-104-
at,lied chemical corporation
SPECIALTY CKKMICALf, DIVISION
IKCUSTRIAL UVCiliHi-: GuIDL'LIWIi NO. H~
ISSUE Pi 14. 1074 Page-XI
7. APPROVALS: A/ /, /e}7"f
Manayer - Environmental Control is Date
[). Z j.J
K '
Director of Environmental and
Process Technology
^ rx f /•?)'/
"Date
8. Initial Distribution:
W. S. Ferguson, R. ^obcl, J. C. Bishop, E. c. 3ailey (3),
W. C. Parle, M. Snltaman, File G.6.G. 2.4 (2) . C 7 J (?<•)
&.f. US i<> ^ /&. 2* /''/•< jij***'
UllFiclmw
Attach.
-------
APPENDIX
B
CHLORAMINE T PROCEDURE FOR BENZIDINE
DETECTABILITY LIMITS
-------
-106-
DETECTABILITY LIMITS FOR BENZIDINE
(CHLORAMINE T PROCEDURE)
Matrix Detectability Limit
Clear Stream Waters 0.1 ppb
Wastewater Treatment Plant Effluent 0.2 ppb
Primary Clarifier Effluent 0.2 - 0.5 rpb
Raw Wastewater 2 - 5 ppb
Nitrous Acid Treatment Effluent 10 - 20 npnylO ppb
-------
APPENDIX
C
MASS BALANCE QUESTIONAIRE SURVEY
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-108-
QUESTIONAIRE INFORMATION sheet
EPA Benzidine-Based Dye Usage Survey
Introduction
Benzidine is a well known cancer causing agent that can cause bladder tumors. It is
for this reason that benzidine has come under the toxic pollutant discharge standards that
currently are being promulgated by the Environmental Protection Agency.
Certain dyes are produced using benzidine as a raw material. As in any chemical re-
action^ certain quantity of the benzidine remains unreacted in the dye mixture. That is,
benzidine is an impurity in the dye just as mercury can be an inpurity in caustic. Man-
ufacturers of benzidine-based dyes certify that their dye products contain no more than
20 pp~i of benzidine. Generally, however, the dyes contain no more than 5 to 10 ppm of
benzidine. These levels have been judged to be "extremely safe" from the worker exposure/
health standpoint.
For the protection of drinking water supplies and aquatic life, however, the EPA has
proposed a standard of 125 ppb (0.125 ppm) for wastewaters that are discharged either direct!
to receiving waters or to publically-owned treatment works. Dye applicators would meet
these proposed standards if the benzidine in the benzidine-based dyes we~e diluted'100-fold
as the dyes were used in the plant. Several heavy dye applicators whose plants I personally
visited have dilution ratios of one to two-thousand. That is, the concentration of benzidine
in their discharges averaged 0.25 to 10 ppb (500X to 12.5X below the proposed discharge
standard). It is noteworthy, that the plants visited included a paper mill, a textile
mill. and a leather tanning plant.
Even though it now appears that all dye applicators likely are in compliance with the
proposed standard for benzidine, the EPA originally proposed that all benzidir.e-based dye
applicators be required to analytically monitor their effluents to ensure that their dis-
charges were in compliance with the standards. Such monitoring, however, is an expense
that probably is unwarranted in light of the low concentration levels of benzidine that
v/ere subsequently found in the wastewaters of selected dye applicators' manufacturing^
facilities. Based on this new evidence the EPA decided that a "mass balance" monitoring
approach could serve to ensure protection of the environment and compliance with the
standard.
The "mass balance" monitoring approach requires the '.ise only of inventory records:
I.e., knowing how many pounds of benzidine-based dyes were used during a particular time
period and knowing the total quantity of water discharged from the plant during the same
time period, one can calculate the maximum concentration of benzidine that could possibly
be present in the wastewater assuming that 20 ppm of benzidine is present in the dye and
that all of it is discharged into the wastewater. The "mass balance" or inventory monitoring
approach certainly is more economical than an analytical monitoring approach which would
require routine sampling and analysis and the acquisition of relatively sophisticated
analytical instrumentation.
If the "mass balance" approach is to be adopted, however, it is important to show prior
to adoption that the concentrations of benzidine that could be present in the wastewaters
of dye ap'plicators is materially less than the proposed standard (125 ppb). Accordingly,
an appropriate data base is required. It is in this context that your assistance is being
solicited.
-------
109-
Data Base Required
To evaluate thejnaximum likely concentration of benzidine that could be contained
in the wastewaters of dye applicators I am asking you and fourteen other manufacturing con-
cerns (five representatives each for the paper, leather, and textile industries) to survey
your inventory records for the calendar years 1974 and 1975 and identify that monzh of the
tv/o-year period during which your firm used the greatest quantity of benzidine-based dyes.
Please refer to the attached lists provided by Allied Chemical Corporation and 6AF Corpor-
ation if you are in question as to which dyes and dye mixes are benzidine-based.
After having identified the heavy-use month, then record on the attached data sheet
the quantity (pounds) of benzidine-based dyes used each day during that.month. For the
same period record the quantity of water discharged daily by the plant. If you do not have
the water usage information readily available, please feel free to use your best estimate
for v/ater flows.
Two additional questions regarding the use of sodium hydrosulfite or similar reducing
agents have also been included on the questional re. These have been included to assess the
potential for the possible reduction of benzidine-based ayes in the presence of strong re-
ducing agents to benzidine itself. Please answer these questions to the best of your know-
ledge,
Confidentiality
The data that you are providing will be presented for the record at a hearing regard*! r:
the toxic pollutant effluent standards for benzidine. It will be employed to support^ the
case for using the "mass balance" approach for monitoring the wastewaters of dye applicators
in lieu of the analytical approach. This, of course, is extremely beneficial to your cause.
You will note that the questionaire has been given an identification number. All dis-
closures of your data will be made only with reference to that identification number.
No other identification will be made. I, and I alone, will hold the key which identifies
the industrial firms surveyed with the ID code number. This key will be disclosed to no one,
period.
Survey Distribution
Upon completion of the survey you will be provided a copy of summarized data tabulated
by ID code number for all of the industries surveyed. This is for your information and
future reference.
Thomas M. Keinath, Ph.D.
Route #2, Box 272-A
Seneca, South Carolina 29678
Home: 803/654-2992
Office: 803/656-3276
-------
-110-
QUESTICN'AIRE
Usage of Benzidine-Based Dyes
(Survey for the Environmental Protection Agency)
* * * Identification No.
* * *
I. Benzidine-Sased Ova Usage
JK) For the heaviest benzidine-based dye usage month which occurred during either
the 1974 or 1975 calendar years tabulate below the quantity of dye used daily
and the corresponding quanuicy of process water used by the entire manufactu-
ring facility.
Quantity of
Date Benzidine-Based
(day) Dyes Used
(pounds/day)
Quantity of
Water Used Date
(gallons/day) (day)
Quantity of
Benzidine-Based
Dyes Used
(pounds/day)
Quantity of
Water Used
(gallons/day)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
(B) Month and Year of Data Base: /
month year
II. Does your manufacturing facility use sodium hydrosulfite or a cimilar reducing agent?
[ ] Yes; [ ] No. If the answer is yes, (1) what quantity would be used during an
average month, pounds/month; (2) what quantity wouild be used during a maximum
use day, pounds/day; and (J3) for what purpose is the reducing agent employed,
III. Does your manufacturing facility reductively strip any of the benzidine-based dyes
(listed on the attachments) from dyed material or goods ming either sodium hydro-
sulfite or a similar reducing agent? [ ] Yes; [ J No. !f the answer is yes; (1)
how frequently do you do so (please give narrative stateirent)
(2) What quantity of material would be stripped during an average month,
pounds/month; and (3) what quantity of material would be stripped during a maximum
(stripping) day pounds/day.
-------
-111-
6 A F CORPORATION
November 12, 1975
BEN Z IDT N t DYES
PRIMARY BENZIDINE DYES:
Phenazo Black BH
Phenazo Black BH 50
Phenazo Black BH 150
Phenamine Blue B3 Cone
Phenamine Blue BBN
Supranol Red PG Extra
Supranol Red PRX
Paper Scarlet 3BP
Paper Scarlet BP
Phenamine Scarlet B
Phenamine Fast Red F
Paper Orange R
Phenamine Green G
Phenamine Green BG
Phenamine Black E
Phenamine Black E 200
Phenamine Black ER-180
Phenamine Black ER-200
Phenamine Dark Green B
Fastusol Brown LBRS
Fastusol Brown LBRS 200
Phenamine Brown MN
Phenamine Brown MB 150
Phenamine Fast Brown T
Phenamine Fast Brown TSL
Phenamine Brown D3G Cone.
Phenamine Black RW
Phenamine Black MP 200
Dressing Black SS
Direct Blue 2
Direct Blue 2
Direct Blue 2
Direct 3lue 6
Direcet Blue 6
Acid Red 85
Acid Red
Direct Red 39
Direct Red 37
Direct Red 37
Direct Red 1
Direct Org 8
Direct Green 6
Direct Green 6
Direct Black 38
Direct Black 38
Direct Black 38
Direct Black 38
Direct Green 1
Direct Brown 95
Direct Brown 95
Direct Brown 2
Direct Brown 2
Direct Brown 31
Direct Brown 31
Direct Brown 1A
Direct Black 4
Direct- Black 38
Acid Black 29
-------
-1.1?-
6 A F CORPORATION
DYES CONTAINING BENZIDINE DYES:
Phenazo Brown RS
Direct Brown YY 133
Penetrating Black AL
Chrome Leather Brown HS
Suede Black AXC
Penetrating Black FS
Nyliton Fast Black AW
Fastusol Brown TM
Fastusol Blue PF
Fastusol Brown BRLU
Union Olive Green 408 NC New
Union Olive Green 408 IDF
Union Govt Black I
Phenamine Black ERH
Phenamine Black LB
Suede Leather Black WM
Suede Leather Black WMR
Phenamine Black GAC
Phenamine Brown SB
Phenamine Brilliant Blue BBR New
Chrome Fast Orange 3RLA
Union Government Black
Chrome Leather 31acked
Acid Black Brown BA
Nyliton Fast Black DSR
Fastusol Grey LRS
Fastusol Fast Brown RLS
Fastusol Brown BRL
Aniline SAP Brown DGS
Phenamine Brown TC
Phenamine Dark Brown NZ
Leather Black FL
Phenamine Black Dy-20C
Phenamine Dark Green H
Suede Leather Black WMB
Phenamine Fast Brown TG
Phenamine Red DB
Phenamine Black ERB
-------
-113-
ALLIED CHEMICAL
BENZIDINE DYES
Erie Green G?D
Erie Green MT
Erie Green WT
Erie Fast Orange G
Erie Orange 2R
Milling Orange R
Milling Scarlet G
Erie Bordeaux B
Erie Congo 43
Erie Fast Red FD
Erie Scarlet 3
Erie Congo 4B?
Diazir.e 3 lack KX
Erie Black KS
Erie Black GPNF
Erie. Black GXR
Erie Black GXOO
Erie Black NUG
Diazine Black HP
Niagara Blue 23
Niagara Blue 2BC
Erie Brown 3GN
Erie Catechine 3G
Erie Fast 3rown 3
Erie Fast Brown 3R3.
Solantine Brown BRL
Solantine Brown 3RLS
11/10/75
-------
-114-
allied chemical
BENZIDINB-BASSD DYE MIXES
Acid Brown TM
Milling Scarlet 2BNH
Naccoprint Scarlet HCH
Acid Violet T",7?
Bottom Black ADS
Bottom Black 23189
Leather Black B?T
Patent Black 36543
Penetrating Black KM
Suede Black A3X
Penetrating Black PV
Erie Black MXG
Erie Black 3P
Para Black RRM New
Para Black MHC
Para Black MCC
Leather Black BLN
Direct Brown BNS
Leather Brown AXW-
Direct Khaki US
Direct Khaki US 90%
Nacco Brown GG-3U
Nacco Brown GG 90%
Padding Brown HVL
Brie Catechina G-Q818
Direct Brown NRL
Erie Brown S-5617
Direct Brown L-53901
Leather Dark Brown GAR
Direct Tan E-46774
Direct Brown D-33484
Direct Brown x-74462
Nat'l Leather Brown CL-138
Direct Brown MH
Ramil Brown JAD
Paper Brown RP
Penetrating Black A
Wool Black S-10565-C
Erie Black 5R
Direct Black KF
Penetrating Black MSB
Direct Buff 9611*
Seal Brown CF
Florist Green A 99529
Red Shop Towel Dye
Leather Black MFT
Direct Black FPC
Latex Tan ATG
Erie Fast Black SHG 150%
Erie Black RCC
Leather 31ue Black MOS
Nat'l Direct Blue 23R
Direct Seal Brown 41355
Direct Brown S-10519-1
Leather Black 19347 New
Direct Blue TF
Erie Brown .GGRD
Bottom Brown-GL-103
Direct Gray C-13141
Erie Brilliant Brown S-9 4 39
Erie Fast Brown B-S
Direct 3rown C-12376
PF Direct 3rown WEN
Direct Garnet C-11678
Seal Brown NBS
Leather Tan SVC
Acid Brown R-63739
Alum. Dark Brown 53109
Direct Brown K 74462
Direct Brown MH
Erie Fast Brown GRS
Leather. Dark Olive AS3
Ramile Light Olive DCS
Direct Catechin'e S-9329
Leather Brown ST
Sandal Glove MWL
Aluminum Brown PMC
Direct Printing Brown TH
Direct Brown 3R
Acid Grey AMT
Special Black RAM
Acid Grey AMTH
Resorcir.e Brown 3RN
Resorcine Brown DK
Direct Brown S-10519-1
Direct Brown D 33484
Leather Brown FLC
Nat'l Leather Brown BP
Erie Green MAT C-12672
Direct Paper Green GPD
Erie Fast' Scarlet 4BSN
11/10/75
-------
APPENDIX
D
CORRESPONDENCE OF GAF & ALLIED CHEMICAL CORPORATION
TO CLIENTS REGARDING OXIDATIVE/REDUCTIVE STRIPPING PROCEDURES
-------
. r •
11C —.— Tp.
ifcwzibnti: i»mTs 1Q/23/7.S ¦—
Itear Mx. Cu*toi/.er:
A number of important and useful GAP dyes uee benridir.e a» a raw
material. (see attached list). Our records show that your company purchase#
certain of tUtee dyes. We have becouie awatc of a possible. enyironaiental
problem that could result fro© the use of feuch benzidine based dyes in
a prevfou&ly unforeseen way under certain processing conditions.
The possible environmental hazard with which we are concerned is
associated with stripping, where this is required, fend, in pit titular,
where reductive stripping agents tie used, euch as sodiuo hydrosulfite.
It has been observed that be;izidinfc-bas«:d dyes way undergo chemical
reaction in the preterite of strong reducing agents to regenerate bfcnaj-dine.
In the course of a normal stripping operation the t*t»7.idit»e so formed
toay then becotue a component of the waste water discharged Jror. the process.
While tiO specific U.S. Environmental Protection Agency regulation
has yet been issued governing the discharge of benzidine ioto wastewaters,
ve Jiave be«D advised that each A regulation Is under consideration.
Accordingly, it is recommended that no reductive stripping be perforcued
by the dyer, Rather, when stripping la required, oxidative stripping should
be employed, e.g. using sodium hypochlorite. Information on this mode of
stripping, including methods to minimise the necessity of stripping, will b«
Supplied by (JAP Corporation technical service on request at .
We would appreciate your bringing tliis information to the attention
of appropriate personnel in your organisation. Should you t«ave any questions
on this natter, please contact u**
Very truly yours,
-------
-117-
f "f
)
SfcF Cotj
DRirM IALSL:
PLEASE HCT£: It stripping is required oxidative snipping should
be employed. 0&e ©f reductive ettipping agents in
treating materials dy«d with this product my produce
benzidine end &houLd therefore U: avoided.
-------
-118-
G A F CORPORATION
November 12, 1975
BENZIDINE DYES
PRIMARY BENZIDINE DYES:
Phenazo Black BH
Direct Blue 2
Phenazo Black BH 50
Direct Blue 2
Phenazo Black BH 150
Direct Blue 2
Phenamine Blue BB Cone
Direct Blue 6
Phenamine Blue BBN
Direcet Blue
6
Supranol Red PG Extra
Acid Red 85
%¦
Suprartol Red PRX
Acid Red *
1*
Paper Scarlet 3BP
Direct Red 39
Paper Scarlet BP
Direct Red 37
Phenamine Scarlet B
Direct Red 37
Phenamine Fast Red F
Direct Red 1
Paper Orange R
Direct Org 8
Phenamine Green G
Direct Green
6
Phenamine Green BG
Direct Green
6
Phenamine Black E
Direct Black
38
Phenamine Black E 200
Direct Black
38
Phenamine Black ER-180
Direct Black
38
Phenamine Black ER-200
Direct Black
38
Phenamine Dark Green B
Direct Green
1
Fastusol Brown LBRS
Direct Brown
95
Fastusol Brown LBRS 200
Direct Brown
95
Phenamine Brown MN
Direct Brown
2
Phenamine Brown MB 150
Direct Brown
2
Phenamine Fast Brown T
Direct Brown
31
Phenamine Fast Brown TSL
Direct Brown
31
Phenamine Brown D3G Cone.
Direct Brown
1A
Phenamine Black RW
Direct Black
4
Phenamine Black MP 200
Direct Black
38
Dressing Black SS
Acid Black 29
-------
-119-
G A F CORPORATION
Page 2
DYES CONTAINING BENZIDINE DYES:
Phenazo Brown RS
Direct Brown YY 133
Penetrating Black AL
Chrome Leather Brown HS
Suede Black AKC
Penetrating Black FS
Nyliton Fast Black AW
Fastusol Brown TM
Fastusol Blue PF
Fastusol Brown BRLU
Union Olive Green 408 NC New
Union Olive Green 408 IDF
Union Govt Black I
Phenamine Black ERH
Phenamine Black LB
Suede Leather Black WM
Suede Leather Black WMR
Phenamine Black GAC
Phenamine Brown SF
Phenamine Brilliant Blue BBR New
Chrome Fast Orange 3RLA
Union Government Black
Chrome Leather Blacked
Acid Black Brown BA
Nyliton Fast Black DSR
Fastusol Grey LRS
Fastusol Fast Brown RLS
Fastusol Brown BRL
Aniline SAP Brown DGS
Phenamine Brown TC
Phenamine Dark Brown NZ
Leather Black FL
Phenamine Black Dy-200
Phenamine Dark Green H
Suede Leather Black WMB
Phenamine Fast Brown TG
Phenamine Red DB
Phenamine Black ERB
-------
-120-
6A-F Ojyp ,
Rensselaer lH
-------
Allied. ,
Chemical
Specialty Chemicals Division
P.O. Do* I087R
Morristown. New Jersey 07960
-121-
November 10, 1975
Our records show that your company purchases dyes containing
benzidine-based material (see attached list) from Allied Chemical.
We have become aware of a possible environmental problem that
could result from the use of such benzidine-based dyes in a pre-
viously unforeseen way under certain processing conditions. The
possible environmental hazard with which we are concerned is the
use of these dyes with reductive stripping agents, e.g., sodium
hydrosulfite or similar reducing agent, where this is required.
It has come to our attention that benzidine-based dyes may be
chemically reduced to benzidine when such dyes come into contact
with strong reducing agents. This benzidine may then become a part
of the wastewater discharged into your receiving waters.
While no specific U.S. Environmental Protection: Agency regu-
lation has yet been issued governing the discharge of benzidine
into wastewaters, we have been advised that such a regulation is
being considered.
Thus, it is recommended that no reductive stripping be per-
formed by the dyer. Rather, when stripping is required, oxidative
stripping should be employed, e.g., using sodium hypochlorite.
Our recommended procedure for oxidative stripping is attached.
We would appreciate your bringing this information to the
attention of appropriate personnel in your organization. Should
you have any questions on this matter, please contact me at the
above address or call me on 201-455-2154.
Very truly yours,
C. tl>
C. H. Vance
Manager, Technical Service
Dyes tuffs and Intermediates
Attachments
-------
-122-
ALLIED CHEMICAL
BENZIDINE DYES
Erie Green GPD
Erie Green MT
Erie Green WT
Erie Fast Orange G
Erie Orange 2R
Milling Orange R
Milling Scarlet G
Erie Bordeaux 3
Erie Congo 4B
Erie Fast Red FD
Erie Scarlet 3
Erie Congo 4BP
Diazine Black HX
Erie Black HS
Erie Black GPNF
Erie Black GXR
Erie 31ack GXOO
Erie Black NUG
Diazine Black HP
Niagara Blue 23
Niagara Blue 2BC
Erie Brown 3GN
Erie Catechine 3G
Erie Fast Brown B
Erie Fast Brown 3RB
Solantine Brown BRL
Solantine Brown BRLP
-------
-123-
ALLIED CHEMICAL
BENZIDINE-BASED DYE MIXES
Acid Brown TM
Milling Scarlet 2BNH
Naccoprint Scarlet HCH
Acid Violet T*\T
Bottom Black ADS
Bottom Black 23189
Leather 31ack BPT
Patent Black 36543
Penetrating Black KM
Suede 31ack A3K
Penetrating Black PV
Erie alack NXG
Erie Black BP
Para Black RRM Mew
Para Black MHC
Para Black MCC
Leather Black SL3
Direct Brown BNS
Leather Brown AXW
Direct Khaki US
Direct Khaki US 90%
Nacco Brown GG-3U
Nacco Brown GG 90%
Padding Brown HVL
Erie Catechine G-Q818
Direct Brown NRL
Erie Brown S-5617
Direct Brown L-53901
Leather Dark Brown GAX
Direct Tan E-46774
Direct Brown D-33484
Direct Brown K-74^62
Nat'l Leather Brown CL-138
Direct Brown MH
Ramil Brown JAD
Paper Brown RP
Penetrating Black A
Wool Black S-10565-C
Erie Black 5R
Direct Black KF
Penetrating Black MSB
Direct Buff 9611
Seal Brown CF
Florist Green A 99529
Red Shop Towel Dye
Leather Black MFT
Direct Black' FPC
Latex Tan ATG
Erie Fast 3lack SHG 150%
Erie Black RCC
Leather Blue Black MOS
Nat'l Direct Blue 2BR
Direct Seal Brown 41855
Direct Brown S-1061J-1
Leather Black 193.47 New
Direct Blue TF
Erie Brown GGRD
Bottom Brown GL-103
Direct Grey C-13141
Erie Brilliant 3rown S-9489
Erie Fast 3rown B-S
Direct Brown C-12875
PF Direct 3rown WEN
Direct Garnet C-11673
Seal Brown MBS
Leather Tan STC
Acid Brown R-63739
Alum. Dark Brown 53109
Direct Brown K 74462
Direct Brown MH
Erie Fast Brown GRS
Leather Dark Olive ASB
•Ramile Light Olive DCS
Direct Catechine S-9329
Leather Brown ST
Sandal Glove MWL
Aluminum Brown PMC
Direct Printing Brown TH
Direct Brown 3R
Acid Grey AMT
Special Black RAM
Acid Grey AMTH
Resorcine Brown 3RN
Resorcine Brown DK
Direct Brown S-10519-1
Direct Brown D 33484
Leather Brown FLC
Nat'l Leather Brown BP
Erie Green MAT C-12672
Direct Paper Green GPD
Erie Fast Scarlet 4BSN
11/10/75
-------
-124-
11/10/75
OXIDATIVE STRIPPING OF DIRECT, BENZIDINE- DERIVED DYES FROM DYED MATERIALS
The dyed material is rewet in a hot bath containing 1% Q.W.F. of
soda, ash and the amount of anionic vetting agent normally used
for wetting.
Rinse clear of excess dye washed out of material-
Draw a fresh bath at 80° F.
Add a suitable chlorine compound.
Run 30 minutes at 80° F.
Raise to 120° F. and run 20 minutes.
Add 1% Q.W.F. Acetic Acid 56%.
Run 20 minutes.
Rinse two tines in fresh baths at 120° to 140° F.
Draw a fresh bath at 80° F.
Add sodiua bisulfite at a concentration of 0.500 grams per liter.
Rinse in a fresh bath at 30° F.
Draw a fresh bath for redyeing The material.
Note:
TVro generally used commercially available chlorine compounds are:
1. MHTH" a dry granular calcium hypochlorite containing 70% available
chlorine.
2. Liquid Chlorine Bleach - a solution of sodiua hypochlorite containing
front 12% to 15% available chlorine.
For maximum stripping of most direct dyed shades, a concentration of about
0.15% available chlorine is needed is bath.
Use 2 grams per liter of HTH
or
12 grams per liter of Liquid Chlorine Bleach.
Some shades can be stripped with lesser amounts of available chlorine and
some shades ma>^ require up to:
3 grams per liter of HTH
or
12 grams per liter of Liquid Chlorine Bleach.
Some modifications of this procedure may be required to accommodate variations
in equipment and "operating procedures.
-------
TECHNICAL REPORT DATA
fflcaie mad Instructions on the reverse before completing)
1. BEPOfl7 NO. 2.
EPA-440/9-76-018
3. RECIPIENT'S ACCESSIOf*NO.
4. TITLE AND SUBTITLE
Benzidine: Wastewater Treatment Technology
5. REPORT DATE
Pub. June 1976
S. PERFORMING ORGANIZATION CODE
7. ^tJTHOn(S)
Thomas M. Keinath, Ph.D.
3. PERFORMING ORGANIZATION REPORT NO.
3 performing organization name and address
Thomas M. Keinath
Route 2 Box 272-A
Seneca, South Carolina 29678
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
P.O. # WA-6-99-1309-A and
68-01-3390
12. sponsoring agency name and ADDRESS
Office of Water Planning and Standards
U.S. Environmental Protection Agency
401 M Street, SW
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
is. supplementary notes
Some editing was performed by EPA
16. ABSTRACT
This report was prepared to provide technologic supporting information for toxic
pollutant effluent standards proposed by EPA under Section 307(a}_ of the Federal
Water Pollution Control Act Amendments of 1972. The report identifies potential
technologies, assesses implementation feasibility, estimates final effluent
characteristics and estimates installation and operation costs for manufacture of
benzidine, manufacture of benzidine-based dyes, and applicators of benzidine-based
dyes.
,7. KEY WOROS ANO DOCUMENT ANALYSIS
s descriptors
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Wastewaters
Waste Treatment
Cost Analysis
Cost Comparison
Manufacturers
Toxic Pollutant Effluent
Standards
Federal Water Pollution
Control Act
18. DISTRIBUTION statement
PvELFASE tINTIMITIS)
!
19 SECURITY CI^ASSfTOis Report)
Unclassified
21. NO. OF PAGES
¦fi* A3!
20 SECURITY CLASS (Thispage)
Unclassified
32. PRICE
* t>.0O
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FIGURE 19
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