-------
underlying data to utilize the methodology. Because plant
specific long-term flow and pollutant level averages were
generated from different data sources with varying degrees of
supporting daily monitoring data, a decision was made to rely on
nonparametric analysis procedures. The nonparametric procedures
utilized were the k-sample Kruskal-Wallis test, k-sample Van der
Waerden test, and Wilcoxon 2-sample test (or equivalent
Mann-Whitney U test). These procedures are sensitive to
differences in location (i.e., shifts) in the pollutant specific
distributions of plant averages being compared, and are
equivalent to testing whether the.medians of plant averages for
the groups of interest are statistically different.
Three types of statistical comparisons were performed to examine
the issue of subcategorization, and they are discussed below.
a. Overall Test of Equality of Pollutant Distributions of_
Subcategories A, B, C and D
For each sampling point (i.e., influent or effluent) with respect
to mass (Ibs/day) and concentration units (mg/1), pollutant
specific averages and discharge flow values (thousand gallons per
day) were compared for those plants that belong exclusively to
each of the four subcategories. For example, the distribution of
influent BOD5_ averages (concentration units of mg/1) for those
plants participating exclusively in subcategory A were compared
simultaneously to the distributions of averages for plants
exclusively in subcategory B, exclusively in subcategory C, and
exclusively in subcategory D. Thus, this comparison represents
an overall test on a pollutant-specific basis that distributions
of averages reported by plants exclusively within each of these
subcategories are statistically the same. Rejection of this test
of equality indicates that at least one of the subcategory's
distributions differs from the other three distribution
subcategories. Table IV-2 summarizes results of the
Kruskal-Wallis and Van der Waerden nonparametric procedures of
the above hypothesis that the four subcategories are the same.
As stated earlier, these two procedures are both nonparametric
methodologies. While these procedures test the same hypothesis,
the individual test statistics for these procedures are based on
different quantities (i.e., the Kruskal-Wallis test is based on
rank scores while the Van der Waerden test is based on inverse
normal scores). Table IV-2 summarizes the results of these two
test procedures on a pollutant specific basis. Flow, influent
COD (Ibs/day), influent TSS (mg/1), and influent TSS (Ibs/day)
were the only comparisons for which no significant difference was
detected.
For each unique subcategory, Table IV-3 presents the pollutant-
specific arithmetic average of the plant averages used in the
nonparametric analyses. The table illustrates the trend that
subcategories A and C tend to have greater pollutant levels than
subcategories B and D.
42
-------
TABLE IV-2
Summary of Kruskal-WaVlis and Van der Waerden Tests of
Equality of the Four Subcategories
Pollutant
FLOWKGD = Discharge Flow (K gal/day)
IN80D = Influent BOD (mg/1)
EFBOD = Effluent BOD (mg/1)
INBODLB = Influent BOD (Ibs/day)
EFBODLB = Effluent BOD (Ibs/day)
INCOD = Influent COD (mg/1)
EFCOD = Effluent COD (mg/1)
INCODLB = Influent COD (Ibs/day)
EFCODLB = Effluent COD (Ibs/day)
INTSS = Influent TSS (mg/1)
EFTSS = Effluent TSS (mg/1)
INTSSLB = Influent TSS (Ibs/day)
EFTSSLB = Effluent TSS (Ibs/day)
K-W Test
Van der Waerden Test
**
*
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**
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**
*
**
*Significant statistical difference exists among the four subcategories
for the cited pollutant variable. Significant difference has a test statistic
whose probability p is between .01 and .05 (i.e. .01
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b. Comparison of Distribution of Averages of "High" Subcategory
Plants with Distribution of Averages of "Low" Subcategory
Plants
Having determined that at least one distribution for the averages
of plants operating exclusively in one of the four cited
subcategories differed for the majority of pollutant variable
comparisons, the four subcategories were grouped into "high" and
"low" raw waste subcategories. The "high" group was defined to
include plants that belonged to Subcategory A only, C only, or A
and C only. Similarly, the "low" group was defined to include
plants that belonged Subcategory B only, D only, or B and D only.
(That is, plants that operated in A and C only or in B and D only
were added to the plants used in the preceding overall analysis.)
Thus, the distribution of averages for plants assigned to the
"high" group was compared with the distribution of averages for
plants assigned to the "low" group. Again a nonparametric
statistical procedure was used to compare the distributions. The
Wilcoxon procedure was used for these pollutant-specific two
group comparisons. In general, the results of the tests indicate
that, on a pollutant-specific basis, the "high" and "low" groups
of plants differ statistically. In all cases the two groups were
determined to be significantly different (i.e., the probability
associated with the Wilcoxon test procedure was less than 0.05).
Each of the 13 pollutant-specific comparisons has an associated
test statistic probability considerably less than 0.05.
For each group, Table IV-4 presents pollutant-specific arithmetic
averages of the plant averages used in the two group (i.e.,
"high" vs. "low" comparisons) nonparametric analyses.
c. Statistical Comparison of Distributions of Plants within the
"High" Group and within the "Low" Group
To determine whether combining A and C plants into the "high"
group and B and D plants into the "low" group was reasonable,
statistical comparisons were performed within each of these
groups using single Subcategory plants only. That is, for a
specified pollutant, the distribution of averages for "A" only
plants was compared to the distribution of averages for "C" only
plants. Similarly, pollutant-specific distribution comparisons
were made between "B" only and "D" only plants. Because the
number of plants involved in these analyses were smaller than in
the earlier analyses, the decision was made to utilize the
intermediate computer results produced for the Wilcoxon procedure
in conjunction with a set of referenced tables for the
nonparametric Mann Whitney U-test to provide an exact test of
significance rather than relying on the normal theory
approximation produced in the computer output. Since the Mann-
Whitney U and Wilcoxon 2-Sample procedures are equivalent, the
Wilcoxon results can be utilized in this manner. No differences
were detected between "A" only and "C" only plants. For "B" only
45
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and "D" only plants influent BOD5_ (mg/1) and influent COD (mg/1)
were found to differ. All other comparisons did not indicate
differences between "B" and "D" only plants.
3. Summary of Results
The results of the overall comparisons of the individual
subcategories substantiate the hypothesis that, in general,
pollutant levels do differ by subcategory. (134) In general, no
differences were found between A only and C only plants, while
two influent pollutant variables (INBOD, INCOD) were found to
differ between B only and D only plants. The remainder of B only
and D only plant comparisons yielded no statistical differences.
Based on the above results and on the fact that A and C plants
tend to be higher than B and D plants on flow and pollutant
levels, "high" (A, .C, A/C) and "low" (B, D, B/D) groups of plants
were defined. Comparisons of these two groups consistently
indicated significant differences for flow and pollutant levels.
A more detailed discussion of the statistical analyses performed
is found in "Statistical Support for Pharmaceutical Rulemaking
September 1983", a report that may be found in the record of this
rulemaking. (135)
F. CONCLUSIONS OF SUBCATEGORY ANALYSIS AND DECISION TO MAINTAIN
THE EXISTING SUBCATEGORIZATION SCHEME
The analyses of the most recent data discussed above indicate
that the subcategorization scheme should separate fermentation
and chemical synthesis plants (subcategory A and C plants) from
extraction and formulation plants (subcategory B and D plants) in
so far as regulations controlling the discharge of conventional
and the nonconventional pollutant COD are concerned.
Specifically, the analyses show that the influent and effluent
conventional pollutant concentrations and COD concentrations as
well as discharge flows of subcategory A and C plants are similar
and that these same characteristics for B and D plants are also
similar. The analyses also indicate that the characteristics of
the subcategory A and C plant group are not similar to the
corresponding characteristics of the subcategory B and D plant
group. These differences indicate that different effluent
discharge levels of conventional and nonconventional pollutants
would be expected when plants in these groups employed the same
control technology. However, the existing subcategory scheme
accommodates these differences. Since permitting authorities and
the regulated industry are familar with the original
subcategorization scheme and the format in the Code of Federal
Regulations, the Agency has decided to maintain the existing
subcategorization scheme.
47
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-------
SECTION V
WASTE CHARACTERIZATION
A.
INTRODUCTION
The Agency, through an extensive data gathering effort, has
studied qualitatively and quantitatively the wastewaters of the
pharmaceutical industry. This effort provided the baseline data
necessary for determining the significant pollutants present in
the wastewaters of the pharmaceutical industry and, subsequently,
the regulatory scope for the pharmaceutical manufacturing point
source category.
As a result of earlier studies, particularly the 1976 Development
Document, the EPA had available a limited amount of data which
characterized the wastewater discharges of the pharmaceutical
manufacturing industry. However, not only were some of these
data dated, but for the most part they were related only to such
traditional" pollutant parameters as BOD5^ COD, and TSS.
Information on the 126 toxic pollutants or classes of toxic
pollutants was almost nonexistent. In order to fill this void,
the Agency instituted a number of programs aimed at gathering
from the pharmaceutical industry additional data on both toxic
and traditional pollutants.
addressed considering the
Wastewater characterization has been
following:
(1) Traditional pollutants
(2) Priority pollutants
(3) Wastewater flow
This section reviews the sources of data and describes the
results which provide the basis for the limitations and
standards.
B. TRADITIONAL POLLUTANTS
Traditional pollutants considered for regulation are BOD!> COD,
TSS, and pH. The reasoning behind their selection and the
omission of others is reviewed in Section VI. Three of these,
BOD5., TSS, and pH are listed as conventional pollutant parameters
and one, COD, is listed as nonconventional.
1
Sources of Data
a. Previous studies - The 1976 Development Document, which
supported the 1976 BPT regulations, comprises the main source of
previously developed information.
49
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b. 308 Survey - During 1978, the pharmaceutical industry
was surveyed to obtain wastewater data and related plant
information in support of this new rulemaking effort. The first
308 questionnaire was sent to member companies of the
Pharmaceutical Manufacturers Association (PMA). The content of
this questionnaire appears as Appendix B of the Proposed
Development Document. The second phase of this survey was aimed
at the remainder of the industry, and the questionnaire employed
is in Appendix D of the Proposed Development Document.
Substantial differences in both the form and question content of
these forms resulted from shifts of program emphasis between the
times of their distribution. Recipients are listed in Appendices
C and E of the Proposed Development Document. Survey/response
statistics are reviewed in Section II of the Proposed Development
Document. Traditional pollutant (BOD5_, COD, and TSS) levels as
indicated in the 308 portfolio data, are summarized in Appendix I
of the Proposed Development Document. Flow data are summarized
in Appendix J of the Proposed Development Document.
c. Long-term data - Plants were selected for further
survey of long-term plant log data on end-of-pipe treatment
influents and effluents, with respect to BOD5., COD, "and TSS. The
development of a long-term data base, covering at least a full
year's data for representative plants, was necessary to allow EPA
to establish performance averages for representive groups of
industry treatment plants in terms of both pollutant levels and
effluent variability. A summary of long-term data is presented
in Table V-l.
A brief description of ' plants covered by the long-term data
program follows. Some, but not all, of the plants also appear in
the screening/verification plant list, subsequently used in
priority pollutant analysis.
The flow values presented herein are long-term daily averages
developed from the log data submitted by each plant. These may
differ from flows reported in the 308 questionnaires due to the
different time periods in which they were established and/or
different modes of operation during those time periods.
Plant 12015 is a Subcategory D plant which appears among the
screening plants and the long-term data plants. Activated sludge
and powdered activated carbon are used to treat 0.101 MGD of
wastewater from pharmaceutical manufacture.
Plant 12022 is a Subcategory A and C plant that is a screening
plant and a long-term data plant. Plant 12022 discharges 1.45
MGD of wastewater from its treatment facilities which include
activated sludge, trickling filters, equalization,
neutralization, and primary clarification.
Plant 12026 is a Subcategory C plant which is a screening plant,
a long-term data plant, and a verification plant. This plant
50
-------
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discharges 0.161 MGD of pharmaceutical process wastewater after
treatment by equalization, neutralization, activated sludge, and
a polishing pond.
Plant 12036 is a Subcategory A plant which is both a screening
plant and a long-term data plant. This plant discharges 0.855
MGD of wastewater from pharmaceutical manufacture, which is
treated by activated sludge, trickling filters, an aerated
lagoon, and a final stabilization lagoon.
Plant 12097 is a Subcategory C and D plant which is a screening
plant as well as a long-term data plant. The chemical waste
treatment unit consists of equalization, neutralization,
physical-chemical treatment, filtration, and chemical
stabilization. This plant discharges 0.640 MGD of wastewater
from pharmaceutical processes.
Plant 12098 is a Subcategory D plant. Activated sludge is used
to treat pharmaceutical process wastewaters which amount to 0.005
MGD.
Plant 12117 is a Subcategory B and D plant. Activated sludge
used to treat 0.101 MGD of pharmaceutical process wastewater.
is
Plant 12123 is a Subcategory C and D plant which uses only
primary treatment to treat 0.932 MGD of wastewater from
pharmaceutical manufacture.
Plant 12160 is a Subcategory. D plant. Pharmaceutical process
wastewater is treated with activated sludge. The flow of
wastewater is 0.029 MGD.
Plant 12161 is an Subcategory A, C, and D plant which appears as
both a screening plant and a long-term data plant.
Pharmaceutical process wastewaters are treated by neutralization,
primary clarification, equalization, activated sludge, and
polishing ponds. The amount of wastewater discharged is 1.65
MGD.
Plant 12186 is a Subcategory C and D plant. Activated sludge and
an aerated lagoon are used to treat 0.370 MGD of pharmaceutical
process wastewaters.
Plant 12187 is a Subcategory C plant. The 1.07 MGD of
pharmaceutical process wastewaters is treated with a trickling
filter.
Plant 12235 is a Subcategory C plant. Primary treatment is the
only treatment used for pharmaceutical process wastewater. (This
plant was excluded from the variability analysis since it is not
a direct discharger.)
52
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Plant 12236, a Subcategory C plant, is a screening plant, a
verification plant, and a long-term data plant. The 0.816 MGD of
pharmaceutical process wastewaters are treated .with equalization,
neutralization, primary sedimentation, and activated sludge.
Plant 12248 is a Subcategory D plant. Activated sludge is used
to treat the 0.110 MGD of pharmaceutical process wastewater.
Plant 12257 is a Subcategory A, B, C, and D plant. This plant is
both a screening plant and a long-term data plant. The treatment
system components are equalization, neutralization, and activated
sludge. The amount of pharmaceutical process wastewater
discharged is 0.755 MGD.
Plant 12294 is a Subcategory C and D plant. Activated sludge is
used to treat the 0.118 MGD of pharmaceutical process wastewater.
Plant 12307 is a Subcategory D plant. Two biological treatment
units, an activated sludge unit and an aerated lagoon, are used
to treat the 0.002 MGD of pharmaceutical process wastewater.
Plant 12317 is a Subcategory D plant. Activated sludge is used
to treat the 0.740 MGD of pharmaceutical process wastewater.
Plant 12420 is a Subcategory B and D plant. This plant is
included in both the screening plants and the long-term data
plants. Activated sludge is used to treat the 0.164 MGD of
pharmaceutical process wastewater.
Plant 12439 is a Subcategory C and D plant. Plant 12439 is- both
a screening and a long-term data plant. Process wastewaters are
treated by equalization, neutralization, primary sedimentation,
activated sludge, and an aerated lagoon. Long-term flow data was
not available.
Plant 12459 is a Subcategory D plant with a discharge flow of
0.049 MGD. The only method of wastewater treatment utilized is
an aerated lagoon.
Plant 12462 is a Subcategory A plant with an average flow of
0.209 MGD. The wastewater treatment employed includes activated
sludge and an aerated lagoon.
2. Results and Bases for Limits
The Agency analyzed all traditional pollutant wastewater data
submitted to the Agency in order to establish final BPT TSS
limitations for all subcategories and alternate BOD5_ and COD
limitations for Subcategory B, D and E plants. These data were
from 51 direct dischargers and consisted of 308 portfolio data,
long-term monitoring submissions, and data obtained in comments
on the November 1982 proposal. These data appear in Table IV-I.
Analysis of these data is discussed in Section VIII.
53
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C. PRIORITY POLLUTANTS
The Settlement Agreement list of priority pollutants and classes
of priority pollutants potentially includes thousands of specific
compounds. However, for purposes of rulemaking, the Agency
selected 126 specific pollutants for consideration. These are
listed in Table V-2.
Thirty-three priority pollutants are present in the wastewater of
at least one of the plants sampled. However, few of the priority
pollutants are individually widespread in their occurrence or
high in concentration. The significance of these facts as they
affect the choice of pollutants to be regulated is discussed in
Section VI.
1. Sources of Data
a. 308 Portfolio Survey - The 308 Portfolio Survey was an
invaluable source of information for developing profiles of the
pharmaceutical manufacturing industry. Similarly, this survey
proved to be a major source of data for waste characterization
purposes. Not only did it provide more recent and detailed
information on traditional pollutant parameters and wastewater
flow characteristics, but the 308 Portfolio was the first major
source of data on the use and/or generation of priority
pollutants by this industry.
One purpose of the 308 survey was directed at quantifying the
nature and extent of priority pollutants in the pharmaceutical
industry. Of the 464 pharmaceutical manufacturing plants in the
comprehensive 308. Portfolio Data Base, 212 responded to the
questions concerning priority pollutants. Of the 115 different
priority pollutants identified, chloroform, methylene chloride,
phenol, toluene, and zinc were reported as being the most
frequently used as raw materials for manufacturing operations.
None of the priority pollutants were reported by even as many as
ten respondents as being intermediate or final products. Some
priority pollutants (such pesticide-related compounds as endrin
and heptachlor) were reported as being analyzed in the effluents
of the manufacturing plants (most probably due to the mixing of
pharmaceutical and nonpharmaceutical wastewaters), but not as
being a pharmaceutical manufacturing raw material or final
product.
The 308 data base indicates that, although the pharmaceutical
manufacturing industry uses and therefore might discharge a large
number of priority pollutants, broad occurrence of specific
chemical compounds is limited. Priority pollutant information
submitted by the pharmaceutical manufacturing plants is presented
in Appendix H of the Proposed Development Document.
54
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TABLE V-2
LIST OF EPA-DESIGNATED PRIORITY POLLUTANTS
*No. Compound
IB
2V
3V
4V
5B
6V
7V
8B
9B
10V
nv
12B
13V
14V
15V
16V
17B
18B
19V
2 OB
21A
22A
23V
24A
25B
26B
27B
28B
29V
30V
31A
32V
33V
34A
35B
36B
37B
38V
39B
40B
41B
42B
43B
44V
acenaphthene
acrolein
acrylonitrile
benzene
benzidine
carbon tetrachloride
chlorobenzene
1,2,4-trichlorobenzene
hexachlorobenzene
1,2-dichloroethane
1,1,1-trichloroethane
hexachloroethane
1,1-dichloroethane
1,1,2-trichloroethane
1,1,2,2-tetrachloroethane
chlofoethane
bis(chloromethyl) ether**
bis(2-chloroethyl) ether
2-chloroethylvinyl ether
2-chloronaphthalene
2,4,6-trichlorophenol
parachlorometa cresol
chloroform
2-chlorophenol
,2-dichlorobenzene
,3-dichlorobenzene
,4-dichlorobenzene
3,3'-dichlorobenzidine
,1-di ch1oroethy1ene
,2-trans-dichloroethylene
2,4-dichlorophenol
1,2-dichloropropane
1,3-dichloropropylene
2,4-dimethyIphenol
2,4-dinitrotoluene
2,6-dinitrotoluene
1,2-diphenylhydrazine
ethylbenzene
fluoranthene
4-chlorophenyl phenyl ether
4-bromophenyl phenyl ether
bis(2-chloroisopropyl) ether
bis(2-chloroethoxy) methane
methylene chloride
No.
7 OB
71B
72B
73B
74B
75B
76B
77B
78B
79B
BOB
81B
82B
83B
84B
85V
86V
87V
88V
89P
90P
91P
92P
93P
94P
95P
96P
97P
98P
99P
100P
101P
102P
103P
104P
105P
106P
107P
108P
109P
HOP
111P
112P
113P
Compound
diethyl phthalate
dimethyl phthalate
benzo(a}anthracene
benzo(a)pyrene
3,4-benzofluoranthene
bejizo (k) f luoranthane
chrysene
acenaphthylene
anthracene
benzo(gh i)pery1ene
fluorene
phenanthrene
dibenzo(a,h)anthracene
indenod , 2,3-C,D)pyrene
pyrene
tetrachlorethylene
toluene
trichloroethylene
vinyl chloride
aldrin
dieldrin
chlordane
4,4'-DDT
4,4'-DDE
4,4'-ODD
alpha-endosulfan
beta-endosu1f an
endosulfan sulfate
endrin
endrin aldehyde
heptachlor1
heptachlor epoxide
alpha-BHC
beta-BHC
gamma-BBC
delta-BHC
PCB-1242
PCB-1254
PCS-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
toxaphene^
(lindane)
55
-------
45V methyl chloride 114M
46V methyl bromide 115M
47V bromoform 116
48V dichlorobromomethane 117M
49V trichlorofluoromethane** 118M
50V dichlorodifluoromethane** 119M
51V chlorodibromomethane 120M
52B hexachlorobutadiene 121
53B hexachlorocyclppentadiene 122M
54B isophorone 123M
55B naphthalene 124M
56B nitrobenzene 125M
57A 2-nitrophenol 126M
58A 4-nitrophenol 127M
59A 2,4-dinitrophenol 128M
60A 4,6-dinitro-o-cresol 129B
61B N-nitrosodimethylamine
62B N-nitrosodiphenylamine
63B N-nitrosodi-n-propylamine
64A pentachlorophenol
65A phenol * V
66B bis(2-ethylhexyl) phthalate A
67B butyl benzyl phthalate B
68B di-n-butyl phthalate P
69B di-n-octyl phthalate M
antimony (total)
arsenic (total)
asbestos (fibrous)
beryllium (total)
cadmium (total)
chromium (total)
copper (total)
cyanide (total)
lead (total)
mercury (total)
nickel (total)
selenium (total)
silver (total)
thallium (total)
zinc (total)
2,3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDI
volatile organics
acid extractables
base/neutral extractab]
pesticides
metals
** Deleted from the list of priority pollutants as per 46 FR 2264,
56
-------
b. PEDCo Reports - Concurrent with the efforts to profile the
pharmaceutical manufacturing industry using the 308 Portfolio
survey, PEDCo Environmental, Inc. undertook a study to detail the
various manufacturing processes/steps that are used in the
production of fermentation, extractive, and synthesized
Pharmaceuticals.
In their studies, PEDCo examined recent industry data and
selected those products that comprise the major areas of
production for each of the three manufacturing subcategories
(i.e., A, B and C). With these major product lines as a base,
they then consulted all available literature describing the step-
by-step procedures to be used in the production of each
substance. As a result, PEDCo was able to identify certain
priority pollutants that were known to be used by the
pharmaceutical industry. These pollutants are listed in Table V-
3.
Because of the size and complexity of the industry and the myriad
of products manufactured, it was not practical for a study of
this kind to identify every priority pollutant that could be
used.
c. RTP Study - In December 1978, EPA's Office of Air Quality
Planning and Standards at Research Triangle Park, North Carolina
published a document (70) providing guidance on air pollution
control techniques for limiting emissions of volatile organic
compounds from the chemical synthesis subcategory of the
pharmaceutical industry.
As part of this study, the Pharmaceutical Manufacturers
Association (PMA) surveyed selected pharmaceutical plants to
determine estimates of the ten largest volume volatile organic
compounds that each company purchased and the mechanism by which
they leave the plant (i.e., sold as product, sent to the sewer,
or emitted as an air pollutant).
Table V-4 presents a compilation of the results of this survey.
Of the twenty-six reporting companies, 25 indicated that their
ten largest volume volatile organics accounted for 80 to TOO
percent of their total plant usage. (The other company stated
that the ten highest volume compounds only accounted for 50
percent of its total plant usage.) These 26 companies accounted
for 53 percent of the domestic sales of ethical Pharmaceuticals
in 1975.
Included in the list of 46 compounds presented in Table V-4 are
seven priority pollutants. These compounds are methylene
chloride, toluene, chloroform, benzene, carbon tetrachloride,
1,1,1-trichloroethane, and 1,2-dichlorobenzene.
Table V-5 presents a summary and analysis of the data outlined in
Table V-4. Priority pollutants represent approximately 27
57
-------
TABLE V-3
SUMMARY OF PRIORITY POLLUTANT INFORMATION: PEDCo REPORTS
Priority Pollutants Identified As Used Int
Subcateqory AT
benzene
chloroform
1,1-dichloroethylene
1,2-trans-dichloroethylene
phenol
copper
zinc
Subcategory C3
benzene
carbon tetrachloride
chlorobenzene
chloroethane
chloroform
1,1-dichloroethylene
1,2-trans-dichloroethylene
methylene chloride
methyl chloride
methyl bromide
nitrobenzene
2-nitrophenol
4-nitrophenol
phenol
toluene
chromium
copper
cyanide
lead
zinc
Total No. of Pollutants: 23
1 Reference No. 42
2 Reference No. 41
3 Reference No. 43
Subcategory B2
benzene
carbon tetrachloride
1,2-dichloroethane
chloroform
methylene chloride
phenol
toluene
cyanide
lead
morcury
nickel
zinc
58
-------
OO 1000000^0000 IOO I O O O O O "A "A ICMOO
C5 O\ tr\ \& C5 ^v OO C3 ^^ ""H ^D ^^ ^0 ^D ^0 F^ ^^ ^J* ^5 ^1* ^fr ^1 ^H ^J* ^3
«Cj* OO ^^ ^~^ "^ OO ^^ f"*"* ^^4 ^^N ©0 **~^ ^t* ^^ ^O ^^N OO f^ *-T** ^^ *v>4 ^^ C^
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H < JJ-
tf\ OO "^V
M *
CO CM
i ^fr ^J* O^ '^N C1^ ^^ i
^ * % *» * *s
CM < -H < < '
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oo
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-H -H VO
VN. ON
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OCM-«''N.CM.St- «CO
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-H -H CO
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'gcfl
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gSotui'B
Methy
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Metha
Iff
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I I O I O I I O I O I O O I I I
so so N. f"\ so o
sT tC r»» -H
ON
\O
O 1 1 i
too too
«M i SO O4
CM
CM < « 1
iooo -s
MH o:
8'5
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6
8.1
R)
1
a-1
%
*
g
TJ
O
.5 **
CO *«H
-3 «n .
a
or
S XJ
+ Annual
60
-------
TABLE V-5
SUMMARY OF VOLATILE ORGANIC COMPOUND EMISSION DATA: RTF STUDY
Amount;
Item;
Amount purchased (metric tons)
Amount discharged (metric tons)
Amount recovered within the
plant (metric tons)
Total amount used in plant
(sum of items 1 and 3)
(metric tons)
Percent recovered
Percent of total used that is
discharged
Percent of total used that is
discharged to sewer
Percent of total discharged that
is discharged to sewer
Total
Compounds
(total of 46)
85,170
86,142
441,320
526,490
83.8%
16%
2.7%
16.7%
Priority
Pollutants
(total of 7)
19,565
19,595
126,020
145,585
86.6%
13.5%
1.3%
9.7%
61
-------
percent of the total volatile organic usage in the segment of the
industry analyzed. However, priority pollutants represent only
13 percent of the total mass discharge of volatile organics to
the plant sewers.
Table V-5 also indicates that of the total quantity of all
volatile organic compounds discharged, only a fraction (16.7
percent) is discharged via wastewater. The priority pollutant
volatile organics are discharged with the wastewater in an even
lower proportion (9.7 percent).
d. RSKERL/ADA Study - The Robert S. Kerr Environmental Research
Laboratory at Ada, Oklahoma (RSKERL/ADA) conducted for the
Effluent Guidelines Division (EGD) an applied research study
entitled "Industry Fate Study" (90). The purpose of this report
was to determine the fate of specific priority pollutants as they
pass through a biological treatment system. In the course of
this study, priority pollutants associated with the manufacture
of Pharmaceuticals at two industrial facilities were identified.
The results of these wastewater analysis are reported in Appendix
K of the Proposed Development Document. These priority
pollutants are listed in Table V-6 with similar data from the RTF
Study, the PEDCo Reports, and the Screening/Verification Program.
RSKERL/ADA data are limited since they are from only two plants.
However, they do serve to supplement the other data in Table V-6.
e. Wastewater Sampling Programs - Information on priority
pollutants from the aforementioned reports and surveys was
largely qualitative, although the 308 Portfolio did contain some
quantitative data. Moreover, those reports did not always
distinguish between pollutants used by a plant and pollutants in
the final effluent. To expand the data base, EPA initiated the
Screening and Verification sampling program under which a number
of plants representative of the pharmaceutical manufacturing
industry were sampled for priority pollutants and for the
traditional pollutants (BOD5., COD, and TSS) in a two phase
program. The first phase, called the screening phase, involved
26 plants and covered a broad cross-section of the industry.
This was followed by a verification phase which limited the
sampling to only five carefully selected plants. Augmentation of
the existing data base with the analytical results of the
Screening/Verification program along with the qualitative
information from the other studies provided the Agency with
sufficient information with which to characterize the industry's
wastewaters.
The screening program was conducted to determine the presence or
absence of priority pollutants in the wastewaters of a number of
pharmaceutical plants and to provide a quantitative estimate of
those present. The information was then used to limit the search
to specific priority pollutants for the verification program and
to identify plants likely to provide information to characterize
accurately the industry wastewaters.
62
-------
Priority
Pollutant
TABLE V-6
SUMMARY OF MAJOR* PRIORITY POLLUTANTS IDENTIFIED
FROM MULTIPLE SOURCES OF INFORMATION
Screening S
RTP PECCo RSKERL/ 308 Verification
Study Recorts ADA Portfolio Sampling Program
Acid Extractables
65 Pbenol
Ease Extractables
T5T72-Dicfalorofcenzene
Volatile Crcianica
4 Benzene
6 Carbon Tetrachloride
11 1,1,1 - Trichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-Trans-Cichlcroethylene
38 Ethylbenzene
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
44 Methylene Chloride XX X
66 Toluene XX X
Petals
119 CfcroiriutP XX X
120 ccpper X XX X
122 lead XXX X
123 Mercury XX X
124 Nickel X X
128 Zinc X X X X
Cthera
121 Cyanide X x x X
* For this table toxic compounds were defined as "major"
priority pollutants in accordance with the following criteria for
each data source:
FTP - The pollutant was reported by at least one plant (26 plants
reporting)
EEDCo - The pollutant was found in two or more sufccategories (130
plants studied).
BSKERL/ADA The pollutant was reported by at least one plant (2
plant study).
308 - The pollutant was identified fcy 25 or more plants (464
plants surveyed).
Screening/Verification - The pollutant was detected at ten or
ffore plants (26 plants sampled).
63
-------
Major processing areas and subcategory coverage, range of
wastewater flows, and an assortment of both in-plant and end-of-
pipe treatment technology/techniques were used as selection
criteria for the screening plants. Multiple subcategory plants,
as well as plants within only one subcategory, were deliberately
sought. Similarly, EPA made a special effort to include plants
with wastewater flows less than 1000 GPD and more than 2.5 MGD.
Descriptions of the plants and of the sampling points are
presented in Appendix 0 of the Proposed Development Document.
Included in the screening group were nine direct dischargers,
seven indirect dischargers, three zero dischargers and seven
plants which utilized more than one mode of discharge. In the
latter group there were three plants that were both indirect and
zero dischargers, three plants that were both direct and zero
dischargers and one plant that utilized all three modes of
discharge. The screening plants and their subcategory
designations are listed below:
Plant ID No. Subcategory
Plant ID No. Subcategory
12015
12022
12026
12036
12038
12044
12066
12097
12108
121 19
12132
12161
12204
D
AC
C
A
ABCD
AD
BCD
CD
ACD
AB
AC
ACD
ABCD
12210
12231
12236
12248
12256
12257
12342
1241 1
12420
12439
12447
12462
12999
BC
AD
C
D
ABCD
ABCD
ACD
BCD
BD
CD
ABCD
A
CD
The verification program was developed to confirm the presence of
the priority pollutants that were identified by the screening
program and to provide quantitative pollutant data with a known
precision and accuracy. The analytical results from these
episodes serve as a basis for technology selection and for use in
the rulemaking effort.
Selection of the five plants for the verification program was
based in part on general criteria presented in Section II of the
Proposed Development Document. A criterion mentioned earlier and
which weighed heavily in the final selection process was the
assortment of major priority pollutants that were being used as
raw materials for the manufacture of Pharmaceuticals. Table V-7
lists the priority pollutants which appear in the waste streams
of each of the screening plants. Other plant specific
64
-------
TABLE V-7
SUMMARY OF PRIORITY POLLUTANT OCCURRENCE
SCREENING PLANT DATA
No. of Occurrences
Detected Above 500
No.*
IB
2V
3V
4V
5B
6V
7V
SB
9B
10V
11V
12B
13V
14V
15V
16V
17B***
18B
19V
20B
21A
22A
23V
24A
25B
26B
27B
28B
29V
30V
31A
32V
33V
34A
35B
36B
37B
38V
39B
Compound
acenaphthene
acrolein
acrylonitrile
benzene
benzidine
carbon tetrachloride
chlorobenzene
1 ,2,4-trichlorobenzene
hexachlorobenzene
1 ,2-dichloroethane
1,1, 1-trichloroe thane
hexachloroethane
1 , 1-dichloroe thane
1 , 1 ,2-trichloroethane
1, 1,2,2-tetrachloroe thane
chloroethane
bis(chloromethyl) ether
bis(2-chloroethyl) ether
2-chloroethylvinyl ether
2-chloronaphthalene
2,4,6-trichlorophenol
parachlorometa cresol
chloroform
2-chlorophenol
1 ,2-dichlorobenzene
1 , 3-dichlorobenzene
1,4-dichlorobenzene
3, 3'-dichlorobenzidine
1 , 1 -dichloroethy lene
1-2-trans-dichloroethylene
2, 4-dichlorophenol
1 ,2-dichloropropane
1 , 3-dichloropr opylene
2,4-dimethylphenol
2, 4-dinitrotoluene
2,6-dinitrotoluene
1 ,2-dipheny Ihydrazine
ethylbenzene
fluoranthene
Influent
(25)**
4 (16%)
15 (60%)
1 (4%)
3 (12%)
5 (20%)
5 (20%)
8 (32%)
4 (16%)
4 (16%)
2 (8%)
1 (4%)
1 (4%)
16 (64%)
1 (4%)
2 (8%)
1 (4%)
5 (20%)
1 (4%)
1 (4%)
2 (8%)
1 (4%)
1 (4%)
12 (48%)
1 (4%)
Effluent ug/L in
(20)** Effluent (20)**
3 (15%)
1 (5%)
4 (20%) 1
4 (20%)
1 (5%)
1 (5%)
9 (45%)
2 (10%)
1 (5%)
1 (5%)
2 (10%)
Max. Effluent
Level
ug/L
120
16
500
33
14
20
110
180
15
14
160
65
-------
TABLE V-7 (continued)
No. of Occurrences
Detected
No.*
40B
41B
42B
43B
44V
45V
46V
47V
48V
49V***
50V***
51V
52B
53B
54B
55B
56B
57A
58A
59A
60A
61B
62B
63B
64A
65A
66B
67B
68B
69B
70B
71B
72B
73B
74B
75B
76B
77B
78B
79B
SOB
81B
82B
Compound
4-chlorophenyl phenyl ether
4-bromophenyl phenyl ether
bis(2-chloroisopropyl) ether
bis(2-chloroethoxy) methane
methylene chloride
methyl chloride
methyl bromide
bromoform
dichlorobromomethane
trichlorofluoromethane
dichlorodifluoromethane
chlorodibromomethane
hexachlorobutadiene
hexachlorocyclopentadiene
isophorone
naphthalene
nitrobenzene
2-nitrophenol
4-nitrophenol
2,4-dinitrophenol
4,6-dinitro-o-cresol
N-nitrosodimethylamine
N-nitrosodiphenylamine
N-nitrosodi-n-propylamine
pentachlorophenol
phenol
bis(2-ethylhexyl) phthalate
butyl benzyl phthalate
di-n-butyl phthalate
di-n-octyl phthalate
diethyl phthalate
dimethyl phthalate
benzo(a) anthracene
benzo(a) pyrene
3,4-benzofluoranthene
benzo(k) f luoranthane
chrysene
acenaphthylene
anthracene
benzo(ghi) perylene
fluorene
phenanthrene
dibenzo(a,h) anthracene
Influent
(25)**
3 (12%)
17 (68%)
1 (4%)
1 (4%)
1 (4%)
2 (8%)
1 (4%)
1 (4%)
3 (12%)
3 (12%)
1 (4%)
2 (8%)
14 (56%)
10 (40%)
2 (8%)
3 (12%)
1 (4%)
2 (8%)
1 (4%)
1 (4%)
Effluent
(20)**
2(100%)
15 (75%)
1 (5%)
1 (5%)
1 (5%)
4 (20%)
8 (40%)
4 (20%)
1 (5%)
Above; 500
ug/L"in
Effluent (20)**
2
Max. Effluent
Level
ug/L
2600
44
15
15
120
68
15
20
66
-------
TABLE V-7 (continued)
No. of Occurrences
Detected
Compound
Influent
(2$)**
Effluent
(20)**
Above 500
ug/L'in
Effluent (20)**
No.*
83B indeno(l,2,3-C,D)pyrene
84B pyrene
85V tetrachloroethylene 4 (16%) 2 (10%)
86V toluene 16 (64%) 5 (25%)
87V trichloroethylene 3 12%) 2 (10%)
88V vinyl chloride
89P aldrin
90P dieldrin
91P chlordane
92P 4,4'-DDT
93P 4,4'-DDE
94P 4,4'-DDD
95P alpha-endosulfan
96P beta-endosulfan
97P endosulfan sulfate
98P endrin
99P endrin aldehyde
100P heptachlor
101P heptachlor epoxide
102P alpha-BHC
103P beta-BHC
104P gamma-BHC (lindane)
105P delta-BHC
106P PCB-1242
107P PCB-1254
108P PCB-1221
109P PCB-1232
11 OP PCB-1248
11 IP PCB-1260
112P PCB-1016
113P toxaphene
114M antimony (total) 10 (40%) 3 (15%)
115M arsenic (total) 5 (20%) 3 (15%)
116 asbestos (fibrous)
117M beryllium (total) 1 (16%)
118M cadmium (total) 8 (32%)
119M chromium (total) 23 (92%)
120M copper (total) 24 (96%)
121 cyanide (total) 11 (4*%)
122M lead (total) 13 (52%)
123M mercury (total) 16 (6*%)
124M nickel (total) 1* (56%) 9 (45%)
125M selenium (total) 7(28%) 3(15%)
Max. Effluent
Level
ug/L
18
1350
11
2
5
(10%)
(25%)
15 (75%)
16 (80%)
10 (50%)
9 (45%)
12 (60%)
90
30
2.0
40
304
63
7700
400
1.58
310
56
67
-------
TABLE V-7 (continued)
No. of Occurrences
126M
127M
128M
129B
Compound
Detected
silver (total)
thallium (total)
zinc (total)
2,3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDD)
Influent
(25)**
7 (28%)
5 (20%)
21 (84%)
Effluent
(20)**
3 (15%)
4 (20%)
17 (85%)
Above 500
ug/L-in
Effluent (20)**
Max. Effluent
Level
ug/L
40
29
403
* V - volatile organics
A - acid extractables
B - base/neutral extractables
P - pesticides
M- metals
** Indicates number of plant streams.
*** Deleted from further consideration by 46 FR 10723 and 46 FR 2266.
68
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characteristics that were considered in the final selection
process are summarized below on a plant-by-plant basis.
Plant No. 1241 1 . Plant 124-11 was found to have in its waste
streams three of the common priority pollutants used by the
industry: methylene chloride, chloroform, and toluene. The
presence of these pollutants, a process area involving three
subcategories, utilization of a solvent recovery system, and
pretre.atment of wastewater followed by aerated lagoon treatment
justified this plant for verification sampling.
Plant No. 12038. This plant was selected for sampling in the
verification program because of its use of potential BAT
technology including steam stripping, aerobic biological
treatment, and thermal oxidation. The presence of several
priority pollutants, including nitrosamines, the existence of a
large historical data base relating to nitrosamines, and the
inclusion of both pesticides and Pharmaceuticals in the
manufacturing operations at the plant were factors also
considered in the selection process.
Plant No. 12236. Limitation to one subcategory, reported flows
of about 0.81 MGD, use of cyanide as raw material, and treatment
of its wastewaters by the activated sludge process qualified this
plant for the verification program. Also of interest were its
use of in-plant treatment processes including cyanide destruction
and solvent recovery.
Plant No. 12026. A treatment train consisting of activated
sludge, aerated lagoon, and polishing pond after in-plant
treatment by solvent recovery were the reasons this plant was
selected for verification sampling. It has a reported flow of
0.101 MGD and belongs in Subcategory C.
Plant No. 12097. Plant 12097 is a multiple subcategory (C, D)
plant with a reported flow of 0.035 MGD. Its use of cyanide in
production and a treatment system consisting of in-plant solvent
recovery, activated sludge, and physical-chemical treatment were
considered in selecting this plant.
2. Results of Screen i ng/Ver i f i cat ion Program
A plant-by-plant summary of the analytical results from the
sampling program is presented in Appendix G of the Proposed
Development Document.
Table V-8 lists the traditional and priority pollutants that were
identified and the frequency at which they were found to be
present in the waste streams. Although a number of the priority
pollutants appeared in the waste stream, only a few of them were
sufficiently repetitive to cause concern. Pesticides and PCBs
were detected in one of the plant's effluent but were not due to
pharmaceutical-related activity.
-------
TABU- V-8
ANALYSIS OF PRIORITY POLLUTANT CONCENTRATIONS (ug/1)
Screening/Verification Data Rase
Influent
Based on Values Equal to or
Priority Pollutant Nu
Add
21
24
31 *
34
57
5ft
60
64
65
Rase
1
25
27
35
42
54
62
66
P
Extractables
2 ,4 ,6-tri chl orophenol
?-chlorophenol
2 ,4-di chl orophenol
2, 4-dimethyl phenol
2-n1trophenol
4-n1trophenol
4,6-d1n1tro-o-cresol
pentachl orophenol
phenol
Neutral s
acenaphthene
1 . 2-d1 chl orobenzene
1 ,4-d1 chl orobenzene
2,4-d1n1trotoluene
hi s (2-chl orol soprooyl )
ether
Isophorone
N-nl trosodl phenyl amlne
h1s(2-ethylhexyn
Greater
mber of
lants
1
1
1
1
2
2
1
2
20
2
2
1
1
2
2
1
R
than (10 uq/n
Number of
Observations Minimum Maximum
1
1
1
1
2
2
1
2
36
2
2
1
1
2
2
1
10
20
50
10
62
23
181
L5
42
12
35
12
90
63
300
11
12
10
20
50
10
62
119
1600
15
62
51,000
92
20
-------
67
68
70
76
80
81
butyl benzyl phthalate
di-n-butyl pbthalate
diethylL phthalate
anthracene
fluoxene
(henanfchrene
3
4
1
1
1
1
3
ffi
H
11
H
n
Volatile Orqanics
4
6
7
10
11
14
15
23
29
33
38
44
45
47
49
65
86
87
tenzen«
carbon tetrachloride
chlocofcenzene
1 , 2-dicbloroethane
1,1, 1-ftrichloroethane
1, 1 ,2-<:richloroethane
1,1,2,2-tetrachloro-
ethane
chlcroiEorm
1, 1-dioMoroetbylene
1,3-diohlcrcpropylene
etbylbenzene
ffethylune chloride
ntetbyl chloride
broaofoi:m
trichlorof luorctne thane
tetrachloroethylene
toluene
tricblOEoethylene
11
3
4
8
8
2
1
14
1
1
9
18
2
1
1
8
14
2
19
5
6
17
11
2
11
22
11
11
18
3H
4)
2
11
«
2$
2
12
18
61
14
27
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719
20
61
14
27
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18
20
61
14
27
14
250
19
61
14
27
14
406
1
IS 10,300 120 1586 3186
12 300 18 81 124
11 123,000 3206 36,405 55,025
12 14,000 62 2516 4944
17 1,300 22 169 383
19 20 20 20 1
20 20 20 20
26 1620 170 396 470
230 230 230
100 100 100 100
11 42,000 2H 3237 10,020
16 200,000 11,356 37,952
59 13,000 8,600 7,565 5,439
12 12 1.2 12
970 970 970 970
14 36 31 28 10
50 227,000 310 21,075 50,223
11 124 68 68 80
71
-------
88 vinyl chloride
Hetale
114 antimony
115 arsenic
118 cadmium
119 chromium
120 copper
122 lead
*123 xrercury
124 nickel
125 selenium
126 silver
127 thallium
128 zinc
.Cther
121 cyanide
130 ECO{mg/l)
131 COD(uig/l)
132 1SS (ng/1)
14
14
14
8
n
-------
Effluent
Priority Pollutant Number of Number of
Plants Observations Minimum Maximum. Median
Acid
3*
58
65
Ease
42
66
68
70
60
Extractablea
2, 4-dimethylg henol
4-nitzophenol
phenol
Keutral
bis (2-chloroisaproEylJ
ether
bis (2-ethy Ifaexy 1)
phthalate
di-n-butyl &;hthalate
diethyl pbthalate
fluorene
1
1
9
1
6
2
2
1
1
1
12
1
9
2
2
1
15
15
10
181
10
10
10
10
15
15
126
181
68
15
20
10
15
15
23
181
30
13--
15
10
Standards
Mean Deviation
15
15
47
181
36
13
15
10
*
-
46
-
21
4
7
Volatile Organica
2
4
6
10
1.1
21
29
38
44
45
acrolein
tenzene
carbon tetrachloride
1,2-dichloroethane
1,1, 1- trie h lor oe thane
chloroform
1,1-dichloroetyhlene
ethylbenzene
fftbylene chloride
ethyl chloride
1
1
2
5
4
6
1
3
14
2
1
1
2
9
6
7
1
3
21
4
100
120
16
22
10
14
180
14
12
100
100
120
61
500
33
150
180
22
8100
410
100
12'0;
39
62
20
90
180
17
120
310
100
120
39
158
21
79
180
18
863
283
32
169
11
55
-
4
1852
139
73
-------
49 trichlorof luoroirethane
85 tetrachloroethylene
86 toluene
£7 trichloroethylene
Petals
114 antinony
115 arsenic
118 cadmium
119 chromium
120 copper
122 lead
*123 mercury
124 nickel
125 selenium
126 silver
127 thallium
128 zinc
Cther
121 cyanide
**130 BOO
**131 COD
*132 TSS
*A11 non-remarked data considered
**Ex£ressed in mg/1
1
1
4
1
2
3
1
13
13
9
11
8
2
1
2
17
6
13
13
13
1
1
4
1
5
6
1
21
25
14
19
16
5
1
5
32
11
25
30
29
420
18
too
HI
20
10
40
10
1'»
13
0.1
19
12
40
10
13
30
10
216
0.1
420
18
315
14
51
20
40
304
106
400
1.3
300
56
40
129
2009
7700
1090
3293
1200
420
18
185
14
31
12
40
27
31
33
0.7
51
45
40
11
118
100
84
528
88
420
18
196
14
34
13
40
77
38
64
0.7
83
42
40
37
240
'827
155
911
237
-
.
89
*
15
4
.
94
24
100
0.5
81
18
52
378
2282
211
921
338
74
-------
Wastewaters entering and leaving the end-of-pipe wastewater
treatment train were among those waste streams that were sampled
in this program. Concentration levels for many of the priority
pollutants in the final effluent are relatively low. The reasons
for this are: (1) in-plant treatment and process controls to
minimize specific wastewater pollution, (2) dilution of
concentrated process wastewater with other less concentrated
wastewaters, and (3) incidental removal of some specific chemical
pollutants by end~of-pipe treatment.
D. MASTEWATER "FLOW CHARACTERISTICS
In order to characterize the waste from plants in the
pharmaceutical industry, a determination was made from 308 data
of the total industry wastewater flow rate and its component
process subcategory flows for direct and indirect dischargers.
In Table V-9, actual plant flow data are compared to flows
thought to be characteristic of the various subcategories. These
are based on actual single-subcategory plant total flow adjusted
for the number of occurrences for each subcategory. The averages
of these flows are also useful as base-case flows for cost
analysis.
Approximately 70 percent of the direct and indirect dischargers
(not including zero dischargers) within the 308 Data Base
reported wastewater flows totaling about 80 MGD. Of this, about
45 MGD is from 25 reported direct dischargers. (This estimate
does not include the process flow from plant 12256 which has not
been accurately determined.)
Using the reported single-subcategory plant flows as a means of
estimating flow attributable to each subcategory, the plants not
reporting flow are estimated to add another 13 MGD (93 MGD total
estimated discharge flow for the plants in the data base). Table
V-9 summarizes reported and estimated wastewater flows for the
industry as represented by the 308 Data Base; this information is
more comprehensively covered in Appendix J of the Proposed
Development Document.
E. PRECISION AND ACCURACY PROGRAM
The Precision and Accuracy (P/A) Study is a fundamental,
continuing program to insure the reliability and validity of
analytical laboratory techniques. The P/A program is not
utilized as a separate data base in support of the proposed
limitations, but is used primarily to substantiate the data
illustrated in Table V-10.
Precision refers to the reproducibility among replicate
observations. In an Analytical Quality Control Program,
precision is determined not on reference standards, but by the
use of actual wastewater samples which cover a wide range of
75
-------
TABLE V-9
ANALYSIS OF WASTEWATER FLOW CHARACTERISTICS
(BASIS: 308 DATA)
Direct Discharger Flow (All plants reporting data)
(Without Inclusion of Plant 12256)
Indirect Discharge Reporting Flow (178 plants)
Total Flow Reported
Total Single Subcategory Flow/No, plants (with data)
Subcat . A
Subcat. B
Subcat. C
Subcat. D
1 .30/3
0.67/15
8.80/34
9.80/131
« 0.435
«= 0.045
- 0.260
« 0.075
45 MGD
(15)
35
30 MGD
Indirect Discharger Estimated Flow for Non-Reporting Plants
Subcat. A
Subcat. B
Subcat. C
Subcat. D
0.435 X 5 occurrences
0.045 x 16 occurrences
0.260 x 14 occurrences
0.075 x 90 occurrences
Estimated Unreported Flow
Total Discharge Flow Estimated for Data Base
(Without Inclusion of Plant 12256)
2,175 MGD
0.72
3.64
6.75
13
93 MGD
(63)
76
-------
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77
-------
concentrations and a variety
encountered by the analyst.
of interfering materials usually
Accuracy refers to a degree of difference between observed and
actual values. Accuracy should also be determined on actual
wastewater samples routinely analyzed and, preferably, on the
same series as those used in the precision determinations.
Through this process, data obtained by analysis of multiple
samples were compared to demonstrate that (a) they present
clearcut evidence that the analyst is indeed capable of analyzing
the samples for that particular parameter (i.e., he has the
standard method under control and is capable of generating valid
data) and (b) the data can be used in the evaluation of daily
performance in reference to replicate samples, spiked samples,
and in the preparation of quality control charts. This type' of
quality assurance program is applicable to and can be adapted for
all types of analytical procedures.
TRW and Radian performed, on a split-sample basis, a P/A study on
a series of 24-hour composite influent and effluent samples
collected from a single pharmaceutical manufacturing plant
(12236) representing Subcategory C (chemical synthesis).
Extraction of the non-volatile organic (NVO) sample for the basic
recovery study was performed using continuous, liquid/liquid
extractors. Volatile Organics (VOAs) wer'e analyzed using the
purge-and-trap procedure adopted for this study. Standard
spiking levels were used by both laboratories as specified by
EPA. The extract volumes were selected depending upon expected
concentration of the priority pollutants in the sample and the
established linear response range of the GC/MS instruments. All
pollutants detected in the samples are summarized in Table V-10.
The values reported by the two laboratories for priority
pollutants are well within the detection limits of GC/MS
analysis, with the exception of the values reported for methylene
chloride, toluene, and chloromethane. The values from the two
laboratories are also moderately close to each other. In some
cases, methylene chloride, toluene, and chloromethane were
present in such high concentrations that, although reasonable
recovery and quantitation could be obtained, the results are not
meaningful due to instrument saturation. The high levels of
these compounds apparently did interfere with the analysis of
other priority pollutants. Recoveries of 2,4-dimethylphenol,
benzidine, and the phthalates were low and erratic.
The detection of some of the priority pollutants could be the
result of contamination by sources in the field or laboratory.
It is common practice to equip automatic composite samplers with
polyvinyl chloride (tygon) tubing. Phthalates are widely used as
plasticizers to ensure that -the tubing remains soft and flexible.
These compounds have a tendency to migrate to the surface of the
tubing and leach out into water passing through the sample
78
-------
tubing. Results of analyses shown in Table V-10 indicate the
phthalates vary between laboratories. Sample contamination is
possible and, therefore, some of the results cannot be
conclusively attributed to the wastewater.
79
-------
-------
A.
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
INTRODUCTION
The priority (toxic) and traditional (conventional and
nonconventional) pollutants characterized in Section V are
discussed in this section in light of their occurrence in
pharmaceutical industry wastewaters and their effects on the
environment.
B. TRADITIONAL POLLUTANTS
The Clean Water Act of 1977 (P.L. 95-217) requires the
Administrator to establish effluent limitations and standards for
traditional pollutants. Among these, the conventional parameters
of biochemical oxygen demand (BOD), total suspended solids (TSS),
pH, and oil and grease and the nonconventional parameters of
chemical oxygen demand (COD), total organic carbon (TOO, color,
ammonia, nitrogen, and phosphorus were considered. Those chosen
as representative of specific and persistent pollution problems
across the industry were BOD5., TSS, COD and pH.
These pollutant parameters were identified in 100 percent of the
plant effluents for which data were obtained. Pollutant levels
in treatment influent and untreated effluent streams are
frequently high, particularly in Subcategories A and C
(fermentation and synthesis, respectively).
Other conventional parameters subject to regulation under the
Administrator's discretion are oil and grease, and fecal
coliform. Although they do appear as problems in some plant
process wastewater, oil and grease are neither sufficiently
widespread nor severe enough to justify regulation on an industry
wide basis. Fecal coliform is not of significance in the
industrial wastewater effluents of this industry. Similarly, the
nonconventional parameters of color, phosphorus and various forms
of nitrogen are not judged to present a frequent enough problem
to justify regulation on a national basis. TOC is considered to
be so closely related to BOD and COD that separate attention is
not necessary.
1. Biochemical Oxygen Demand
BOD is the quantity of oxygen required for the biological and
chemical oxidation of waterborne substances under ambient or test
conditions. Substances that may contribute to the BOD include
carbonaceous organic materials usable as a food source by aerobic
organisms; oxidizable nitrogen derived from nitrites, ammonia,
and organic nitrogen compounds that serve as food for specific
bacteria; and such chemically oxidizable materials as ferrous
iron, sulfides, sulfite, and similar reduced-state inorganics
81
-------
that will react with dissolved oxygen or that are metabolized by
bacteria.
The BOD of a waste adversely affects the dissolved oxygen
resources of a body of water by reducing the oxygen available to
fish, plant life, and other aquatic species. Total exhaustion of
the dissolved oxygen in water results in anaerobic conditions and
the production of such undesirable gases as hydrogen sulfide and
methane. The reduction of dissolved oxygen can be detrimental to
fish populations, fish growth rate, and organisms used as fish
food. A total lack of oxygen due to excessive BOD can result in
the death of all aeroJDic aquatic inhabitants in the affected
area.
Water with a high BOD indicates the presence of decomposing
organic matter and associated increased bacterial concentrations
that may degrade water quality and minimize potential uses of the
water. This organic material promoting a high BOD can also
increase algal concentrations and cause blooms.
2. Total Suspended Solids
Suspended solids in wastewater are normally measured as total
suspended solids. They can include both organic and inorganic
materials. The inorganic materials may include sand, silt, clay,
and, possibly, toxic metal compounds. The organic fraction may
include such materials as grease, oils, animal and vegetable
waste products, fibers, microorganisms (algae, for example), and
many other dispersed insoluble organic compounds. These solids
may settle rapidly and form bottom deposits that are often a
mixture of both organic and inorganic solids.
Solids may be suspended in water .for a time and then settle to
the bed of the stream or lake. They may be inert; they may be
slowly biodegradable materials; or they may be rapidly
decomposable substances. While in suspension, they increase the
turbidity of the water, reduce light penetration, and thereby
impair the photosynthetic activity of aquatic plants. After
settling to the stream or lake bed, the solids can form sludge
banks which, if largely organic, create localized dead areas in
the water body and result in anaerobic and undesirable benthic
conditions. Aside from any toxic effect attributable to
substances leached out by water, suspended solids may kill fish
and shellfish by causing abrasive injuries, by clogging gills and
respiratory passages, by screening light, and by promoting and
maintaining the development of noxious conditions through oxygen
depletion. Suspended solids also reduce the recreational value
of the water.
3. Chemical Oxygen Demand
COD is a chemical oxidation test devised as an alternate method
of estimating the total oxygen demand of a wastewater. Since the
82
-------
method relies on the oxidation-reduction system of chemical
analyses rather than on biological factors, it is more precise,
accurate, and rapid than the BOD5_ test. The COD test is widely
used to estimate the total oxygen demand (ultimate rather than 5-
day BOD) required to oxidize the compounds in a wastewater. It
is based on the fact that, with the assistance of certain
inorganic catalysts, strong chemical oxidizing agents under acid
conditions can oxidize most organic compounds.
The COD test measures organic matter that exerts an oxygen demand
and that may affect public health. It is a useful analytical
tool for pollution control activities. Most pollutants measured
by the BODS^ test can be measured by the COD test. In addition,
pollutants more resistant to biochemical oxidation can also be
measured as COD. COD is a more inclusive measure of oxygen
demand than BOD5_ and results in higher oxygen demand values than
BOD5.
The COD of a wastewater normally exceeds BODS^ since it is usually
constituted of those materials contributing to the BOD level plus
those more resistant to biochemical oxidation. Joint
consideration of COD and BOD measurements can indicate the
relative biodegradability of the pollutants and the levels of the
chemical pollutants not easily bio-oxydized. The correlation
between the COD and BOD concentrations in a specific plant waste
resulting from a particular operation is applicable only to that
waste. Furthermore, the level of organic pollutants as indicated
by COD do not correlate with the level of individual priority
pollutants.
Compounds more resistant to biochemical oxidation are of great
concern because of their slow, continuous oxygen demand on the
receiving water and also because of their potentially harmful
effects on the health of humans and aquatic life. Many of these
compounds result from industrial discharges; some of the
compounds have been found to have carcinogenic, mutagenic, and
similar adverse effects. Concern about these compounds has
increased as a result of demonstrations that their long life in
receiving waters (the result of a low biochemical oxidation rate)
allows them to contaminate downstream water intakes. The
commonly used systems of water purification are not effective in
removing these types of materials and such disinfection as
chlorination may convert them into even more hazardous materials.
C. PRIORITY POLLUTANTS
The frequency and level of priority pollutant occurrence in the
wastewaters of the industry were considered in order to determine
the manner in which these pollutants might be regulated. The
diversity of process and materials employed by the industry
brings about a broad presence, with virtually every toxic
pollutant compound listed in the modified comprehensive
Settlement Agreement present in the effluent of at least one
83
-------
plant. However, none are present in the effluent in all or
a predominant part of the industry.
even
Under the provisions of Paragraph 8 of the Settlement Agreement
in Natural Resources Defense Council, Inc. v. Train, 8 ERC 2120
(D.D.C. 1976), modified, 12 ERC 1833 (D.D.C. 1979) modified by
Orders dated October 26, 1982, and August 2, 1983, guidance is
provided to the Agency on exclusion of specific priority
pollutants, subcategories", or categories from regulations under
the effluent limitations guidelines, standards of performance and
pretreatment standards. (1)(2) This paragraph is excerpted below:
"8(a) The Administrator may exclude from regulation under
the effluent limitations and guidelines, standards of
performance, and/or pretreatment standards contemplated by
this Agreement a specific pollutant or category or
subcategory of point sources for any of the following
reasons, based upon information available to him:
(i) For a specific pollutant or a subcategory or
category, equally or more stringent protection is already
provided by an effluent, new source performance, or
pretreatment standard or by an effluent limitation and
guideline promulgated pursuant to Section(s) 301, 304, 306,
307(a), 307(b) or 307(c) of the Act;
(ii) For a specific pollutant, except for pretreatment
standards, the specific pollutant is present in the effluent
discharge solely as a result of its presence in intake
waters taken from the same body of water into which it is
discharged and, for pretreatment standards, the specific
pollutant is present in the effluent which is introduced
into treatment works (as defined in Section 212 of the Act)
which are publicly owned solely as a result of its presence
in the point source's intake waters, provided however, that
such point source may be subject to an appropriate effluent
limitation for such pollutant pursuant to the requirements
of Section 307;
(iii) For a specific pollutant, the pollutant is not
detectable (with the use of analytical methods approved
pursuant to 304(h) of the Act, or in instances where
approved methods do not exist, with the use of analytical
methods which represent state-of-the-art capability) in the
direct discharges or in the effluents which are introduced
into publicly-owned treatment works from sources within the
subcategory or category; or is detectable in the effluent
from only a small number of sources within the subcategory
and the pollutant is uniquely related to only those sources;
or the pollutant is present only in trace amounts and is
neither causing nor likely to cause toxic effects; or is
present in amounts too small to be effectively reduced by
technologies known to the Administrator; or the pollutant
84
-------
will be effectively controlled by the technologies upon
which are based other effluent limitations and guidelines,
standards of performance, or pretreatment standards; or
(iv) For a category or subcategory, the amount and the
toxicity of each pollutant in the discharge does not justify
developing national regulations i'n accordance with the
schedule contained in Paragraph 7(b).
(b) The Administrator may exclude from regulation under
the pretreatment standards contemplated by this Agreement
all point sources within a point source category or point
source subcategory:
(i) If 95 percent or more of all point sources in the
point source category or subcategory introduce into
treatment works (as defined in Section 212 of the Act) which
are publicly owned only pollutants which are susceptible to
treatment by such treatment works and which do not interfere
with, do not pass through, or are not otherwise incompatible
with such treatment works; or
(ii) If the toxicity and amount of the incompatible
pollutants (taken together) introduced by such point sources
into treatment works (as defined in Section 212 of the Act)
that are publicly owned is so insignificant as not to
justify developing a pretreatment regulation..."
a. Pollutants Excluded from Direct Discharger Regulations
Table. V-7 lists the occurrence, frequencies and levels of
priority pollutants found in samples collected in the screening
survey. The priority pollutant data provided in the 308 data
base was used to help develop the group of plants which were then
screened for priority pollutants. However, these data were not
used to support Paragraph 8 exclusion of priority pollutants
found in the S/V study because many of the 308 priority pollutant
responses were incomplete or of a non-quantitative nature. This
was due in part to the fact that many plants had not performed a
priority pollutant scan of their wastewater. The 308 priority
pollutant data were used to exclude those which were uniquely
related to individual sources or occur as the result of
non-pharmaceutical operations.
Compounds numbered 17B, 49V, and 50V have been deleted by 46 FR
10723 on February 4, 1981 and 46 FR 2266 on January 8, 1981. The
remaining list of priority pollutants was considered under the
individual subparagraphs of Paragraph 8. The compounds that can
be excluded under each provision are tabulated in Tables VI-1
through VI-4, with those which can be excluded by more than one
provision being noted by an asterisk (*).
85
-------
TABLE VI-1
PRIORITY POLLUTANTS EXCLUDED FROM DIRECT DISCHARGER REGULATIONS
BASED ON
CONTROL BY OTHER LIMITATION TECHNOLOGIES
Paragraph 8 (a) (i) "For a specific pollutant effectively controlled by
the technology upon which are based upon other effluent
limitations guidelines, standards of performance, or pretreatment
standards ..."
4V benzene
23V chloroform
11V* 1,1,1-trichloroethane
13V* 1,2-dichloroethane
38V ethyl benzene
45V methyl chloride
85V tetrachloroethylene
86V toluene
87V* trichloroethylene
58A* 4-nitrophenol
59A* 2,4-dinitrophenol
65A phenol
25B* 1,2-dichlorobenzene
(Air stripping and/or biodegradation)
(Air stripping)
(Air stripping)
(Air stripping)
(Air stripping and/or biodegradation)
(Air stripping)
(Air stripping)
(Air stripping and/or biodegradation)
(Air stripping)
(Biodegradation)
(Bi odegradati on)
(Biodegradation)
(Biodegradation)
Indicates exclusion under two or more separate provisions of
Paragraph 8.
V - Volatile organics
A - Acid extractables
B - Base/neutral extractables
P - Pesticides
M - Metals
-------
TABLE W-2
PRIORITY POLLUTANTS OCCLUDED FROM DIRECT DISCHARGER REGULATIONS
BASED ON
LOW-LEVEL PRESENCE
Paragraph 8 (a) (iii) "For a specific pollutant...present only in trace
amounts and is neither causing nor likely to cause toxic
affects; or is present in amounts too small to be effectively
reduced by technologies known to the Administrator..."
6V* carbon tetrachloride 27B*
7V chlorobenzene 28B*
11V* 1,1,1-trichloroethane 35B*
13V* 1,1-dichloroethane 36B*
14V* 1,1,2-trichloroethane 39B*
15V* 1,1,2,2-tetrachloroethane 40B*
16V* chloroethane 4 IB*
19V* 2-chloroethylvinyl ether 43B*
30V* 1,2-trans-dichloroethylene 52B*
32V* 1,2-dichloropropane 53B*
33V* 1,3-dichloropropylene 54B*
38V* ethylbenzene 55B*
46V* methyl bromide 56B*
47V* brornoform 6 IB*
48V* dichlorobromomethane 62B*
51V* chlorodibromomethane 63B*
85V* tetrachloroethylene 66B**
87V* trichloroethylene 67B**
88V* vinyl chloride 68B**
21A* 2,4,6-trichlorophenol 69B**
22A* parachlorometa cresol 70B**
24A* 2-chlorophenol 71B**
31A* 2,4-dichlorophenol» 72B*
34A* 2,4-dimethylphenol 73B*
37A* 1,2-diphenylhydrazine 74B*
57A* 2-nitrophenol 75B*
58A 4-nitrophenol 76B*
59A* 2,4-dinitrophenol 77B*
64A* pentachlorophenol 78B*
65A phenol 79B*
IB* acenaphthene SOB*
5B* benzidine 8 IB*
8B* 1,2,4-trichlorobenzene 82B*
9B* hexachlorobenzene 83B*
12B* hexachloroethane 84B*
18B* bis(2-chloroethyl) ether 129B*
20B* 2-chloronaphthalene
25B* 1,2-dichlorobenzene 114M
26B* 1,3-dichloroberizene 115M
1,4-dichlorobenzene
3,3-dichlorobenzidine
2,4-dinitrotoluene
2,6-dinitrotoluene
fluoranthene
4-chlorophenyl phenyl ether
4-bromophenyl phenyl ether
bis(2-chloroethoxy) methane
hexachlorobutadiene
hexachlorocyclopentadiene
isophorone
naphthalene
nitrobenzene
N-nitrosodimethylamine
N-nitrosodiphenylamine
N-nitrosodi-n-propylamine
bis(2.rethylhexyl) phthalate
butyl benzyl phthalate
di-n-butyl phthalate
di-n-octyl phthalate
diethyl phthalate
dimethyl phthalate
benzo(a)anthracene
benzo(a)pyrene
3,4-benzofluoranthene
benzo(k)fluoranthane
chrysene
acenaphthylene
anthracene
benzo(ghi)perylene
fluorene
phenanthrene
dibenzo(a,h)anthracene
indeno(l ,2,3-C,D)pyrene
pyrene
2,3,7,8-tetrachloro-dibenzo-p-
dioxin.(TCDD)
antimony (Total)
arsenia (Total)
87
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TABLE VI-2 (CONPD.)
PRIORITY POLLUTANTS EXCLUDED FROM DIRECT DISCHARGER REGULATIONS
BASED ON
LOW-LEVEL PRESENCE
117M* beryllium (Total)
118M* cadmium (Total)
119M chromium (Total)
120M copper (Total)
122M lead (Total)
123M mercury (Total)
124M nickel (Total)
125M* selenium (Total)
126M* silver (Total)
127M thallium (Total)
* Indicates exclusion under two or more separate provisions of Paragraph 8.
** Phthalates likely resulting from sample contamination.
V - Volatile organics
A - Acid extractables
B - Base neutral extractables
P - Pesticides
M - Metals
88
-------
TABLE VI-3
PRIORITY POLLUTANTS EXCLUDED FROM DIRECT DISCHARGER REGULATIONS
BASED ON
INFREQUENT OCCURRENCE
Paragraph 8 (a) (iii) "For a specific pollutant...detectable in the effluent
from only a small number of sources within the subcategory
and the pollutant is uniquely related to only those sources..."
2V acrolein 60A
3V acrylonitrile 64A*
6V* carbon tetrachloride IB*
(tetrachloromethane) 5B*
7V* chlorobenzene 8B*
10V* 1,2-dichloroethane 9B*
13V* 1,1-dichloroethane 12B*
14V* 1,1,2-trichloroethane 18B*
15V* 1,1,2,2-tetrachloroethane 20B*
16V* chloroethane 25B*
19V* 2-chloroethyl vinyl 26B*
(mixed) 27B*
29V 1,1-dichloroethylene 28B*
30V* 1,2-trans-dichloroethylene 35B*
32V* 1,2-dichloropropane 36B*
33V* 1,3-dichloropropylene 39B*
(!93-dichloropropene) 4 OB*
38V* ethylbenzene 4 IB*
45V methyl chloride 42B
(chloromethane) 43B*
46V* methyl bromide 52B*
(bromomethane) 53B*
47V* bromoform 54B*
(tribromomethane) 55B*
48V* dichlorobromomethane 56B*
51V* chlorodibromomethane 61B*
85V* tetrachloroethylene 62B*
87V* trichloroethylene 63B*
88V* vinyl chloride 72B*
(chloroethylene) 73B*
21A* 2,4,6-trichlorophenol 74B*
22A* parachlorometa cresol 75B*
24A* 2-chlorophenol 76B*
31A* 2,4-dichlorophenol 77B*
34A* 2,4-dimethylphenol 78B*
37A* 1,2-diphenylhydrazine 79B*
58A* 4-nitrophenol SOB*
59A* 2,4-dinitrophenol 81B*
4,6-dinitro-o-cresol
pentachlorophenol
acenaphthene
benzidine
1,2,4-trichlorobenzene
hexachlorobenzene
hexachloroethane
bis(2-chloroethyl) ether
2-chloronaphthalene
1,2-dichlorobenzene
1,3-dichlorobenzene
1,4-dichlorobenzene
3,3-dichlorobenzidine
2,4-dinitrotoluene
2,6-dinitrotoluene
fluoranthene
4-chlorophenyl phenyl ether
4-bromophenyl phenyl ether
bis(2-chloroisopropyl) ether
bis(2-chloroethoxy) methane
hexachlorobutadiene
hexachlorocyclopentadiene
isophorone
naphthalene
nitrobenzene
N-nitrosodi methylamine
N-nitrosodiphenylamine
N-nitrosodi-n-propylamine
benzo(a)anthracene
benzo(a)pyrene
3,4-benzofluoranthene
benzo(k)fluoranthene
chrysene
acenaphthylene
anthracene
anthracene
fluorene
phenanthrene
89
-------
TABLE VI-3 (CONPD.)
PRIORITY POLLUTANTS EXCLUDED FROM DIRECT DISCHARGER REGULATIONS
BASED ON
INFREQUENT OCCURRENCE
82B*
83B*
84B*
129B*
89P**
90P**
91P**
92P**
93P**
94P**
95P**
96P**
97P**
98P**
99P**
100P**
101P**
102P**
103P**
104P**
105P**
106P**
107P**
108P**
109P**
HOP**
111P**
112P**
113P**
117M*
118M*
125M*
126M*
dibenzo(a,h) anthracene
indeno(l,2,3-C,D)pyrene
pyrene
2,3,7,8-tetrachloro-dibenzo-p-
dioxin(TCDD)
aldrin
dieldrin
chlordane
alpha-endosulfan
beta-endosulfan
endosulfan sulfate
endrin
endrin aldehyde
heptachlor
heptachlor epoxide
alpha-BHC
beta-bhc
gamma-BHC (lindane)
delta-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
toxaphene
beryllium (Total)
cadmium (Total)
selenium (Total)
silver (Total)
* Indicates exclusion under two or more separate provisions of Paragraph 8.
** Infrequent presence due to operations on site other than pharmaceutical.
V - Volatile organics
A - Acid extractables
B - Base neutral extractables
P - Pesticides
M - Metals
90
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TABLE VI-4
PRIORITY POLLUTANTS EXCLUDED FROM DIRECT DISCHARGER REGULATIONS
BASED ON
PRESENCE IN AMOUNTS TOO SMALL TO BE EFFECTIVELY REDUCED
BY TECHNOLOGIES KNOWN TO THE ADMINISTRATOR
66B
68B
70B
114M
115M
118M
119M
120M
122M
123M
124M
125M
126M
127M
128M
Bis(2-ethylhexyl) phthalate
Di-n-butylphthalate
Diethylphthalate
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
B = Base neutral extractable
M = Metal
91
-------
Table VI-1 lists compounds whose incidental removal is likely to
be brought about by technologies instituted to meet other
limitations and indicates the incidental mechanism(s) responsible
for removal. A significant example is phenol whose
biodegradability makes it likely that substantial removal will be
accomplished by activated sludge, aerated lagoons, or other
biological treatment systems targeted for BOD removal. Air
strippable volatiles are also likely to be removed through
aeration and exposure to the atmosphere.
Table VI-2 lists pollutants present at levels insufficient to
justify regulation. Some are present at no more than trace
amounts (at or below the detection limits) and others at levels
below or essentially the same as removal capabilities of
applicable technologies. Those compounds with sufficient
volatility and low solubility to be effectively steam stripped
can be removed to no better than about 50 micrograms per liter
(pg/1). (72) Earlier consideration by the Agency (98) of the
treatability of a number of the more significant priority
pollutants indicates the following typical treatability criteria,
expressed on a 5-day maximum basis:
8B 1,2,4-Trichlorobenzene
11V 1,1,1-Trichloroethane
13V 1,1-Dichloroethane
23V Chloroform
25B 1,2-Dichlorobenzene
26B 1,3-Dichlorobenzene
27B 1,4-Dichlorobenzene
44V Methylene Chloride
55B Naphthalene
86V Toluene
4V Benzene
69B Di-n-Octyl Phthalate
50-100
500-600
500-600
500-600
400-500
400-500
400-500
500
400-500
400
400
100
Metal treatability levels are indicated in Table VI-5. The
priority pollutants in Table VI-2 were excluded based on a
comparison of the aforementioned treatability levels with the
screening and verification effluent data in Appendix G of the
Proposed Development Document.
Also included in Table VI-2 are a number of phthalates whose
presence is likely the result of sample contamination by sampling
equipment.
Table VI-3 considers the frequency of occurrence in the
Screening/Verification plant data. Those occurring infrequently,
even though at significant levels, are excluded where a review of
process wastewater from all of the Screening/Verification plants
indicates that such occurrence is mainly related to those limited
sources. Some priority pollutants analyzed in the effluent
wastewater of one or more Screening/Verification plants are
92
-------
TABLE VI-5
ESTIMATED ACHIEVABLE LONG-TERM AVERAGE EFFLUENT
CONCENTRATIONS FOR THE PRIORITY POLLUTANT METALS
Final Concentration (»q/l)*
Metal
Antimony
Arsenic
Beryllium
Cadmium
Copper
Chromium III
Lead
Mercury
Nickel
Silver
Selenium
Thallium
Zinc
Lime
Settling
800-1500
500-1000
100-500
100-500
500-1000
100-500
300-1600
-
200-1500
400-800
200-1000
200-1 000
500-1500
Lime
Filter
400-800
500-1000
1 0-1 00
50-100
400-700
50-500
50-600
1 00-500
100-400
100-500
1 00-500
400-1200
Sulfide
Filter
-
50-100
-
10-100
50-500
~
50-400
10-50
50-500
50-200
-
20-1200
References
116
118,
116
117,
124,
117,
121,
113,
119,
126
118,
122,
120,
118,
120,
116
116
114,
120,
118,
125
118,
123,
115,
120,
120,
124
121,
123,
121,
118,
121
123,
119,
124, 125
118,
121,
121,
128
124
126
123,
124
*Estimated achievable levels reported in the Inorganic Chemicals
Manufacturing Development Document (Ref. 127) based on additional
references cited.
93
-------
clearly not the result of pharmaceutical operations. For
example, one plant is known to also produce pesticides and
consequently exhibits pesticides in the mixed wastewater.
Table VI-4 lists those pollutants which are present in amounts
too small to be effectively reduced by the technologies known to
the Administrator. At proposal, methylene chloride was included
in this list. With the exception of methylene chloride, there
has been no change in our rationale for not establishing effluent
limitations guidelines and standards for the TVOs., In the case
of methylene chloride, at proposal EPA stated that discharges
were controlled by effluent limitations reflecting the best
practicable control technology currently available. After
proposal, EPA received no comments on the proposed exclusion of
this toxic pollutant. However, a reexamination of the existing
information on the use and discharge of methylene chloride by
direct discharging pharmaceutical plants indicates that, in fact,
treatable levels of methylene chloride may remain even after the
implementation of BPT (i.e., biological treatment).
Available data show that in cases where the concentrations of
methylene chloride discharged to biological treatment systems are
greater than 5 mg/1, treatable concentrations of methylene
chloride remain in the effluent. Methylene chloride is used in
about 15 percent of all fermentation, chemical synthesis, and
extraction processes and to a lesser extent in formulation
operations. EPA's data show that 15, of the 51 direct discharging
pharmaceutical plants use methylene chloride in their
manufacturing processes. For these reasons, EPA reconsidered its
original Paragraph 8 determination.
The Agency considered establishing more stringent BAT effluent
limitations guidelines for methylene chloride based on in-plant
steam stripping technology in addition to biological treatment.
This treatment technology would insure that only low effluent
concentrations of methylene chloride would be discharged.
However, EPA found that the costs of , installing and operating
steam strippers to control methylene chloride are not
insignificant. The Agency estimates that nine direct discharging
plants would incur average capital and average total annual costs
of $0.736 million and $0.712 million (1982 dollars),
respectively, per plant. EPA estimates that the installation of
steam stripping technology would reduce current discharge levels
of methylene chloride by 60,700 pounds per year at these plants.
This compares to the 651,000 pounds per year of methylene
chloride that are now removed by biological treatment, the best
practicable control technology currently available for this
industry. EPA also determined that steam stripping technology is
extremely energy intensive and would increase energy use at these
nine direct dischargers by the equivalent of 94,300 barrels of
oil per year. The Agency projects that the average methylene
chloride removal cost resulting from the application of steam
94
-------
stripping technology would be $103 per pound, when the full value
of the recovered solvent is assumed.
After considering the relative toxicity of this pollutant in
light of these costs, and all the other factors, EPA decided not
to issue categorical regulations limiting methylene chloride
discharges from the pharmaceutical industry based on the
addition of treatment technology beyond biological treatment.
The Agency has also decided not to establish limitations based on
biological treatment because they would not effect a further
removal of methylene chloride. Another factor, while not
directly a basis for these decisions, confirmed the
reasonableness of the weight EPA accorded to cost and energy
factors. The Agency determined that much of the methylene
chloride which would be removed by steam stripping will otherwise
volatilize during biological treatment. Our data indicate that
the volatilized methylene chloride will not be at levels which
create a health risk.
Data on the capabilities of steam stripping and biological
treatment technologies to reduce the discharge of methylene
chloride and on the cost of installing and operating steam
strippers to control toxic volatile organics is presented in
Section VII and Appendix A. This information may be used by
permit writers in developing permit Limitations for methylene
chloride on a case-by-case basis where necessary.
The one priority pollutant detected at sufficient levels and
frequency to warrant control by all direct dischargers is
cyanide.
b. Pollutants Excluded from Regulation under Pretreatment
Standards
Paragraph 8(b) (ii) of the Settlement Agreement allows for the
exclusion of those pollutants whose toxicity and amounts (taken
together) are so insignificant as not justify regulation under
pretreatment standards. These pollutants which were found in the
wastewater of 11 indirect discharger screening plants are listed
in Table VI-6 and include toxic metals, phenols, methyl chloride
and various phthalates. (The presence of the last group of
pollutants cannot be attributed with certainty to pharmaceutical
manufacturing operations.) These pollutants were found
infrequently and at low concentrations and, therefore, are not
required to be controlled by pretreatment standards. Eighteen
other pollutants (cyanide and 17 toxic solvents) which are listed
in Table VI-7 were considered for control by pretreatment
standards. The remaining toxic pollutants were not detected in
the wastewater of indirect discharging pharmaceutical plants.
After examining all of the available data, EPA 'has concluded
that, with the exception of cyanide, methylene chloride and
chloroform, these pollutants should be excluded from regulation
-------
TABLE VI-6
POLLUTANTS EXCLUDED FROM PRETREATMENT STANDARDS
No. Compound
1W 1,1,2-trichloroethane
15V 1,1,2,2-tetrachloroethane
16V chloroethane
19V 2-chloroethylvinyl ether
32V 1,2-dichloropropane
33V 1,3-dichloropropylene
48V dichlorobromomethane
51V chlorodibromomethane
88V vinyl chloride
IB acenaphthene
5B benzidine
8B 1,2,4-trichlorobenzene
9B hexachlorobenzene
12B hexachloroethane
18B bis(2-chloroethyl) ether
20B 2-chloronaphthalene
25B 1,2-dichlorobenzene
26B 1,3-dichlorobenzene
27B 1,4-dichlorobenzene
28B 3,3'-dichlorobenzidine
35B 2,4-dinitrotoluene
36B 2,6-dinitrotoluene
37B 1,2-diphenylhydrazine
39B fluoranthene
40B 4-chlorophenyl phenyl ether
41B 4-bromophenyl phenyl ether
42B bis(2-chloroisopropyl) ether
43B bis(2-chloroethoxy) methane
52B hexachlorobutadiene
53B hexachlorocyclopentadiene
54B isophorone
55B naphthalene
56B nitrobenzene
61B N-nitrosodimethylamine
62B N-nitrosodiphenylamine
63B N-nitrosodi-n-propylamine
66B bis(2-ethylhexyl) phthalate
67B butyl benzyl phthalate
68B di-n-butyl phthalate
No. of Occurrences
in Indirect
Wastewaters
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
5*
0
0
Max. Indirect
Wastewater
Concentration
12
12
2700*
Basis For
Exclusion
Infrequent
ii
it
ii
ti
it
ti
11 & low level
11 & low level
it
it
it
ii
* Phthalate occurrence likely the result of sample contamination by sample tubing.
96
-------
TABLE VI-6 (Continued)
No.
69B
70B
71B
73B
74B
75B
76B
77B
78B
79B
SOB
81B
82B
83B
84B
129B
89P
90P
91P
92P
93P
Compound
95P
96P
97P
98P
99P
100P
101P
102P
103P
104P
105P
106P
107P
108P
109P
HOP
HIP
112P
113P
114M
115M
117M
118M
119M
di-n-octyl phthalate
diethyl phthalate
dimethyl phthalate
benzo(a) pyrene
3,4-benzofluoranthene
benzo(k) f luoranthane
chrysene
acenaphthylene
anthracene
benzo(ghi) perylene
fluorene
phenanthrene
dibenzo(a,h) anthracene
indeno(l,2,3-C,D) pyrene
pyrene
2,3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDD)
aldrin
dieldrin
chlordane
4,4'-DDT
alpha-endosulfan
beta-endosulfan
endosulfan sulfate
endrin
endrin aldehyde
heptachlor
heptachlor epoxide
alpha-BHC
beta-BHC
gamma-BHC (lindane)
delta-BHC
PCB-1242
PCB-1254
PCB-1.221
PCB-1232
PCB-1248
PCB-1260
PCB-1.016
toxaphene
antimony (total)
arsenic (total)
beryllium (total
cadmium (total)
chromium (total)
No. of Occurrences
in Indirect
Waste waters
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
7
3
2
3
11
Max. Indirect
Wastewater
Concentration
Basis For
Exclusion
Infrequent
it
n
n
n
210
2
32
650
treatable level
n
it
n
n
n
it
ii
ii
n
97
-------
TABLE VI-6 (Continued)
No.
120M
122M
123M
12m
125M
126M
127M
128M
116
Compound
copper (total)
lead (total)
mercury (total)
nickel (total)
selenium (total)
silver (total)
thallium (total)
zinc (total)
No. of Occurrences
in Indirect
Wastewaters
11
8
7
8
3
1
2
10
Max. Indirect
Wastewater
Concentration
150
286
50
630
30
21
43
522
Basis For
Exclusion
treatable level
it
it
it
ti
n
it
it
n
it
98
-------
TABLE VI-7
POLLUTANTS CONSIDERED FOR PRETREATMENT STANDARDS
Max. Wastewater
No. of Occurrences Concentration Level
(ug/L)
590
121
cyanide ^
Volatile Organics:
2V
3V
4V
6V
7V
10V
11V
13V
23V
29V
30V
38V
44V
47V
85V
86V
87V
acrolein 2
acrylonitrile 1
benzene 6
carbon tetrachloride 1
chlorobenzene 2
1,2-dichloroethane 2
1,1,1-trichloroethane *
1 , 1 -dichloroe thane 3
chloroform 6
l,l»dichloroethylene 2
1 ,2-trans-dichloroethylene 1
ethylbenzene 3
methylene chloride 9
bromoform 1
tetrachloroethylene 1
toluene ^
trichloroethylene 1
100
100
580
300
11
290
360,000
27
1,350
10
550
21
890,000
12
2
1,050
7
99
-------
by the provisions of Paragraph 8 of the Settlement Agreement.
Thirteen of these pollutants have been excluded because their
amount and toxicity, taken together, are so insignificant as not
to justify developing uniformly applicable pretreatment
regulations. Of the remaining, there are two (benzene and
toluene) which, while not as insignificant, nonetheless are
unlikely to pass through POTWs.
In the case of benzene and toluene, the data indicate that direct
discharger median percent reductions exceed POTW median percent
reductions by less than 5 percent (100 percent for direct
dischargers versus 99 percent for benzene and 97 percent for
toluene at POTWs). In light of the fact that EPA had less data
in the POTW studies on benzene and toluene than it had for some
other pollutants and in light of the variability in analyzing
samples for organic priority pollutants at the concentrations
typically found in end-of-pipe biological systems at POTWs and
pharmaceutical plants, EPA believes that differences of 5 percent
or less between the direct discharger and POTW data for benzene
and toluene are unlikely to reflect real differences in treatment
efficiency. Therefore, EPA has determined that benzene and
toluene do not pass through POTWs.
However, a potential interference problem could exist for these
two toxic volatile organics because of a potential fire/explosion
hazard. Benzene and toluene water mixtures have low flash
points. Relatively small concentrations of these solvents in
water mixtures (about 180 ing/1) can cause spontaneous combustion
in the vapor space above the water mixture under certain
conditions. EPA's latest information indicates that
fire/explosions, while not impossible, are unlikely. Benzene and
toluene levels above the minimum concentrations required to cause
combustion have not been reported in discharges from plants in
the pharmaceutical industry. Because pass through does not occur
and interference is unlikely> there is no basis for establishing
nationally applicable categorical pretreatment standards for
benzene or toluene. However, under the general pretreatment
regulation, 40 CFR 8403.5, an individual POTW may establish
pretreatment standards if benzene and toluene discharges from
pharmaceutical users result in interference. Section VII of this
document contains suggested pretreatment standards for benzene
and toluene, based on steam stripping, for consideration by POTWs
establishing standards under 8403.5.
At direct discharging pharmaceutical manufacturing plants,
chloroform is reduced to levels that are below its treatability
through volatilization in biological treatment systems.
Therefore, we have excluded chloroform from BAT regulations under
the provisions of paragraph 8(a)(iii) of the Settlement
Agreement. As for indirect dischargers, the Agency has found
that POTWs to which high concentrations of chloroform are
discharged achieve high chloroform removal (greater than 95
percent). Therefore, POTWs receiving high concentrations of
100
-------
chloroform as a result of pharmaceutical discharges are unlikely
to experience pass through. For the above reasons, EPA has
decided not to establish pretreatment standards controlling
chloroform from indirect discharging pharmaceutical plants.
Through this process, the Agency determined that only methylene
chloride was a candidate for national PSES and PSNS regulations.
To address the issue of pass through, EPA studied 50 well-
operated POTWs that use biological treatment to determine the
extent to which priority pollutants, including methylene
chloride, are reduced by such POTWs.(136) The Agency also
conducted a sampling episode in response to comments on the
proposed regulation in order to determine whether pass through of
toxic volatile organics is occurring at POTWs as the result of
discharges from pharmaceutical plants. During this sampling
episode, the influent and effluent of a well operated POTW having
secondary treatment in-place as well as the effluent from a
pharmaceutical plant were sampled to determine the levels of
toxic volatile organics present. The results of the sampling
episode indicate that there is pass through of methylene chloride
at the sampled POTW and that this pass through is principally the
result of discharges of methylene chloride from a pharmaceutical
manufacturing facility. A more complete discussion of the
sampling episode and the results may be found in the contractor's
report entitled "Pretreatment Standards Evaluation for the
Pharmaceutical Manufacturing Category - Data Evaluation Report",
August, 1983.(137)
EPA found, however, that the installation and operation of steam
strippers to reduce methylene chloride discharges to POTWs by
pharmaceutical plants would result in costs that are not
insignificant. EPA estimates that 25 indirect discharging plants
would incur capital and total annual costs of $0.748 million and
$0.768 million (1982 dollars), respectively, per plant. The
Agency projects that one indirect discharging pharmaceutical
plant would close if required to install steam stripping
technology. Steam strippers are also equally energy intensive at
indirect discharging plants as at direct dischargers. EPA
estimates that the operation of steam strippers at the 25 plants
would increase energy usage by the equivalent of 315,000 barrels
of oil per year. For these reasons and because EPA concluded
that regulation of methylene chloride at direct dischargers is
inappropriate, the Agency has decided not to establish
categorical PSES and PSNS for methylene chloride.
Data on the capabilities of steam stripping technology to reduce
the discharge of methylene chloride and on the cost of installing
and operating steam strippers to control toxic volatile organics
is presented in Section VII and Appendix A. This information may
be used by municipalities in developing pretreatment standards
for methylene chloride on a case-by-case basis where necessary.
101
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
A. INTRODUCTION
This section addresses the technologies currently used or
available to remove or reduce wastewater pollutants generated by
the pharmaceutical manufacturing industry. Although wastewater
flow and raw waste load vary from plant to plant, pharmaceutical
wastewaters are treatable by the technologies discussed below.
Many possible combinations of in-plant source controls and
technologies and end-of-pipe treatment systems are capable of
reducing pollutant discharges. However, each individual plant
must make the final decision concerning the specific combination
of pollution control measures best suited to its particular
situation.
In identifying appropriate control and treatment technologies,
the Agency assumed that each manufacturing plant had already
installed or would install the equipment necessary to comply with
the 1976 BPT limitations. The treatment technologies currently
in-place at plants in the pharmaceutical industry, as reported in
308 responses, are listed in Appendix L of the Proposed
Development Document. Thus, the technologies described below are
those which can further reduce the discharge of pollutants into
navigable waters or POTWs. They are divided into two broad
classes: in-plant and end-of-pipe technologies.
Since the ultimate receiving point of a plant's wastewater (e.g.,
POTW vs. river) can be critical in determining the overall
treatment effort required, information on ultimate discharge is
also presented in this section.
B. IN-PLANT SOURCE CONTROL
The intent of in-plant source control is to reduce or eliminate
the hydraulic and/or pollutant loads generated by specific
sources within the overall manufacturing process. By
implementing controls at the source, the impact on and
requirements of subsequent downstream treatment systems can be
minimized.
Many of the newer pharmaceutical manufacturing plants are
designed with the reduction of water use and subsequent mini-
mization of contamination as part of the overall planning and
plant design criteria. Improvements also have been made in
existing plants to provide better control of their manufacturing
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processes and other activities and the resultant environmental
effects. Some examples of in-plant source controls that have
been effective in reducing pollution loads are as follows:
(1) Production processes have been modified or combined and
reaction mixtures have been concentrated to reduce waste
loads as well as to increase yields. Processes have also
been reviewed and revised to reduce the number of toxic
substances used.
(2) Efforts have been made to concentrate and segregate wastes
at their source to minimize or eliminate wastes where
possible. New process equipment has been designed to
produce effluents requiring no further treatment.
(3) Several techniques have been employed to reduce the volume
of fermentation wastes discharged to end-of-pipe treatment
systems. One approach involves concentrating "spent beer"
wastes by evaporation and then dewatering and drying waste
mycelia. The resulting dry product in some instances has
sufficient economic value as an animal feed supplement to
offset part of the drying cost.
(4) Several plants have installed automatic TOC-monitoring
instrumentation or both pH and TOC monitoring to permit
early detection of process upsets that may result in
excessive discharges to sewers.
(5) The recovery of waste solvents is a common practice among
plants using solvents in their manufacturing processes.
However, to reduce further the amount of waste solvent
discharge, plants have instituted such measures as (a)
incineration of solvents that cannot be recovered eco-
nomically, (b) incineration of "bottoms" from solvent
recovery units, and (c) design and construction of solvent
recovery columns which operate beyond the economical
recovery point.
(6) The use of barometric condensers can result in significant
water contamination, depending upon the nature of the
materials entering the discharge water stream. In addition,
barometric condensers use very large quantities of water,
which results in substantial increases in the total amount
of process-wastewater. (For example, plant 12256 utilizes
more than 20 MGD of once-through barometric condenser
water.) On the other hand, several plants are using surface
condensers which do not involve direct contact
contamination.
(7) Several plants are using a recirculation system as a means
of greatly reducing the amount of contaminated water being
discharged from water-sealed vacuum pumps.
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(8) Reduction of once-through cooling water by recycling through
cooling towers is used in numerous plants and results in
decreased total volume of discharge.
(9) Separation of manufacturing area stormwater is practiced
throughout the industry and often facilitates the isolation
and treatment of contaminated runoff.
(10) Spill prevention is recognized in the industry as a critical
aspect of pollution control. In addition to careful
management of materials and methods, such preventive steps
as impoundment basins are utilized in many cases.
(11) Wash waters can be reduced or eliminated in many situations
by use of dry cleanup methods. Containment control and
removal of either liquid or solid dry process wastes can
often be accomplished using little or no water. This
particular approach can possibly completely eliminate
wastewater discharge, especially in subcategory D
(Formulation) plants, where washwater is often the only
wastewater source.
C.
IN-PLANT TREATMENT
Besides implementing source controls to reduce or eliminate the
waste loads generated within the manufacturing process, plants
may also employ in-plant treatment directed at removing certain
pollutants before they are combined with the plant's overall
wastewaters and are thus diluted.
This concept of in-plant treatment of a segregated stream is of
major importance. First, treatment technologies can be directed
specifically toward a particular pollutant. Also, since
wastewater treatment and pollutant removal costs are strongly
influenced by the volume of water to be treated, the costs
involved in treating a segregated stream are considerably less
than they would be in treating combined wastewater. Also,
chemicals other than those being treated are less likely to
interfere with the treatment technology if treatment occurs
before commingling.
In-plant treatment processes can be visualized as end-of-pipe
treatment for a particular production process or stage within the
plant itself, designed to treat specific waste streams. Although
in-plant technologies can remove a variety of pollutants, their
principal applications are for the treatment of toxic or priority
pollutants. In the pharmaceutical manufacturing industry, three
classes of priority pollutants are of particular importance. As
indicated in Section V, the major priority pollutants are
solvents, metals, and cyanide. Thus, the discussions presented
below on in-plant technologies concern the treatment of these
three classes of pollutants.
105
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The 308 data base was the principal source of information
relating to the use of in-plant treatment in the pharmaceutical
industry. Most of this information came from the Supplemental
308 Portfolio responses. In addition, while not specifically
requested in the original 308 Portfolio, some in-plant treatment
information was obtained from the original 308 Portfolio plants.
It was gathered via three mechanisms: a) some plants provided
"additional" data or comments relative to in-plant treatment on
the questionnaire; b) a small amount of information was gathered
by direct contact with plant personnel; and c) the wastewater
sampling programs discussed in Section II identified tne use of a
few in-plant technologies. Some information on in-plant steam
stripping was also obtained following proposal (a) as a result of
the Agency's efforts to locate an appropriate plant at which to
evaluate the performance of steam stripping technology and (b) as
a result of responses obtained from a post proposal 308
questionnaire concerning the discharge of toxic volatile organics
by indirect discharging pharmaceutical plants. The responses to
this 308 questionnaire will be discussed in the part of this
section that deals with steam stripping.
Table VI1-1 presents a summary of in-plant treatment technologies
identified from the various data bases along with the number of
plants that employ each process.
1 Cyanide Destruction Technologies
Cyanide destruction is employed in the pharmaceutical industry,
as noted by the 308 responses by limited direct inquiry, and by
information from the S/V program.
Two treatment processes have been found to be effective in
treating cyanide-bearing waste streams in the pharmaceutical
industry; chemical oxidation and high pressure and temperature
hydrolysis. Chemical oxidation is a reaction in which one or
more electrons are transferred from the chemical being oxidized
to the chemical initiating the transfer (oxidizing agent). As a
result of the valance change, the oxidized substance can then
react to form a more desirable compound. The hydrolysis
treatment requires the application of high temperature and
pressure to break down chemical bonds; the end result is that
more tolerable substances are formed (e.g., C02 and N02). Under
some circumstances, cyanide ions may combine with metals to form
inert complexes which may interfere with removal of both the
cyanide and the metal. Of the comonmly encountered metals,
106
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TABLE VII-1
SUMMARY OF IN-PLANT TREATMENT PROCESSES
In-Plant Technology Number of Plants
Cyanide Destruction 9
Chromium Reduction 1
Metals Precipitation 4
Solvent Recovery 30
Steam Stripping . 3
Other Technologies 21
Evaporation 10
107
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chromium, manganese, and iron form inert complexes, while nickel
and mercury form labile complexes;
Cyanide Complexes
Inert
Cr (CN)6-«
Mn
Fe
Labile
Ni (CN)4~2
Hg (CN)4-2
Although they are classified as inert, cyanide will be released
from the inert complexes over an extended period of time.
However, this time period may exceed the residence time in the
cyanide destruction unit and cyanide from these complexes would
not be destroyed. The labile complexes will present no
interference with cyanide destruction.
An evaluation of cyanide limitations practically achievable by
chemical oxidation and hydrolysis technologies must consider the
following:
(1) Theoretical reaction equilibrium limits.
(2) Conditions under which cyanate reversion can occur.
(3) Competitive reactions resulting in increased oxidant
consumption.
(4) Chemical interferences such as iron complexing and the
processing alternatives necessary to avoid them.
(5) Physical interferences which might hamper reactant
availability and design methods to overcome them.
a.
Chlorination
Destruction of cyanide by oxidation either with chlorine gas
under alkaline conditions or with sodium hypochlorite is a very
common method of treating industrial wastewaters containing
cyanide. Although more costly, sodium hypochlorite is less
hazardous and is simpler to handle. Oxidation by chlorine' under
alkaline conditions can be described by the following two-step
chemical reaction:
C12 + NaCN + 2 NaOH » NaOCN + 2 NaCl + H2O
3C12 + 6NaOH + 2NaOCN = 2 NaHC03 + N2 + 6 NaCl
2 H20
Cyanide is oxidized to cyanate completely and rapidly at a pH of
about 9.5 to 10.0. Usually 30 minutes are required to insure a
complete reaction. The oxidation of cyanide to cyanate is
108
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accompanied by a marked reduction
thousandfold reduction in toxicity.
in volatility and a
However, since cyanate may revert to cyanide under some
conditions, additional chlorine is provided to oxidize cyanate to
carbon dioxide and bicarbonate. At pH levels around 9.5 to 10.0,
several hours are required for the complete oxidation of the
cyanate, but only one hour is necessary at a pH between 8.0 and
8.5. Also, excess chlorine must be provided to break down
cyanogen chloride, a highly toxic intermediate compound formed
during the oxidation of cyanate.
Although stoichiometric oxidation of one part of cyanide to
cyanate requires only 2.73 parts of chlorine, in practice 3 to 4
parts of chlorine are used. Complete oxidation of one part
cyanide to carbon dioxide and nitrogen gas theoretically requires
6.82 parts of chlorine, but nearly 8 parts are normally necessary
in practice. The chlorine required in practice is higher than
the theoretical amount because other substances in the wastewater
compete for the chlorine.
Soluble iron interferes seriously with the alkaline chlorination
of cyanide wastes. Iron and cyanide form a stable complex which
is impervious to chlorine oxidation. Similar difficulties result
from formation of nickel cyanides. However, it has been reported
that ferrocyanides are treatable by alkaline chlorination at a
temperature of 71<>C (160°F) and at a pH of about 12.0. (109)
Ammonia also interferes with the chlorine oxidation process since
the chlorine demand is increased by the formation of chloramines.
When cyanide is only being oxidized to cyanate, it is usually not
economical to remove the ammonia by breakpoint chlorination,
which requires almost 10 parts of chlorine per part of ammonia.
Complete cyanate formation can be accomplished by allowing an
extra 15 minutes contact time. An example of a cyanide
destruction system using chlorination is shown in Figure VII-1.
Because of some of the advantages of the chlorination process,
this technology has received widespread application in the
chemical industry as a whole. It is a relatively low cost system
and does not require complicated equipment. It also fits well
into the flow scheme of a wastewater treatment facility. The
process will operate effectively at ambient conditions and is
well suited for automatic operation, thus minimizing labor
requirements. This technique is used by pharmaceutical
manufacturers who use cyanide in chemical synthesis.
The chlorination process, however, does have limitations and
disadvantages. For example, toxic, volatile intermediate-reaction
products can be formed. Thus, it is essential to control
properly the pH to ensure that all reactions are carried to their
end point. Also, for waste streams containing other oxidizable
matter, the chlorine may be consumed in oxidizing these materials
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and this may interfere with the treatment of the cyanide.
Finally, for those systems using gaseous chlorine, a potentially
hazardous situation exists when it is stored and handled.
The oxidation of cyanide-bearing wastewaters by using chlorine
under basic conditions is a classic technology. However, its use
by the pharmaceutical industry is limited to a few plants. In
the Agency's study of the electroplating industry, EPA learned
that cyanide levels around 40 vq/l are achievable by in-plant
chlorination processes, if reaction interferences are not
present. (109) In addition, the Final Development Document for
the Inorganic Chemicals Industry (71) indicates that the free
cyanide level after chemical oxidation treatment is generally
below 100 ug/1. The extent to which the various materials found
in pharmaceutical wastewater may interfere with chlorine
oxidation is not known. The presence of interfering substances
in pharmaceutical manufacturing wastewater may, in fact, prevent
the attainment of these levels using the alkaline chlorination
method.
Chemical oxidation of cyanide is currently the most prevalent
technique used by pharmaceutical plants to destroy cyanide.
However, the available data from plants using this method does
not permit an adequate evaluation of the cyanide destruction
capability of this technique as applied to pharmaceutical
wastewater and, therefore, no data describing this the method has
been used in the development of final cyanide regulations for the
pharmaceutical manufacturing point source category.
b.
Ozonation
Ozone is a good oxidizing agent and can be used to treat process
wastewaters that contain cyanide. In fact, ozone oxidizes many
cyanide complexes (for instance, iron and nickel complexes) that
are not broken down by chlorine. Ozonation is primarily used to
oxidize cyanide to cyanate.
With traces of copper and manganese as catalysts, cyanide is
reduced to very low levels, independent of starting
concentrations and the form of the complex. The oxidation of
cyanide by ozone to cyanate occurs in about 15 minutes at a pH of
9.0 to 10.0, but the reaction is almost instantaneous in the
presence of traces of copper. The pH of the cyanide waste is
often raised to 12.0 in order that complete oxidation occurs
before the pH drops to 8.0, at which point cyanide begins to
evolve in the form of HCN.
Oxidation of cyanate to the final end products, nitrogen and
bicarbonate, is a much slower and more difficult process unless
catalysts are present. Therefore, since ozonation will not
readily effect further oxidation of cyanate, it is often coupled
with such independent processes as dialysis or biological
oxidation.
Ill
-------
The ozonation treatment process is being used on an increasing
basis. Its initial applications in treating metal finishing
wastewater have shown it to be quite effective for cyanide
removal. Like chlorination, the ozonation process is well suited
to automatic control and will operate effectively at ambient
conditions. Also, the reaction product (oxygen) is beneficial to
the treated wastewater. Since the ozone is generated on-site,
procurement, storage, and handling problems are eliminated.
The ozonation process does have drawbacks. It has higher capital
and operating costs than chlorination and similar toxicity
problems; also, as with chlorination, increased ozone demand is
possible if other oxidizable matter is present in the waste
stream. Finally, in most cases, the cyanide is not effectively
oxidized beyond the cyanate level.
c. Alkaline Hydrolysis
Removal of cyanide from process wastewaters can be accomplished
without the use of strong oxidizing chemicals. For the alkaline
hydrolysis system, the principal treatment action is based upon
the application of heat and pressure. In this process, a caustic
solution is added to the cyanide-bearing wastewaters to raise the
pH to between 9.0 and 12.0. Next, the wastewater is transferred
to a continuous flow reactor where it is subjected to tem-
peratures of about 165°C to 185°C (329°F to 365°F) and pressures
from approximately 90 to 110 psi. The breakdown of cyanide in
the reactor is generally accomplished with a residence time of
about 1.5 hours. An example of an alkaline hydrolysis system for
treating cyanide-bearing wastewaters is shown in Figure VI1-2.
The absence of specific chemical reactants in this process
eliminates procurement, storage, and handling problems. As with
other cyanide processes, alkaline hydrolysis is well suited to
automatic control.
In the pharmaceutical industry, wastewaters having high
concentrations of cyanide are more likely to be treated by
alkaline hydrolysis, for economic reasons.
As in the case of chlorination, data are available regarding the
pharmaceutical industry's use of alkaline hydrolysare for cyanide
treatment. The data available from these plants indicated that
the cyanide levels reached by this technology are similar to
those achieved by the chlorination process. Long-term
performance data has been submitted by two plants (12236 and
12235) which use this method to destroy cyanide in their
wastewater. The available data indicate that an average effluent
level of 5.25 mg/1 is achievable for cyanide. This level is a
direct measure of what is achievable as a result of the alkaline
hydrolysis technique.
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2. Metals Removal Technologies
This discussion of metals removal technologies is presented even
though the Agency is not promulgating effluent guidelines
limitations for metals. It is intended to aid permit writers and
others who may, at some point, have an interest in the
performance of these technologies.
Proven metals treatment technologies are based upon precipitation
and filtration. Based on the solubility products (Ksp) quoted
for insoluble metal salts (113), the concentration of metal ions
in a saturated solution can be calculated and are listed below:
Compound
Metal Ion
Concentration (yq/1)
CuS
NiS
ZnS
HgS
Cu(OH)2
Ni(OH)-,
Zn(OH)2
Cr(OH)3
1
3
3
1
1
6
6
2
.6
.5
.5
.5
.8
.7
X
X
X
X
X
X
X
X
1
1
1
1
1
1
1
1
Q-36
Q-2S
0-25
0-52
Q-19
0-15
0-14
Q-31
1
8
2
3
x 10~10
x 10-*
X 10-5
x 10~l«
25
400
1 x 10-3
6 x 10-i
These concentrations represent theoretically achievable levels.
Comparison of theoretically achievable treatment levels of metal
priority pollutants to levels specified in final regulations for
other categories (i.e., metal finishing) shows that sulfide
precipitation is theoretically capable of removing the metals to
levels several orders of magnitude lower than the levels that are
practically achieved. Theoretical metal concentrations resulting
from hydroxide precipitation are also lower then the levels
generally achievable by hydroxide precipitation as practiced.
Thus, in most cases, the solubility level will not be the
controlling factor in establishing minimum levels. Practical
limits of removal are dictated by other circumstances, many of
which are peculiar to particular treatment processes. The
efficiency of physical removal of precipitated solids by such
means as filtration or clarification is limited by such particle
characteristics as particle size and stability, which are
functions of pH and of other chemicals present. Many metal
cations are subject to chemical complexing that transforms them
into an unprecipitable species, causing interference with their
removal.
Treatment system performance under industrial operating
conditions is shown in Table VI-5. The levels shown are
estimates of practical attainable long-term average effluent
concentrations for priority pollutant metals. Of the six metals
of special interest in this study, copper, chromium, lead, and
114
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nickel are generally amenable to reductions to approximately 500
»g/l at the point of metals treatment. Although zinc reductions
to about 500 vg/1 are reported, 1,200 ^g/1 may be a more
realistic limit for the zinc content of wastewater since a higher
final concentration is also reported for all three treatment
methods. Mercury concentrations, though not treatable by
alkaline precipitation, may be reduced to around 50 ug/1 after
sulfide precipitation and filtration.
a.
Chemical Reduction
Chromium and some other metals must be reduced from their high
valence states before they can be precipitated. This is
accomplished by chemical reduction, a reaction in which one or
more electrons are transferred from the chemical initiating the
transfer (reducing agent) to the chemical being reduced.
An application of chemical reduction in the treatment of
industrial wastewater is in the reduction of hexavalent chromium
to trivalent chromium. Chromium is a common metal contaminant in
pharmaceutical industry wastewaters; its chemical reduction is
employed as an in-plant treatment by the industry. The reduction
enables the trivalent chromium in conjunction with other metal
salts to be separated from solution by precipitation. Sulfur
dioxide, sodium bisulfite, sodium metabisulfite, and ferrous
sulfate are strong reducing agents in aqueous solution and are,
therefore, useful in industrial waste treatment facilities for
the reduction of hexavalent chromium to trivalent chromium.
The chemical reduction of chromium wastes by sulfur dioxide is a
well-known and widely accepted treatment technology in numerous
plants employing chromium or other high valence ions in their
manufacturing operations. An application of this technology to
treat process wastewaters containing chromates is described in
Figure VII-3. The reactions involved may be illustrated as
follows:
3S05
3H20
= 3H,S03
3H2S03 + 2H2Cr04 = Cr2(S04)3 + 5H20
This reaction is favored by a low pH;, a value of 2.0 to 3.0 is
normally required for complete reduction. At pH levels above
5.0, the reduction rate is slow. Such oxidizing agents as
dissolved oxygen and ferric iron interfere with the reduction
process by consuming the reducing agent. The sulfate precipitate
can be removed by filtration or clarification.
Chemical reduction has been used quite successfully to treat
large concentrations of hexavalent chromium {e.g., from metal
finishing operations). This method is well suited to automatic
control and may be used under ambient conditions.
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Chemical reduction, however, is not without some limitations.
Careful pH control is required for effective reduction. In
addition, when waste streams contain other reducible matter, the
reducing agent may be consumed, depleting that available for
treatment of the metals. Also, for those systems using sulfur
dioxide, a potentially hazardous situation exists when it is
stored and handled. Data indicate that chromium levels below 500
Mg/1 can be achieved from in-plant chromium reduction processes
in combination with hydroxide precipitation followed by
clarification.(109)
b. Alkaline Precipitation
The solubility of metal hydroxides, in most cases, is a function
of pH; therefore, the success of metal hydroxide precipitation
treatment is heavily dependent on the pH level of the solution.
In order to achieve optimum formation of solid metal hydroxides,
the pH of the wastewater must be adjusted to the range (usually
moderately alkaline) found to be most effective for the metal(s)
involved. This is accomplished by measured addition of lime to
the wastewater with concurrent pH monitoring.
Following the attainment of optimum pH conditions, the solid
metal hydroxides are coagulated (using coagulating agents) in a
clarifier and deposited as sludge. Proper clarifier design and
good coagulation are important prerequisites for efficient metals
removal by alkaline precipitation.
If substantial sulfur compounds are present in the wastewater,
caustic soda (sodium hydroxide) may be used instead of lime to
prevent calcium sulfate formation which would increase sludge
volume. Treatment chemicals for adjusting pH prior to
clarification may be added to a rapid mix tank, to a mix box, or
directly to the clarifier, especially in batch clarification. If
such metals as cadmium and nickel are in the wastewater, a pH in
excess of 10.0 is required for effective precipitation. This pH,
however, is unacceptable for discharged wastewater; therefore,
the pH must be reduced by adding acid. The acid is usually added
as the treated wastewater flows through a small neutralization
tank prior to discharge. An example of a metals removals system
using alkaline precipitation is shown in Figure VII-4.
There are several advantages to the use of alkaline
precipitation. In the first place, it is a well demonstrated
wastewater treatment technology. It is well suited to automatic
control and will operate at ambient conditions. Also, in many
instances, preceding treatment steps adjust the waste (especially
pH) to aid the alkaline precipitation process. The end result is
that the costs associated with this technology may be
substantially lower than those for other processes. However,
this method is subject to interference when mixed wastes are
treated. In addition, this process can generate relatively high
quantities of sludge that also require disposal.
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Alkaline precipitation is a classic technology being used by
plants in a number of industry categories, although its use by
the pharmaceutical industry has been limited. The EPA study to
develop BPT regulations for the electroplating industry (109)
indicated that the alkaline precipitation process is capable of
achieving the following long-term effluent levels: 300 ug/1 for
chromium and zinc, 200 ug/1 for copper, 100 ug/1 for lead, and
500 ug/1 for nickel.
c. Sulfidle Precipitation
In this process, heavy metals are removed as a sulfide
precipitate. Sulfide is supplied by adding a very slightly
soluble metal sulfide that has a solubility somewhat greater than
that of the sulfide of the metal to be removed. Normally,
ferrous sulfide is used. It is fed into a precipitator where
excess sulfide is retained in a sludge blanket that acts both as
a reservoir of available sulfide and as a medium to capture
colloidal particles.
The process is applicable for treatment of all heavy metals. The
process equipment required includes a pH adjustment tank, a
precipitator, a filter, and pumps to transport the wastewater.
The filter is optional and may be a standard, dual-media pressure
filter.
A variation of the process utilizes sulfide for reducing
hexavalent chromium. Ferrous sulfide at a pH of 8.0 to 9.0 acts
as an agent to reduce the hexavalent chromium and then
precipitates it as a hydroxide in one step. Hexavalent chromium
wastes do riot have to be isolated and pretreated by reduction to
the trivalent form.
With respect to the generated sludge, sulfide sludges have been
found to be less subject to leaching than hydroxide sludges.
However, sulfide precipitation produces sludge in greater volumes
(requiring more available storage space) and requires greater
expenditures for chemicals than does alkaline precipitation.
Pollutant levels after treatment with sulfide precipitation are
very similar to the pollutant levels after alkaline
precipitation.
3. Solvent Recovery and Removal
Solvents are used extensively in the pharmaceutical manufacturing
industry. Because such materials are expensive, most
manufacturers try to recover them in order to purify them for
reuse whenever possible. Solvent recovery operations typically
employ such techniques as decantation, evaporation, distillation,
and extraction. The feasibility and extent of recovery and
purification are governed largely by the quantities involved and
by the complexity of solvent mixtures to be separated. If
recovery is not economically practicable, the used solvents may
119
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have to be disposed of by means of incineration, landfilling,
deep-well injection, or contract disposal.
Even when an effort is made to recover solvents, some wastewater
contamination can be expected. Removal of small quantities of
organic solvents from the segregated wastewater can ' be
accomplished by such techniques as steam stripping or carbon
adsorption. Further removal of solvents from combined
end-of-pipe wastewater may result from biological treatment or
from surface evaporation in the treatment system.
4. Steam Stripping
a.
Introduction
Steam stripping is the transfer of the volatile constituents of a
wastewater to the vapor phase which occurs when steam is passed
through a preheated wastewater. Extremely volatile compounds can
be steam stripped from wastewater in flash tanks which provide
essentially one stage of liquid-vapor contact. More difficult
separations are conducted in columns filled with packing
materials which provide large surface areas for liquid-vapor
contact. Conventional fractionating columns, which contain a
series of liquid-vapor contact stages, are used for the most
difficult separations. Flash tanks, packed towers, and plate
columns are used extensively in the chemical process industries
and their designs are discussed in chemical engineering
textbooks. (138) (139) (140) Hwang and Fahrenthold have
considered the thermoclynamic aspects of steam stripping organic
priority pollutants from wastewater. (72) The authors predict the
effluent concentrations theoretically achievable by steam
stripping and the actual number of liquid-vapor contact stages
required.
Steam stripping is an available technology for removal of
methylene chloride, toluene, chloroform, and benzene. Section
VIII presents suggested limits for these four pollutants based on
the performance of wastewater steam strippers at a pharmaceutical
plant. Steam stripper operations at plant 12003 are discussed
following the general discussion of steam stripping.
b. General
In a steam stripper, the components of a wastewater are separated
by partial vaporization. When contacted with steam, the volatile
organic compounds in a wastewater are driven into the vapor
phase. The extent of the separation is governed by the physical
properties of the organic compounds, the temperature and pressure
at which the stripper is operated, and the arrangement and type
of equipment used.
A column used to steam strip solvents from wastewater is shown on
Figure VI1-5. Solvent contaminated process wastewaters and
120
-------
COOLING
WATER
VENT TO
EMISSIONS
CONTROL
OPTIONAL
I CONDENSATE
| DRUM
STRIPPED
WASTEWATER
RECOVERED
SOLVENT
PACKED
OR
TRAY
COLUMN
^ RECYCLE
P> TO GRAVITY
PHASE
SEPARATION
TANK
\ STEAM
RECOVERED
SOLVENT
FIGURE VII-6. TYPICAL EQUIPMENT FOR STEAM STRIPPING SOLVENTS FROM WASTEWATER.
121
-------
condensed overhead vapors from the stripper are allowed to
accumulate in a gravity phase separation tank. When the
equilibrium solubility of the solvents in water is reached, the
difference between the specific gravities of the water and the
solvents results in the formation of two immiscible liquid
layers. One layer contains the immiscible solvents; the other
layer is an aqueous solution which is saturated with solvents.
The solvent layer is pumped to storage. The composition of the
recovered solvent and economic factors will determine whether the
solvent is reused within the plant, disposed of, used as
incinerator fuel, sold to other industrial users, or sold to a
solvent reclamation facility. Solvents recovered by steam
stripping are normally not reused directly in pharmaceutical
synthesis because of FDA purity requirements.
The aqueous layer from the gravity phase separation tank is
pumped through a preheater where the temperature is raised by
heat exchange with the stripper effluent. If the feed contains
high concentrations of suspended solids, a filter can be
installed prior to the preheater to prevent fouling in the
preheater and the column.
After preheating, the solvent saturated water is introduced at
the top or near the middle of the column and flows by gravity
through the stripper. The hot effluent, which is discharged at
the bottom of the stripper, is used as a heating medium in the
feed preheater. Steam is injected through a sparger and rises
countercurrent to the flow of the water.
The solvent laden overhead vapors are condensed and the organic
and aqueous layers are allowed to separate by gravity in a
condensate drum. The solvent can be recovered by decanting the
immiscible liquid layers, or by recycling the condensed vapors
directly to the gravity phase separation tank. This practice is
particularly advantageous in cases where the wastewater to be
steam stripped contains low concentrations of the solvent to be
recovered. As the condensate mixes with the wastewater already
in the tank, the solvent concentration increases to the point
where a two phase mixture is formed. The aqueous phase, which is
fed to the column, will be saturated with solvent. The most
economical operation of a wastewater steam stripper occurs when
the feed is saturated with the solvent to be recovered.
In certain situations, reflux may be required to produce overhead
vapors which, when condensed, will separate into immiscible
liquid layers. Initially, the condensate is allowed to
accumulate in a condensate drum. When the solvent concentration
exceeds the water solubility limit, two liquid layers form. The
solvent rich layer is pumped to storage. A portion of the
solvent saturated aqueous layer is returned to the column
(refluxed) and the remainder is recycled to the gravity phase
separation tank. The reflux is introduced at a position above
the point where the feed enters the column.
122
-------
At plants where steam pressure fluctuations can occur, automatic
feedback controllers are commonly used to maintain the desired
solvent concentrations in the stripper bottoms and overhead
vapors. A detailed discussion of the use of automatic feedback
controllers for this purpose is included in the 4th Edition of
the Chemical Engineers Handbook. (141)
Information gathered by the Agency indicates that steam stripping
is used to remove organic solvents and other pollutants from
wastewater discharges from at least six pharmaceutical plants and
that steam stripping is also used to treat similar wastewaters in
other industries. Data on the removal of toxic volatile organic
pollutants in steam strippers at plants where pesticides and
organic chemicals are manufactured are presented in the Proposed
Development Document for Effluent Limitations Guidelines and
Standards for the Pesticides Point Source Category.(142) Steam
stripping operations at an indirect discharging pharmaceutical
manufacturer are discussed below.
c. Steam Stripper Operations at Plant 12003
Plant 12003 has the capability to operate at least eight
different steam strippers. The strippers are located throughout
the plant within production buildings or at central solvent
recovery operations in other buildings. Steam stripping enables
the plant to meet a POTW requirement that the concentration of
explosive vapors in the plant sewer pipes not exceed 40 percent
of the lower explosion limit (LED. The LEL is monitored in each
production area with a flame-thermocouple sensor. Gas samples
are automatically taken and analyzed by gas chromatography if the
solvent vapor concentration exceeds 30 percent of the LEL. The
stripped wastewaters are combined with sanitary and other process
wastewaters in a pretreatment system which consists of oil
skimming, pH adjustment, and flow equalization.
The recovered solvents from the stripping operations are
currently stored for disposal by contract hauling. Plant
personnel informed EPA that they were considering using some of
the recovered solvents as fuel for an incinerator. Agency
representatives visited plant 12003 during the week of May 23-27,
1983, and sampled the influent and effluent from a packed column
stripper and a steam distillation flash tank.
d. Packed Column Steam Stripper
Five days of operating data from a packed column steam stripper
used to remove methylene chloride from wastewater at plant 12002
are shown in Table VI1-2. In addition to methylene chloride,
analysis by plant personnel confirmed that methanol, diethyl
ether, and pyridine were present in the wastewater. Usually, the
stripper operates approximately 12 hours a day, five days a week.
During periods of low production, the stripper is shut down and
123
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wastewaters are allowed to accumulate. When the stripper resumes
operation, it operates continuously for several days in a row.
The major portion of the feed to the stripper is wastewater from
a batch chemical synthesis operation. The feed is pumped to the
underground settling tank shown on Figure VII-6. In the settling
tank the wastewater separates into two layers - immiscible
methylene chloride and an aqueous solution saturated with
methylene chloride and small amounts of methanol, diethyl ether,
pyridine, and other solvents listed in the footnotes of Table
VI1-2. The immiscible methylene chloride is pumped off the
bottom of the settling tank to a spent solvent holding tank. The
aqueous solution is pumped to the stripper feed tank. The feed
rate to the column is controlled by an automatic flow valve on
the discharge side of the feed purnp.
The wastewater is pumped through an influent filter and a
preheater before it enters the top of the column through a liquid
distributer - a special pipe outlet which serves to wet the tower
packing uniformly. The ten-inch diameter column contains one
19-foot section packed with one-inch diameter stainless steel
pall rings. Steam is injected through a sparger in the bottom of
the stripper. The overhead vapors from the stripper are
condensed and recycled to the underground settling tank.
The results of the five days of verification sampling are shown
in Table VII-2. The average influent concentration of methylene
chloride was 8,800 mg/1. The column influent also contains high
concentrations of inorganic salts. According to plant personnel,
the influent and effluent filters shown on Figure VII-6 were
installed to prevent fouling in the feed preheater. The average
effluent concentration of methylene chloride was 6.9 mg/1 when
the column was operated close to the design specifications of
98°C overhead vapor temperature. This corresponds to greater
than 99 percent removal of methylene chloride in the packed
column stripper. The packed column was operating under upset
conditions, as indicated by a drop in the temperature of the
overhead vapors below 85°C, during 10 of the 40 overhead
temperature readings taken during sampling.
e.
Steam Flash Tank
Five days of operating data from a steam flash tank used to strip
toluene from wastewater at plant '12003 are shown in Table VI1-3.
In addition to toluene, analysis by plant personnel confirmed
that methanol, ethanol, acetone, isopropanol, methyl ethyl
ketone, and diethyl ether were present in the wastewater. The
flash tank normally operates 7 hours a day, 5 days a week.
129
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Wastewaters from batch pharmaceutical processes, a vacuum pump
system, and steam ejectors are accumulated in two 5,000 gallon
settling tanks as shown on Figure VI1-7. A connecting line
maintains the liquid height at the same level in both tanks. The
accumulated wastewater separates into two liquid layers -
immiscible toluene and an aqueous solution of toluene and small
amounts of methanol, ethanol, acetone, isopropanol, methyl ethyl
ketone, diethyl ether, and other solvents listed in the footnotes
of Table VII-3. The immiscible toluene flows by gravity to a
spent solvent holding tank. The aqueous solution is pumped
through two preheaters and enters the top of the 500 gallon flash
tank through a spray nozzle. Toluene is stripped from the
wastewater by steam which is injected through a sparger in the
bottom of the flash tank. The overhead vapors are partially
condensed arid introduced to a condensate drum. The liquid
condensate is recycled to the settling tanks. Uncondensed vapors
from the condensate drum enter a scrubber where they are absorbed
in previously uncontaminated cooling water. The scrubber water
is recycled to the settling tanks and the scrubbed vapors are
vented to an emissions control system.
As shown in Table VII-3, the concentration of toluene in the
influent to the flash tank ranged from 320.5 mg/1 to 4,300 mg/1.
It is suspected that the high influent concentration of 4,300
mg/1 on May 27 was caused by a low liquid level in the settling
tanks. This probably resulted in a portion of the immiscible
toluene being fed to the column along with the miscible solution
of toluene and water. The effluent concentration of toluene
ranged from 0.39 mg/1 to 229.0 mg/1. The high effluent
concentration of 229.0 mg/1 occurred on May 26 when the tank
operated under upset conditions. The temperature of the overhead
vapors during the upset period was 91°C; the average temperature
of the overhead vapors during the rest of the week was 99°C. The
average influent and effluent concentrations for the five day
period were 516 mg/1 and 4.5 mg/1, respectively, excluding the
upset periods. This corresponds to greater than 99 percent
removal of toluene in the flash tank.
f. Data Applicability
The vapor-liquid equilibrium relationship of an organic compound
in a wastewater forms the basis for determining its removability
by steam stripping. The magnitude of the vapor-liquid
equilibrium constant serves as a measure of the theoretical
removal effectiveness.
133
-------
g
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134
-------
The vapor-liquid equilibrium constant, or K-value, is defined as
the ratio of the equilibrium mole fraction of an organic compound
in the vapor phase,y^, to its equilibrium mole fraction in the
wastewater phase, x-j
, _ *1
Ki= X1
The vapor-liquid equilibrium constant can be calculated from:
where Yl is the activity coefficient of the organic compound i in
the wastewater, p. is the vapor pressure of the pure substance
at the steam stripper operating temperature, and P is the total
pressure. This expression, which holds for low pressures, is a
simplified form of the rigorous thermodynamic equation. The
vapor-liquid equilibrium constants calculated by Hwang and
Fahrenthold for aqueous solutions of toluene, benzene, methylene
chloride, and chloroform are listed below.(72)
Compound
Toluene
Benzene
Methylene Chloride
Chloroform
Average K-Value at 100°C & .1 Atm
1 ,156
1 ,215
941.4
635.5
The suggested limits in Section VIII for benzene are based on the
performance of the steam distillation flash tank in removing
toluene from pharmaceutical process wastewater at plant 12003.
The suggested limits for chloroform are based on the performance
of the packed column steam stripper in removing methylene
chloride from pharmaceutical process wastewater at plant 12003.
In both cases, the use of identical limits is justified by the
above similarities between the vapor-liquid equilibrium
constants.
g. Other Data Gathering
In order to determine the extent to which the wastewaters of
indirect discharging pharmaceutical plants were contaminated by
toxic volatile organics, the Agency sent 308 questionnaires to
nine indirect discharging plants which had indicated the use of
toxic volatile organics. The Agency also sent questionnaires to
six other plants that had commented on the proposed pretreatment
standard for total toxic volatile organics (see 47 FR 53585,
Nov. 26, 1982).(141) The Agency sought information on wastewater
contamination by toxic volatile organics in order to develop its
plant-by-plant cost estimates for steam stripping technology. A
copy of the questionnaire that was sent to the participating
pharmaceutical plants may be found in the record of this
rulemaking.
135
-------
Responses to the questionnaire were received from
company response for another plant not sent a
Five plants reported contamination of part of
wastestream by one or more toxic volati
concentrations greater than 10 mg/1. The median
process wastewater contaminated by toxic volatile
percent at the five plants. This percentag
development of plant-by-plant steam stripping
discussed in Appendix A.
5. Carbon Adsorption
16 plants (one
questionnaire) .
their process
le organics at
percentage of
organics was 26
e was used in
costs which is
Adsorption is defined as the adhesion of dissolved molecules to
the surface of solid bodies with which they are in contact.
Granular activated carbon particles have two properties that make
them effective and economical adsorbents. First, they have a
high surface area per unit volume which results in faster, more
complete adsorption. Second, they have a high hardness value
which lends itself to reactivation and repeated use.
The adsorption process typically is preceded by preliminary
filtration or clarification to remove insolubles. Next, the
wastewaters are placed in contact with carbon so adsorption can
take place. Normally, two or more beds are used so that
adsorption can continue while a depleted bed is reactivated.
Reactivation is accomplished by heating the carbon between 870°C
to 980°C (1600°F to 1800°F) to volatize and oxidize the adsorbed
contaminants. Oxygen in the furnace is normally controlled at
less than 1 percent to avoid loss of carbon by combustion.
Contaminants may be burned in an afterburner.
Carbon adsorption is primarily designed to remove dissolved
organic material from wastewater, although it can to some extent
remove chromium, mercury and cyanide. A discussion of the
technical and economic feasibility of activated carbon adsorption
technology may be found in "Treatability of Priority Pollutants
in Wastewater by Activated Carbon," S. T. Hwang and P.
Fahrenthold, U.S. EPA, 1979.
The potential use for this technology by the pharmaceutical
industry is limited. Concentrations of most of the toxic
pollutants (metals, volatile organics and cyanide) characteristic
of pharmaceutical wastewater are generally reduced more
effectively and with less cost by the previously discussed
technologies or through biological treatment than by activated
carbon adsorption. Phenols, the other group of pollutants found
in pharmaceutical wastewaters are biodegradeible and their
concentrations can be reduced by improved biological treatment.
Carbon adsorption is particularly applicable in situations where
organic material in low concentrations not amenable to treatment
by other technologies must be removed from wastewater.
136
-------
The equipment necessary for an activated carbon adsorption
treatment system consists of a preliminary clarification and/or
filtration unit to remove the bulk of the solids, two or three
columns packed with activated carbon, and pumps and piping. When
on-site regeneration is employed, a furnace, quench tanks, a
spent carbon tank, and a reactivated carbon tank are generally
required. Contract regeneration at a central location is a
frequent commercial practice.
An example of
Figure VII-8.
an activated carbon adsorption unit is shown in
Carbon adsorption systems are compact, will tolerate variation in
influent concentrations and flow rates and can be thermally
desorbed to recover the carbon for reuse. Economic application
of carbon adsorption is limited to the removal of low pollutant
concentrations. Competititive adsorption of non-target
constituents, as well as blinding by suspended solids, can cause
interference.
D. END-OF-PIPE TREATMENT
In-plant treatment processes are used to treat specific
pollutants in segregated waste streams; end-of-pipe (EOP)
technologies usually are designed to treat a number of pollutants
in a plant's overall wastewater discharge. The types and/or
stages of EOP treatment are primary treatment, biological
treatment, and tertiary treatment. Depending on the nature of
the pollutants to be removed and the degree of removal required,
combinations of the available technologies are used.
As in the case of in-plant treatment, the 308 Portfolio data base
was the principal source of information for identifying the use
of EOP treatment by the pharmaceutical industry. This
information was requested in both 308 Portfolio mailings. As a
cross-check for accuracy and completeness, the 308 Portfolio
responses were compared with information available from the other
data bases.
Table VII-4 presents a summary of the EOP technologies identified
by the various data bases, along with the number of plants that
employ each process.
1
Primary Treatment
Primary treatment, a form of physical/chemical treatment, refers
to those processes that are nonbiological in nature. Primary
treatment involves (a) the screening of the influent stream to
remove large solids and (b) gravity separation to remove
settleable solids and floating materials. Commonly used primary
treatment technologies in the pharmaceutical industry are coarse
solids removal, primary sedimentation, primary chemical
flocculation/clarification, and dissolved air flotation.
137
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SURFACE
WASH
CARBON
BED SURFACE
CARBON
INLET &
OUTLET
^,-SAND
GRAVEL
FILTER BLOCK
WATER OUTLET
FIGURE VH-8
ACTIVATED CARBON ADSORPTION UNIT
138
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TABLE VII-4
SUMMARY OF END-OF-PIPE TREATMENT PROCESSES
(Data Base: 308)
End-of-Pipe Technology
Equalization
Neutralization
Primary Treatment
Coarse Settleable Solids Removal
Primary Sedimentation
Primary Chemical Flocculation/Clarification
Dissolved Air Flotation
Biological Treatment
Activated Sludge
Pure Oxygen
Powdered Activated Carbon
Trickling Filter
Aerated Lagoon
Waste Stabilization Pond
Rotating Biological Contactor
Other Biological Treatment
Physical/Chemical Treatment
Thermal Oxidation
Evaporation
Additional Treatment
Number of Plants
62
80
61
41
37
12
3
76
52
1
2
9
23
9
1
2
17
3
6
Polishing Ponds
Filtration
' Multimedia
Activated Carbon
Sand
Other Polishing
Secondary Chemical Flocculation/Clarification
Secondary Neutralization
Chlorination
40
10
17
7
4
5
17
5
5
11
Note: Subtotals may not add to totals because: 1) some plants employ
more than one treatment process? 2) minor treatment processes
were not listed separately; 3) details for some treatment
processes were not available.
139
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2. Biological and Tertiary Treatments
Biological treatment is the principal method by which many
pharmaceutical manufacturing plants are now meeting existing BPT
regulations. Although it is discussed as a single EOF treatment
alternative, biological treatment actually encompasses a variety
of specific technologies such as aerated lagoons, activated
sludge, trickling filters, and rotating biological contactors.
Since there are numerous publications available that describe all
aspects of the operations (advantages, limitations, and other
pertinent facts), discussions, of these specific treatment
processes will be presented in only moderate detail in this
document. Although each has its own unique characteristics, they
are all based on one fundamental principle: the reliance on
aerobic and/or anaerobic biological microorganisms for the
removal of oxygen-demanding compounds.
An aerated lagoon is one example of a treatment facility which
utilizes aerobic biological processes. It is essentially a
stabilization basin to which air is added either through
diffusion or mechanical agitation. The air provides the oxygen
required for aerobic biodegradation of the organic waste. If
properly designed, the air addition will provide sufficient
mixing to maintain the biological solids in suspension so that
they can be removed in a secondary sedimentation tank. After
settling, sludge may be recycled to the head of the lagoon to
ensure the presence of a properly acclimated seed. When operated
in this manner, the aerated lagoon is analogous to the activated
sludge process. The viable biological solids level in an aerated
lagoon is low when compared to that of an activated sludge unit.
The aerated lagoon relies primarily on detention time for the
breakdown and removal of organic matter; aeration periods of 3 to
8 days or more are common.
The activated sludge process is also an aerobic biological
process. The basic process components include an aerated
biological reactor, a clarifier for separation of biomass, and a
piping arrangement to return separated biomass to the biological
reactor. The aeration requirements are similar to those* of an
aerated lagoon in that aeration provides the necessary oxygen for
aerobic biodegradation and mixing to maintain the biological
solids in suspension. The available activated sludge processes
that are used in the treatment of wastewaters include
conventional, step-aeration, tapered-aeration, modified-aeration,
contact-stabilization, complete-mix and extended-aeration.
A trickling filter is a fixed-growth biological system where a
thin-film biological slime develops and coats the surfaces of the
supporting medium as wastewater makes contact. The film consists
primarily of bacteria, protozoa, and fungi that feed on the
waste. Organic matter and dissolved oxygen are extracted and the
metabolic end products are released. Although very thin, the
biological slime layer is anaerobic at the bottom so hydrogen
140
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sulfide, methane, and organic acids are generated. These
materials cause the slime to periodically separate (slough off)
from the supporting medium and be carried through the system with
the hydraulic flow. The sloughed biomass must be removed in a
clarifier.
Trickling filters are classified by hydraulic or organic loading
as "low rate" or "high rate." Low-rate filters generally have a
hydraulic loading rate of 1 to 4 million gal./acre/day (or an
organic loading rate of 300 to 1,000 Ib. BOD5_/acre-ft./day), a
depth of 6 to 10 feet, and no recirculation. High-rate filters
have a hydraulic loading rate of 10 to 40 million gal./acre/day,
an organic loading rate of 1,000 to 5,000 Ib. BOD5_/acre-f t./day,
a depth of 3 to 10 feet, and a recirculation rate of 0.5 to 4.0.
High-rate filters can be single or two stage. The medium
material used in trickling filters must be strong and durable.
The most suitable medium in both the low and high-rate filters is
crushed stone or gravel graded to a uniform size.
The rotating biological contactor (RBC) process consists of a
series of disks constructed of corrugated plastic plates and
mounted on a horizontal shaft. These disks are placed in a tank
with contour bottom and immersed to approximately 40 percent of
the diameter. The disks rotate as wastewater passes through the
tank and a fixed-film biological growth similar to that on
trickling filter media adheres to the surface. Alternating
exposure to the wastewater and the oxygen in the air results in
biological oxidation of the organics in the wastes. Biomass
sloughs off (as in the trickling filter) and is carried out in
the effluent for gravity separation. Direct recirculation is not
generally practiced with the rotating biological disks.
There are other biological treatment techniques not specifically
mentioned in this section which utilize either aerobic or
anaerobic biodegradation or both. These are stabilization ponds,
anaerobic lagoons and facultative lagoons. In facultative
lagoons, the bacterial reactions include both aerobic and
anaerobic decomposition.
Besides the direct utilization of these treatment processes,
biological treatment also encompasses two other approaches; in
this report, they are referred to as biological enhancement and
biological augmentation. Generally, these variations are
accomplished by (a) modifications made in the conventional
biological treatment itself or (b) conventional processes
combined into a multi-stage system. Examples of biological
enhancement are pure oxygen activated sludge and biological
treatment with powdered activated carbon. Biological
augmentation could be trickling filter/activated sludge,
activated sludge/ rotating biological contactor, aerated
lagoon/polishing pond, or any combination of two or more
conventional biological treatment processes.
141
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The differences in performance due to differences in the number
of biological treatment stages employed rest on the applicability
of plug-flow/back-mix effects. A true plug-flow system, such as
a narrow channel lagoon, approaches equivalence to an infinity of
stages if the food/microorganism (F/M) ratio is maintained. This
tends to beneficially maximize the availability of nutrients, a
function of the concentration of biodegradable pollutants. A
fully back-mixed system (as an activated sludge unit tends to be)
operates throughout at its exit concentration. It is thus a
distinct, finite stage incremental with any stage before it or
after it.
In practice, these distinctions are not clearcut. Since there is
some back-mixing even in a channelled lagoon, separations of
units or even of cells within one unit may be beneficial. Also,
in most mixed systems, the concentration gradient established is
sufficient for some increase in the effective nutrient
concentration and, consequently, the optimum microorganism
concentration.
In many systems, design factors other than the concentration-
induced driving force may overshadow the concentration gradient
and prevent simple performance correlation.
Comprehensive consideration of the criteria affecting bio-
reaction performance suggests the following to be significant:
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Influent concentration of pollutants.
Resistive characteristics of the BOD pollutants and the
resultant K value (i.e., how easily the BOD is
biodegraded). «
Presence of potential interfering pollutants (e.g.,
constituents toxic to the microorganisms).
Bio-reaction characteristics and concentration of the
microorganisms present.
Dissolved oxygen content and distribution at
the point of adequate 02 availability.
least to
Sludge recycle as it may affect microorganism
availability and character as represented by the F/M
ratio.
Contact efficiency of pollutants and microorganisms, as
may be induced by agitation, flow pattern, and MLVSS.
142
-------
(8) Availability and balance of nutrients, including
nitrogen and phosphate.
(9) Required target effluent.
(10) Temperature (e.g., seasonal effects).
The proper design of biological systems in addition to developing
optimum operating criteria, must also take into account how much
of the system's potential capacity will be used so that an
optimum modification approach will be available. The most
economical approach may be simple adjustments of operating
variables to exploit existing capacity fully. The adjustments
may require such minor changes as increasing agitation, power
input, or sludge recycle rate or, at the extreme, may require the
addition of an independently functioning system. In many cases,
the optimum upgrade may be a combination of existing component
units integrated with balanced new units. This is likely to
result in a system complex dictated in part by performance
requirements and in part by equipment already in place.
Some examples of typical augmented biological configurations
shown in Figure VII-9.
are
Tertiary treatment usually means any treatment following a
biological treatment system. The treatment technologies are
quite varied and are normally applied for the removal of such
pollutants as a specific priority pollutant class, nitrogen,
color, and so forth. Some tertiary treatment processes are also
applicable to in-plant or primary treatment schemes. The
location in the overall treatment concept determines whether the
operation is termed a tertiary treatment process.
Biological treatment systems are mainly . intended to reduce the
level of the traditional pollutants BOD and COD. Some priority
pollutants may be removed incidentally, even though not targeted
by the treatments.
Biological treatment removal efficiency is a function of
treatment intensity, detention time, and such system
characteristics as bioreaction rate constant, biomass
concentration, and biomass contact efficiency. The configuration
of the system is important since it affects these factors, but
the effectiveness is not necessarily benefitted by splitting the
bioreaction into a number of steps. In a plug-flow
(non-backmixed) system, there is a continuation of reaction and
little inherent effect of staging as in certain separation
techniques and driving force systems. There may be reaction rate
advantages in a back-mixed system which might accrue from
staging, but these must be evaluated for a specific system
considering microorganism availability, contact efficiency and
other factors.
143
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144
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Economic concerns often dictate a design which uses (a) one
biotechnique in preference to others (b) more than one technique
as the reaction progresses (e.g., activated sludge and trickling
filter) or {b) various arrangement configurations. However,
these design choices are highly site and waste specific, and
generalizations should be avoided in the comparison of systems
and in the choice a particular treatment configuration.
One of the Agency's data-gathering programs requested long-term
traditional pollutant data from the industry. The long-term data
consisted of raw daily or weekly influent and effluent data that
covered a period of about one year and were obtained from 22
plants employing some type of biological treatment. Additional
long-term data was submitted after proposal by new plants and
also by plants that had submitted data prior to the proposal.
For purposes of predicting what the industry can achieve in the
way of traditional pollutant control by biological enhancement,
the long-term data represent the best available data. Summaries
of the long-term data are presented in Table V-l. The data
submitted by plants before and after proposal are summarized in
Table IV-1. Many of these plants have achieved performance which
is better than that required by the BPT regulations for BOD^, COD
and TSS. These data were used to develop final BPT TSS
limitations and proposed NSPS limitations for the pharmaceutical
industry.
3. Solids Removal
Removal of. solids from wastewater can occur at several points in
the treatment sequence. Grit removal by screening, filtration,
or sedimentation is often necessary as a preliminary step in
primary treatment. After secondary biological treatment, it is
generally necessary to complete the removal of sludge and other
solids by means of clarification, filtration, or a special
operation such as flotation. Further solids removal occurs in
tertiary treatment stages.
a.
Clarification
Clarification is a method of removing suspended or colloidal
solids by means of gravity sedimentation. Since the settling
rate of suspended solids is dependent on particle size and
density (the smaller the particle size and the closer the density
to that of water, the slower the settling rate), flocculant or
coagulant aids sometimes must be added to promote bridging
between particles and to render them more settleable. A slow
settling rate and the stability of colloidal mixtures make
chemical clestabilization and agglomeration of colloidal
suspensions necessary.
Clarifiers are usually large containment vessels that have a
continuous water throughput. A conventional clarification system
utilizes a rapid mix tank to mix chemicals with the entering
145
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water; the wastewater is then subjected to slow agitation.
Provision for the removal of settled solids is also a necessary
part of the system.
Typical clarifiers are shown in Figure VII-10.
b. Filtration
Filtration is a basic solids removal technology in water and
wastewater treatment. Silica sand, anthracite coal, garnet, and
similar granular inert materials are among the most common media
used, with gravel serving as a support material. These media may
be used separately or in various combinations. Multimedia
filters may be arranged in relatively distinct layers by
balancing the forces of gravity, flow, and buoyancy of the
individual particles. This is accomplished by selecting
appropriate filter flow rates, media grain size, and media
densities.
The most common filtration system is the conventional gravity
filter. It normally consists of a deep bed of granular media in
an open-top tank. The direction of flow through the filter is
downward and the flow rate is dependent solely on the hydrostatic
pressure of the water above the filter bed. Another type of
filter is the pressure filter. In this case, the basic approach
is the same as a gravity filter, except the tank is enclosed and
pressurized.
As wastewater is processed through the filter bed, the solids
collect in the spaces between the filter particles.
Periodically, the filter media must be cleaned. This is
accomplished by backwashing the filter (reversing the flow
through the filter bed). The flow rate for backwashing is
adjusted in such a way that the bed is expanded by lifting the
media particles. This expansion and subsequent motion provides a
scouring action which effectively dislodges the entrapped solids
from the media grain surfaces. The backwash water fills the tank
up to the level of a trough below the top lip of the tank wall.
The backwash is collected in the trough, fed to a storage tank,
and recycled into the waste treatment stream. The backwash flow
is continued until the filter is clean.
An example of a filtration unit is shown in Figure VII-11.
c. Flotation
Flotation is an optional method of clarification utilized to
treat some industrial waste in which the suspended solids have
densities less than that of water. Air-assisted flotation may be
applied to some systems with solids slightly heavier than water.
As with conventional clarifiers, flocculants are frequently
employed to enhance the efficiency of flotation.
146
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CONTROL
VALVE
;v- i//i":
FIGURE vn-n
FILTRATION UNIT
148
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E. ULTIMATE DISPOSAL
In any evaluation of control and treatment technologies, one of
the most important considerations is the ultimate disposal
methods used by the industry. Whether a plant is a direct
discharger to surface waters, an indirect discharger to POTWs, or
a zero discharger can be a critical factor in determining what
technologies are most appropriate for controlling its waste
discharge. Table VI1-5 summarizes the methods used by the
pharmaceutical manufacturing industry for the ultimate disposal
of its process wastewaters. This table was prepared from a
listing of each plant's individual disposal methods (see Appendix
C).
Approximately 12 percent of the 466 manufacturing plants have
direct discharges. Seven of these plants also have indirect
discharges, while another nine use zero discharge methods for
some of their smaller waste streams. The majority of the
industry are indirect dischargers. About 59 percent of the
plants in the Agency's latest data base discharge to POTWs.
Seven of these plants also have direct discharges (non-process)
and another 25 use zero discharge techniques for some of their
smaller waste streams. Almost 29 percent of the manufacturing
plants use only such zero discharge methods as contract disposal,
evaporation, ocean dumping, or complete recycling or do not
generate process wastewaters requiring disposal. Seventy-five
percent of the zero dischargers were classified as such because
they generated no process wastewaters requiring disposal.
149
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TABLE VII-5
SUMMARY OF WASTEWATER DISCHARGES
Methods of Discharge
Number of Plants
in the Industry
Number of Plants
by Subcategories
Direct Only 42
Direct with Minor Zero 9
Discharge
Total Direct Dischargers 51
Indirect Only 256
Indirect with Minor Zero 21
Discharge
Total Indirect Dischargers 277
Combined Direct/Indirect 4
Dischargers
SUBTOTAL 332
Zero Dischargers 134
TOTAL 466
6
2
8
19
7
26
1
35
37
B
4
4
8
54
8
63
1
16
6
22
70
15
85
2
D
27
4
31
207
17
224
3
72 109 258
27 114
81 136 372
NOTE: Subcategory counts will not equal industry totals because of
multiple subcategory plants.
FATE OF WASTEWATERS AT ZERO DISCHARGE PLANTS (TOTAL INDUSTRY)
Discharge Method
Zero
Dischargers
Direct
w/Zero
Indirect
w/Zero
No Process Wastewater
Contract Disposal
Deep Well Injection
Evaporation
Land Application
Ocean Dumping
Recycle/Reuse
Septic System
Subsurface Discharge
No Data
Total
98
7
0
7
6
2
2
6
4
_2
134
0
3
1
1
3
1
0
0
0
0
7
2
3
5
2
1
2
3
25
150
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SECTION VIII
ANALYSIS OF LONG TERM DATA FOR POLLUTANTS OF CONCERN
This section describes the analysis of long-term cyanide data
submitted to EPA by pharmaceutical plants utilizing biological
treatment systems and in-plant cyanide destruction. Also
described in this section are the analyses of data obtained by
the Agency as a result of its steam stripper sampling efforts and
the analyses of the data used to develop final BPT TSS
limitations and final BPT alternative concentration-based BOD5_
and COD limitations. The first part of this section details
which plant data were used to develop the final and suggested
limitations and discusses reasons for the deletion of some of the
submitted data. Data verification procedures are described as
well as the contents of the data base on which limitations are
based. The second part of this section describes the statistical
methodology used to determine appropriate daily maximum and
maximum 30-day average variability factors.
A. DESCRIPTION AND TECHNICAL ANALYSIS OF DATA
The Agency used data from one facility (12236) to develop the
proposed cyanide limitations and standards based on in-plant
cyanide destruction and biological treatment (47 FR 53584;
November 26, 1982). Included in the proposed regulations was a
additional data on the performance of cyanide
systems in use by pharmaceutical manufacturing
After proposal, the Agency received data on the
of cyanide destruction systems from three plants
(12135, 12235 and 12236). The discussion in this section focuses
on how these data were used to derive final cyanide limitations
and standards.
request for
destruction
facilities.
performance
In the preamble to the proposed regulation, the Agency stated
that, based on available information from other industries, a
pretreatment standard of 1.2 mg/1 for total toxic volatile
organics (TTVO) might be appropriate if adequate supporting data
could be obtained from the pharmaceutical industry. The
technology basis for this suggested standard was in-plant steam
stripping. In response to comments on this suggested standard,
the Agency gathered data on the performance of a steam stripper
and flash tank at plant 12003 by sampling steam stripper and
flash tank influent and effluent streams. Although the Agency is
not proposing or promulgating regulations based on steam
stripping technology, analysis of the data obtained since
proposal will be presented in this section along with suggested
limitations for certain toxic volatile organics.
in November of 1982, the Agency proposed a BPT TSS limitation for
all subcategories of plants based on a long-term average
concentration of 75 mg/1. This limitation was derived by
151
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averaging the effluent TSS concentrations of all plants with
biological treatment in-place and was intended to replace the
existing BPT TSS limitations on subcategory B, D, and E plants
and to establish BPT TSS limitations for subcategories A and C
for which BPT TSS limitations had not been established. In
response to a comment on these proposed limitations, the Agency
has evaluated the latest data on the performance of biological
treatment systems with regard to TSS and concluded that the BPT
TSS limitation should be related to the BPT BOD5_ limitation. The
Agency also proposed alternative BPT concentration-based
limitations for BOD5_ and COD for all subcategories. These
limitations were proposed in order that plants with low average
raw waste BOD5_ and COD concentrations would not have to comply
with more stringent BPT limitations on BOD5_ and COD than the
proposed BCT BOD5_ and BAT COD limitations. No comments were
received on these proposed alternative concentration-based
limitations. Although BCT BOD5_ and BAT COD limitations are not
being finalized in this rulemaking, the Agency is finalizing BPT
alternative concentration-based BOD5_ and COD for three
subcategories based on its analysis of conventional and
nonconventional pollutant data from facilities in these
subcategories.
The data analyses performed and the results of these analyses in
each of the above areas are discussed below:
1
Cyanide Destruction Data Analysis
The Agency proposed cyanide limitations based on data submitted
by plant 12236. These data were gathered during the 1978-79
period and consisted of a series of daily measurements of
end-of-pipe cyanide concentrations. The wastewater from the
cyanide destruction system at the plant was combined with other
waste streams, some of which contained small concentrations of
cyanide as low as 1.0 mg/1. These combined streams were then
subjected to biological treatment and the effluent from
biological treatment systems was monitored for cyanide.
Consequently, the concentrations used to develop the proposed
limits were not a direct measure of the performance of the
cyanide destruction system at this plant. Also, in its comments
on the proposed regulation, this plant indicated that these data
were gathered during a period when the processes which generated
cyanide wastes were operating at less than normal capacity.
Plant 12236 submitted new cyanide data on the effluent from
cyanide destruction corresponding to the period of time of its
earlier submission. This plant also submitted cyanide effluent
data, both in-plant and end-of-pipe, from a later time period in
which the cyanide waste generating processes were operating at
normal capacity. The Agency also received similar data on the
performance of cyanide destruction technology from two other
plants (12235 and 12135.). Plants 12235 and 12236 used the
alkaline hydrolysis technique, while plant 12135 employed the
alkaline chlorination technique for cyanide destruction.
152
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After an evaluation of each data set, the Agency decided to use
the recently submitted data from plants 12235 and 12236 to
develop long-term average cyanide concentrations and variability
factors. These data sets were chosen based on three
considerations: (1) the cyanide destruction units were operated
to the limit of their capacity during the period that the data
were obtained, (2) the data were obtained during periods at the
plant when the processes which generate cyanide bearing wastes
were operating at normal capacity and (3) the submitted data
directly measured the performance of cyanide destruction. After
analysis of the data from plant 12135, the Agency concluded that
the system at the plant was not being operated in order to
achieve the effluent concentrations of cyanide that are
consistent with the design specifications of the unit. The
pre-proposal data submitted by plant 12236 was not used because
it was obtained during periods when the cyanide waste generating
processes were operating at less than normal capacity.
After deciding on which data sets to use in developing the final
cyanide limitations and standards, the Agency performed a data
screening analysis on individual data points from these data
sets. This analysis was identical to that performed during the
development of the proposed regulations. (See "Statistical
Support for Pharmaceutical Rulemaking - September, 1983" for
details of this analysis.) The result of this analysis was that
four data points from each submission were targeted as suspect
results. These points were deleted from the data sets after
contact with plant personnel indicated that these observations
were not consistent with the proper operation of these units.
For the cyanide destruction unit data, long-term average
concentrations, the number of observations and the calculated
variability factors for each set of observations are presented in
Table VIII-1. The calculation of the variability factors will be
discussed later in this section. The long-term average of the
cyanide destruction unit effluent concentrations derived from
each data set (12235 and 12236) were weight-averaged according to
the number of observations available in each data set to yield a
long-term average performance value. Weight-averaged variability
factors were also calculated in the same way. These results also
appear in Table VIII-1.
The maximum 30-day average and daily maximum cyanide limitations
and standards which are derived from the multiplication of the
long-term weighted average performance values and the
weight-averaged variability factors are found in Table VIII-2.
These limitations and standards are appropriate if monitoring for
purposes of demonstrating compliance with the limitations and
standards is conducted on the effluent from the cyanide control
technology unit. If monitoring by direct dischargers who use
biological systems to treat the effluent from cyanide destruction
systems along with the remainder of the plant process wastewater
is conducted after biological treatment, then a different set of
153
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TABLE VIII-1
LONG TERM AVERAGE CYANIDE CONCENTRATIONS (LTAs) AND
VARIABILITY FACTORS (VFs)
FROM CYANIDE DESTRUCTION UNITS
Plant
LTA
ling/1)
12235 3.28
12236 6.52
Weighted LTA = 5.25
Weighted 30-Day Maximum Average V.F.
Weighted Daily Maximum VF = 6.39
No. of
Observations
189
293
30-Day
Max.
2.06
1.62
Daily
Max. V.F.
7.31
5.79
= 1.79
154
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TABLE VIII-2
30-DAY MAXIMUM AVERAGE AND DAILY MAXIMUM LIMITATIONS
AND STANDARDS FOR CYANIDE*
Regulation
BPT, BAT, PSES
PSNS and NSPS
30-Day Maximum
Average concentrations (mg/1)
9.4
Daily Maximum
Concentration (mg/1)
33.5
* These concentration limitations and standards apply to the effluent
from cyanide destruction system and only if all cyanide bearing wastes
are being treated by the cyanide destruction unit.
155
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numerical limitations apply. These alternate limitations were
developed by accounting for that removal of cyanide which occurs
as the result of biological treatment. The Agency attempted to
estimate the removal of cyanide achieved by biological treatment
from the post-proposal data submitted by plant 12236. However,
although daily in-plant and end-of-pipe effluent data pairs were
submitted covering about nine months, no cyanide concentration
data on the influent to biological treatment was available. The
fact that process streams containing relatively low
concentrations of cyanide were not treated by cyanide destruction
but were mixed with the treated cyanide waste stream and other
non-cyanide bearing waste streams prior to biological treatment
prevented the Agency from determining the removal of cyanide by
the biological system.
Some data were available from the S/V program on the removal of
cyanide by biological treatment systems. The average percent
removal of cyanide achieved by the biological treatment systems
of plants in the S/V program was 70 percent. The Agency is also
aware that the median cyanide removal percentage calculated from
the data gathered during the Agency's 50 plant POTW study was 59
percent.(136) EPA based its estimate of the cyanide removal
capability of biological treatment systems on the POTW data. The
Agency believes that the pharmaceutical plants with biological
treatment will achieve at least this level of removal because the
biological treatment systems of direct dischargers on average
have longer detention times and more aeration than do the POTWs
in EPA's study. Based on this information, EPA determined
alternate limitations which are appropriate when monitoring after
biological treatment.
A number of factors have been considered in developing alternate
cyanide limitations and standards. These include the variability
in the effluent cyanide concentrations from a biological system,
the removal of cyanide achieved by biological treatment and the
effect of dilution by other process streams not containing
cyanide. A limitation based on cyanide destruction plus
biological treatment that is appropriate for direct dischargers
who monitor for cyanide at the final discharge point (or
end-of-pipe) was developed by first multiplying the long-term
average cyanide destruction effluent concentration (5.25 mg/1) by
the median biological treatment removal factor (0.41 which equals
1.00-0.59). The resulting long-term average cyanide
concentration (2.15 mg/1) was then multiplied by a variability
factor calculated from end-of-pipe cyanide data to yield
equivalent maximum 30-day average and daily maximum
concentrations which account for the cyanide reduction attainable
by cyanide destruction in combination with biological treatment.
(These variability factors have been developed from end-of-pipe
cyanide destruction data submitted by plant 12236 and are found
in Table VIII-3.) These allowable concentration limits were then
multiplied by a dilution factor R which equals the ratio of the
cyanide contaminated wastewater to the total process wastewater
156
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TABLE VII1-3
30-DAY MAXIMUM AVERAGE AND DAILY MAXIMUM VARIABILITY
FACTORS DERIVED FROM END-OF-PIPE DATA FROM PLANT 12236
Long Term
Average CN Cone.
(rag/1)
0.33
No. of
Observations
293
30-Day Max.
Ave. V.F.
1.53
Daily Maximum
V.F.
2.73
157
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discharge flow to yield the alternate maximum 30-day average and
daily maximum end-of-pipe limitations and standards. The above
calculations are presented below:
1. Equivalent Long-Term Average Cyanide Concentration
(5.25 mg/lXl .00-0.59) =2.15 mg/1
2. Equivalent Limitations and Standards
Max. 30-Day Ave. = (2.15) (1.53) R = 3.3 R mg/1
Daily Maximum = (2.15)(2.73)R = 5.9 R mg/1
The ratios of equivalent limitations and standards to the
end-of-cyanide destruction limitations and standards are
(3.3)(R)/(9.4) or (0.35HR) and (5.9)(R)/(33.4) or (0.18)(R) for
the maximum 30-day average and daily maximum limitations and
standards, respectively. These ratios are included in the
explanation following each direct discharger regulation (BPT, BAT
and NSPS) and are to be used to convert from end-of-cyanide
destruction limitations and standards to alternate final effluent
or end-of-pipe limitations and standards (see 48 FR 49808).
Indirect dischargers who conduct end-of-pipe compliance
monitoring must comply with the end-of-cyanide destruction
limitations multiplied by the dilution factor R. The cyanide
limitations and standards which are applicable at the alternate
monitoring points for direct and indirect dischargers are listed
in Table VIII-4. The following rules apply to direct dischargers
concerning the alternate limitations and standards:
(1) If all cyanide-containing waste streams are diverted to a
cyanide destruction unit and the effluent from the cyanide
destruction unit is discharged to a biological treatment system,
self-monitoring may be conducted at the final effluent discharge
point in which case the alternate maximum 30-day average and
daily maximum limitations cited above apply.
(2) If all cyanide-containing waste streams are not treated in a
cyanide destruction unit or if the effluent from the cyanide
destruction unit is not discharged to a biological treatment
system, self monitoring must be conducted at the final effluent
discharge point and the alternate limitations apply.
2. Analysis p_f Steam Stripper Data
The Agency analyzed forty effluent samples from a packed column
steam stripper and ten effluent samples from a flash tank
stripper located at plant 12003. The packed column stripper was
used to steam strip methylene chloride, while the flash tank was
used to steam strip toluene. The average influent concentrations
treated by these strippers were 8,800 mg/1 and 516 mg/1 for
methylene chloride and toluene, respectively. It should be noted
that these influent concentrations are not equivalent to the
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Regulation
BPT, BAT
and NSPS
BPT, BAT
and NSPS
PSES and PSNS
PSES and PSNS
TABLE VIII-4
ALTERNATE CYANIDE LIMITATIONS AND STANDARDS
Monitoring
Point
B
A
B
30-Day Maximum
Average (mg/1)
9.4
3.3 R
9.4
9.4 R
A = End-of-cyanide destruction unit
B = Final effluent point
Daily Maximum
:Tnig/T)
33.5
5.9 R
33.5
33.5 R
159
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actual concentrations of streams being stripped because part of
the feed stream consists of recycled condensed overhead streams
which are saturated with methylene chloride and toluene.
Nonetheless, the average removal efficiencies of both strippers
were better than 99 percent.
Along with the effluent concentration data from both strippers,
the Agency also collected other operational data to determine if
the effluent concentration observations were made when the unit
was being operated in accordance with design specifications.
These data are summarized in Tables VI1-2 and VI1-3. When the
effluent methylene chloride concentration data were reviewed in
the context of operational data collected, EPA determined that
when the overhead temperature on the stripper unit was below
85°C, high effluent bottom concentrations of methylene chloride
were observed. Consequently, 10 of the 40 concentrations
reported in Tables VI1-2 and VI1-3 were not used to develop an
average performance value for the steam stripping of methylene
chloride. The average performance value determined for the
remaining 30 observations is 6.94 mg/1, which is within the
design range of the stripper. The variability factors associated
with this average performance are found in Table VII1-5.
The Agency also collected steam stripping data from a flash tank
used to steam strip toluene.' All the data obtained (10
observations of effluent toluene concentrations) were compared
with the available data on the unit operation for the same time
period. The Agency determined that one observation was made
while the unit was operating under upset conditions (the overhead
temperature at the time the observation was made was considerably
below the average overhead temperature at the time that the other
observations were made). The average performance value of the
flash tank steam stripper with regard to the steam stripping of
toluene was 4.48 mg/1. The variability factors associated with
the nine observed data points used to generate this average
performance value are found in Table VII1-5.
In the preamble to the final regulation, the Agency states that
four TVOs (methylene chloride, benzene, chloroform and toluene)
were listed as possible candidates for regulation and that
suggested limitations for controlling the discharge of these TVOs
would be presented in this document. Although the Agency has
only presented data (see Section VII) which describes the
effluent levels that can be achieved by the application of steam
stripping technology to wastewaters containing high
concentrations of methylene chloride and toluene, the Agency
believes that these data can be used to recommend limits for
benzene and chloroform as well.
As noted in Section VII, benzene and toluene have similar
vapor-liquid equilibrium constants as do methylene chloride and
chloroform. Since vapor-liquid equilibrium constants determine
the extent to which waste streams containing volatile components
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TABLE VII1-5
Average Concentrations and Variability Factors
Derived From Steam Stripping Data
Pol 1utant
Methylene
Chloride
To!uene
Average of
Observations
(mg/1)
6.94
4.48
No. of
Observations
30
9
Variability Factors
30-Day Max. Daily
Average Maximum
1.37
1.81
5.07
9.70
161
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can be steam stripped, the Agency believes that the application
of a flash tank steam stripper to streams having high
concentrations of benzene should result in effluent levels equal
to those presented for toluene in Section VII. Similarly, the
Agency believes that the application of a packed column steam
stripper to streams containing high concentrations of chloroform
should produce effluent levels equal to those obtained for
methylene chloride in Section VII. Therefore, two sets of
suggested TVO limits are presented in Table VII1-6; one for
benzene and toluene and one for methylene chloride and
chloroform.
3. Conventional Pollutant Data Analysis
a. BPT TSS Limitations
As explained previously, in November of 1982, the Agency proposed
a BPT TSS limitation for all subcategories of plants based on a
long-term average concentration of 75 mg/1. This limitation was
intended to replace the overly stringent BPT TSS limitations on
subcategory B, D and E plants and to establish BPT TSS
limitations for subcategory A and C plants. The original overly
stringent BPT TSS limitations were based on data from two plants
whose operations were not characteristic of the entire range of
operations employed at plants in the B, D, and E subcategories.
One commenter on the proposed rules stated that a single number
concentration limit for TSS is not appropriate for high raw waste
load plants, but may be appropriate for low raw waste load
plants.
The existing BPT regulations, promulgated in 1976, are based on
the application of biological treatment. They require that each
pharamaceutical plant, regardless of subcategory, achieve a 90
percent reduction in BOD5_. Biological treatment systems are
designed to remove BOD by converting soluble BOD into insoluble
matter, TSS. The TSS generated in the biological system is
removed using sedimentation technology. The amount of TSS
removed is a function of the design of the clarifier or settling
pond. The level of TSS entering the sedimentation system is
directly related to the amount of soluble BOD removed. Because
each plant has a different BOD raw waste concentration, each must
remove a different amount of soluble BOD to comply with the
percent reduction limitations. This leads to the generation of a
different amount of TSS at each plant that must be removed in the
clarifier or settling pond. A single number concentration limit
for TSS is not compatible with the BPT percent reduction BOD
limitations, which, in practice, vary from plant to plant over a
range of 15 mg/1 to almost 400 mg/1. A single number limitation
would require some plants to install more advanced treatment than
that technology identified as BPT. It would also mean that low
raw waste load plants would be able to operate their treatment
systems inefficiently and still comply with the proposed single
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TABLE VII1-6
Suggested TVO Limitations
Pollutant
Methylene Chloride
Chloroform
Toluene
Benzene
30-Day Maximum
Average Limit (mg/1)
9.5
9.5
8.1
8.1
Daily Maximum
Limit (mg/1)
35.2 *
35.2
43.5
43.5
163
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number limitation. Consequently, relating the effluent TSS
concentration to either the influent or effluent BOD5.
concentration generated at each plant appears to be the most
equitable and reasonable way of establishing TSS limitations
based on biological treatment.
Consistent with the previous discussion, the Agency first
attempted to develop a mathematical relationship between the
average effluent TSS and average influent BOD5. concentrations for
plant subcategory groups (A, C and AC) and (B, D and BD) from
dcfta submitted by plants with biological treatment in-place (see
Table VIII-7). Plants which had some form of effluent filtration
in-place were specifically excluded from this analysis because
effluent filtration was not identified as part of the BPT
technology train. The Agency chose these plant groups because
the subcategorization analysis (see Section IV) indicated that
the influent and effluent characteristics of plants in these
groups are similar. It was hypothesized that different
relationships between influent BOD5. and effluent TSS would
probably be obtained for these two groups of plants. Using the
data at hand, various linear and non-linear relationships were
considered and estimated for each group of plants. Statistical
relationships could not be established for each group of plants
(that is, statistical tests did not support the existence of
proposed relationships in both plant groups with a sufficient
degree of confidence). More importantly, the Agency was
concerned with establishing such relationships based on small
numbers of pairs of average influent BOD and effluent TSS values,
some of which were based on daily monitoring data, while others
were simply reported averages without supporting data.
Therefore, the Agency did not rely on estimated mathematical
relationships between effluent TSS and influent BOD5. for
individual plant subcategories.
Since the effluent BOD5. and TSS concentrations from a biological
treatment system are related, the Agency calculated the ratios of
average effluent TSS to average effluent BOD5.. These ratios
appear in Table VIII-7. The mean and median ratios were
calculated for four subcategory plant groups; (1) A, C and AC,
(2) B, D and BD, (3) A, C and AC and B, D and BD, and (4) all
plants regardless of subcategory. These mean and median ratios
are found in Table VIII-8. An inspection of the data in this
table shows a slight variation in the mean ratios of the four
subcategory plant groups while the median ratio is 1.7 for all
groups. In establishing a relationship between the BPT effluent
BOD5. concentration and the BPT effluent TSS concentration, the
Agency was faced with the choice of using the mean ratios or the
median ratio. The Agency chose the latter approach for two
reasons. First, the median ratio is consistent with ratios of
the BPT maximum 30-day average TSS and BOD5. limitations
established for related industrial categories based on biological
treatment (see Table VIII-9). Secondly, the use of the median
value is indicated because there is considerable disparity as
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Table VIII-7
Ratios of Effluent TSS (mg/1) To Effluent BOD (mg/1)
for Biological Treatment Plants Without Effluent Filtration
PLANT CODE
12038
12119
20165
12022
12026
12036
12132
12187
1 2236
12462
33333
20257
55555
11111
12015
1 2089
12098
12085
12117
12239
12248
12283
12287
12298
12307
12459
12463
1 2471
20037
20201
20319
Sub-
category
A,B,C,D
A,D
B,C
A,C
C
A
A,C
C
C
A
C
C
C
C
D
B,D
D
D
B
D
D
D
D
D
D
D
B,D
B
D
D
D
Inf.
BOD mg/1
662.
ND
123
2141.6
3670
1570.8
2898.4
ND
1361.6
1765.4
3115.2
484
2949
948.8
232.6
ND
ND
ND
34.5
1573
294.4
ND
ND
ND
ND
69.5
102.2
50
ND
ND
ND
Eff.
BOD mg/1
28.3
7.3
25
110.2
108.1
33.1
66.6
707.3
156
117.5
121
143
79
164.5
9.70
13
409.9
32.2
1.94
284
26
35
56
15
11.4
3.8
5.7
14
20
6
15
Eff.
TSS mg/1
17.2
70.2
16
84.9
283.7
78.2
452.9
60.5 '
108
582.3
212
74
62
385.0
10.8
13
392.1
29.6
16
174
60.4
50
13
26
32.30
16.7
9.6
59
47
14
8.5
Ratio
Eff. TSS
Eff. BOD
0.6
9.6
0.6
0.8
2.6
2.4
6.8
0.1
0.7
5.0
1.8
0.5
0.8
1.7
1.1
1.0
1.0
0.9
8.3
0.6
2.3
1.4
0.2
1.7
2.9
4.4
1.7
4.2
2.4
2.3
0.6
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TABLE VIII-8
Summary of Median and Mean Ratios of Effluent
TSS to Effluent BODs for Various Plant Groups
Group Subcategories N.
1 A, C, A/C 11
2 B, D, B/D 17
3 ' B, D, B/D, A, C, A/C 28
4 All Combinations 31
N = Numbers of Observations
Mean
2.1
2.2
2.1
2.3
Median
1.7
1.7
1.7
1.7
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TABLE VIII-9
Comparison of Ratios of BPT 30-Day
Maximum Average Limitations for TSS(mg/l) and BOD(mg/l)
Established for Related Industrial Categories Based on Biological Treatment
Industry
Organic Chemicals
Plastics and Synthetic
Fibers*
Leather Tanning
Pulp and Paper*
TSS(mg/l)
45
111
110
BODR(mg/l)
37
76
70
Ratio
1.2
1.5
1.6
*Subcategory Average
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well as uncertainty with regard to the number of individual
observations used to compute the data averages found in Table
VIII-7. Some of the data averages are based on long-term data
submissions and data submitted after the November 1982 proposal
(i.e. these averages were calculated from known numbers of
observations). On the other hand, the number of observations
used to compute the averages found in the 308 Portfolio
submissions is not known. Therefore, a weight averaging
procedure utilizing the number of data points used to develop the
averages was not possible. Since the use of a weight averaging
procedure to determine the mean ratio was not possible and
because an unweighted average provides equal weighting, the
Agency chose the median ratio (1.7) to establish BPT TSS
limitations for all subcategories.
Therefore, the Agency has determined that the final effluent TSS
limitations which are applicable to all subcategories of plants
regulated in the 1976 regulations, will state that the BPT TSS
limitation applicable to a given plant will be equal to the
average effluent BODji concentration achieved after 90 percent
reduction from the raw waste level multiplied by a factor of 1.7.
This product is then multiplied by the maximum 30-day average
variability factor which is 3.0 to yield the 30-day maximum
average limitation. The variability factor remains unchanged
from the 1976 regulation.
b.
Alternative BPT BODS and COD Limitations
The Agency has reviewed the available data on the performance of
biological treatment systems with regard to the pollutants BOD5_
and COD in connection with the 1976 BPT limitations on the
discharge of these pollutants. The Agency has determined that
the biological treatment operations of subcategory B and D
facilities are characterized by significant lower raw waste and
effluent BODJ5 and COD concentrations than those of subcategory A
and C facilities (see Section IV). Consequently, an application
of the 90 percent BODJ5 and 74 percent COD reduction requirements
would mean that some subcategory B and D plants would have to
achieve significantly lower effluent concentrations of BOD^ and
COD than are required of most subcategory A and C plants as the
result of the application of the same requirements. After
reviewing the technology basis of the 1976 regulation, the Agency
has determined that alternative minimum concentration-based
limitations on the discharge of BODjj^ and COD are appropriate to
be consistent with the technology basis of the 1976 regulation.
These alternative limitations will have the practical effect of
ensuring that subcategory B and D plants with low raw waste loads
of BOD_5_ and COD will not have to achieve inordinately low
effluent concentrations of BOD_5_ and COD as a result of BPT.
The alternative maximum 30-day average BPT BODj[ limitation is
obtained by multiplying the long-term average effluent BOD5_
concentration characteristic of low raw waste subcategory B and D
168
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facilities employing biological treatment (15 mg/1) by the BPT
BOD5. variability factor (3.0). The 15 mg/1 average effluent
concentration is also approximately equivalent to the BODS^
performance criterion for POTWs with secondary treatment. The
alternative maximum 30-day average BPT GOD limitation is obtained
by multiplying the long-term average effluent COD concentration
characteristic of low raw waste subcategory B and D facilities
(TOO mg/1) by the BPT COD variability factor of 2.2. The TOO
mg/1 average effluent concentration approximates the highest
average effluent concentration reported by a subcategory B or D
facility in compliance with both of the BPT percent reduction
limitations (95.8 mg/1).
While the Agency has not collected post-BPT data from research
only (Subcategory E) plants, the information from the 1976 BPT
rulemaking indicates that the BOD5. and COD influent
characteristics of subcategory E only type facilities are quite
similar to those of subcategory B and D facilities. Therefore,
the alternative BPT BOD5_ and COD concentration-based limitations
will apply to subcategory E facilities as well as to subcategory
B and D facilities.
B. EFFLUENT VARIABILITY ANALYSIS
1. Introduction
The quantity of pollutants discharged from wastewater treatment
systems varies daily. EPA accounts for this variability in
deriving standards limiting the amount of a pollutant that may be
discharged. The statistical procedures used by EPA to analyze
the variability of conventional and toxic pollutant discharges
from the pharmaceutical industry are described below.
2. Daily Variability Factors
The daily variability factor is defined as the ratio of the
estimated 99th percentile of the distribution of daily pollutant
values to the estimated mean value of the distribution. For a
specific pollutant discharged from a facility, EPA estimated the
mean and 99th percentile from all daily effluent values which
were not deleted on the basis of being erroneous or descriptive
of aberrant performance.
In developing daily variability factors, the Agency considered
both parametric (e.g., normal, lognormal) and nonparametric
estimation procedures. In the course of examining the various
parametric approaches and the data, it became apparent that no
individual parametric distributional assumption would apply to
all plant/pollutant data sets. For that reason, the Agency
relied on a nonparametric procedure when enough daily data were
available to apply the procedure and on a 2-parameter lognormal
distribution when the amount of data was not sufficient to
utilize the nonparametric procedure. Nonparametric procedures do
169
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not require satisfying assumptions on the form of the probability
distribution of the underlying data. The specific nonparametric
procedure has been used previously by the Agency to determine
daily variability factors for other industries (e.g., BPT
pesticide industry regulations). The lognormal distribution has
also been used with effluent discharge data, because such data
are generally skewed to a few large values and are bounded in the
lower concentration range by zero. This dual approach provides a
consistent methodology which minimizes the number of statistical
assumptions required to analyze the data, while utilizing as much
plant data as possible for the treatment technologies of
interest.
The nonparametric procedure estimates the 99th pe re-entile from a
set of daily discharge measurements by determining the smallest
ordered discharge value in that set of values which is greater
than or equal to the population 99th percentile with probability
at least 0.5. That is, for a specified value of n, determine the
smallest ordered value X(j.) such that:
P[X(j) > 99th percentile]- 1 - J
. .
(.99)1 (.Ol)""1 > .5
The smallest ordered discharge value, satisfying this criterion,
was determined by nonparametric methods (see, e.g., J.D. Gibbons,
Nonparametric Statistical Inference, McGraw-Hill, 1971 (86)). An
estimate chosen in this manner is sometimes referred to as a 50
percent reliable estimate, or 50 percent tolerance level, for the
99th percentile and is interpreted as the value below which 99
percent of the values of a future sample of size n will fall with
probability 0.5. Nonparametric tolerance estimates have a lower
bound on the number of observations required to construct such an
estimate. For a nonparametric tolerance estimate of the 99th
percentile, a minimum sample size of 69 observations is needed in
order to satisfy the specified probability criterion of at least
0.5. Therefore, the nonparametric procedure was applied only for
plant/pollutant data sets with 69 or more observations. The
arithmetic average of a facility's daily effluent values was used
for the denominator of the nonparametric daily variability
factor.
170
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For plant/pollutant data sets with less than 69 daily
observations, a 2-parameter lognormal distribution was used to
estimate the 99th percentile and long-term average of the daily
variability factor. The 2-parameter lognormal distribution is
the probability distribution whose natural logarithm has a normal
distribution, and is characterized by parameters » and * relative
to its logarithmic distribution. If Y^ = In Xi7_i =1, ..,, n,
then the estimates of the parameters are fl = Y (sample mean of
the natural logarithms), and
The daily variability factor is then calculated as
A *.*
VF
A
E(X)
Where 1 - 2.326, the standard -normal 99th per cent ile and
n
21
is used to determine a minimum variance unbiased estimate of
E(X).
3. Thirty-day Average Variability Factor
A 30-day average variability factor VF30) is defined as the ratio
of the estimated 99th percentile of the distribution of 30-day
averages of daily pollutant values to the estimated long-term
mean value. A 30-day average is the arithmetic jnean of 30-daily
measurements; the sets of measurements used in determining each
monthly average are assumed to be distinct. The long-term mean
is the long-term arithmetic mean of 30-day averages and is the
same as the long-term mean estimated from the daily pollutant
values.
The 30-day average variability factors were developed on the
basis of a statistical result known as the Central Limit Theorem
(CLT). The theorem states that, under general and nonrestrictive
assumptions the distribution of a sum of a number of random
variables, say n, is approximated by the normal distribution.
The approximation improves as the number of terms in the sum
increases. The CLT is quite general in that no particular
distributional form is assumed for the distribution of the
individual values. Thus, this approach is also nonparametric.
In most applications (as in determining 30-day variability
171
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factors), the theorem is used to approximate the distribution of
the average of n observations of a random variable. The result
is important because it makes it possible to compute approximate
probability statements about the average in a wide range of
cases. For instance, it is possible to compute a value below
which a specified percentage (e.g., 95 or 99 percent) of the
averages on n observations are likely to fall. Most textbooks
state that 25 or 30 observations are sufficient for the
approximation to be valid although in many cases 10 or 15 are
adequate. In applying the CLT to the determination of 30-day
limitations, EPA approximates the distribution of the average of
30 observations drawn from the distribution of daily
measurements.
Various forms of this theorem exist and are applicable for
different situations. A key assumption in the most familiar
version of the Central Limit Theorem is that the individual
measurements are independent. That is, it is assumed that
measurements made on successive days, or any fixed number of days
apart, are statistically independent or not related. This
assumption of independence is rarely satisfied in an absolute
sense in effluent data. In many cases, however, the assumption
is satisfied to a degree sufficient to yield a suitable result.
Because many of the facilities used to determine variability
factors were known to have substantial detention periods, such
effluent data can be expected to exhibit some evidence of
dependency in the daily data. The Central Limit Theorem can
still be used to develop 30-day average variability factors in
the case of dependent data but some of the necessary calculations
must be modified to account for the dependency and more samples
(i.e., larger n) may be required for the approximation to be
adequate. In the case of positive dependence (the usual
situation with effluent data), the modification will result in a
larger estimate of the variance of the mean of 30 observations
than would be obtained if independence is assumed. This in turn
results in a larger 30-day average variability factor than would
be obtained if independence is assumed.
The technical details of adjusting the variance for the case of
data dependency are presented below. As stated above, the
Central Limit Theorem will still hold for dependent observations
with the modification that the variance must be adjusted to
reflect the dependence among individual daily measurements. The
covariance between daily measurements is one way to express this
dependence; the most straightforward approach to effect the
necessary modification is to estimate the variance directly
including all the appropriate covariance terms. The variance
estimate is based on the following: Let Xt, X2, ..., Xn denote n
random variables each with mean n and variance *2. In the case
of the effluent data, the Xi_, i = 1, ..., n, represent n daily
measurements on a particular pollutant and are assumed to have
the same mean and variance. The covariance between Xi_ and Xj_ is
(pk)(«y)2 where k « (i - j|, i * j and pk -is the correlation
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between measurements k units apart. Correlation is another
measure of dependence and is related to covariance. Regardless
of the distribution of the Xi^ the mean and variance of the
average
are:
mean
var
and
n-1
In + 2 Y (n - k) pk]
k=l
In the case that Xi^ and Xj_ are independent, the correlation and
covariance between them are zero. Therefore, var (Xn) =
^ [n + 0] « ^ which is the well known expression for the
n* n
variance of a mean of n independent observations.
Given a set of N measurements on the variable X, denoted by X,,
X2, ..., XN, the mean and variance of the average of n dependent
observations of X, denoted by Xn, are estimated by
A
and
S* [n t 2 T (n - k)rk]
k«l
respectively, where
o A _
s2 - T (Xj > ? )2
i-1 N-1
and
rk * estimate of pk, the correlation between measurements that
are k units apart (k < n)
N-k
(Xj - u )(Xj+k - fr )/(N-k)*
? )2/(N - 1)
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In order to estimate the variance of Xn, there must be a
sufficient number of measurements to estimate the n - 1
correlations. In the case of an average of 30 observations,
there are 29 (lag) correlations that must be estimated.
Thirty-day variability factors (incorporating dependence) were
estimated for a plant/pollutant data set only if two or more
pairs were available to estimate each of the necessary 29
correlations. If sufficient data were not available to estimate
these correlations, then the Central Limit Theorem was utilized
assuming independence. Thus, the 30-day variability factor was
calculated as * £- .1/2 / where V(x30) was estimated1
VF30 » u +
£- .1/2
V(Xjiy)
as described above, with 2 -
percentile.
2.326, the standard normal 99th
*See Wilks, S.S., Mathematical Statistics, Wiley & Sons, 1963, p.
552
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SECTION IX
EFFLUENT REDUCTION ATTAINABLE THROUGH THE APPLICATION
OF THE BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
A.
GENERAL
The best practicable control technology currently available (BPT)
generally is based upon the average of the best existing
performance, in terms of treated effluent discharged, by plants
of various sizes, ages, and unit processes within an industry or
subcategory. Where existing performance is uniformly inadequate,
BPT may be transferred from a different subcategory or category.
Limitations based on transfer of technology must be supported by
a conclusion that the technology is, indeed, transferable and a
reasonable prediction that it will be capable of achieving the
prescribed effluent limits (see Tanners' Council of America v.
Train, 540 F.2d 1188 (4th Cir. 1976)). BPT focuses on
end-of-pipe treatment technology rather than process changes or
internal controls except where such changes or controls are
common industry practice.
BPT considers the total cost of the application of technology in
relation to the effluent reduction benefits to be achieved from
the technologies. The cost/benefit inquiry for BPT is a limited
balancing, which does not require the Agency to quantify benefits
in monetary terms (see, e.g., American Iron and Steel Institute
v. EPA, 526 F.2d 1027 (3rd Cir. 1975)). In balancing costs in
relation to effluent reduction benefits, EPA considers the volume
and nature of existing discharges, the volume and nature of
discharges after application of BPT, the general environmental
effects of the pollutants, and the costs and economic impacts of
the required pollution control level. The Act does not require
or permit consideration of water quality problems attributable to
particular point sources or industries, or water quality
improvements in particular water bodies (see Weyerhaeuser Company
v. Costle, 5907 F.2d 1101 (D.C. Cir. 1978)).
B. REGULATED POLLUTANTS
1. Prior Regulations
EPA promulgated interim final BPT regulations for the
pharmaceutical manufacturing point source category on
November 17, 1976 (41 FR 50676; 40 CFR Part 439, Subparts A-E).
Pollutants regulated included BOD5_, COD, and pH for all
subcategories and TSS for subcategories B, D, and E.
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2. Current Regulations
In addition to the pollutants regulated under the previous
rulemaking, regulated pollutants now include TSS for
subcategories A and C and cyanide for subcategories A, B, C and
D. EPA is also modifying TSS limitations in subcategories B, D,
and E by establishing alternative minimum effluent BOD5_ and COD
concentrations in subcategories B, D and E.
C. IDENTIFICATION OF THE BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE
The best practicable control technology currently available for
the control of BOD5_, COD, pH and TSS for the pharmaceutical
manufacturing point source category in BPT regulations issued in
1976 (41 FR 50676) is biological treatment. Biological treatment
is also the technology basis for TSS limitations being
promulgated for subcategories A and C.
Best practicable control technology for the control of cyanide is
cyanide destruction and biological treatment.
D.
BPT EFFLUENT LIMITATIONS
Final BPT TSS limitations which apply to all subcategories and
BPT cyanide limitations which apply to subcategories A, B, C and
are summarized below:
Parameter
TSS (mg/1)
Total Cyanide (mg/1)
Alternate A
Alternate B
Maximum Daily
30-Day Average Maximum
1.7 times BPT
BOD5_ Concentration
Limitation
9.4 33.5
9.4(.35)R 33.5(.18)R
Alternate A: Measure at effluent from cyanide destruction unit.
Applies only when all cyanide-bearing wastes are diverted to
a cyanide destruction unit and subsequently are discharged
to a biological treatment system.
Alternate B: Measure at final effluent discharge point.
"R" equals the dilution ratio of the cyanide contaminated
streams to the total process wastewater discharge flow.
waste
The existing BPT limitations for BOD5, COD and pH remain
unchanged. However, alternative 30-day average maximum
concentrations were established for BOD5_ and COD for three
subcategories (B, D and E). The alternative limitations were
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considered appropriate following a technical analysis of the
latest available data. A plant shall not be required to attain a
maximum 30-day average effluent limitation of less than the
Equivalent of 45 mg/1 for BOD5_ and 220 mg/1 for COD.
E. RATIONALE FOR THE SELECTION OF THE TECHNOLOGY BASIS OF BPT
Biological treatment was selected as the technology basis for BPT
regulations issued in 1976 (41 FR 50676). TSS regulations
established in the current rulemaking merely reflect discharge
levels associated with biological treatment required to achieve
BOD5_ limitations and, therefore, require no new technology.
Cyanide destruction was selected as the technology basis for
cyanide limitations as it is a technology currently in use in the
pharmaceutical industry as well as other industries. Its use
results in significant reductions in cyanide levels in
pharmaceutical industry effluents.
F. METHODOLOGY USED FOR THE DEVELOPMENT OF BPT EFFLUENT
LIMITATIONS
1. TSS Limitation
In November of 1982, the Agency proposed a BPT TSS limitation for
all subcategories of plants based on a long-term average
concentration of 75 mg/1. This limitation was intended to
replace the overly stringent BPT TSS limitations for subcategory
B, D, and E plants and to establish BPT TSS limitations for A and
C subcategory plants. The original BPT TSS limitations for
subcategories B, D and E were based on data from two plants whose
operations were not characteristic of the entire range of
operations employed at plants in the B, D, and E subcategories.
The Agency received comments on the proposed regulation stating
that a single number concentration limit for TSS is not
appropriate for the pharmaceutical industry.
The existing BPT regulations, which are based on the application
of biological treatment, require that each pharmaceutical plant,
regardless of subcategory, achieve a 90 percent reduction in
BOD5_. A single number concentration limit for TSS is not
consistent with the existing BPT percent reduction BOD5_
limitations, which when converted to long-term average BOD5_
effluent concentrations, vary from plant to plant over a wide
range (e.g., from about 15 mg/1 to almost 400 mg/1). A single
number TSS limitation would require some plants to install more
advanced treatment than that technology identified as BPT. It
would also mean that low raw waste load plants would be able to
operate their treatment systems inefficiently and still comply
with the proposed single number limitation. After analyzing all
available data, the Agency found that effluent TSS concentrations
from biological treatment systems usually are greater than
corresponding effluent BOD5_ concentrations. EPA found that the
3.77
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median ratio of effluent TSS concentrations to effluent BOD5_
concentrations after biological treatment is 1.7 for both the
subcategory A and C and the subcategory B and D plant groups.
Consequently, the Agency is finalizing BPT TSS limitations for
all five subcategories which are equal to a multiple of 1.7 times
the existing BPT BOD£ limitations. Supporting data and
calculation of the BOD5/TSS ratio is presented in Section VIII.
2. Cyanide Limitations
EPA estimates that about 7 to 10 percent of all pharmaceutical
plants use and generate waterborne cyanide waste on a regular or
intermittent basis. Cyanide destruction units are in-place in
several plants. EPA requested that the pharmaceutical industry
provide long-term data describing the performance of these units.
Three plants provided data on the performance of cyanide control
technology.
These new data measured both the performance of in-plant cyanide
destruction systems directly and in combination with biological
treatment. EPA is finalizing BPT and BAT effluent limitations
guidelines, NSPS, PSES, and PSNS for cyanide based on data from
these plants. The regulations include provisions for monitoring
either in-plant after cyanide destruction or end-of-pipe. The
data and calculation of cyanide limits are presented in detail in
Section VIII.
3. Alternative BPT,
Limitations
BODS and COD
Concentration-Based
The Agency is also promulgating alternative concentration-based
BOD5. and COD BPT limitations for all subcategories. Revisions to
BPT were originally proposed in November 1982 because without the
proposed modification in BPT BODS^ and COD limitations, some
plants would have had concentration-based BCT and BAT limitations
that were less stringent than the percent reduction-based BPT
limitations. This condition would have been inconsistent with
the requirements of the Clean Water Act. No comments were
received on these alternative limitations.
Although EPA is not yet promulgating final BCT limitations for
BOD5_ or BAT limitations for COD, a review of the available
influent and effluent BOD5. and COD data indicate that the
alternative BODI5 and COD limitations are appropriate in any case
for subcategories B, D, and E. These alternative limitations
establish minimum concentration levels consistent with EPA's
assessment of a realistic estimate of the lowest attainable
long-term average BOD5_ and COD concentrations representative of
the capability of the best practicable control technology
currently available in treating pharmaceutical industry
wastewaters. In the low raw waste load B, D, and E
subcategories, percent removal limitations would, in some
instances, be below that capability. Such alternative
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limitations are not necessary for subcategory A or C plants
because available data indicate that raw waste loads are
sufficiently high at chemical synthesis and fermentation plants
that percent removal limitations will not be as low as the
alternative limitations established for subcategories B, D, and
E. The calculation of alternate concentration-based limits is
presented in Section VIII along with a discussion of the
rationale for adopting them.
G. COST OF APPLICATION AND EFFLUENT REDUCTION BENEFITS
BPT regulations for cyanide and TSS are expected to require
expenditures at eight plants (cyanide destruction at four plants,
TSS control at five plants, with one of these plants requiring
both). Total investment and annual costs are estimated to be
$1.05 million and $0.41 million, respectively (1982 dollars).
EPA estimates that these regulations will result in the removal
of 127,000 pounds per year of cyanide from the effluent of
pharmaceutical plants.
H. NONWATER QUALITY ENVIRONMENTAL IMPACTS
Sections 304(b) and 306 of the Act require EPA to consider the
non-water quality environmental impacts (including energy
requirements) of certain regulations. In conformance with these
provisions,
pollution,
summarized below.
EPA considered the effect of these regulations on air
solid waste generation, and energy consumption as
1 .
Solid Waste
EPA estimates that the total solid waste generated to attain the
new BPT TSS limitations will be approximately 138,000 additional
pounds per year of wastewater treatment sludge. This is equal to
an incremental increase of about 0.3 percent over that currently
generated by the pharmaceutical industry to meet existing BPT
BOD5_ limitations. The solid wastes generated through wastewater
treatment at pharmaceutical plants have not been listed as
hazardous in regulations promulgated by the Agency under Subtitle
C of the Resource Conservation and Recovery Act (RCRA) (see 45 FR
33066; May 19, 1980). Accordingly, it does not appear likely
that the wastewater sludges generated by pharmaceutical plants
under the new BPT TSS limitations will be subject to the
comprehensive RCRA program establishing requirements for persons
handling, transporting, treating, storing, and disposing of
hazardous wastes. The Agency's estimates of the costs of this
regulation include the cost of handling these sludges as a
non-hazardous waste.
No sludge will be generated as a result of complying with BPT
effluent limitations for cyanide.
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2.
Air Pollution
EPA does not believe that cyanide removal will cause the
generation of air pollutants; additionally, the Agency does not
anticipate that compliance with the modified and new BPT TSS
limitations will result in the generation of additional air
pollution from pharmaceutical plants.
3. Energy Requirements
EPA estimates that the achievement of the cyanide and the new and
modified TSS BPT effluent limitations will increase energy
consumption by approximately 0.01 percent of present facility use
for all plants.
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SECTION X
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
CURRENTLY AVAILABLE
A.
GENERAL
The 1977 Amendments added Section 301(b)(2)(E) to the Act
establishing "best conventional pollutant control technology"
(BCT) for discharges of conventional pollutants from existing
industrial point sources. Conventional pollutants are those
defined in Section 304(a)(4) [biological oxygen demanding
pollutants (BOD5J, total suspended solids (TSS), fecal coliform,
and pH], and any additional pollutants defined by the
Administrator as "conventional" [oil and grease, 44 FR 44501,
July 30, 1979].
BCT is not an additional limitation but replaces BAT for the
control of conventional pollutants. In addition to other factors
specified in Section 304(b)(4)(B), the Act requires that BCT
limitations be assessed in light of a two part
"cost-reasonableness" test (see American Paper Institute v. EPA,
660 F.2d 954 (4th Cir. 1981)). The first test compares the cost
for private industry to reduce its conventional pollutants with
the costs to publicly owned treatment works for similar levels of
.reduction in their discharge of these pollutants. The second
test examines the cost-effectiveness of additional industrial
treatment beyond BPT. EPA must find that limitations are
"reasonable" under both tests before establishing them as BCT.
In no case may BCT be less stringent than BPT.
EPA published its methodology for carrying out the BCT analysis
on August 29, 1979 (44 FR 50732). EPA was later ordered by the
Court of Appeals for the Fourth Circuit to correct data and
methodological errors in its BCT cost test and to develop a new
BCT methodology (see American Paper Institute v. EPA, 660 F.2d
954 (4th Cir. 1981)). A revised BCT methodology was proposed on
October 29, 1982 (see 47 FR 49176). A final BCT methodology has
not been promulgated.
Modified BPT, and BAT limitations, NSPS, PSES, and PSNS were
proposed for the pharmaceutical industry on November 26, 1982.
At that time, BCT effluent limitations were also proposed based
on the proposed BCT methodology contained in 47 FR 49176.
As the final BCT methodology has not yet been
document does not address BCT limitations.
promulgated, this
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SECTION XI
EFFLUENT REDUCTION ATTAINABLE THROUGH THE APPLICATION OF THE
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATIONS GUIDELINES
A. GENERAL
As a result of the Clean Water Act of 1977, the achievement of
BAT has become the principal national means of controlling
wastewater discharges of toxic pollutants. The factors
considered in establishing the best available technology
economically achievable (BAT) level of control include the costs
of applying the control technology, the age of process equipment
and facilities, the process employed, process changes, the
engineering aspects of applying various types of control
techniques, and non-water quality environmental considerations
such as energy consumption, solid waste generation, and air
pollution (Section 304(b)(2)(B)). In general, the BAT technology
level represents, at a minimum, the best economically achievable
performance of plants of shared characteristics. Where existing
performance is uniformly inadequate, BAT technology may be
transferred from a different subcategory or industrial category.
BAT may include process changes or internal controls, even when
not common industry practice.
The statutory assessment of BAT "considers" costs, but does not
require a balancing of costs against effluent reduction benefits
(see Weyerhaeuser v. Costle, 11 ERC 2149 (D.C. Cir. 1978)).
However, in assessing BAT, EPA has given substantial weight to
the reasonableness of costs. The Agency has considered the
volume and the nature of discharges, the volume and nature of
discharges expected after application of BAT, the general
environmental effects of the pollutants, and the costs and
economic impacts of the required pollution control levels.
Despite this expanded consideration of costs, the primary
determinant of BAT is effluent reduction capability using
economically achievable technology.
The Agency has decided to regulate the toxic pollutant cyanide
under BAT. Regulations for cyanide have been made equal to BPT.
The available data on cyanide control was evaluated in terms of
the cyanide generating processes and the performance of available
treatment technology employed by direct discharging
pharmaceutical plants. EPA was unable to identify levels of
cyanide control that are more stringent than that which will
occur after application of cyanide destruction technology in
combination with biological treatment. The identification of the
technology basis for cyanide control, rationale for its selection
and effluent reduction benefits are presented in more detail in
Section IX.
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The Agency at this time is not promulgating BAT limitations for
the nonconventional pollutant COD. Additional information on the
identity of the pollutants that contribute to COD and on
applicable COD removal technologies is required before EPA can
evaluate COD control options. Therefore, the Agency is
postponing a final decision on appropriate BAT limitations for
the nonconventional pollutant COD until a later date. The Agency
is continuing its investigation of appropriate COD removal
technologies and their costs.
B. BAT EFFLUENT LIMITATIONS
Final BAT limitations which apply to subcategories A, B, C and D
are summarized below:
Parameter
Total Cyanide
Alternate A
Alternate B
COD
Maximum Daily
30-Day Average Maximum
9.4 33.5
9.4(.35)R 33.5(
(Reserved)
18)R
Alternate A: Measure at effluent from cyanide destruction unit.
Applies only when all cyanide-bearing wastes are diverted to
a cyanide destruction unit and subsequently are discharged.
to a biological treatment system.
Alternate B: Measure at final effluent discharge point.
"R11 equals the dilution ratio of the cyanide contaminated waste
streams to the total process wastewater discharge flow.
BAT COD limitations are being reserved for promulgation at a
later date. Additional information on the identity of pollutants
that contribute to COD and applicable COD removal technologies is
required before EPA can fully evaluate COD control options.
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SECTION XII
NEW SOURCE PERFORMANCE STANDARDS
A.
GENERAL
New source performance standards (NSPS) are established under
Section 306 of the Act and are based on the best available
demonstrated technology. New plants have the opportunity to
design the best and most efficient manufacturing and wastewater
treatment technologies. Therefore, Congress directed EPA to
consider the best demonstrated process changes, in-plant
controls, and end-of-process treatment technologies that reduce
pollution to the maximum extent feasible. As a result,
limitations for NSPS should represent the most stringent
numerical values attainable through the application of
demonstrated control technology for all pollutants (conventional,
nonconventional, and toxic).
The only pollutants regulated under NSPS at this time are the
toxic pollutant cyanide and the conventional pollutant pH. NSPS
for the conventional pollutants BOD5 and TSS are being proposed
in a separate rulemaking. Regulations for the control of the
nonconventional pollutant COD are being deferred at this time.
NSPS for cyanide are being promulgated equal to BPT and BAT
effluent limitations. There are no data available that indicate
that further levels of cyanide control can be achieved by new
sources. The technology basis, the rationale for its selection
and the methodology for development of limitations are discussed
in Sections VIII and IX of this document. NSPS requirements for
pH are established equal to those for. BPT and, therefore, will
have no resulting cost or impacts'. A discussion of pH can be
found in the Development Document for Interim Final Effluent
Limitations Guidelines and Proposed New Source Performance
Standards for the Pharmaceutical Manufacturing Point Source
Category (U.S. EPA, December 1976).
B.
NSPS
Final NSPS which apply to subcategories A, B, C and D are
summarized below:
Parameter
Total Cyanide
Alternate A
Alternate B
Maximum
30-Day Average
9.4
9.4(.35)R
Daily
Maximum
33.5
33. 5(
18)R
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Alternate A: Measure at effluent from cyanide destruction unit.
Applies only when all cyanide-bearing wastes are diverted to
a cyanide destruction unit and subsequently are discharged
to a biological treatment system.
Alternate B: Measure at final effluent discharge point.
"R" equals the dilution ratio of the cyanide contaminated waste
streams to the total process wastewater discharge flow.
NSPS COD limitations are being reserved for promulgation at a
later date. Additional information on the identity of pollutants
that contribute to COD and applicable COD removal technologies is
required before EPA can fully evaluate COD control options.
NSPS BOD5, and TSS limitations are being proposed concurrently
with promulgation of these final regulations. A detailed
discussion of the proposed limitations is contained in Proposed
Development Document for Effluent Limitations Guidelines and
Standards for the Pharmaceutical Manufacturing Point Source
Category (U.S. EPA, September 1983).
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A.
SECTION XIII
PRETREATMENT STANDARDS FOR NEW AND EXISTING SOURCES
GENERAL
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES) that must be achieved
within three years of promulgation. PSES are designed to control
the discharge of pollutants that pass through, interfere with, or
are otherwise incompatible with the operation of POTWs. The
Clean Water Act of 1977 requires pretreatment for toxic
pollutants that pass through the POTW in amounts that would
violate direct discharger effluent limitations or interfere with
the POTW's treatment process or chosen sludge disposal method.
The legislative history of the 1977 Act indicates that
pretreatment standards are to be technology-based, analogous to
the best available technology for removal of toxic pollutants.
EPA has generally determined that there is pass through of
pollutants if the percent of pollutants removed by a well-
operated POTW achieving secondary treatment is less than the
percent removed by the BAT model treatment system. The general
pretreatment regulations, which served as the framework for the
categorical pretreatment regulations for the Pharmaceuticals
industry can be found at 40 CFR Part 403 (43 FR 27736, June 26
1978; 46 FR 9462, January 28, 1981).
Section 307(c) of the Clean Water Act of 1977 requires EPA to
promulgate pretreatment standards for new sources (PSNS) at the
same time that it promulgates NSPS. New indirect dischargers,
like new direct dischargers, have the opportunity to incorporate
the best available demonstrated technologies including process
changes, in-plant control measures, and end-of-pipe treatment and
to use plant site selection to ensure adequate treatment system
installation. Pretreatment standards for new sources (PSNS),
like PSES are to control the discharge of pollutants that pass
through, interfere with, or are otherwise incompatible with the
operation of POTWs. The Agency considers the same factors in
promulgating PSNS as it considers in promulgating PSES.
The only pollutant regulated under PSNS and PSES is the toxic
pollutant cyanide. PSES and PSNS are presented below. The
technology basis for pretreatment standards as for BPT is cyanide
destruction. The rationale for the selection of that technology
and the methodology for the development of effluent limitations
is discussed in Sections VIII and IX.
At proposal, the Agency stated it . was considering establishing
pretreatment standards to control TVO discharges because
available data indicated that pass through of TVOs occurs at
POTWs. A standard of 1.2 mg/1 for total toxic volatile organics
was suggested in the preamble to the proposed rules, pending the
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availability of adequate supporting data on the performance of
steam stripping technology.
One POTW and one State Agency commented that pretreatment
standards controlling TVOs should be promulgated. Industry
commenters questioned the need for TVO pretreatment standards in
view of the low concentrations of toxic volatile organics in POTW
effluents. They also questioned the achievability of a 1.2 mg/1
discharge level with steam stripping technology.
In the proposed regulation, 17 TVOs were listed as possible
candidates for regulation by pretreatment standards. After
reexamining all of the available data, EPA concluded that, with
the exception of methylene chloride and chloroform, these
pollutants should be excluded from regulation by the provisions
of paragraph 8 of the Settlement Agreement. Thirteen of these
pollutants have been excluded because their amount and toxicity,
taken together, are so insignificant as not to justify developing
uniformly applicable pretreatment regulations (see Section VI).
Of the remaining four, there are two (benzene and toluene) which,
while not as insignificant, nonetheless are unlikely to pass
through POTWs.
To address the issue of pass through, EPA studied 50 well-
operated POTWs that use biological treatment to determine the
extent to which priority pollutants are reduced by such POTWs.
In the case of benzene and toluene, the data indicate that direct
discharger median percent reductions exceed POTW median percent
reductions by less than 5 percent (100 percent for direct
dischargers versus 99 percent for benzene and 97 percent for
toluene at POTWs). In light of the fact that EPA had less data
in the POTW studies on benzene and toluene than it had for some
other pollutants and in light of the variability in analyzing
samples for organic priority pollutants at the concentrations
typically found in end-of-pipe biological systems at POTWs and
pharmaceutical plants, EPA believes that differences of 5 percent
or less between the direct discharger and POTW data for benzene
and toluene are unlikely to reflect real differences in treatment
efficiency. Therefore, EPA has determined that benzene and
toluene do not pass through POTWs.
However, a potential interference problem could exist for these
two toxic volatile organics because of a potential fire/explosion
hazard. Benzene and toluene water mixtures have low flash
points. Relatively small concentrations of these solvents in
water mixtures (about 180 mg/1) can cause spontaneous combustion
in the vapor space above the water mixture under certain
conditions. The Agency's latest information indicates that
fire/explosions, while' not impossible, are unlikely. Benzene and
toluene levels above the minimum concentrations required to cause
combustion have not been reported in discharges from plants in
the pharmaceutical industry. Because pass through does not occur
and interference is unlikely, there is no basis for establishing
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nationally applicable categorical pretreatment standards for
benzene or toluene. However, under the general pretreatment
regulation, 40 CFR 8403.5, an individual POTW may establish
pretreatment standards if benzene and toluene discharges from
pharmaceutical users result in interference. Section VIII of the
Development Document contains suggested pretreatment standards
for benzene and toluene, based on steam stripping, for
consideration by POTWs establishing standards under 8403.5.
At direct discharging pharmaceutical manufacturing plants,
chloroform is reduced to levels that are below its treatability
through volatilization in biological treatment systems.
Therefore, EPA excluded chloroform from BAT regulations under the
provisions of paragraph 8(a)(iii) of the Settlement Agreement.
As for indirect dischargers, the Agency found that POTWs to which
high concentrations of chloroform are discharged achieve high
chloroform removal (greater than 95 percent). Therefore, POTWs
receiving high concentrations of chloroform as a result of
pharmaceutical discharges are unlikely to experience pass
through. For the above reasons, EPA decided not to establish
pretreatment standards controlling chloroform from indirect
discharging pharmaceutical plants. Suggested chloroform
standards may be found in Section VIII and may be used by
municipalities in developing pretreatment standards on a
case-by-case basis where necessary.
EPA also considered the effect that other toxic pollutants, which
were found in significant concentrations in the wastewater of
pharmaceutical plants, would have on the operation of POTWs. One
group of pollutants, phenol and the various phenol type
pollutants, is adequately biodegraded by the biological treatment
systems of direct dischargers and the evidence available from the
40-plant POTW study (117) indicates that the concentrations of
these pollutants as discharged by pharmaceutical plants can be
adequately reduced by the secondary treatment works of POTWs.
The concentrations of toxic metals discharged by indirect
discharging pharmaceutical plants are low enough that no pass-
through or interference problems result from this discharge at
POTWs. Therefore, no pretreatment standards are required to
control the discharge of toxic metals, phenol and phenol related
pollutants from pharmaceutical plants.
Through this process, the Agency determined that only methylene
chloride was a candidate for national PSES and PSNS regulations.
The Agency found that the installation and operation of steam
strippers to reduce methylene chloride discharges to POTWs by
pharmaceutical plants would result in costs that are not
insignificant. The Agency estimates that 25 indirect discharging
plants would incur capital and total annual costs of $0.748
million and $0.768 million (1982 dollars), respectively, per
plant. EPA projects that one indirect discharging pharmaceutical
plant would close if required to install steam stripping
technology. Steam strippers are also equally -energy intensive at
189
-------
indirect discharging plants as at direct dischargers. The Agency
estimates that the operation of steam strippers at the 25 plants
would increase energy usage by the equivalent of 315,000 barrels
of oil per year. For these reasons and because EPA concluded
that regulation of methylene chloride at direct dischargers is
inappropriate, the Agency decided not to establish categorical
PSES and PSNS for methylene chloride.
Data on the capabilities of steam stripping technology to reduce
the discharge of methylene chloride and on the cost of installing
and operating steam strippers to control toxic volatile organics
is presented in Section VII and Appendix A of this document.
This information may be used by municipalities in developing
pretreatment standards for methylene chloride on a case-by-case
basis where necessary.
B.
PSES and PSNS
Final PSES and PSNS which apply to subcategories A, B,
are summarized below:
C and D
Parameter
Total cyanide
Alternate A
Alternate B
PSES and PSNS
30-Day Maximum
Average
9.4
9.4R
Daily
Maximum
33.5
33. 5R
Alternate A: Measured at effluent from cyanide destruction unit
before dilution with other streams. Applicable only if all
cyanide-containing wastes streams are diverted to the
cyanide destruction unit.
Alternate B: Measured at final effluent discharge point.
"R" equals the dilution ratio of the cyanide contaminated waste
stream to the total process wastewater flow.
C. COST OF APPLICATION AND EFFLUENT REDUCTION BENEFITS
Only one out of the 277 indirect discharging plants is expected
to incur costs; the estimated capital and annual costs are $0.42
million and $0.26 million, respectively (1982 dollars). PSES for
cyanide will result in the removal of 148,000 pounds of cyanide
per year from the nation's waters.
Regulations for indirect discharging new sources (PSNS) are the
same as those for existing sources. Therefore, no incremental
impacts are expected from implementation of PSNS. Since PSNS is
190
-------
equal to PSES,
removal.
it will result in no additional incremental
D. NONWATER QUALITY ENVIRONMENTAL IMPACTS
Cyanide PSES and PSNS limitations will result in no additional
solid waste generation or discharge of air pollutants. EPA
estimates that compliance with PSES to control cyanide discharges
to POTWs will increase overall energy use by 0.07 percent at the
affected indirect discharging pharmaceutical plant. Because PSNS
are identical to PSES, there will be no incremental energy usage
resulting from compliance with PSNS.
191
-------
-------
SECTION XIV
REFERENCES
1 .
2.
3.
4.
5.
6.
7.
8.
9.
10.
1 1 .
12.
13.
14.
Anderson, Dewey R., et al_. , "Pharmaceutical Wastewater:
Characteristics and Treatment," Industrial Wastes, March/
April 1971, pp. 2-6.
APHA Project Staff, Factbook '76, Prescription Drug
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APHA Project Staff, Handbook of_ Nonprescroption Drugs,
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Breaz, Emil, "Drug Firm Cuts Sludge Handling Costs," Water
and Wastes Engineering, January 1972, pp. 22-23.
Burns and Roe submittal to the U.S. EPA, "Burns and Roe
Review of TRC Data Base," May 8,1978, revised June 7, 1978 .
Burns and Roe submittal to
Profile," February 15, 1978.
the U.S. EPA, "Preliminary
Burns and Roe submittal to the U.S. EPA, "Profile Report No.
2, 308 Portfolio, Subcategory A Report," June 2, 1978.
Burns and Roe submittal to the U.S. EPA, "Profile Report No.
3, Industry Population," June 22, 1978.
Burns and Roe submittal to the U.S. EPA, "Profile Report No.
4, Fate of Industry Wastewater," August 18,1978.
Burns and Roe submittal to the U.S. EPA, "Profile Report No.
5, Treatment Technology," September 8, 1978.
Burns and Roe submittal to the U.S. EPA, "Profile Report No.
6A, Production Data by Plant Site," August 30, 1978.
Burns and Roe submittal to the U.S. EPA, "Summary Report No.
1, Pharmaceutical Manufacturing Data Base Acquisition,"
February 14, 1978.
Burns and Roe submittal to the U.S. EPA, "Summary Report No.
1A, 308 ' Portfolio Development, Pharmaceutical Manu-
facturing," May, 1978.
Burns and Roe submittal to the U.S. EPA, "Summary Report
No.2, 308 Portfolio Computerization, Phase I, Pharmaceutical
Manufacturing," February 24, 1978.
393.
-------
15. Burns and Roe submittal to the U.S. EPA, "Summary Report No.
3, Industrial Subcategorization, Review of Alternatives,"
February 14, 1978.
16. Burns and Roe submittal to the U.S. EPA, "Summary Report No.
4, Pharmaceutical Manufacturing Point Source Category
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17. Burns and Roe submittal to the U.S. EPA, "Summary Report No.
5, 308 Portfolio Computerization, Phase II, Pharmaceutical
Manufacturing," April 21, 1978.
18. Burns and Roe submittal to the U.S. EPA, "Screening Plants
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19. Burns and Roe submittal to the U.S. EPA, "308 Treatment
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1978.
20. Burns and Roe submittal to the U.S. EPA, "Profile Report No.
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21. Crame, Leonard W., "Activated Sludge Enhancement: A Viable
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24. Echelberger, Wayne F., Jr., "Treatability Investigations for
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28.
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pp. 5697.
Monday, January 31, 1977
194
-------
29.
30.
31 .
32.
33.
34.
35.
Federal Register, Vol. 42, No. 24 -
1977, pp. 6813-6814.
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1977, pp. 39182-39193.
Friday, February 4,
Tuesday, August 2,
36.
37.
38.
40.
41 .
42.
43.
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of Priority Pollutants in the Extractive Manufacture of
Pharmaceuticals," October 1978.
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of Priority Pollutant Materials in the Fermentation
Manufacture of Pharmaceuticals," no date.
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Pharmaceuticals," March 1979.
195
-------
44. Shumaker, Thomas P., "Carbon Treatment of Complex Organic
Wastewaters," presented at Manufacturing Chemists Associ-
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45. Stracke, R.J., and Bauman, E.R., "Biological Treatment of a
Toxic Industrial Waste - Performance of an Activated Sludge
and Trickling Filter Plant: Salisbury Laboratories," 1976.
46. Struzeski, E.J., Jr., "Waste Treatment in the
Pharmaceuticals Industry/Part 1," Industrial Wastes,
July/August 1976, pp. 17-21. pp. 17-21.
47. Struzeski, E.J., Jr., "Waste Treatment in the
Pharmaceuticals Industry/Part 2," Industrial Wastes,
September/October 1976, pp. 40-43.
48. Stumpf, Mark R., "Pollution Control at Abbott", Industrial
Wastes, July/August 1973, pp. 20-26.
49. "Super Bugs Rescue Waste Plants," Chemical Week, November
30, 1977, p. 47 (unauthored).
50. The Directory of_ Chemical Producers - U.S.A., Medicinals,
Stanford Research Institute, Menlo Park, CA., 1977.
51. The Executive Directory of. U.S. Pharmaceutical Industry,
Third Edition, Chemical Economics Services, Princeton, NJ.
52. U.S. EPA, "Assessment of the Environmental Effect of the
Pharmaceutical Industry," Contract No. 68-03-2510, December
1978.
53. U.S. EPA, "Characterization of Wastewaters from the Ethical
Pharmaceutical Industry," Report No. 670/2-74-057, July
1974.
54. U.S. EPA, "Control Techniques for Volatile Organic Emissions
from Stationary Sources," Contract No. 68-02-2608, Task 12,
September, 1977.
55. U.S. EPA, "Development Document for Interim Final Effluent
Limitations Guidelines and Proposed New Source Performance
Standards for the Pharmaceutical Manufacturing Point Source
Category," Report No. 440/1-75/060, December 1976.
56. U.S. EPA, "Development Document for Proposed Existing Source
Pretreatment Standards for the Electroplating Point Source
Category," Report No. 440/1-78/085, February 1978.
57. U.S. EPA, Draft of "Pretreatment Standards for Ammonia,
Phenols, and Cyanides", Contract No. 68-01-3289, March 1976.
196
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58. U.S. EPA, "Pharmaceutical Industry: Hazardous Waste Gen-
eration, Treatment, and Disposal," Report No. SW-508, 1976.
59. U.S. EPA, "Preliminary Evaluation of Sources and Control of
the Wastewater Discharges of Three High Volume
Pharmaceutical Production Processes," Contract No. 68-03-
2870, November 1977.
60. U.S. EPA, "Sampling and Analysis Procedures for Screening of
Industrial Effluents for Priority Pollutants," April 1977.
61. U.S. EPA, ''Waste Treatment and Disposal Methods for the
Pharmaceutical Industry," Report No. 330/1-75-001, February
1975.
62. Willey, William J., and Vinnecombe, Anne T., Industrial
Microbiology, McGraw-Hill, 1976.
63. Windholz, Martha, The Merck Index, 9th Edition, Merck and
Co., Rahway, NJ, 1976.
64. Wu, Yeun C. and Kao, Chiao F., "Activated Sludge Treatment
of Yeast Industry Wastewater," Journal Water Pollution
Control Federation, Vol. 48, No. 11, November 1976, pp.
2609-2618.
65. DeWalle, F.B., et a_l. , "Organic Matter Removal .by Powdered
Activated Carbon Added to Activated Sludge," Journal Water
Pollution Control Federation, "April 1977.
66. Grieves, C.G., et al., "Powdered Activated Carbon
Enhancement of Activated Sludge for BATEA Refinery
Wastewater Treatment," Proceedings of the Open Forum on
Management of Petroleum Refinery Wastewater, June 6-9, 1977.
67. Grulich, G., e_t al_. , "Treatment of Organic Chemicals Plant
Wastewater with DuPont PACT Process," presented at AICHE
Meeting, February 1972.
68. Heath, H.W., Jr., "Combined Powdered Activated Carbon -
Biological ("PACT") Treatment of 40 MGD Industrial Waste,"
presented to Symposium on Industrial Waste Pollution Control
at ACS National Meeting, March 24, 1977.
69. Button, D.C., and Robertaccio, F.L., U.S. Patent 3,904,518,
September 9, 1975.
70. U.S. EPA, "Control of Volatile Organic Emissions from the
Manufacture of Synthesized Pharmaceutical Products," Report
No. 450/2-78-029, December 1978.
3.97
-------
71. U.S. EPA, "Draft Development Document Including the Data
Base for Effluent Limitations Guidelines (BATEA), New Source
Performance Standards, and Pretreatment Standards for the
Inorganic Chemicals Manufacturing Point Source Category,"
Contract No. 68-01-4492, April 1979.
72. Hwang, Seong T., and Fahrenthold, Paul, "Treatability of the
Organic Priority Pollutants by Steam Stripping," presented
at A.I.Ch.E. meeting, August 1979.
73. Burns and Roe submittal to the U.S EPA, "Executive Summary
of Effluent Limitations Guidelines for the Pharmaceutical
Industry," July 1979.
74. Burns and Roe submittal to the U.S. EPA, "Supplement to the
Draft Contractors Engineering Report for the Development of
Effluent Limitations Guidelines for the Pharmaceutical
Industry," July 1979.
75. Fox, C.R., "Removing Toxic Organics from Wastewater,"
Chemical Engineering and Process, August 1979.
76. Boznowski, J.H., and Hanks, D.L., "Low-Energy Separation
Processes," Chemical Engineering, May 7, 1979, pp. 65-71.
77. Heist, James A., "Freeze Crystallization," Chemical
Engineering, May 7, 1979, pp. 72-82.
78. Hanson, Carl, "Solvent Extraction-An Economically
Competitive Process," Chemical Engineering, May 7, 1979, pp.
83-87.
79. Region 2 S&A Chemistry Section memo to William Telliard of
Effluent Guidelines Division, "Quantitative. Organic Priority
Pollutant Analyses-Proposed Modifications to Screening
Procedures for Organics," December 12, 1978.
80. Arthur D. Little submittal to the U.S. EPA, "Economic
Analyses of Interim Final Effluent Guidelines for the
Pharmaceutical Industry," August 1976.
81. Arthur D. Little submittal to the U.S. EPA, "Preliminary
Economic Assessment,of the Pharmaceutical Industry for BATEA
Effluent Limitation Guidelines Studies," February 1978.
82. Office of Quality Review to Robert B. Schaffer of Effluent
Guidelines Division, "Treatability of "65" Chemicals Part B-
Adsorption of Organic Compounds on Activated Charcoal,"
December 8, 1977.
83. Waugh, Thomas H., "Incineration, Deep Wells Gain New
Importance," Science, Vol. 204, June 15, 1979, pp. 1188-
1190.
3.98
-------
84.
85.
86.
87.
88.
89.
90.
91 .
92.
93.
94.
95.
96.
97.
Wild, Norman H., "Calculator Program for Sour-Water-Stripper
Design," Chemical Engineering, February 12, 1979, pp. 103-
113.
M & I preliminary submittal to the U.S. EPA, "A Demonstrated
Approach for Improving Performance and Reliability of
Biological Wastewater Treatment Plants," December 1977.
Gibbobs, J. D., Nonparametric
McGraw-Hill, 1971.
Statistical Inference,
Swan, Raymond, "Pharmaceutical Industry Sludge: Drug Makers
Face Waste Management Headache," Sludge, July-August 1979,
pp. 21-25.
Robins, Winston K., "Representation of Extraction
Efficiencies," Analytical Chemistry, Vol. 51, No. 11,
September 1979, pp. I860, 1861.
Dietz, Edward A., and Singley, Kenneth F., "Determination of
Chlorinated Hydrocarbons in Water by Headspace Gas
Chromotography," Analytical Chemistry, Vol. 51, No. 11,
September 1979, pp. 1809-1 81"4 .
U.S. EPA, "Indicatory Fate Study," Report No. 600/2-79-175,
August 1979.
U.S. EPA, "Biological Treatment of High Strength
Petrochemical Wastewater," Report No. 600/2-179-172, August
1979.
U.S. EPA, "Activated Carbon Treatment of Industrial
Wastewaters: Selected Technical Papers," Report .No.
600/2-79-177, August 1979.
U.S. EPA, "Biodegradation and Treatability of Specific
Pollutants," Report No. 600/9-79-03, October 1979.
Interagency Regulatory Liasion Group, "Publications on Toxic
Substances: A Descriptive Listing," 1979.
Federal Register, Vol. 44, No. 233 - Monday, December 3,
1979, pp. 69464-69575.
Engineering-Science, Inc. submittal to the U.S. EPA,
"Effectiveness of Waste Stabilization Pond Systems for
Removal of the Priority Pollutants," December 1979.
U.S. EPA, "Seminar for Analytical Methods for Priority
Pollutants," May 1978.
3.99
-------
98. Strier, Murray P., "Pollutant Treatability: A Molecular
Engineering Approach," Vol. 14, No. 1., January 1980, pp.
28-31.
99. U.S. EPA, "Fate of Priority Pollutants in Publicly Owned
Treatment Works - Pilot Study," Report No. 440/1-79-300,
October 1979.
100. Malina, Joseph F., Jr., "Biodisc Treatment," no date.
101. Gloyna, Earnest F., and Tischler, Lial F., "Design of Waste
Stabilization Pond Systems," presented at International
Association on Water Pollution Research, Conference on
Developments on Land Methods of Waste Treatment and
Utilization, October 1978.
102. Gulp, Russell L., "GAC Water Treatment Systems," Public
Works, February 1980, pp. 83-87.
103. Lawson, C.T., and Hovious, V.C., "Realistic Performance
Criteria for Activated Carbon Treatment of Wastewaters from
the Manufacture of Organic Chemicals and Plastics," Union
Carbide Corporation, February 14, 1977.
104. U.S. EPA, "Development of Treatment and Control Technology
for Refractory Petrochemical Wastes," Report No. 600/2-79-
080, April 1979.
105. Pharmaceutical Manufacturers Association, "Administrative
Officers of the Member Firms and Associates of the PMA,"
October 1976.
106. Manufacturing Chemists Association submittal to Paul
Fahrenthold of Effluent Guidelines Division, "Comments on
the Molecular Engineering Approach to Effluent Guideline
Development," January 23, 1979.
107. Chemical Manufacturers Association submittal to the U.S. EPA
"CMA Comments on EPA's Proposed Leather Tanning and
Finishing Effluent Limitations Guidelines and Standards,"
March 27, 1980.
108. U.S. EPA, "Ambient Water Quality Criteria," Criteria and
Standards Division, unpublished draft report.
109. U.S. EPA, "Development Document for Effluent Limitations
Guidelines and New Source Performance Standards for the
Copper, Nickel, Chromium, and Zinc Segment of the
Electroplating Point Source Category," Report No. 440/1-74-
003a, March 1974.
200
-------
T10. Walk, Haydel and Associates, Inc., "Summary Report for the
Pharmaceutical BAT'/Priority Pollutant Orientation Study,"
Contract No. 68-01-6024, Work Assignment No., 3, May 20,
1980.
111. Considine, Douglas M, (ed.), Chemical and Process Technology
Encyclopedia, McGraw Hill Book Co., New York, N.Y., 1974.
112. Hawley, Gessner G., The Condensed Chemical Dictionary, 9th
edition, Van Nostrand Reinhold Co., New York, N.Y., 1977.
113. Calspan Corp., "Addendum to Development Document for
Effluent Limitations Guidelines and New Source Performance
Standards, Major Inorganic Products Segment of Inorganic
Chemicals Manufacturing Point Source Category," Contract No.
68-01-3281, 1978.
114. Coleman, R.T., J..D. Colley, R.F. Klausmeiser, D.A. Malish,
N.P. Meserole, W.C. Micheletti, and K. Schwitzgebel,
"Treatment Methods for Acidic Wastewater Containing
Potentially Toxic Metal Compounds," EPA Contract No. 68-02-
2608, U.S. Environmental Protection Agency, 1978. 220 pp.
115. Colley, J.D., C.A. Muela, M.L. Owen, N.P. Meserole, J.B.
Riggs, and J.C. Terry, "Assessment of Technology for Control
of Toxic Effluents from the Electric Utility Industry," EPA
600/7-78-090, U.S. Environmental Protection Agency, 1978.
116. Hannah, S.A., M. Jelus, and J.M. Cohen, "Removal of Uncommon
Trace Metals by Physical and Chemical Treatment Processes,"
Journal Water Pjpillrut.ion Control Federation, 49(11): 2297-
2309, 1977.
117. Larsen, H.P., J.K. Shou, and L.W. Ross, "Chemical Treatment
of Metal Bearing Mine Drainage," Journal Water Pollution
Control Federation, 45(8): 1682-1695, 1973.
118. Maruvama, T., S.A. Hannah, and J.M. Cohen, "Metal Removal by
Physical and Chemical Treatment Processes," Journal Water
Pollution Control Federation, 47(5):962-975, 1975.
119. Nilsson, R., "Removal of Metals by Chemical Treatment of
Municipal Waste Water," Water Research, 5:51-60, 1971.
120. Patterson, J.W., and R.A. Minear, "Wastewater Treatment
Technology," Illinois Institute of Technology, 1973.
121. Patterson, J.W., "Wastewater Treatment Technology," Ann
Arbor Science Publishers, Inc., Ann Arbor, Micigan, 1975.
122. Patterson, J.W., H.E. Allen, and J.J. Scala, "Carbonate
Precipitation for Heavy Metals Pollutants," Journal Water
Pollution Control Federation, 49(12):2397-2410, 1977.
201
-------
123. Schlauch, R.M., and A.C. Epstein, "Treatment of Metal
Finishing Wastes by Sulfide Precipitation," EPA-600/2-75-
049, U.S. Environmental Protection Agency, 197?,, 89 pp.
124. Scott, M.C., "Sulfex - A New Process Technology for Removal
of Heavy Metals from Waste Streams,"" The 32nd Annual Purdue
Industrial Waste Conference, Lafayette, Indiana, 1977, 17
pp.
125. Scott, M.C., "Heavy Metals Removal at Phillips Plating,"
WWEMA Industrial Pollution Conference, St. Louis, Missouri,
1978, 16 pp.
126. Sorg, T.J. O.T. Love, and G.S. Logsdon, "Manual of Treatment
Techniques for Meeting the Interim Primary Drinking Water
Regulations," EPA-600/8-77-005, U.S. Environmental
Protection Agency, 1977. 73 pp.
127. U.S. EPA, "Development Document for Proposed Effluent
Limitations Guidelines, New Source Performance Standards,
and Pretreatment Standards for the Inorganic Chemicals
Manufacturing Point Source Category," Contract No. 440/1-
80/007-6, June 1980.
128. Sabadell, J.E., "Traces of Heavy Metals in Water Removal
Processes and Monitoring," EPA-902/9-74-001. U.S.
Environmental Protection Agency, 1973.
129. U.S. EPA, "Analytical Methods for the Verification Phase of
the BAT Review," June 1977.
130. The Research Corporation of New England subrnittal to the
U.S. EPA, "Assessment of the Environmental Effect of the
Pharmaceutical Industry," December 1978.
131. Catalytic, Inc., "Computerized Wastewater Treatment Model,"
Prepared for U.S. EPA, 1980.
132. Catalytic, Inc., Submittal to Burns and Roe, "Computer Print
Out - Pharmaceutical Analysis," January 29, 1980.
133. U.S. EPA, "Fate of Priority Pollutants in Publicly Owned
Treatment Works - Interim Report," October 1980.
134. Roegner, Russell, "Statistical Analysis Supporting
Subcategorization for the Pharmaceutical Industry," U.S.
EPA, September 14, 1983.
135. "Statistical Support for Pharmaceutical Rulemaking
September 1983," SRI International, September 1983.
136. "Fate of Priority Pollutants in Publicly Owned Treatment
Works - Final Report," U.S. EPA, September, 1983.
202
-------
137, "Pretreatment Standards Evaluation for the Pharmaceutical
Manufacturing Category," EPA Contract No. 68-01-6675, B.C.
Jordan Co., August 1983.
138. Treybal,, R.E., Mass - Transfer Operations, Third Edition/
McGraw-Hill Book Company, New York, NY, 1980.
139. McCabe., W.L., and 3.C. Smith, Unit Operations of Chemical
Engineering, Third Edition, McGraw-Hill Book Company, New
York, NY, 1976.
140,
141
Peters, M.S., and K.D. Timmerhaus, Plant
Economics for Chemical Engineers,
Design and
Second Edition,
McGraw-Hill Book Company, New York, NY, 1968.
Chemical Engineers Handbook, 4th Edition, McGraw-Hill Book
Company, New York, NY, 1963.
142. U.S. Environmental Protection Agency, Proposed Development
Document for Effluent Limitations Guidelines and Standards
for
the Pesticides
Point
Source
Category,
EPA
440/1-82/D79-b, Washington, D.C., November 1982.
203
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SECTION XV
LEGEND OF ABBREVIATIONS
AA
A. C.
AE
atm
avg.
BADCT
BAT (BATEA)
bbl.
BCT
B-N
BOD5
BPT (BPCTA)
Btu
°C
C.A.
cal.
cc
cfm
cfs
cm
CN
COD
cone.
cu .m.
deg.
DO
E.Col.
Eq.
°F
Fig.
F/M
fpm
fps
ft
g
gal.
GC
GC/MS
gpd
gpm
hp
hp-hr
HPLC
atomic absorption
activated carbon
Acid extractables
atmosphere
average
Best Available Demonstrated Control
Technology
Best Available Technology Economically
Achievable
barrel
Best Conventional Control Technology
Base - Neutral Extractables
Biochemical Oxygen Demand, five day
Best Practicable Control Technology
Currently Available
British Thermal Unit
degrees Centigrade
carbon adsorption
calorie
cubic centimeter
cubic feet per minute
cubic feet per second
centimeter
cyanide
Chemical Oxygen Demand
concentration
cubic meter
degree
dissolved oxygen
Escherichia coli - coliform bacteria
equation
degrees Fahrenheit
Figure
Food to microorganisms ratio
(Ibs BOD/1bs MLSS)
feet per minute
feet per second
foot
gram
gallon
Gas chromatography
Gas chromatography/Mass
Spectroscopy
gallon per day
gallon per minute
horsepower
horsepower-hour
High Pressure Liquid Chromatography
205
-------
hr
in
kg
KW
KWh
1
1/kkg
Ib
m
M
mg
MGD
mg/1
inin
ml
MLSS
MLVSS
mm
MM
mole
mph
mu
NH3-N
N03-N
NPDES
NSPS
02
P04
P-
pH
POTW
pp.
ppb
ppm
PSES
psf
psi
PSNS
RBC
R.O.
rpm
RWL
sec.
Sec.
SIC
SOx
sg.
sq. ft.
per day
liter
hour
inch
kilogram
kilowatt
kilowatt hour
liter
liters per 1000 kilograms
pound
meter
thousand
milligram
million gallons
milligrams per
minute
milliliter
mixed liquor suspended solids
mixed liquor volatile suspended
solids
millimeter
million
gram molecular weight
mile per hour
millimicron
ammonia nitrogen
nitrate nitrogen
National Pollutant Discharge
Elimination System
New Source Performance Standards
Oxygen
phosphate
page
potential hydrogen or hydrogen-ion
index (negative logrithm of the
hydrogen-ion concentration)
Publicly Owned Treatment Works
pages
parts per billion
parts per million
Pretreatment Standards for Existing
Sources
pounds per square foot
pounds per square inch
Pretreatment Standards for New Sources
Rotating Biological Contactor
reverse osmosis
revolution per minute
raw waste load
second
Section
Standard Industrial
Oxides of Sulfur (e,
square
square foot
Classification
,g. sulfate)
206
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ss
STP
SRWL
TDS
TKN
TLM
TOC
TOD
TSS
VOA
vol
wt
yd
u
ug
ug/1
suspended solids
standard temperature and pressure
standard raw waste load
total dissolved solids
total Kjedahl nitrogen
median tolerance limit
total organic carbon
total oxygen demand
total suspended solids
Volatile Organic Analysis
volume
weight
yard
micron
microgram
microgram per liter
note: symbols for chemical elements and compounds are in accordance
with IUPAC and standard chemical nomenclature.
207
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-------
SECTION XVI
ACKNOWLEDGMENTS
The U.S. Environmental Protection Agency wishes to acknowledge
the contributions to this project by Environmental Science and
Engineering, Inc.,- of Gainesville, Florida. The key contributors
were John Crane, Bevin Beaudet, Susan Albrecht, Russell Bowen,
Leonard Carter, and Margaret Parrel1. We also wish to thank the
following personnel of the E.C. Jordan Co., of Portland, Maine,
for their assistance: Willard Warren, Conrad Bernier, Robert
Steeves, Michael Crawford, and Neal Jannelle.
In the early stages of this project, the following members of the
Burns and Roe Industrial Services Corp. made significant
contributions to the data base development and technical
analysis: Arnold Vernick, Barry Langer, Jeffrey Arnold, Tom
Fieldsend, Thomas Gunder, Vaidyanathan Ramaiah, Mark Sadowski,
Mary Surdovel, Jeffrey Walters, and Samuel Zwickler. The
following personnel at Walk, Haydel and Associates, Inc. also
provided technical support for this regulatory effort: John
Beaver, Forrest Dryden, E. Jasper Westbrook, Richard Melton,
Ronald Rossi, Miles Seifert, Efrain Toro, Fred Zak, Paul
Schneider, and Anita Junker.
The assistance of PEDCo, of Cincinnati, Ohio, is also
acknowledged for their technical input in this project. The
efforts of the Research Corporation of New England (TRC) in
developing and maintaining an open literature data base are also
appreciated.
We wish to acknowledge the plant managers, engineers, and other
representatives of the pharmaceutical industry without whose
cooperation and assistance in site visits and information
gathering, the completion of this project would have been greatly
hindered. We also thank the environmental committees of the
Pharmaceutical Manufacturers Association for their assistance.
The assistance of all personnel at EPA Regional Offices and State
environmental departments who participated in the data gathering
efforts is greatly appreciated.
Appreciation is expressed to those at EPA Headquarters who
contributed to the completion of this project, including: Louis
DuPuis, Henry Kahn, Russ Roegner, Joseph Yance, Rob Ellis, Jean
Noroian, Susan Green, John Ataman, and Kathleen Ehrensberger,
Office of Analysis and Evaluation, Office of Water Regulations
and Standards; Alexander McBride, Rod Frederick, Richard Healy,
William Kaschak, Rich Silver, and Ruth Wilbur, Monitoring and
Data Support Division, Office of Water Regulations and Standards,
Susan Lepow and Catherine Winer, Office of General Counsel;
209
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Mahesh Podar, Office of Policy and Resource Management; and Bruce
Newton, Office of Water Enforcement.
Within the Effluent Guidelines Division, Jeffery Denit, Joseph
Vitalis, Gregory Aveni, Glenda Colvin, Kointheir Ok, Pearl. Smith,
Glenda Nesby, Carol Swann, Linda Wilbur, Marvin Rubin, James
Gallup, Devereaux Barnes, Kaye Storey, Robert Schaffer, Paul
Fahrenthold, Michael Kosakowski, Dan Lent, and Susan Delpero made
significant contributions to this project.
210
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APPENDIX A
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
A.
INTRODUCTION
Previous sections describe the respective BPT, BAT, NSPS, PSES,
and PSNS control options that were considered as the basis for
final rules. This section summarizes the cost, energy, and other
non-water quality impacts (including implementation requirements
and the generation of air pollution, noise pollution, and iolid
waste) of these various treatment options.
As explained previously, this document does not address Agency
efforts to establish BCT effluent limitations guidelines for the
pharmaceutical industry. EPA is also postponing a final decision
on appropriate BAT limitations and NSPS for COD until more data
are obtained and appropriate COD removal technologies are
identified. The reader is referred to the development document
supporting the November 1982 proposal for the latest published
information on cost, energy, and non-water quality aspects of BCT
technology options and technology options for control of COD at
direct discharging plants. Additionally, EPA decided to propose
rather than to promulgate new source performance standards for
the conventional pollutants BOD5_ and TSS. For the latest
information, on NSPS technology options for controlling
conventional pollutants, see Proposed Development Document for
New Source Performance Standards for the Pharmaceutical
Manufacturing Point Source Category (U.S. EPA, September 1983).
B.' METHODOLOGY FOR DEVELOPMENT OF COSTS -
1 .
Introduction
This section describes how estimates of the costs of
implementation of the technology options were developed. The
actual cost of implementing these treatment options can vary at
each individual facility, depending on the design and operation
of the production facilities and on local conditions. EPA
developed treatment costs that are representative of costs
anticipated to be incurred at existing and new source direct and
indirect discharging plants in the pharmaceutical industry. The
methodology for development of costs is summarized below. To
develop the cost estimates presented in this section, the Agency
relied on information contained in Section VIII of the
Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards for the
Pharmaceutical Manufacturing Pofnt Source Category (U.S. EPA7
December 1976) and Supplement A to that document (55), the
Catalytic Treatment Model, and on information contained in the
April 5, 1982, issue of Chemical Engineering. These materials
can be found in the record of the final rulemaking.
211
-------
2. Model Plant Approach
EPA estimated the costs of implementing the control and treatment
options discussed in Sections VII and VIII in order to determine
the economic impact of each technology option. EPA based its
cost estimates for cyanide and TVO control and treatment on model
plant raw waste characteristics. However, in the case of the BPT
TSS limitations, plant specific cost estimates were developed.
EPA selected model plant sizes that cover the range of the
anticipated sizes of new and existing plants in the
pharmaceutical industry. From the model plant costs, EPA
constructed cost curves that were used to predict costs that
would be incurred at each individual pharmaceutical plant in
complying with the technology options considered as the basis of
final regulations. These individual plant cost estimates were
then used to estimate the potential economic impact associated
with each technology option.
3. Cost Estimating Criteria
In order to develop cost estimates for the treatment options
under consideration, criteria were developed relating to capital,
operating, and energy costs. These criteria are presented in
Table A-l. EPA's estimates are pre-engineering estimates and are
expected to have a variability consistent with this type of
estimate, on the order of plus or minus 30 percent.
*
All costs presented are in terms of 1982 dollars. Since
construction costs escalate, these estimates may be adjusted
through the use of appropriate cost indices. The most accepted
and widely-used cost index in the engineering field is the
Engineering News Record (ENR) construction cost index. The ENR
Index for cost data presented in this document is 3,825. All
total annual costs stated herein include capital recovery costs
equal to 22 percent of the total capital costs. All total
capital costs include engineering and contingency costs along
with equipment and installation costs.
C. COSTS FOR IMPLEMENTATION OF BPT OPTIONS CONTROLLING BODS,
COD, AWTSS
As explained in Section VIII, EPA considered the option of
modifying existing BPT BOD5. and COD effluent limitations for
subcategories B, D, and E. The modified BOD5_ and COD limitations
would, in certain instances, relax the 1976 BPT limitations for
those pollutants to be consistent with EPA's assessment of the
minimum concentration levels attainable through the application
of the best practicable control technology currently available,
as defined in the 1976 rulemaking. No costs are associated with
this option because it involves the relaxation of existing
limits.
212
-------
TABLE A-l
COST ESTIMATING CRITERIA
1. Capital costs are for 1982: ENR = 3825
2. Steam stripping capital cost: 4.74 times purchased equipment cost
3. Miscellaneous Construction Costs:
4.
5.
6.
Piping:
Electrical:
Instrumentation:
Site Preparation:
20% of installed equipment cost2
14% of installed equipment cost2
8% of installed equipment cost2
6% of installed equipment cost2
Engineering and Contingencies are 30%
including installed equipment, piping,
and site preparation costs.
of total installed costs,
electrical, instrumentation,
Annual fixed costs are 22% of capital expenditures.
Operation/Maintenance Costs:
Labor:
steam stripping, $29,000/man-year
including taxes and fringe benefits^
(Eng. Tech. level V) $24,000/man-year
including taxes and fringe benefits^
(Eng. Tech. level IV)
1. Cran, John, Chemical Engineering, April 6, 1981.
2. Development Document for Interim Final Effluent Limitations Guidelines
and Proposed New Source Performance Standards for the Pharmaceutical
Manufacturing Point Source Category, U. S. EPA, Washington, D. C.,
December 1976. (TJT
3. "National Survey of Professional, Administrative, Technical, and
Clerical Pay, March 1981," U. S. Department of Labor, September 1981. (7)
4- Proposed Development Document for Effluent Limitations Guidelines and
Standards for the Pharmaceutical Point Source Category, U. S. EPA,
Washington, D.C., November 1982.. (2)
5. Vendor and Supplier Quotations to Environmental Science and Engineering,
Inc., Gainesville, Florida, 1982 and 1983. (8)
213
-------
-2-
3% of total capital costs4
$8.64/cubic yard (non-hazardous)5
$0.046/kilowatt-hour6
$5.73/1000 pounds7
Maintenance:
Sludge Disposal:
Electricity:
Steam:
Chemicals:
hydrated lime: $51/ton8
sulfuric acid (66°): $85/ton8
anhydrous ammonia: $392/ton|
phosphoric acid (80%): $618/torP
chlorine gas: $441/ton8
polymer: $2.54/lb8
6. "Electric Utility Company Monthly Statement," March 1980 - Forward:
Federal Energy Regulatory Commission., Form 5, as cited in Monthly
Energy Review, U. S. Department of Energy, Energy Information Administration,
DOE/EIA-0035 (81/12), December 1981. (9)
7. Treatability Manual, Volume IV. Cost Estimating, EPA-60018-80-042d,
U. S. Environmental Protection Agency, Office of Research and Development,
July 1980.
8. Innovative and Alternative Technology Assessment Manual, U. S. EPA,
Office of Water Program Operations, Washington, D. C., February 1980.
(10)
214
-------
EPA also considered the option: of modifying, the existing BPT
effluent TSS limitations for subcategories B, D, and E and
establishing a BPT TSS limitation for subcategories A and C. EPA
based the new and. modified BPT TSS limitations on the application
of biological treatment, which is the same technology that formed
the basis of BPT effluent limitations for subcategories A, B, C,
D, and E. Thus, in general, EPA expects that no incremental
costs will be incurred in meeting limitations based on biological
treatment. However, EPA identified five plants that comply with
the 1976 BPT BOD5. limits that would not comply with the new or
modified TSS limits that EPA believes are characteristic of
well-designed and well-operated biological treatment systems.
Therefore, EPA developed plant specific estimates of the
incremental costs that would be incurred at these five plants to
meet the new and modified TSS limits. These costs are shown in
Table A-2 and include total capital and annual costs for the
installation and operation of clarification technology, including
polymer addition for the five plants. The design criteria for
these clarifiers are identical to those specified in Supplement A
to the 1976 BPT Development Document. Total annual costs include
costs for sludge disposal, polymer addition, maintenance and
labor. Total capital costs include costs for two clarifiers to
be operated in parallel, polymer feed facilities and pumps.
D. COSTS FOR IMPLEMENTATION OF TOXIC POLLUTANT CONTROLS
Agency analyses indicate that toxic pollutant raw waste
concentrations are likely to be similar for plants in all four
subcategories where toxic pollutants are used or generated in the
manufacturing process. For this reason, EPA developed one model
treatment system for removal of cyanide and one model treatment
system for control of toxic volatile organics. These models can
be applied uniformly to plants in all subcategories.
1
Cyanide Control
The cost estimates for cyanide control were generated by the
Catalytic Treatment Model based on the design criteria specified
in Section VIII of the November 1982 Development Document. Table
A-3 presents design criteria for a cyanide destruction unit. The
cyanide removal mechanism assumed for purposes of developing cost
estimates is oxidation with hypochlorite in an alkaline
environment. The Agency assumed that the cyanide destruction
unit would be employed in-plant to treat waste streams
contaminated with cyanide prior to dilution by other
non-contaminated streams. Capital costs for the cyanide
destruction unit include costs for a two-stage concrete reaction
vessel, a pH control system, an oxidation reduction potential
control system, a chlorinator, a vaporizer, circulation pumps,
two reagent feed systems (sodium hypochlorite and caustic),
detention tanks and mixers. The annual costs include costs for
chemicals, energy, maintenance and labor.
215
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TABLE A-2
INCREMENTAL COST REQUIREMENTS FOR ACHIEVING
BPT TSS LIMITATIONS
PLANT CODE
12098
12160
12248
12462
1 2471
TOTAL
CAPITAL COSTS
$92,000
$92,000
$92,000
$102,000
$92,000
$470,000
ANNUAL COSTS*
O&M COSTS
1
$24,000
$25,000
$27,000
$37,000
$27,000
$140,000
$19,000
$19,500
$21,000
$29,000
$21 ,000
$109,500
*A11 annual costs assume 22% capital recovery,
216
-------
TABLE A-3
DESIGN CRITERIA FOR CN REMOVAL
BY ALKALINE CHLORINATION
EFFECTIVENESS: Cyanide destruction by sodium hypochlorite addition
APPLICATION LIMITATIONS: Inf. TSS <^ 50 mg/1
DESIGN BASIS: Mean Flow 26,000 gal/day subcategory C continuous operation
CONTACT TIME:
FIRST STAGE 10 minutes
SECOND STAGE 30 minutes
CHEMICAL REQUIREMENTS:
15 parts HYPOCHLORITE per part CN
17 parts NaOH* per part CN
pH 8-9.5
MAJOR EQUIPMENT:
Two stage, concrete reaction vessel with mixer
pH control system
ORP control system
Oxidation - chemical feed system
''or chemical equivalent
217
-------
Table A-4 presents estimates of the installation and operating
costs of the cyanide destruction unit in treating three different
wastewater flow rates. EPA used these three sets of cost
estimates to develop the cost curves presented in Figures A-l and
A-2. The curves were used to predict costs that would be
incurred at individual plants in meeting cyanide limitations and
standards based on the application of cyanide destruction
technology. In estimating plant-specific costs, EPA assumed that
the process stream to be treated would be 10 percent of the total
plant process wastewater flow rate. This is the same assumption
that was made in estimating total industry costs that were
presented in the development document supporting the November
1982 proposed rules. The Agency received no comments addressing
this aspect of the proposed regulation.
2. Toxic Volatile Organics Control
Table A-5 presents design criteria for a steam stripper to reduce
the discharge of toxic volatile organics. The Agency assumed
that the steam stripper would be employed in-plant to treat waste
streams contaminated with toxic, volatile organics prior to
dilution by other non-contaminated waste streams. Batch
treatment was assumed in the estimation of installation and
operating costs for the treatment of low volume TVO waste streams
(less than 57,600 GPD), while continuous systems were costed for
the treatment of high volume TVO waste streams (greater than
57,600 GPD).
performance of this
suggested limitations
presented in Section
The design criteria presented in Table A-5; were developed for a
packed column-type stripper. The Agency decided to develop costs
based on the design of a packed column steam stripper because the
type of stripper forms the basis of the
for methylene chloride and chloroform
VIII. The design characteristics of the
packed column stripper include a packing volume of 63 percent, a
19 foot tray to tray packed column and packing consisting of one
inch porcelain saddles. The design assumes a hydraulic loading
of 18.3 gpm per sq. ft. Whenever the design diameter calculated
from the flow and hydraulic loading was greater than 3.5 feet,
multiple columns were costed assuming parallel operation. The
capital costs include costs for the following equipment: the
column(s), the packing, the feed preheater (heat exchanger), the
filter, the overhead condenser, tanks and pumps. The annual
costs include costs for steam, electricity, cooling water,
maintenance and labor.
Table A-6 presents estimates of the installation and operating
costs of the steam stripper in treating nine different wastewater
flow rates. EPA used these nine sets of cost estimates to
develop the capital and annual cost curves shown in Figures A-3
and A-4, respectively. The curves were used to predict costs
that would be incurred at individual plants in 'meeting TVO
limitations and standards based on the application of steam
218
-------
TABLE A-4
CYANIDE DESTRUCTION
CAPITAL AND ANNUAL COSTS
FLOW VARIATION
1982 CAPITAL COSTS
CHEMICALS
Hypochlorite
Caustic
ENERGY
LABOR
MAINTENANCE
CAPITAL AMORTIZATION
1982 ANNUAL COSTS
13,000 gpd
$67,200
5,000
1,100
200
7,200
2,200
14,800
$30,500
26,000 gpd
$105,000
9,900
2,300
300
7,200
3,300
23,100
$46,100
52,000 gpd
$165,200
19,800
4,600
600
7,200
5,200
36,300
$73,700
219
-------
FIGURE A-l
CYANIDE DESTRUCTION
CAPITAL COSTS
' * 6 7 * ' 1°00
FLOW RATE (1000 GPD)
220
-------
FIGURE A-2
CYANIDE DESTRUCTION
Annual COSTS
10
100
a 4 5 7 » 9 TO
FLOW RATE (1000 GPD)
221
-------
TABLE A-5
DESIGN CRITERIA FOR STEAM STRIPPER
EFFECTIVENESS: Reduction of toxic volatile organics concentrations by
steam stripping
APPLICATION LIMITATIONS: Concentration of the organic volatile in the
entering wastewater feed is at or near saturation
DESIGN BASIS: 19 ft. tray to tray packed column.
1 inch porcelain saddles packing
63% packing volume
18.3 gpm/ft hydraulic loading
TSS of influent stream less than or equal to 50 mg/1
Diameter > 3.5 ft., multiple columns, costed for parallel
operation 316 stainless steel
MAJOR EQUIPMENT: Column (continuous operation, spare column costed)
packing
feed preheater
feed prefilter
overhead condenser
tanks
pumps
STEAM REQUIREMENTS: 0.156 pound steam/pound feed
222
-------
TABLE A-6
CAPITAL ITEMIZED COSTS FOR BATCH OPERATION
FLOW (GPD)
COLUMNS
PACKING
FEED PREHEATER
OVERHEAD CONDENSER
PRE FILTER
TANKS
PUMPS
TOTAL EQUIPMENT
(4.74 x Equipment)
TOTAL CAPITAL
JAN 1978 $
TOTAL CAPITAL COST
1982 $
500
15,620
2,88'6
31 ,800
4,500
1,200
11,400
2,000
69,406
328,984
470,945
1000
15,620
2,886
31 ,800
4,500
1,200
12,000
2,000
70,506
334,198
478,408
5000
15,620
2,886
31 ,800
4,500
1,200
12,500
2,000
70,506
334,198
478,408
10,000
15,620
1,511
33,500
5,200
1,200
16,500
2,100
75,631
358,491
513,184
50,000
19,454
2,336
41,900
6,000
1,200
23,200
2,300
96,390
456,900
654,058
ENR Jan 1978 = 2672
Aug 1978 = 3825
223
-------
TABLE A-6 (cont'd)
CAPITAL ITEMIZED COSTS FOR CONTINUOUS OPERATION
FLOW (MGD)
COLUMNS
PACKING
FEED PREHEATER
OVERHEAD CONDENSER
PRE FILTER
TANKS
PUMPS
TOTAL EQUIPMENT
TOTAL CAPITAL (1/78 $)
4.74 x Equipment Costs
TOTAL CAPITAL COST
1982 $
0.0576
31 ,240
1,511 *
15,600
7,100
1,200
19,000
3,100
78,751
373,280
534,355
0.288
35,571
5,046
47,700
10,800
1,200
38,700
5,100
144,117
683,115
977,887
0.576
59,285
8,410
87,500
15,900
2,400
58,200
5,700
237,395
1,125,252
1,610,812
1.152
106,713
15,074
167,100
23,900
2,400
91 ,400
7,100
413,687
1,960,876
2,807,017
ENR Jan 1978 = 2672
Aug 1978 = 3825
224
-------
TABLE A-6 (cont'd)
ANNUAL ITEMIZED COSTS FOR BATCH OPERATON
FLOW (GPD)
1978 CAPITAL COSTS
STEAM
STEAM FOR PREHEATING
COOLING WATER
ELECTRICITY
LABOR
MAINTENANCE
(3% of Capital)
CAPITAL RECOVERY
(22% Capital)
TOTAL ANNUAL
Jan. 1978 $
TOTAL ANNUAL COST
1982 $
500
328,984
609.55
341 .28
29.20
60.23
7,628.5
9,870
72,376
90,915
130,146
1,000
334,198
1,219.10
682.55
58.4
120.45
7,628.5
10,026
73,524
93,259
133,501
5,000
334,198
6,095.5
3,412.8
292
602.3
39,967.5
10,026
73,524
133,920
191,708
10,000
358,491
12,191
6,825.5
584
1,204.5
40,150
10,755
78,868
150,578
215,554
50,000
456,900
60,955
34,128
2,920
6,023
80,300
13,707
100,518
298,551
427,379
ENR: Jan. 1978 - 2672
Avg. 1982 - 3825
225
-------
TABLE A-6 (cont'd)
ANNUAL ITEMIZED COSTS FOR CONTINUOUS OPERATON
FLOW (MGD)
1978 CAPITAL COSTS
STEAM
STEAM FOR PREHEATING
COOLING WATER
ELECTRICITY
LABOR
MAINTENANCE
(Z% of Capital)
CAPITAL RECOVERY
(22% Capital )
TOTAL ANNUAL
Jan. 1978 $
TOTAL ANNUAL COST
1982 $
0.0576
373,280
70,220
39,315
3,364
6,938
88,301
11,198
82,122
301 ,458
431,541
0.288
683,115
351,101
196,574
16,819
34,690
88,301
20,493
150,285
858,263
1,228,614
0.576
1,125,252
702,202
393,150
33,638
69,379
88,301
33,758
247,555
1,567,983
2,244,586
1.152
1,960,876
1,404,403
786,298
67,277
138,758
88,301
58,826
431 ,393
2,975,256
4,259,115
ENR: Jan. 1978 - 2672
Avg. 1982 - 3825
226
-------
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228
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stripping technology. In estimating plant-specific costs, EPA
assumed that the process stream to be treated would be 26 percent
of the total plant process wastewater flow rate. This is
different from the assumption that was made in estimating total
industry costs that were presented in the development document
supporting the November 1982 proposed rules.
The Agency received comments contending that its estimates of
steam stripping costs that were presented in the proposed
development document were understated. As part of the Agency's
review of . its cost estimating procedures, EPA obtained
information on the percentage of process wastewater that is
contaminated with toxic volatile organics. The Agency determined
that 26 percent is a representative estimate of the quantity of
process wastewater flow contaminated by toxic volatile organics
when these compounds are used or generated at pharmaceutical
plants..
E. ENERGY AND NONWATER QUALITY IMPACTS
The implementation of the control and treatment options
considered as the basis of final rules are expected to have only
a small effect on current energy demand, solid waste generation,
air pollutant generation, and noise potential. .The one exception
is the substantial steam requirement for removing toxic volatile
organics from pharmaceutical wastewaters through the application
of steam stripping technology. This section addresses the
non-water quality aspects of the control and treatment options
considered by EPA in developing final BPT and BAT limitations and
NSPS, PSES, and PSNS for the pharmaceutical manufacturing point
source category.
1. Energy Requirements
a.
BPT
Incremental energy associated with the treatment options
considered as the basis of modified and new BPT limitations is
limited to power requirements for additional pumps and agitators.
The 1976 BPT regulations are based on the application of
biological treatment. The technology option considered as the
basis for new BPT TSS limits for subcategories A and C and
modified BPT TSS limits for subcategories B and D. is biological
treatment. Therefore, in general, the Agency expects no
additional energy demand to result from attainment of TSS limits
based on the application of biological treatment. However, as
discussed previously, EPA identified five pharmaceutical plants
that comply with the 1976 BPT BOD_5 limits that would not comply
with the TSS limits presented in Section IX that EPA believes are
characteristic of well-designed and well-operated biological
treatment systems. Therefore, EPA developed plant-specific
estimates of the incremental technology that would be required to
meet the new and modified TSS limits considered for subcategories
229
-------
A and C and for subcategories B and D, respectively. EPA
estimates that the incremental energy use at these five plants
will be 0.01 percent more than the current energy usage at direct
discharging pharmaceutical plants.
Table A-7 summarizes Agency estimates of total energy used at
existing direct discharging plants for the baseline case and
after the application of cyanide removal technology. Total
energy is presented in terms of equivalent barrels of No. 6 fuel;
purchased electrical energy (kwh) required is converted to heat
energy (BTU) at a conversion of 10,500 BTU/kwh, which reflects
the average efficiency of electrical power generation.
b.
BAT and NSPS
No technology options were identified to effect a further removal
of cyanide from wastewaters discharged by existing or new direct
discharging pharmaceutical plants. Therefore, there is no
incremental energy usage associated with BAT cyanide removal
technology options.
Table A-8 summarizes Agency estimates of total energy used at
existing and new direct discharging pharmaceutical plants for the
baseline case and after the application of steam stripping
technology to remove toxic volatile organics.
c.
PSES and PSNS
Table A-9 summarizes Agency estimates of total energy used at
existing indirect discharging pharmaceutical plants for the
baseline case and after the application of cyanide removal
technology. No technology options were identified to effect a
further removal of cyanide from wastewaters discharged by new
indirect discharging pharmaceutical plants. Therefore, there is
no incremental energy usage associated with PSNS technology
options.
Table A-10 summarizes Agency estimates of total energy used at
existing and new indirect discharging pharmaceutical plants for
the baseline case and after the application of steam stripping
technology to remove toxic volatile organics.
2. Solid Waste Generation
No significant incremental solid waste generation is associated
with the treatment options considered as the basis of modified
and new BPT limitations, BAT limitations, NSPS, PSES, or PSNS.
No appreciable quantities of sludge will be generated through the
application of steam stripping or cyanide removal technologies.
A small amount of solid waste will be generated at the five
plants that are now in compliance with the 1976 BPT BOD5. limits,
but do not comply with the TSS limits presented in Section IX.
The Agency estimates that the incremental solid waste generated
230
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TABLE A-7
BPT CYANIDE DESTRUCTION
ENERGY REQUIREMENTS
BASE LINE
ENERGY
(BBL oil/yr)
110,560
INCREMENTAL
ENERGY
(BBL oil/yr)
65
TOTAL
ENERGY
(BBL oil/yr)
110,625
231
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TABLE A-8
BAT STEAM STRIPPING
ENERGY REQUIREMENTS
BASE LINE
ENERGY
(BBL oil/yr)
110,560
INCREMENTAL
ENERGY
(BBL oil/yr)
94,300
TOTAL
ENERGY
(BBL oil/yr)
204,860
232
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TABLE A-9
PSES CYANIDE DESTRUCTION
ENERGY REQUIREMENTS
BASE LINE
ENERGY
(BBL oil/yr)
110,560
INCREMENTAL
ENERGY
(BBL oil/yr)
75
TOTAL
ENERGY
(BBL oil/yr)
110,635
233
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TABLE A-10
PSES STEAM STRIPPING
ENERGY REQUIREMENTS FOR METHYLENE CHLORIDE REMOVAL
BASE LINE
ENERGY
(BBL oil/yr)
110,560
INCREMENTAL
ENERGY
(BBL oil/yr)
315,000
TOTAL
ENERGY
(BBL oll/yr)
425,560
234
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at these five plants will be 42 percent more than that
currently generated at these five plants in complying with the
1976 BPT BOD5_ limitation.
3. Air Pollution and Noise Pollution
The technologies under consideration are not a significant source
of noise pollution or air pollution. EPA anticipates that
implementation of the control and treatment options under
consideration will have no direct impact on air pollution or
noise pollution. Some reduction in air pollution is expected at
facilities that are in compliance with the suggested TVO
limitations, when steam stripping technology is employed. EPA
estimates that if all pharmaceutical plants were in conformance
with the suggested TVO limits, the emissions of methylene
chloride, chloroform toluene and benzene would be reduced by
about 5000, 800, 180, and 160 pounds per day, respectively.
235
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APPENDIX B
GLOSSARY
Abatement. The measures taken to reduce or eliminate pollution.
Absorption. The penetration of one substance (the absorbent)
into the inner structure of another (the absorbate) resulting in
the formation of a homogeneous mixture having the attributes of a
solution.
Acclimation. The ability of an organism to adapt to changes in
its immediate environment.
Acid. A substance which dissolves in water with the formation of
hydronium ions.
Acidulate. To make somewhat acidic.
Act. The Clean Water Act (the Federal Water Pollution Control
Act amendments of 1972, 33 USC 1251 et seq., as amended by the
Clean Water Act of 1977, P.L. 95-217 and the Settlement Agreement
in Natural Resources Defense Council, Inc. v. Train, 8-ERC 2120
(D.D.C. 1976), modified, 12 ERC 1833 (D.D.C. 1979), modified by
Orders dated October 26, 1982, and August 2, 1983).
Activated Carbon.
Carbon which has been heated by high
temperature steam or carbon dioxide to produce an internal porous
particle structure.
Activated Sludge Process. A wastewater treatment process in
which microorganisms absorb dissolved or suspended organic
matter. The significant feature of the process is the recycle of
a biologically-active sludge formed by settling the
micro-organism population from the aeration process in a
clarifier. Waste is treated in a matter of hours instead of
days.
Active Ingredient. The chemical constituent in a medicine which
is responsible for its activity.
Adsorption. Adherence of one substance to the surface of another
substance called the "adsorbent."
Advanced Waste Treatment. Any treatment process employed
following biological treatment for the purpose of increasing
pollutant removal. Advanced waste treatment is also used to
produce a high-quality effluent suitable for reuse. The term
"tertiary treatment" is commonly used .to denote advanced waste
treatment methods.
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Aeration. The process of impregnating a liquid with air by
spraying the liquid in the air, bubbling the air through the
liquid, or agitating the liquid to promote surface absorption of
air (in waste treatment, liquid from the primary clarifier is
mixed with compressed air and with biologically active sludge).
Aerobic. Descriptive of a chemical reaction or a microorganism
that requires the presence of air or oxygen.
Algae. Chlorophyll-bearing organisms occurring in both salt and
fresh water; algae release oxygen into water and are used in
treatment of sewage and plant effluent in a flocculation process.
Alqicide. Chemical agent added to water to destroy algae.
Copper sulfate is commonly used in large water systems.
Alkali.
strongly.
A water-soluble metallic hydroxide that ionizes
Alkalinity. The presence of salts of alkali metals (e.g.,
hydroxides, carbonates, and bicarbonates of calcium, sodium and
magnesium) and usually expressed in terms of the amount of
calcium carbonate that would have an equivalent capacity to
neutralize strong acids.
Alkaloids. Basic (alkaline) nitrogenous botanical products which
produce a marked physiological action when administered to ani-
mals or humans.
Alkylation. The addition of a aliphatic group to a molecule.
Ammonia Nitrogen. A substance produced by the microbiological
decay of plant and animal protein. When ammonia nitrogen is
found in waters, it is indicative of incomplete treatment.
Ampu1e. A sealed glass or plastic bulb containing solutions for
hypodermic injection. :
Anaerobic. Descriptive of a chemical reaction or a microorganism
that does not require the presence of air or oxygen (e.g., the
decomposition of sewage sludge by anaerobic bacteria).
Anion. Ion with a negative charge.
Antagonistic Effect. The simultaneous action of separate agents
opposing each other.
Antibiotic. A substance produced by a microorganism which has
the power, in dilute solution, to inhibit or destroy other
organisms.
Aqueous Solution. A solution containing water.
238
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Arithmetic Mean. The arithmetic mean, or
of items is obtained by adding all
dividing the total by the number of items.
average", of a number
the items together and
Autoclave. A heavy
chemical reactions
equipment using steam
vessel with thick walls for
under high pressure or for
under pressure.
conducting
sterilizing
Azeotrope. A liquid mixture of two or more substances which
behaves like a single substance in that the vapor produced by
partial evaporation of liquid has the same composition as the
liquid. The constant boiling mixture exhibits either a maximum
or minimum boiling point as compared with that of other mixtures
of the same substances.
Bacteria. A type of microorganism often composed of a single
cell with round, rodlike, spiral, or filamentous bodies.
Bacteria exist in soil, water, organic matter, and in the bodies
of plants and animals and are primarily composed of protein and
nucleic acids.
Bacteriophage.
bacteria.
type of virus which attacks and destroys
BADCT. Best Available Demonstrated Control Technology.
Base. A substance that in aqueous solution turns red litmus
blue, furnishes hydroxyl ions, and reacts with an acid to form a
salt and water only.
BAT Effluent Limitations. Limitations for point sources, other
than publicly owned treatment works, which are based on the
application of the best available technology economically
achievable. These limitations must be achieved by July 1, 1983
and are the principal means of controlling the direct discharge
of toxic and non-conventional pollutants to navigable waters.
Batch Process. A process which has an intermittent flow of raw
materials into the the process and a resultant intermittent flow
of product from the process.
BCT Effluent Limitations. Limitations
conventional pollutant control technology
establishing best
for discharges of
conventional pollutants from existing direct dischargers.
Bioassay. A determination made on an organism to determine its
reaction to another substance.
Biochemical Oxygen Demand (BOD5). The quantity of oxygen
required to oxidize the organic material in a sample of
wastewater in a specified time (5 days) and at a specific
temperature (120 degrees C). This quantity is not related to the
oxygen requirements in chemical combustion but is determined by
239
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the biodegradability of the material and by the amount of oxygen
utilized by the microorganisms during oxidation. This test is
universally accepted as the yardstick of pollution and is
utilized to determine the degree of treatment in a waste
treatment process.
Biota. The flora and fauna (plant and animal life) of a body of
water.
Biological Products. In the pharmaceutical industry, medicinal
products derived from animals or humans (e.g., vaccines, toxoids,
antisera, and human blood fractions).
Biological Treatment System. A system that uses microoganisms to
remove organic pollutants from a wastewater.
Blood Fractionation. The separation of
various protein fractions.
human blood into its
Slowdown. The liquid and solid waste materials ejected from a
vessel such as a boiler.
BODS. Biochemical oxygen demand.
Botanicals. Drugs made from a part of a plant, such as roots,
bark, or leaves.
BPT Effluent Limitations. Limitations for point sources, other
than publicly owned treatment works, which are based on the
application of the best practicable control technology currently
available. These limitations must be achieved by July 1,1977.
Brine. Water saturated with a salt.
Buffer. A solution containing both a weak acid and its conjugate
weak base whose pH changes only slightly on the addition of acid
or alkali. ;
Capsule. A gelatinous shell used to contain medicinal chemicals.
Carbohydrate. A compound of carbon, hydrogen, and oxygen, in
which the ratio of hydrogen to oxygen is usually two to one.
Carbonaceous. Containing or composed of carbon.
Catalyst. A substance which changes the rate of a chemical reac-
tion without undergoing a permanent chemical change itself.
Cation. The ion in an electrolyte which carries the positive
charge and which migrates toward the cathode under the influence
of a potential difference.
240
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Cellulose. The major polysaccharide component of the cell walls
of all woods, straws, bast fibers, and seed hairs. It is the
principal raw material of pulp, paper, and paperboard.
Chemical Oxygen Demand (COD). A measure of oxygen-consuming
capacity of organic and inorganic matter present in water or
wastewater. It is expressed as the amount of oxygen consumed
from a chemical oxidant in a specific test.
Chemical Synthesis. The process of chemically combining two or
more constituent substances into a single substance.
Chlorination. The application of chlorine to water, sewage, or
industrial wastes, generally for the purpose of disinfection.
Coagulation. Irreversible combination or aggregation of
semisolid particles to form a clot or mass. This can be brought
about by the addition of certain chemicals, such as lime, alum,
or polyelectrolytes.
Combined Sewer. A sewer which carries both sewage and storm
water run-off.
Composite Sample. A mixture of grab samples collected at the
same sampling point at different times.
Comprehensive Pharmaceutical Data Base. Combined data base
containing the first 308 survey of PMA-member companies and the
second, or supplemental 308 survey.
Concentration. The amount of a given substance in a stated unit
of a mixture or solution.
Conductivity. The property of a substance or mixture that
describes its ability to transfer heat or electricity.
Contact Process Wastewaters. Process-generated wastewaters which
have come in contact with the reactants used in the process.
These include such streams as contact cooling water, filtrates,
concentrates, wash waters, etc.
Continuous Process.
materials , into
product from the process.
_ A process which has a constant flow of raw
the process and a resultant constant flow of
Contract Disposal.
party for a fee.
Disposal of waste products by an outside
Crustaceae. Small animals ranging in size form 0.2 to 0.3
millimeters long which move very rapidly . through the water in
search of food. They have recognizable head and posterior sec-
tions and are a principal source of food for small fish.
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Crystallization. The formation of solid particles within a
homogeneous phase. Formation of crystals separates a solute from
a solution and generally leaves impurities behind in the mother
liquid.
Culture. A mass of microorganisms growing in a medium.
Cyanide, Total. Total cyanide as determined by the test
prodecure specified in 40 CFR Part 136 (Federal Register, Vol.
38, no. 199, October 16,1973).
Cyanide A. Cyanides amenable to chlorination as described in
"1972 Annual Book of ASTM Standards" 1972: Standard 2036-72,
Method B, p. 553.
Derivative.
substance.
A substance extracted from another body or
Desorption. The opposite of adsorption. A phenomenon where an
adsorbed molecule leaves the surface of the adsorbent.
Diluent. A diluting agent.
Direct Discharge. The discharge of process wastewaters to navi-
gable waters such as rivers, streams and lakes.
Disinfectant. A chemical agent which kills bacteria.
Disinfection. The process of killing the larger
not necessarily all) of the harmful and
microorganisms in or on a medium.
portion (but
objectionable
Dissolved Oxygen (DO). The amount of oxygen dissolved in
sewage, water or other liquids, usually expressed in milligrams
per liter or percent of saturation.
Distillation. A method of separating a liquid mixture by
vaporizing it into components or groups of components.
Effluent. A liquid which leaves a unit operation or process.
Elution. (1) The process of washing out or removing with the use
of a solvent. (2) In an ion exchange process, the stripping of
adsorbed ions from an ion exchange resin by passing a solution
through the resin solutions which contain other ions in
relatively high concentrations.
Emulsion. A stable mixture of two or more immiscible liquids
held in suspension.
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Equalization Basin. A holding basin in which variations in flow
and composition of a liquid are averaged. Such basins are used
to provide a flow of uniform volume and composition to a
treatment unit.
Esterification. The combination of an alcohol and an organic
acid to produce an ester and water. The reaction is carried out
in the liquid phase, with aqueous sulfuric acid as a catalyst.
Ethical Products. Pharmaceuticals promoted by advertising to the
medical, dental, and veterinary professions.
Fatty Ac_:Lds. An organic acid obtained by the hydrolysis
(saponification) of natural fats and oils, e.g., stearic and
palmitic acids. These acids, which contain sixteen or more
carbon atoms, are monobasic and and may contain some double
bonds.
Fauna. The animal life adapted for living in a specified
environment.
Fermentation. A chemical change induced by a living organism or
enzyme, specifically bacteria, or the microorganisms occurring in
unicellular plants such as yeast, molds, or fungi.
Fermentor Broth. A slurry of microorganisms in water containing
nutrients (carbohydrates, nitrogen) necessary for the
microorganisms' growth.
Filter Cakes.
from a
or a
diatomaceous
filtration.
Wet solids generated by the filtration of solids
liquid. This filter cake may be a pure material (product)
waste material containing additional fine solids (i.e.,
earth) that have been added to aid in the
Fines. Crushed solids sufficiently fine to pass through a
screen, etc.
Flocculant. A substance that induces the aggregation of
suspended" solids particles in such a way that they form small
clumps. Inorganic flocculants are lime, alum or ferric chloride;
polyelectrolytes are examples of organic flocculants.
Flora. The plant life characteristic of a region.
Flotation. A process for separating suspended solids from a
liquid where the suspended matter (as scum) is raised to the
surface of the liquid in a tank by aeration, vacuum, evolution of
gas, chemicals, electrolysis, heat or bacterial decomposition.
The scum is then removed by skimming.
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Fractionation (or Fractional Distillation). The separation of
constituents of a mixture by vaporization and recondensation over
specific boiling point ranges.
Fungus. Any of a plant-like group of organisms that does not
produce chlorophyll; they derive their food either by decomposing
organic matter from dead plants and animals or by parasitic
attachment to living organisms, thus often causing infections and
disease. Examples of fungi are molds, mildews, mushrooms, and
the rusts and smuts that infect grain and other plants. They
grow best in a moist environment at, temperatures of about 25°C,
with little or no light being required. In sanitary engineering,
fungi are considered to be multicellular, nonphotosynthetic,
heterotrophic protists.
Gland. A device of soft wear-resistant material used to minimize
leakage between a rotating shaft and the stationary portion of a
vessel such as a pump.
Gland Water. Water used to lubricate a gland.
"packing water."
Sometimes called
Grab Sample. (1) Instantaneous sampling.
a random time.
(2) A sample taken at
Grease. In sewage, grease includes fats, waxes, free fatty
acids, calcium and magnesium soaps, mineral oils and other non-
fatty materials.
Hardness. The proportion of calcium carbonate or calcium sulfate
contained in a given sample of water.
Hormone. Any of a number of substances formed in the body which
activate specifically receptive organs when transported to them
by the body fluids. A material secreted by ductless glands
(endocrine glands). Most hormones as well as synthetic analogues
have in common the cyclopentanophenanthrene nucleus.
Indirect Discharge. The discharge of (process) wastewaters to
publicly owned treatment works (POTW).
Injectables. Medicinals prepared in a sterile
suitable for administration by injection.
(buffered) form
Mycelia. The filamentous material which makes up the vegetative
body of a fungus.
New Source. Any facility from which there is or may be a
discharge of pollutants, the construction of which is commenced
after the publication of proposed regulations prescribing a
standard of performance under section 306 of the Act.
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Non-Contact Cooling Water. Water used for cooling that does not
come into direct contact with any raw material, intermediate pro-
duct, waste product or finished product.
Non-Contact Process Wastewaters. Wastewaters generated by a
manufacturing process which have not come in direct contact with
the reactants used in the process. These include such streams as
noncontact cooling water, cooling tower blowdown, boiler
blowdown, etc.
NSPS. New Source Performance Standards.
NPDES. National Pollution Discharge Elimination System. A
federal program requiring industry to obtain permits to discharge
plant effluents to the nation's water courses.
Nutrient. Any substance assimilated by an organism which
promotes growth and replacement of cellular constituents.
Operation and Maintenance. Costs required to operate and
maintain pollution abatement equipment including labor, material,
insurance, taxes, solid waste disposal, etc.
.Organic Loading. In the activated sludge process,the food to
microorganisms (F/M) ratio defined as the amount of biodegradable
material available to a given amount of microorganisms per unit
of time.
Oxidation. At one time, the term oxidation was restricted to
reactions involving oxygen, but its usage has been broadened to
include all reactions where electrons are transferred.
Oxidation Reduction (OR). A class of chemical reactions in which
one of the reacting species gives up electrons (oxidation) while
another species in the reaction accepts electrons (reductions).
Oxidation Reduction Potential (ORP). A measurement that
indicates the activity ratio of the oxidizing and reducing
species present.
Oxygen, Available. The quantity of atmospheric oxygen dissolved
in the water of a stream; the quantity of dissolved oxygen
available for the oxidation of organic matter in sewage.
Oxygen, Dissolved. The oxygen (usually designated as DO)
dissolved in sewage, water or another liquid and usually
expressed in mg/1, parts per million, or percent of saturation.
Parts Per Million (ppm). Parts by weight in sewage analysis;ppm
by weight is equal to milligrams per liter divided by the
specific gravity. It should be noted that in water analysis, ppm
is always understood to imply a weight/weight ratio, even though
in practice volume may be measured instead of a weight.
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Pathogenic. Disease producing.
pH. The value representing the acidity or alkalinity of ' a
solution and defined as the negative logarithm of the hydronium
ion concentration or activity in a solution. ' The number 7
indicates neutrality, numbers less than 7 indicate increasing
acidity and numbers greater than 7 indicate increasing
alkalinity.
Photosynthes is. The mechanism by which chlorophyll-bearing
plants utilize light energy to produce 'carbohydrate and oxygen
from carbon dioxide and water(the reverse 'of respiration.).
Physical/Chemical Treatment System. A system that utilizes
physical (i.e., sedimentation, filtration, centrifugation,
activated carbon, reverse osmosis, etc.) and/or chemical means
(i.e. coagulation, oxidation, precipitation, etc.) to treat
wastewaters.
Plasma. The fluid part of blood, lymph,: or intramuscular fluid
in which cells are suspended.
PMA. Pharmaceutical Manufacturers Association.
Point Source. Any discernible, confined and discrete conveyance,
including but not limited to any pipe, ditch, channel, tunnel,
conduit, well, discrete fissure, container, rolling stock,
concentrated animal feeding operation, or vessel or other
floating craft, from which pollutants are or may be discharged.
Potable Water. Drinking water sufficiently pure for human use.
Potash. Potassium compounds used in agriculture and industry.
Potassium carbonate can be obtained from wood ashes. The mineral
potash is usually a muriate (chloride). Caustic potash is its
hydrated form.
Preaeration. A process where sewage is aerated to replenish
dissolved oxygen prior to primary sedimentation. The objective
is to improve the treatability of the wastewater.
Precipitation. The phenomenon where small particles settle out
of a liquid or gaseous suspension by gravity or when a substance
held in solution passes out of that solution into solid form as a
result of a chemical reaction.
Pretreatment. Any wastewater treatment process used to partially
reduce the pollution load before the wastewater is introduced
into a main sewer system or delivered to a treatment plant for
substantial reduction of the pollution load.
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Process Waste Water.
Any water which, during manufacturing or
comes into direct contact with or results from the
or use of any raw material, intermediate product,
processing
production
finished product, by-product, or waste product.
Process Water. Any.water(solid, liquid or vapor) which, during
the manufacturing process, comes into direct contact with any raw
material, intermediate product, by-product, waste product, or
finished product.
Proprietary Products. Pharmaceuticals manufactured and sold only
by the owner of a patent, trademark, etc.
PSES. Pretreatment Standards for Existing Sources.
PSNS. Pretreatment Standards for New Sources.
Raw Waste Load (RWL). The quantity (kg) of pollutant being
discharged in a plant's wastewater measured in terms of some
common denominator (i.e., kkg of production or sq. ft. of floor
area).
Receiving Waters. Rivers, lakes, oceans or other bodies of water
that receive treated or untreated wastewaters.
Reduction. A process in which an atom (or group of atoms) gains
electrons.
Refractory Orqanics. Organic materials that are only partially
biodegradable in biological waste treatment processes.
Refractory organics include detergents, pesticides, color- and
odor-causing agents, tannins, lignins, ethers, olefins, alcohols,
amines, aldehydes, ketones, etc.
Residual Chlorine. The amount of chlorine left in treated water
that can oxidize contaminants if they enter the stream.
Hypochlorite ion concentration alone is called "free chlorine
residual"; the hypochlorite ion and chloramine concentration
together are called "combined chlorine residual."
Retort. A vessel, commonly a glass bulb with a long neck bent
downward,used for distilling or decomposing substances by heat.
Sanitary Sewers. In a separate system, pipes in a city that
carry only domestic wastewater. The storm water runoff is
handled by a separate system of pipes.
Saprophytic Organism.
matter.
One that lives on dead or decaying organic
Secondary Treatment. The second step in most waste treatment
systems in which bacteria consume the organic part of the wastes.
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Seed. To introduce microorganisms into a culture medium.
Serum. A fluid extracted from an animal for the purpose of
innoculation to effect the cure of a disease.
Settleable Solids. Suspended solids which will settle out of a
liquid waste in a given period of time.
Sewage, Storm. The liquid flowing in sewers during or following
a period of heavy rainfall.
Sewerage. A comprehensive term which includes facilities for
collecting, pumping, treating and disposing of sewage; the
sewerage system and the sewage treatment works.
SIC Codes. Standard Industrial Classification. Numbers used by
the U.S. Department of Commerce to denote segments of industry.
Sludge, Activated. Sludge floe produced in raw or settled sewage
by the growth of bacteria and other organisms in the presence of
dissolved oxygen.
Sludge, Age. The ratio of the weight of volatile solids in the
digester to the weight of volatile solids added per day. There
is a maximum sludge age beyond which no significant reduction in
the concentration of volatile solids will occur.
Sludge, Digested. Sludge digested under anaerobic conditions
until the volatile content has been reduced, usually by
approximately 50 percent or more.
Solution. A homogeneous mixture of two or more substances of
dissimilar molecular structure. In a solution, there is a
dissolving medium (solvent) and a dissolved substance (solute).
Solvent Extraction.
The treatment of a mixture of two or more
components by a solvent that preferentially dissolves one or more
of the components in the mixture.
Steam Distillation. Fractionation process in which steam is used
to provide the heat of the system.
Sterilization. The complete destruction of all living organisms
in or on a medium accomplished by heating to 121°C at 5 psig for
15 minutes.
Steroid. Any one of a large group of substances chemically
related to various alcohols found in plants and animals.
Still Bottom. The residue remaining after distillation of a
material.
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Stlllwell. A pipe, chamber, or compartment with small inlets to
a main body of water. Its purpose is to dampen waves or surges
while permitting the water level within the well to rise and fall
with the major fluctuations of the main body of water.
Stoichiometric. Characterized by being
proportion of
substances exactly right for a specific chemical reaction with no
excess of any reactant or product.
Stripper. A device in which relatively volatile components are
removed from a mixture by distillation or by passage of steam
through the mixture.
Supernatant. Floating above or on the surface.
Surge Tank. A tank for absorbing and dampening the wavelike
motion of a volume of liquid; an in-process storage tank that
acts as a flow buffer between process tanks.
Suspended Solids. The wastes that will not sink or settle in
sewage. The quantity of material deposited on a filter when a
liquid is drawn through a Gooch crucible.
Synergistic. An effect produced by a group of contributors which
is greater than the sum of the individual contributors acting
individually.
Tablet. A small, disc-like mass of medicinal powder used as a
dosage form for administering medicine.
Tertiary Treatment. A treatment process added after secondary
treatment to remove practically all solids and organic matter
from wastewater.
Thermal Oxidation. The combustion of organic materials through
the application of heat in the presence of oxygen.
Total Organic Carbon (TOO. A measure of the amount of carbon in
a sample originating from organic matter only. The test is run
by burning the sample and measuring the carbon dioxide produced.
Total Solids. The total amount of solids in a wastewater both in
solution and suspension.
Toxoid. Toxin treated so as to destroy its toxicity, but still
capable of inducing formation of antibodies.
Vaccine. A killed or modified live virus or bacteria prepared in
suspension for inoculation to prevent or treat certain infectious
diseases.
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Viruses. (1) An obligate intracellular parasitic microorganism
smaller than bacteria. Most can pass through filters that retain
bacteria. (2) The smallest (10-300 urn in diameter) form capable
of producing infection and diseases in man or other large
species. Occurring in a variety of shapes, viruses consist of a
nucleic acid core surrounded by an outer shell (capsid) which
consists of numerous protein subunits (capsomeres). Some of the
larger viruses contain additional chemical 'substances. The true
viruses are insensitive to antibiotics. They multiply only in
living cells where they are assembled as complex macromolecules
utilizing the cells' biochemical systems. They do not multiply
by division as do intracellular bacteria.
Volatile Suspended Solids (VSS]
The quantity of suspended
solids lost after the ignition of total suspended solids.
Water Quality Criteria. Those specific values of water quality
associated with an identified beneficial us(e of the water under
consideration.
Zero Discharge.
Plants that do not discharge wastewaters to
either publicly owned treatment works or to navigable waters.
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APPENDIX C
PHARMACEUTICAL. INDUSTRY
WASTEWATER DISCHARGE METHODS
Plant
Code Ho.
1 2.0-0,0
12001
1:2003
12004
12005
12006
12007
12011
12012
12014
12015
12016
12018
120-19
12021
12022
12023
12024
12026
12030
12031
12035
12036
12037
12038
12040
12042
12043
12044
12048
120.51
12052
12053
120.54
12055
12056
12057
12058
12060
12061
12062
12063
12065
lad-irect
X
X
X
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Direct
X
X.
X
X
Zero
Comment
X
X
Reey/c 1 e/Reuse
Land Application
No Process Wastewater
POTW1
Treatment
Level
P
S
S
S
S
T
S
S
x
X
X
Re cy c1e/Reus e
Private Treatment System
Evaporation
Subsurface Discharge
Subsurface Discharge
Subsurface Discharge
X
Subsurface Discharge
Septic System
T
T
S
S
S
S
S
S
S
P
S
S
S
S
251
-------
12066
12068
12069
12073
12074
12076
12077
12078
12080
12083
12084
12085
12087
12088
12089
12093
12094
12095
12097
12098
12099
12100
12102
12104
12107
12108
12110
12111
12113
12115
12117
12118
12119
12120
12122
12123
12125
12128
12129
12131
12132
12133
12135
12141
12143
12144
12145
12147
12155
12157
12159
12160
12161
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Private Treatment System
:x
X
X
X
Contract Disposal
X
X
X
X
Deep Well Injection
Contract Disposal
Ocean Discharge
Ocean Discharge
Private Treatment System
Subsurface Discharge
X
X
Land Application
No Process Wastewater
T
S
P
P
P
S
P
T
S
P
S
T
P
P
S
S
'S
S
S
S
S
S
T
S
S
X
X
X
Recycle/Reuse
Private Treatment System
252
-------
12166
12168
12171
12172
12173
12174
12175
12177
12178
12183
12185
12186
12187
12191
12194
12195
12198
12199
12201
12204
12205
12206
12207
12210
1221 1
12212
12217
12219
12224
12225
12226
12227
12230
12231
12233
12235
12236
12238
12239
12240
12243
12244
12245
12246
12247
12248
12249
12250
12251
12252
12254
12256
12257
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Evaporation
No Process Wastewater
Evaporation
Private Treatment System
Ocean Discharge
(Also Contract Disposal)
Private Treatment System
S
S
X
X
X
Land Application
Contract Disposal
No Process Wastewater
Subsurface Discharge
Ocean Discharge
Contract Disposal
Evaporation
Contract Disposal
Private Treatment System
S
S
S
S
S
S
S
S
S
S
S
p
S
p
S
p
S
X
(Also Land Application)
Land Application
S
P
T
S
P
S
S
S
S
S
S
S
T
253
-------
12260
12261
12263
12264
12265
12267
12268
12269
12273
12275
12277
12281
12282
12283
12287
12289
12290
12294
12295
12296
12297
12298
12300
12302
12305
12306
12307
12308
12309
12310
12311
12312
12317
12318
12322
12326
12330
12331
12332
12333
12338
12339
12340
12342
12343
12345
12375
12384
12385
12392
12401
12405
12406
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Septic System
Septic System
X
X
X
X
X
X
Contract Disposal
Septic System
Septic System
Land Application
Land Application
S
S
P
T
S
S
P
S
T
S
S
P
S
S
S
P
P
S
S
P
P
S
P
S
S
S
T
254
-------
12407
12409
1241 1
12414
12415
12417
12419
12420
12427
12429
12433
12438
12439
12440
12441
12444
12447
12454
12458
12459
12460
12462
12463
12464
12465
12466
12467
12468
12470
12471
12472
12473
12474
12475
12476
12477
12479
12481
12482
12495
12499
20006
20008
20012
20014
20015
20016
20017
20020
20026
20030
20032
20033
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Contract Disposal
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Land Application
Deep Well Injection
X
X
X
Land Application
Septic System
X
X
X
X
X
X
Land Application
Land Application
Ocean Discharge
No Process Wastewater
Evaporation
No Process Wastewater
No Process Wastewater
Evaporation
S
S
T
T
T
S
S
S
S
S
S
S
S
S
S
p
p
S
p
S
p
255
-------
20034
20035
20037
20038
20040
20041
20045
20048
20049
20050
20051
20052
20054
20055
20057
20058
20062
20064
20070
20073
20075
20078
20080
20081
20082
20084
20087
20089
20090
20093
20094
20099
20100
20103
20106
20108
20115
20117
20120
20125
20126
20134
20139
20141
20142
20147
20148
20151
20155
20159
20165
20169
20173
No Process Wastewater
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
No Process
No Process
No Process
No Process
No Process
No Process
Wastewater
Wastewater
Wastewater
Wastewater
Wastewater
Wastewater
No Process Wastewater
Septic System
Contract Disposal
No Process Wastewater
No Process
No Process
No Process
No Process
No Process
Wastewater
Wastewater
Wastewater
Wastewater
Wastewater
X
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
Evaporation
Septic System
No Process Wastewater
No Process Wastewater
No Process Wastewater
Contract Disposal
No Process Wastewater
No Process Wastewater
No Process Wastewater
Contract Disposal
No Process Wastewater
256
-------
20174
201 76
20177
20178
20187
20188
20195
20197
20201
20203
20204
20205
20206
20208
20209
20210
2021 5
2021 6
20218
20220
20224
2022.5
20226
20228
20229
20231
20234
20235
20.236
20237
20240
20241
20242
20244
20245
20246
20247
'20249
20254
20256
20.257
2.0258
20261
20263
20264
20266
20267
20269
20270
20271
20273
20282
X
X
X
X
X
X
X
X
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
x
X
X
X
X
X
X
X
X
X
X
X
,x
X
X
X
X
X
X
X
X
X
X
X
X
X
No Process Wastewater
No Process Wastewater
Evaporation
No Process Wastewater
Land Application
Land Application
Land Application
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
Contract Disposal
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
Contract Disposal
No Process Wastewater
Mo Process Wastewater
257
-------
20294
20295
20297
20298
20300
20303
20305
20307
20308
20310
20311
20312
20316
20319
20321
20325
20328
20331
20332
20333
20338
20339
20340
20342
20346
20347
20349
20350
20353
20355
20356
20359
20361
20362
20363
20364
20366
20370
20371
20373
20376
20377
20385
20387
20389
20390
20394
20396
20397
20400
20402
20405
20413
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Pro-cess Wastewater
No Process Wastewater
Contract Disposal
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
Evaporation
No Process Wastewater
Contract Disposal
Land Application
Evaporation
Contract Disposal
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
Contract Disposal
258
-------
20416
20421
20423
20424
20425
20435
20436
20439
20440
20441
20443
20444
20446
20448
20450
20452
20453
20456
20460
20462
20464
20465
20466
20467
20470
20473
20476
20483
20485
20486
20490
20492
20494
20496
20498
20500
20502
20503
20504
20507
20509
20511
20518
20519
20522
20526
20527
20529
11111
33333
44444
55555
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
No Process Wastewater
No Process Wastewater
Evaporation
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
Subsurface Discharge
No Process Wastewater
Deep Well Injection
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process Wastewater
No Process
No Process
No Process
No Process
No Process
Wastewater
Wastewater
Wastewater
Wastewater
Wastewater
No Process Wastewater
Contract Disposal
No Process Wastewater
X
X
X
X
259
-------
IpOTW Treatment Level Symbols:
P - Primary
S - Secondary
T - Tertiary
^ Data on POTW treatment level was not requested from the
Supplemental 308 (20000 series) plants
260
-------