-------
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
U.S. EPA. Industry Fate Study. 600/2-79-175, U.S. Environmental
Protection Agency, Washington, D.C., August 1979.
Self-Monitoring Database developed for the Pharmaceutical Manufacturing
Industry.
EPA (ITD, List of Analytes) Sampling Program Database.
SRI. Self-Monitoring Database. October 27, 1983.
Wastewater Sampling Episode Report, May 23-27, 1983, Episode 857.
Prepared by E.G. Jordan Co. for the U.S.EPA Industrial Technology
Division.
Wastewater Sampling Episode Report, September 12-16, 1988, Episode
1356. Prepared by E.G. Jordan Co. for the U.S.EPA Industrial Technology
Division.
Wastewater Sampling Episode Report, September 19-23, 1988, Episode
1623. Prepared by E.G. Jordan Co. for the U.S.EPA Industrial Technology
Division.
Wastewater Sampling Episode Report, June 5-9, 1989, Episode 1748.
Prepared by E.G. Jordan Co. for the U.S.EPA Industrial Technology
Division.
Gardner, D.A., R.A. Osantowski, and P.A. Thompson, Radian Corporation.
Treatment of Pharmaceutical Wastewater by Steam Stripping and Air
Stripping. Prepared for the Risk Reduction Engineering Laboratory, U.S.
Environmental Protection Agency, Office of Research and Development,
September 1992.
Gardner, D.A., P.A. Thompson, and C.A. Beitler, Radian Corporation.
Treatment of Pharmaceutical Wastewater by Distillation - Final Report.
Prepared for the Risk Reduction Engineering Laboratory, U.S.
Environmental Protection Agency, Office of Research and Development,
July 28, 1994.
Osantowski, R., R. Wullschleger, Rexnord Inc. Evaluation of Activated
Carbon for Enhanced COD Removal from Pharmaceutical Wastewater -
Final Report. Prepared for the Water Engineering Research Laboratory,
8-82
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12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
U.S. Environmental Protection Agency, Office of Research and
Development, 1985.
Gardner, D.A., and R.A. Osantowski, Radian Corporation. Pilot Plant
Evaluation of Biological Treatment of Pharmaceutical Wastewater With
and Without PAC Addition. Prepared for the Water Engineering Research
Laboratory, U.S. Environmental Protection Agency, Office of Research and
Development, December 1987.
Memorandum: Biodegradability of Chemical Compounds, from Marc Gill,
Radian Corporation, to Kirsten Mahsman, Radian Corporation, January 21,
1993.
DeRenzo, D.J. Biodegradation Techniques for Industrial Organic Wastes,
1980.
Verschueren, K. Handbook of Environmental Data on Organic Chemicals,
Second Edition, Van Nostrand Reinhold Company, New York, New York,
1983.
Lyman, W.J., W.F. Reehl, and D.H. Rosenblatt. Handbook of Chemical
Property Estimation Methods. McGraw Hill Book Company, New York,
New York, 1982.
Windholz, M., et. al. The Merck Index, Ninth Edition. Merck and Co.,
Inc., Rahway, New Jersey, 1976.
U.S. EPA. Surface Impoundment Modeling System Database (SIMS
Database). September 1989.
Carroll, J.J. What Is Henry's Law? Chemical Engineering Progress.
September 1991.
U.S. EPA, Office of Air Quality Planning and Standards. Models for
Estimating Air Emission Rates from Superfund Remedial Actions. U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina,
March 8, 1993.
Warner, H.P., J.M. Cohen, and J.C. Ireland. Determination of Henry's
Law Constants of Selected Priority Pollutants. EPA/600/D-87/229,
Washington, D.C., July 1987.
8-83
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22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
U.S. EPA. Handbook of RCRA Groundwater Monitoring Constituents;
Physical Properties. EPA/530/R-92-022, U.S. Environmental Protection
Agency, Washington, D.C., September 1992.
U.S. EPA, Office of Research and Development. Treatability Manual,
Volume 1: Treatability Data. EPA/600/8/80/042, U.S. Environmental
Protection Agency, July 1980.
Fredenslund, A., R.L. Jones, and J.M. Prausnitz. Group-Contribution
Estimation of Activity Coefficients in Nonideal Liquid Mixtures, AIChE
Journal, Vol. 21., No. 6, November 1975.
U.S. EPA. Hazardous Waste Treatment, Storage, and Disposal Facilities
Air Emissions Models. EPA 450/3-87-026, Washington, D.C., December
1987.
Gmehling, J. and U. Onken. Vapor-Liquid Equilibrium Data Collection
Aqueous-Organic Systems. Chemistry Data Series, Vol. 1, Part 1.
DECHEMA Deutsche Gesellschaft fur Chemisches Apparatewesen,
Chemische Technik und Biotechnologie e.V., Frankfort, Germany, 1991.
Walas, S.M. Phase-Equilibria in Chemical Engineering. Butterworth-
Hememann, Stoneham, MA, 1985.
Howard, P.H. Handbook of Environmental Fate and Exposure Data for
Organic Chemicals, Vol n. Lewis Publishers, Chelsea, MI, 1989.
Machay, D. and W.Y. Shiu. "A Critical Review of Henry's Law Constants
for Chemicals of Environmental Interest," J. Phys. Chemical Ref. Data.
Vol. 10, No. 4, 1981.
Boston, J.F. Inside-Out Algorithms for Multicomponent Separation
Process Calculations. Presented in Symposium on Computer Applications
to Chemical Engineering Process Design and Simulation, I/EC Division of
ACS, 178th National ACS Meeting, Washington D.C., 1979.
U.S. EPA. Statistical Support Document for the Proposed Effluent
Limitations Guidelines for the Pharmaceutical Manufacturing Industry.
U.S. Environmental Protection Agency, Washington, D.C., February 10,
1995.
8-84
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SECTION 9
POLLUTANT REDUCTION ESTIMATES
9.1
Introduction
EPA obtained data on pollutant loads generated by pharmaceutical manufacturing
processes and the ultimate fate of these loads through the Detailed Questionnaire.
Using these data and the treatment performance data presented in Section 8, the Agency
has developed estimates of untreated and current, pollutant discharge loads from the
pharmaceutical manufacturing industry. The Agency also calculated the pollutant
discharge loads that would remain after implementation of each of the regulatory options
considered.
The following information is presented in this section:
Section 9.2 presents the estimated untreated loads of pollutants in
process wastewaters based on responses to the Detailed
Questionnaire;
Section 9.3 presents the loads of pollutants currently being
discharged based on responses to the Detailed Questionnaire;
Section 9.4 discusses estimated end-of-pipe discharge loads for each
regulatory option; and
Section 9.5 discusses the pollutant load reductions expected through
steam stripping, steam stripping with distillation, advanced biological
treatment, and granular activated carbon treatment.
9.2
Untreated Loads
The Agency estimated untreated loads, by pollutant, which are generated by
pharmaceutical manufacturing processes based on responses to the Detailed
9-1
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Questionnaire. The untreated load was estimated as the sum of the discharge load, air
emissions from wastewater load, and degraded/destroyed load. These loads from the
detailed questionnaire for each facility were summed by pollutant across all facilities
within a subcategory group. Table 9-1 lists the estimated untreated loads for each
pollutant by Subcategory and type of discharge.
The untreated loads for the Subcategory D indirect dischargers were scaled up according
to the methodology discussed in Section 3.2.3 and presented in Reference (1). This
scale-up was used to estimate the total amount of pollutants for all Subcategory D
indirect dischargers, including the facilities which were not sent a Detailed
Questionnaire. The table below summarizes the total amount of pollutant load in
untreated wastewater from Subcategory B and D indirect dischargers.
Total Raw Load for Priority
and Nonconventional
Pollutants (Ibs/yr)
Subcategory 6 and D
Indirect Dischargers from the
Detailed Questionnaire
6,990,000
Subcategory D Indirect
Dischargers Without .
Questionnaire (Estimate)
193,000
: Total Subcategory B and D
Indirect Dischargers
(Estimate)
7,180,000
Current Baseline Loads
The current baseline loads are those loads, by pollutant, which are currently discharged
by pharmaceutical manufacturing processes to a POTW or to surface water based on
responses to the Detailed Questionnaire. Those discharge loads available from the
Detailed Questionnaire for each faculty were summed by pollutant across all facilities
within a subcategory group. Table 9-2 lists the current baseline loads for each pollutant
by subcategory group and type of discharge.
The current baseline loads for the Subcategory D indirect dischargers were scaled up
according to the methodology discussed in Section 3.2.3 and presented in Reference '.
9-2
-------
This scale-up was used to estimate the total amount of pollutants for all Subcategory D
indirect dischargers, including the facilities which were not sent a Detailed
Questionnaire. The table below summarizes the total amount of pollutants currently
discharged by Subcategory B and D indirect dischargers.
Total Current Baseline
Loads for Priority and
Nonconventional Pollutants
(Ibs/yr)
Subcategory Band D
Indirect Dischargers from, the
Detailed; Questionnaire
1,610,000
Subcategory D Indirect
Dischargers Without
: Questionnaire (estimate)
460,000
Total Subcategory B and D
Indirect Dischargers
(estimate)
2,070,000
9.4
End-of-Pine Discharge Loads for Each Regulatory Option
End-of-pipe discharge loads for the proposed BPT, BAT, and PSES regulatory options
are presented by Subcategory and pollutant in this section. (Because EPA proposes to
establish BCT equal to BPT, the discharge loads based on the proposed BCT technology
would be identical to those based on the proposed BPT technology). These loads were
calculated in the following manner. For each facility, current discharge loads were
converted to an estimated current effluent concentration using the pollutant discharge
load, facility process wastewater flow, and a conversion factor. For each facility, current
estimated effluent concentrations were then compared to the long term mean
concentrations at the end of the treatment train for a particular regulatory option. The
lower of these concentrations was used along with the facility flow and an appropriate
conversion factor to determine facility specific end-of-pipe discharge loads 23. Loads
from all facilities within a Subcategory group were then summed to provide the
subcategory-wide estimates.
9-3
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9.4.1
BPT
The regulatory options under BPT address the loads and concentrations of BOD5, TSS,
COD, and cyanide. There are five regulatory options considered under BPT for
Subcategory A and/or C direct discharger facilities and three regulatory options
considered under BPT for Subcategory B and/or D direct discharger facilities. Indirect
dischargers are not regulated under BPT.
The regulatory options considered under BPT for Subcategory A and/or C direct
discharger facilities are: 1) current cyanide destruction followed by current (in-place)
biological treatment; 2) in-plant cyanide destruction, followed by end-of-pipe advanced
biological treatment; 3) in-plant cyanide destruction, followed by end-of-pipe advanced
biological treatment and effluent filtration; 4) in-plant cyanide destruction, followed by
end-of-pipe advanced biological treatment and polishing pond treatment; and 5) in-plant
cyanide destruction, followed by end-of-pipe advanced biological treatment, effluent
filtration, and polishing pond treatment. Estimated end-of-pipe discharge loads for each
of these options are presented below.
Pollutant
BODj
COD
TSS
Cyanide
Subcategory A and C BPT Discharge Loads (Ibs/yr)
Option 1
3,260,000
31,700,000
6,330,000
45
Option 2
2,330,000
21,800,000
4,180,000
7
Option 3
2,330,000
21,800,000
3,170,000
7
Option: 4
2,330,000
21,800,000
2,590,000
7
Option 5
2,330,000
21,800,000
1,020,000
7
The regulatory options considered under BPT for Subcategory B and D direct discharger
faculties are: 1) current (in-place) biological treatment; 2) end-of-pipe advanced
biological treatment; and 3) end-of-pipe advanced biological treatment and effluent
filtration. Because no cyanide is discharged at Subcategory B and D facilities, cyanide
9-4
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destruction is not included as part of the technology basis for these subcategories.
Estimated end-of-pipe discharge loads for each of these options are presented below.
Pollutant
BOD5
COD
TSS
Subcategory B and D BPT Discharge Loads (Ibs/yr)
Option 1
57,500
294,000
82,400
Option 2
47,400
234,000
77,600
Option 3
47,400
234,000
46,600
Because Option 1 for the four manufacturing subcategories represents current treatment
at facilities, the discharge loads corresponding to that option in the tables above
represents current discharge loads. Treatment with filtration and/or polishing ponds
after advanced biological treatment will reduce TSS concentrations in wastewater, as
reflected in the estimated TSS discharge loads. However, the Agency assumed that no
additional reduction in BOD5 and COD would occur as a result of filtration or settling in
polishing ponds.
9.4.2
BAT
The regulatory options considered under BAT address the loads and concentrations of
priority and nonconventional pollutants, including ammonia and cyanide where
appropriate. There are four regulatory options considered under BAT for Subcategory A
and C and B and D direct discharger facilities.
The regulatory options considered under BAT for Subcategory A and C direct
discharging facilities are: 1) in-plant cyanide destruction, followed by end-of-pipe
advanced biological treatment with nitrification; 2) in-plant steam stripping and cyanide
destruction, followed by end-of-pipe advanced biological treatment; 3) in-plant steam
stripping with distillation and cyanide destruction, followed by end-of-pipe advanced
9-5
-------
biological treatment; and 4) in-plant steam stripping with distillation and cyanide
destruction, followed by end-of-pipe advanced biological treatment and granular
activated carbon adsorption (GAG). Table 9-3 presents estimated end-of-pipe discharge
loads for each of these options.
The regulatory options under BAT for Subcategory B and D direct discharging facilities
are the same as those for the Subcategory A and C direct discharging facilities with the
exception of cyanide destruction. Because no cyanide is discharged at Subcategory B
and D facilities, cyanide destruction is not included as part of the technology basis for
these subcategories. For the same reason, treatment technologies specific to ammonia
(i.e., nitrification) are also excluded. Table 9-4 presents estimated end-of-pipe discharge
loads for each of the regulatory options under BAT for B and D direct discharging
facilities.
It should be noted that for certain organic pollutants that are either not strippable or are
present at concentrations below the minimum analytical level, there is no apparent end-
of-pipe wastewater load reduction between Options 1 and 2. Additionally, all regulated
organic pollutants amenable to granular activated carbon (GAC) treatment will be at or
below the minimum analytical level after Option 3. Therefore, no additional load
reduction is apparent between Options 3 and 4. GAC will achieve additional load
removal of COD (and the organics that make up the COD), as demonstrated in the load
reduction tables in Section 9.5.2.
9.4.3
PSES
The regulatory options considered under PSES address the loads and concentrations of
priority and nonconventional organic pollutants, and, where appropriate, ammonia and
cyanide. There are four regulatory options considered under PSES for Subcategory A
and C indirect discharging facilities and three regulatory options considered under PSES
9-6
-------
for Subcategory B and D indirect discharging facilities. Direct dischargers are not
regulated under PSES.
The regulatory options considered under PSES for Subcategory A and C indirect
discharging facilities are: 1) in-plant steam stripping and cyanide destruction; 2) in-plant
steam stripping with distillation and cyanide destruction; 3) in-plant steam stripping with
distillation and cyanide destruction, followed by end-of-pipe advanced biological
treatment; and 4) in-plant steam stripping with distillation and cyanide destruction,
followed by end-of-pipe advanced biological treatment and granular activated carbon
adsorption. Table 9-5 presents estimated end-of-pipe discharge loads for each of these
options.
The regulatory options considered under PSES for Subcategory B and D indirect
discharging facilities are: 1) in-plant steam stripping; 2) in-plant steam stripping with
distillation; and 3) in-plant steam stripping with distillation, followed by granular
activated carbon adsorption. Because no cyanide is discharged at Subcategory B and D
facilities, cyanide destruction is not included as part of the technology basis for these
subcategories. Table 9-6 presents estimated end-of-pipe discharge loads for each of
these options.
The end-of-pipe loads for the Subcategory D indirect discharging facilities were also
scaled up according to the methodology discussed in Section 3.2.3 and in Reference (1).
An estimate of the total end-of-pipe discharge loads for the Subcategory D indirect
discharging facilities including those not sent a Detailed Questionnaire are presented in
the table below.
9-7
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Total Priority and
Nonconventional Pollutant
PSES Option 1 Loads
(Ibs/yr)
Total Priority and
Nonconventional Pollutant
PSES Option 2 Loads
(Ibs/yr)
Total Priority and
Nonconventional Pollutant
PSES Option 3 Loads
(Ibs/yr)
Subcategory B and T>
Indirect Dischargers With
the Detailed Questionnaire
551,000
28,800
28,600
Subcategory D Indirect
Dischargers Without
Questionnaire (estimate)
144,000
1,610
1,590
Total Subcategory B and D
Indirect Dischargers
(estimate)
695,000
30,400
30,200
Certain organic pollutants that are either not strippable, or are present at concentrations
below the minimum analytical level, will not have loads different from current baseline
loads under Option 1 for PSES. Additionally, all regulated organic pollutants at
Subcategory A and C facilities amenable to GAG treatment will be at or below the
minimum analytical level after Option 2. Therefore, no additional load reduction of
regulated organic pollutants is apparent between Options 2 and 3 for Subcategory A and
C indirect discharging facilities. GAC will, however, achieve additional load removal of
COD at these facilities, as demonstrated in the load reduction tables in Section 9.4.3.
Subcategory B and D indirect discharging facilities will achieve load reductions through
GAC for a few of the regulated organic pollutants, as well as COD.
9.5
Pollutant Load Reduction Estimates
Each regulatory option considered consists of a treatment train of technology
components. The set of options considered for each regulation in each Subcategory is
generally a series, where each option builds upon a prior option by adding a technology
component to the treatment train. For example, BAT Option 1 for Subcategory A and C
facilities includes cyanide destruction and advanced biological treatment with
nitrification. BAT Option 2 adds in-plant steam stripping to the treatment train. Load
reductions through each regulatory option are discussed in this section. In some cases,
9-8
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the addition of one treatment technology (e.g., steam stripping) may obviate the need for
a technology that had been part of a prior option (e.g., nitrification).
A cyanide destruction unit is included in every BPT, BAT, and PSES regulatory option
for Subcategories A and C. All load reductions for cyanide are through the cyanide
destruction unit. Therefore, no additional load reductions for cyanide are shown in
options beyond Option 1.
9.5.1
BPT
Load reductions through the cyanide destruction units are 38 Ibs of cyanide/yr for
Subcategory A and C faculties regulated under BPT. These load reductions correspond
to the load reduction between current baseline loads and end-of-pipe discharge loads for
BPT Option 1.
Load reductions through advanced biological treatment for BOD5, TSS, and COD are
shown below. These load reductions correspond to the load reduction between BPT
Options 1 and 2.
Pollutant
BOD5
COD
TSS
Load Reduction through Advanced
Biological Treatment for Subcategory
A and C Direct Dischargers (Ibs/yr)
931,000
9,840,000
2,150,000
Load Reduction through Advanced
Biological Treatment for Subcategory
B and D Direct Dischargers (Ibs/yr)
10,000
59,600
4,820
TSS loads can be further reduced by adding effluent filtration, polishing ponds, or both
effluent filtration and polishing ponds. Load reductions through effluent filtration are
shown below. These load reductions correspond to the load reductions between BPT
Options 2 and 3.
9-9
-------
Pollutant
TSS
Load Redaction through Filtration
for Subcategory A and C Direct
; Dischargers
(Ibs/yr)
• 1,010,000
Load Redaction through Filtration
for Subcategory B and D Direct
Dischargers
(Ibs/yr)
31,000
The load reductions through polishing ponds are shown below. These load reductions
correspond to the load reductions between BPT Options 2 and 4.
Pollutant
TSS
Load Reduction through Polishing Ponds for
: Subcategory A and C Direct Dischargers
(Ibs/yr)
1,590,000
The load reductions through effluent filtration followed by polishing ponds are shown
below. These load reductions correspond to the load reductions between BPT Options 2
and 5.
Pollutant
TSS
Load Reduction Through Effluent Filtration Followed by
Polishing Ponds for A. and C Direct Dischargers
0bs/yr)
3,160,000
9.52
BAT
Table 9-7 presents load reductions through end-of-pipe advanced biological treatment
with nitrification for organic pollutants and ammonia under BAT Option 1. These load
reductions correspond to the load reduction between current baseline loads and BAT
Option 1 loads for both A and C and B and D direct dischargers.
9-10
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Table 9-8 presents load reductions through in-plant steam stripping followed by end-of-
pipe advanced biological treatment for organic pollutants and, for Subcategories A and
C, ammonia under BAT Option 2. Table 9-9 presents load reductions through in-plant
steam stripping with distillation followed by end-of-pipe advanced biological treatment
for organic pollutants and, for Subcategories A and C, ammonia under BAT Option 3.
These load reductions were developed from each facility's current baseline loads to their
proposed load under the regulatory option. In addition, credit was given for steam
stripper or distillation removal of pollutant loads that are estimated as current air
emissions from wastewater.
Current air emissions were estimated by the Agency using the WATER? model,
discussed in detail in Section 12.3. The WATER? model was used to predict the
disposal pathways (i.e., degraded, discharged, or emitted to air) of the organic pollutants
present in untreated pharmaceutical manufacturing wastewaters. The Agency found that
the WATER? model calculated a greater percentage of wastewater organic constituents
emitted to the air than most facilities reported in the Detailed Questionnaire, and that
these air emissions were most likely to occur in open equalization or neutralization units
with mixing in the wastewater treatment system, downstream of any in-plant steam
stripping or distillation unit. For this reason, the pollutant load reductions shown for
BAT Options 2 and 3 include these captured air emissions, in addition to the reduction
to the current end-of-pipe wastewater discharge loads.
For BAT Option 4, the Agency estimated the COD load reduction through treatment by
granular activated carbon adsorption. The Agency estimated that there will be no
measurable additional load reduction of specific regulated organic constituents through
GAC beyond the level of treatment provided by in-plant steam stripping with distillation
followed by advanced biological treatment. The COD load reduction expected under
BAT Option 4 for Subcategory A and C and B and D facilities is presented in the table
below.
9-11
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ICOD Load Reduction Through GAG at A and C
Facilities (Ibs/yr)
4,750,000
COD Load Reduction Through GAC at B and
Facilities (Ibs/yr)
D
451,000
9.5.3
PSES
As discussed in more detail in Section 17 of this document, EPA makes two alternative
proposals concerning the establishment of PSES for the four manufacturing
subcategories. The following discussion corresponds to co-proposal (1), which would
regulate 45 priority and nonconventional pollutants of concern, and ammonia and
cyanide for Subcategories A and C. Co-proposal (2) would regulate 12 priority and
nonconventional pollutants of concern, and ammonia and cyanide for Subcategories A
and C. Load reductions achieved under co-proposal (2) are represented in Tables 9-10,
9-11, and 9-12 by asterisks, which identify the pollutants that would be regulated under
that co-proposal.
Table 9-10 presents load reductions through in-plant steam stripping for priority and
nonconventional pollutants under PSES Option 1. Table 9-11 presents load reductions
through in-plant steam stripping with distillation for priority and nonconventional
pollutants under PSES Option 2. These load reductions were developed based on the
difference between each faculty's current baseline loads and the estimated load under
the regulatory option. In addition, because steam stripping and distillation technology
reduce downstream air emissions from wastewater, credit was given for pollutant loads
that are currently emitted to air that would be captured by these technologies.
Load reductions for the Subcategory D indirect dischargers were also scaled up
according to the methodology discussed in Section 3.2.3 and presented in Reference (1).
An estimate of the total load reductions for the Subcategory D indirect dischargers
including those not sent a Detailed Questionnaire are presented in the table below.
9-12
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Total Load Reduction
Through Steam
Stripping (Ibs/yr)
Total Load Reduction
Through Distillation
(Ibs/yr)
Subcategory B and D
Indirect Dischargers
from the Detailed
Questionnaire
4,130,000
4,660,000
Subcategory D Indirect
Dischargers Without
Questionnaire
(estimate)
323,000
464,000
Total Subcategory B
and D Indirect
Dischargers
(estimates)
4,560,000
5,120,000
Table 9-12 presents load reductions through in-plant steam stripping with distillation
followed by end-of-pipe advanced biological treatment for organic pollutants and
ammonia under PSES Option 3 for Subcategory A and C indirect dischargers. These
load reductions were calculated based on the difference between each facility's current
baseline loads and their estimated load under the regulatory option. Similar to Option 2,
credit was also given for removal of pollutant loads that are estimated as current air
emissions that would be captured by in-plant steam strippers and distillation columns.
There is no option for Subcategory B and D indirect dischargers that includes advanced
biological treatment.
For PSES Option 4 for Subcategory A and C indirect dischargers, the Agency estimated
COD load reduction through granular activated carbon treatment. The Agency estimates
that there will be no measurable additional load reduction of specific regulated organic
constituents through carbon treatment beyond the level of treatment provided by in-plant
steam stripping with distillation followed by advanced biological treatment. For PSES
Option 3 for Subcategory B and D indirect dischargers, the Agency estimated COD load
reduction through granular activated carbon treatment, as well as the load reduction of a
few regulated organic constituents amenable to activated carbon treatment after in-plant
steam stripping with distillation. The COD load reduction and the load reduction of the
affected regulated organics expected through granular activated carbon treatment is
presented in the table below. Load reductions for Subcategory B and D facilities based
9-13
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on Detailed Questionnaire responses, as well as scaled-up to the entire industry are
presented.
COD Load
Reduction Through
GAC (lbs/yr)
Total Organic
Pollutant Load
Reduction Through
GAC (lbs/yr)
Subcategory A
and C Indirect
Dischargers
4,910,000
0
Subcategory B and D Indirect
Dischargers from the Detailed
Questionnaire
2,840,000
194
Total Subcategory
B and D Indirect
Dischargers (estimate
with scale-up)
3,570,000
213
9-14
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Table 9-1
Estimated Untreated Pollutant Loads by
Subcategory Group and Discharge Mode
(lbs/yr)
Pollutant
AandC
Direct
Dischargers
B and D
Direct
Dischargers
AandC
Indirect
Dischargers
B and D
Indirect
Dischargers
Conventionals and COD
BOD5
COD
TSS
77,026,379
170,414,438
23,383,184
1,309,631
2,454,864
565,057
NA
NA
NA
NA
NA
NA
Priority Organics
Benzene
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Priority Organics Subtotal
Cyanide
Priority Pollutant Total
1,700
10,959
402,005
194,604
0
586,115
8,074,997
364,720
3,632,402
13,267,502
41,733
13,309,235
0
0
0
0
0
0
25
1,811
0
1,836
0
1,836
121,400
84,710
488,980
5,148
21,499
6,552
7,170,355
6,693
2,964,688
10,870,025
75,065
10,945,090
0
0
77
0
0
0
780,865
714
2,276
783,932
0
783,932 (a)
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
5,079,688
926,804
333,871
54,000
154
0
0
0
13,339,234
574,641
639,973
144,619
1,607,106
0
824,830
0
9-15
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Table 9-1
(Continued)
Pollutant
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
AandC
Direct
Dischargers
36,400
13,633
763,200
392,049
86,997
339,512
0
264,971
7,460
21,177
0
4,571,456
87,992
0
4,149,197
3,928,205
45,399
701,800
3,337
18,056
63,050
1,838,778
8,501
5,396,359
527,801
; BandD
Direct
Dischargers
0
0
0
0
0
0
0
0
0
0
0
0
0
0
67,674
0
0
230
0
0
0
0
0
38,672
0
A and C
Indirect
Dischargers
30,551
19,578
415,426
978,684
212,508
22,082
325,570
311,071
1,379,516
661,381
131,174
801,666
819,972
69,039
8,847,220
2,428,264
326,623
783,013
352,661
30
74,346
1,566,893
36,479
9,095,624
249,114
BandD
Indirect
Dischargers
0
0
0
109
0
0
0
589
0
0
0
0
355
0
2,525,138
14,675
18,061
2,418
0
0
0
14,624
0
853,366
225,593
9-16
-------
Table 9-1
(Continued)
Pollutant
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone
(MIBK)
Petroleum naphtha
Polyethylene glycol 600
n-Propaaol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia (Aqueous)
Nonconventional Total
A and C
Direct
Dischargers
878
29,136,700
508,763
0
607,950
98,800
13,900
728
0
1,101
617,929
183,257
0
600,080
724,196
62,153,975
2,443,575
64,597,550
BandD
Direct
Dischargers
0
458
0
0
0
0
0
0
200
0
0
0
0
0
0
107,388
28
107,416
A and C
Indirect
Dischargers
16,730
21,633,682
446,024
1,755,690
28,689
0
2,416,611
578,795
93,907
19,326
321,010
816,347
5,770
1,693,165
153,563
74,616,261
4,620,458
79,236,719
BandD
Indirect
Dischargers
350
99,880
0
0
0
0
0
146
181
0
1,803
0
17,381
2
0
6,206,607
302
6,206,909 (a)
(a) Untreated load for facilities for which questionnaire data were available. Estimated total priority and
nonconventional pollutant load for all facilities is 7,183,909 Ibs/yr. See Section 9.2.
NA - Not available
9-17
-------
Table 9-2
Current Pollutant Discharge Loads by
Subcategory Group and Discharge Mode
(ibs/yr)
Pollutant
AandC
Direct
Dischargers
B and D
Direct
Dischargers
AandC
Indirect
Dischargers
BandD
Indirect
Dischargers
Conventionals and COD
BOD,
COD
TSS
3,258,176
31,676,918
6,333,181
57,455
293,661
82,404
NA
NA
NA
NA
NA
NA
Priority Organics
Benzene
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Priority Organics Subtotal
Cyanide
Priority Pollutant Total
0
0
2,018
140,070
0
103,934
145,518
9,000
122,269
522,809
45
522,854
0
0
0
0
0
0
0
0
0
0
0
0
120,200
5,606
177,287
134
21,499
4,294
1,198,531
1,206
257,685
1,786,442
1,084
1,787,526
0
0
32
0
0
0
15,595
714
5
16,346
0
16,346 (a)
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
21,727
9,020
6,071
53,000
8
0
0
0
3,004,969
423,821
208,429
143,554
43,136
0
82,483
0
9-18
-------
Table 9-2
(Continued)
Pollutant
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylform amide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
AandC
Direct
Dischargers
0
908
97,500
392,049
2,844
51
0
307
746
756
0
174
5,040
0
451,601
51,583
1,939
21,181
109
15,404
50
2,180
0
455,581
10,556
BandD
Direct
Dischargers
0
0
0
0
0
0
0
0
0
0
0
0
0
0
7,854
0
0
229
0
0
0
0
0
14,841
0
AandC
Indirect
Dischargers
4,600
17,283
415,426
666,216
95,564
440
218,020
454
1,045,358
660,593
18,155
387,124
745,181
24,422
4,368,801
205,545 •
147,760
310,677
7,075
0
27,894
, 8,449
35,654
2,785,586
14,809
B and D
Indirect
Dischargers
0
0
0
108
0
0
0
589
0
0
0
0
355
0
1,283,544
3
18,061
1,083
0
0
0
100
0
89,648
22,559
9-19
-------
Table 9-2
(Continued)
Pollutant
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone
(MBBK)
Petroleum Naphtha
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia (Aqueous)
Nonconventional Total
A and C
Direct
Dischargers
801
1,905,851
23,400
0
9,843
48,800
11,000
0
0
1,101
50
90,808
0
98,600
2,432
3,793,063
817,732
4,610,795
BandD
Direct
Dischargers
0
98
0
0
0
0
0
0
200
0
0
0
0
0
0
23,230
0
23,230
A and C
Indirect
Dischargers
10,963
12,433,615
310
445,137
2,773
0
623,193
260,583
87,039
11,439
210,186
226,167
3,850
531,326
24,969
30,863,409
530,851
31,394,260
B and D
Indirect
Dischargers
350
44,747
0
0
0
0
0
0
181
0
1,803
0
0
1
0
1,588,751
25
1,588,776 (a)
(a) Load for facilities for which questionnaire data were available. Estimated total priority and
nonconventional pollutant load for all facilities is 2,065,224 Ibs/yr. See Section 9.3.
NA - Not available
9-20
-------
Table 9-3
End-of Pipe Discharge Loads for
Subcategory A and C Facilities Under BAT Options
(lbs/yr)
Pollutant
BAT Option!
BAT Option 2
BAT Option 3
BAT Option 4
Priority Organics
Chloroform
Chloromethane
(Methyl chloride)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Priority Organics Subtotal
Cyanide
Priority Pollutant Total
250
1,155
250
2,705
1
261
4,622
7
4,629
250
1,111
59
304
1
261
1,986
7
1,993
250
1,111
40
304
1
261
1,967
7
1,974
250
1,111
40
304
1
261
1,967
7
1,974
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dunethylformamide
709
127
6,071
720
825
10,521
5,260
2,844
22
307
23
6
39
519
127
5,353
360
825
10,521
5,260
1,955
22
307
23
6
39
519
127
5,353
360
824
10,521
1,052
1,955
22
250
23
6
39
519
127
5,353
360
824
10,521
1,052
1,955
22
250
23
6
39
9-21
-------
Table 9-3
(Continued)
Pollutant
Dimethyl sulfoxide
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
n-Propanol
Pyridiae
Tetrahydrofuran
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia
Nonconventional Pollutant Total
BAT Option 1
121
22,299
20,366
1,939
8,056
109
15,404
50
47
6,808
1,051
801
24,375
1,052
2,211
105
631
1,101
1
27,922
1,052
100
163,076
71,168
234,244
BAT Option 2
121
17,407
13,603
1,939
8,056
109
14,123
50
47
1,341
1,051
801
12,700
1,052
1,685
105
105
1,101
1
1,855
1,052
100
103,721
17,159
120,880
BAT Option 3
121
11,571 '
13,603
1,939
8,056
109
10,525
50
47
1,341
1,051
800
12,700
1,052
1,685
105
105
1,052
1
1,855
1,052
100
89,971
' 17,159
107,130
BAT Option 4
121
11,571
13,603
1,939
8,056
109
10,525
50
47
1,341
1,051
800
12,700
1,052
1,685
105
105
1,052
1
1,855
1,052
100
89,971
17,159
107,130
Values have not been rounded to significant figures.
9-22
-------
Table 9-4
End-of-Pipe Discharge Loads for
Subcategory B and D Facilities Under BAT Options
(lbs/yr)
Pollutant
Acetone
Ethanol
Formaldehyde
Isopropanol
Methanol
Polyethylene Glycol 600
Nonconventional Pollutant Total (a)
BAT Option 1
8
189
63
62
98
200
620
BAT Option 2
8
145
63
11
92
200
519
BAT Option 3
8
94
63
11
92
200
468
BAT Option 4
8
94
63
11
92
200
468
(a) There are no priority pollutant end-of-pipe discharge loads for Subcategory B and D direct discharging
facilities.
Values have not been rounded to significant figures.
9-23
-------
Table 9-5
End-of-Pipe Discharge Loads for
Subcategory A and C Facilities Under PSES Options
(lbs/yr)
Pollutant
PSES Option 1
PSES Option 2
PSES Option 3
PSES Option 4
Priority Organics
Benzene
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethaae
Methylene chloride
Phenol
Toluene
Priority Organics Subtotal
Cyanide
Priority Pollutant Total
252
444
79
2
8,330
3,443
1,541
1,206
2,136
17,433
62
17,495
252
444
79
2
1,083
700
1,541
1,206
2,136
7,443
62
7,505
25
44
79
1
3
26
160
1,206
188
1,732
62
1,794
25
44
79
1
3
26
160
1,206
188
1,732
62
1,794
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
49,715
423,821
9,532
41,742
4,584
14,292
1,498
487,817
95,564
7,960
423,821
1,589
1,245
3,758
12,430
250
8,284
7,785
1,053
423,821
1,589
473
35
252
250
396
2,744
1,053
423,821
1,589
473
35
252
250
396
2,744
9-24
-------
Table 9-5
(Continued)
Pollutant
Cyclohexane
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylainine
N,N-DimethylaniIine
N,N-Dimetliylform amide
Dimethyl sulfojdde
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
MIBK
Petroleum Naphtha
PSES Option 1
30
6,355
422
1,045,358
4,835
10,356
387,124
745,181
24,423
1,641,628
14,496
147,760
310,677
4,249
786
373
7,542
569,547
8,350
2,199
9,810,898
310
2,537
2,773
5,106
260,583
PSES Option 2
30
958
244
1,045,358
90
836
387,124
745,181
2,567
28,392
3,291
147,760
310,677 "
2,274
786
373
985
31,294
2,041
820
34,527
310
2,537
1,256
1,950
3,318
PSES Option 3
3
42
63
26
3
29
195
5,616
95
10,118
3,291
3,734
781
916
40
30
457
1,181
2,041
174
12,491
34
2,537
1,256
25
23
PSES Option 4
3
42
63
26
3
29
195
5,616
95
10,118
3,291
3,734
781
916
40
30
457
1,181
2,041
174
12,491
34
2,537
1,256
25
23
9-25
-------
Table 9-5
(Continued)
Pollutant
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia
Nonconventional Pollutant
Total
PSES Option 1
87,039
11,439
6,695
14,631
95
11,899
194
16,274,455
89,142
16,363,597
PSES Option 2
87,039
757
6,695
14,631
95
2,235
194
3,333,747
89,142
3,422,889
PSES Option 3
87,039
28
82
842
95
403
30
564,333
6,053
570,386
PSES Option 4
87,039
28
82
842
95
403
30
564,333
6,053
570,386
Values have not been rounded to significant figures.
9-26
-------
Table 9-6
End-of-Pipe Discharge Loads for
Subcategory B and D Facilities Under PSES Options
dbs/yr)
Pollutant
PSES Option!
PSES Option 2
PSES Option 3
Priority Pollutants
Methylene chloride
Phenol
Toluene
Priority Pollutant Total
212
714
5
931
212
714
5
931
22
714
5
741
Nonconventional Organics
Acetone
n-Amyl acetate
n-Butyl alcohol
Diethyl ether
Dimethyl sulfoxide
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
n-Hexane
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Polyethylene Glycol 600
Pyridine
Triethylamine
Nonconventional Organics Subtotal
Ammonia
Nonconventional Pollutant Total
4,281
4,233
108
587
355
462,587
2
18,061
1,083
1
16,825
4,233
25
37,231
181
27
1
549,821
25
549,846
557
705
21
226
355
4,212
2
18,061
1,083
1
809
705
3
927
181
27
1
27,876
25
27,901
557
705
21
226
355
4,212
2
18,061
1,083
0
809
705
0
927
181
27
1
27,872
25
27,897
Values have not been rounded to significant figures.
9-27
-------
Table 9-7
Pollutant Load Reduction Through Advanced Biological Treatment
for Subcategory A and C and B and D Direct Dischargers
(Ibs/yr)
Pollutant
Load Reduction for A and C
Direct Dischargers
Load Reduction for B and D
Direct Dischargers
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Priority Pollutant Total
0
0
1,768
138,915
0
103,684
142,813
8,999
122,008
518,186
0
0
0
0
0
0
0
0
0
0
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethylamine
21,018
8,893
0
52,280
0
83
86,979
386,789
0
29
0
0
0
0
0
0
0
0
0
0
0
0
9-28
-------
Table 9-7
(Continued)
Pollutant
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaiiiline
N,N-Dimethylformamide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum Naphtha
Load Reduction for A and C
Direct Dischargers
0
723
750
0
135
4,919
0
429,302
31,217
0
13,125
0
0
0
2,133
0
448,772
9,505
0
1,881,476
22,348
0
7,632
48,695
10,369
0
Load Reduction for B and D
Direct Dischargers
0
0
0
0
0
0
0
7,665
0
0
166
0
0
0
0
0
14,779
0
0
0
0
0
0
0
0
0
9-29
-------
Table 9-7
(Continued)
Pollutant
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia
Nonconventional Pollutant Total
Load Reduction for A and C
Direct Dischargers
0
0
49
62,886
0
97,548
2,332
3,629,987
746,564
4,376,551
Load Reduction for B and D
Direct Dischargers
0
0
. 0
0
0
0
0
22,610
0
22,610
Values have not been rounded to significant figures.
9-30
-------
Table 9-8
Pollutant Load Reduction Through In-Plant Steam Stripping Followed by
End-of-Pipe Advanced Biological Treatment for Subcategory
A and C and B and D Direct Dischargers
(Ibs/yr)
Pollutant
Load Reduction for A and C
Direct Dischargers
Load Reduction for B and D
Direct Dischargers
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Priority Total
789
0
105,178
140,838
0
153,164
1,884,443
8,999
354,311
2,647,722
0
0
0
0
0
0
25
1
0
26
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
AnUine
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl sulfoxide
1,4-Dioxane
1,415,661
9,013
718
53,640
11
11,547
89,071
386,789
23,889
283,920
0
20,327
3,056
994
0
15,912
7,481
0
14
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
9-3'l
-------
Table 9-8
(Continued)
Pollutant
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum Naphtha
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia
Nonconventional Pollutant Total
Load Reduction for A and C
Direct Dischargers
1,841,705
931,650
7
18,173
138
1,333
187
993,009
0
2,136,153
464,930
16
3,260,025
500,527
0
606,265
49,798
10,935
524
0
0
2,257
120,186
0
108,619
696,956
14,064,222
1,794,369
15,858,591
Load Reduction for B and D
Direct Dischargers
23,740
0
0
166
0
0
0
0
0
15,167
0
0
35
0
0
0
0
0
0
0
0
0
0
0
0
0
39,122
(a)
39,150
•"Ammonia is not a pollutant of concern for Subcategory B and/or D direct discharges. There would be incidental ammonia removal
of 28 pounds/yr through this treatment train.
Values have not been rounded to significant figures.
9-32
-------
Table 9-9
Pollutant Load Reduction Through In-Plant Steam Stripping With
Distillation Followed by End-of-Pipe Advanced Biological Treatment
for Subcategory A and C and B and D Direct Dischargers
(Ibs/yr)
Pollutant
. Load Reduction for A and C
Direct Dischargers
Load Reduction for B and D
Direct Dischargers
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Priority Total
789
0
105,178
140,838
0
. 153,183
1,884,443
8,999
354,311
2,647,741
0
0
0
0
0
0
25
1
0
26
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
1,415,661
9,013
718
53,640
11
11,547
89,071
390,997
23,889
283,920
14
0
0
0
0
0
0
0
0
0
9-33
-------
Table 9-9
(Continued)
Pollutant
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimetliylainine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Load Reduction for A and C
Direct Dischargers
0
20,384
3,056
994
0
15,912
7,481
0
1,847,541
931,650
7
18,173
138
4,931
187
993,009
0
2,136,153
464,930
16
3,260,025
500,527
0
606,265
49,798
10,935
Load. Reduction for B and D
Direct Dischargers
0
0
0
0
0
0
0
0
23,791
0
0
166
0
0
0
0
0
15,167
0
0
35
0
0
0
0
0
9-34
-------
Table 9-9
(Continued)
Pollutant
Petroleum Naphtha
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
Nonconventional Organics
Subtotal
Ammonia
Nonconventional Pollutant Total
: Load Reduction for A and C
Direct Dischargers
524
0
49
2,257
120,186
0
108,619
696,956
14,079,170
1,794,369
15,873,539
Load. Reduction for B and D
Direct Dischargers
0
0
0
0
0
0
0
0
39,173
(a)
39,201
'"Ammonia is not a pollutant of concern for Subcategory B and/or D direct discharges. There would be incidental ammonia removal
of 28 pounds/yr through this treatment train.
Values have not been rounded to significant figures.
9-35
-------
Table 9-10
Pollutant Load Reduction Through In-plant Steam Stripping for
Subcategory A and C and B and D Indirect Dischargers
(lbs/yr)
Pollutant
Load Reduction for A and C
Indirect Dischargers
Load Reduction for B and D
Indirect Dischargers
Priority Pollutants
Benzene"
Chlorobenzene"
Chloroform"
Chloromethane"
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride"
Phenol
Toluene"
Priority Pollutant Total
119,948
5,172
283,593
133
13,169
896
4,273,969
0
2,446,728
7,143,608
0
0
74
0
0
0
694,415
0
0
694,489
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cydohexane"
Diethylamine
5,853,155
0
208,112
101,893
20,116
3,065
413,928
339,432
0
637
230,036
1,004,881
0
691,691
0
0
0
0
1
0
0
0
9-36
-------
Table 9-10
(Continued)
Pollutant
Diethyl ether
N,N-Dimethylacetamide
Dimethylamiiie
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane*
a-Hexane*
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve*
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum Naphtha
Load Reduction for A and C
Indirect Dischargers
283,746
0
655,768
7,823
0
0
21,603
4,575,401
1,496,135
0
0
108,285
0
48,740
1,193,015
28,755
3,558,832
171,094
9,014
5,657,638
12,871
1,499,045
5
0
1,487,907
0
Load Reduction for B and O
Indirect Dischargers
2
0
0
0
0
0
0
1,310,308
3,864
0
0
0
0
0
99
0
218,887
199,482
325
8,271
0
0
0
0
0
0
9-37
-------
Table 9-10
(Continued)
Pollutant
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane"
Triethylamine
Xylenes"
Nonconventional Organics
Subtotal
Ammonia*
Nonconventional Pollutant Total
Load Reduction for A and C
Indirect Dischargers
0
4,310
288,418
450,622
5,675
940,711
27,073
29,702,860
1,182,199
30,885,059
Load Reduction for B and D
Indirect Dischargers
0
0
1,775
0
1
1
0
3,439,588
0
3,439,588
"Only a subset of the pollutants that would be treated by this technology would actually receive a standard under co-proposal (2).
Those pollutants are marked with an asterisk.
Values have not been rounded to significant figures.
9-38
-------
Table 9-11
Pollutant Load Reduction Through In-plant Steam Stripping
With Distillation for Subcategory A and C and B and D
Indirect Dischargers
(Ibs/yr)
Pollutant
Load Reduction for A and C
Indirect Dischargers
Load Reduction for B and D
Indirect Dischargers
Priority Pollutants
Benzene*
Chlorobenzene*
Chloroform*
Chloromethane*
(Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride*
Phenol
Toluene*
Priority Pollutant Total
119,948
5,172
283,593
133
20,416
3,639
4,273,969
0
2,446,728
7,153,598
0
0
74
0
0
0
694,415
0
0
694,489
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane*
5,894,908
0
216,055
142,391
20,942
4,927
415,176
818,966
87,779
637
1,008,605
0
695,218
0
0
0
0
88
0
0
9-39
-------
Table 9-11
(Continued)
Pollutant
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl sulfoxide
1,4-DLoxane
Ethanol
Ethyl acetate
Ethylene glycol
Fonnaldehyde
Formamide
Furfural
n-Heptane"
n-Hexane"
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve"
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Load Reduction for A and C
Indirect Dischargers
235,434
283,924
0
660,513
17,343
0
0
43,458
6,188,635
1,507,340
0
0
110,260
0
48,740
1,193,015
35,312
4,097,086
177,402
10,394
15,434,007
12,871
1,500,905
1,522
0
1,491,063
Load Reduction for B and D
Indirect Dischargers
0
363
0
0
0
0
0
0
1,768,683
3,864
0
0
0
0
0
99
0
234,901
203,009
347
44,576
0
0
0
0
0
9-40
-------
Table 9-11
(Continued)
Pollutant
Petroleum Naphtha
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane"
Triethylamine
Xylenes*
Nonconventional Organics
Subtotal
Ammonia*
Nonconventional Pollutant Total
Load Reduction for A and C
Indirect Dischargers
257,265
0
14,992
288,418
450,622
5,675
950,375
27,073
42,645,425
1,182,199
43,827,624
Load Reduction for B and D
Indirect Dischargers
0
0
0
1,775
0
1
1
0
3,961,530
0
3,961,530
'"'Only a subset of the pollutants that would be treated by this technology would actually receive a standard under co-proposal (2).
Those pollutants are marked with an asterisk.
Values have not been rounded to significant figures.
9-41
_
-------
Table 9-12
Pollutant Load Reduction Through In-Plant Steam Stripping With
Distillation Followed by End-of-Pipe Advanced Biological Treatment
for Subcategory A and C Indirect Dischargers
(lbs/yr)
Pollutant
Load Reduction for A and C Indirect
Dischargers
Priority Pollutants
Benzene"
Chlorobenzene"
Chloroform"
Chloromethane (Methyl chloride)*
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride"
Phenol
Toluene"
Priority Pollutant Total
120,175
5,572
283,593
134
21,496
4,313
4,275,350
0-
2,448,677
7,159,310
Nonconventional Organics
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cydohexane"
Diethylamine
5,901,816
0
216,055
143,163
24,666
17,105
415,176
826,854
92,820
664
236,350
9-42
-------
Table 9-12
(Continued)
Pollutant
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformaniide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane"
n-Hexane*
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve*
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum Naphtha
Load Reduction for A and C Indirect
Dischargers
284,104
1,045,332
660,600
18,150
386,929
739,565
45,930
6,206,910
1,507,340
144,027
309,897
111,618
0
49,486
1,193,356
35,840
4,127,199
177,402
11,039
15,456,041
13,147
1,499,045
1,522
0
1,492,987
260,560
9-43
-------
Table 9-12
(Continued)
Pollutant
Polyethylene glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane"
Triethylamine
Xylenes"
Nonconventional Organics Subtotal
Ammonia"
Nonconventional Pollutant Total
Load Reduction for A and C Indirect
Dischargers
0
15,720
295,031
464,412
5,675
952,206
27,237
45,412,976
1,265,289
46,678,265
^Only a subset of the pollutants that would be treated by this technology would actually receive a standard under co-proposal (2).
Those pollutants are marked with an asterisk.
Values have not been rounded to significant figures.
9-44
-------
REFERENCES
1.
2.
3.
Memorandum: Subcategory D Indirect Scale-up Methodology, from
K. Mahsman, Radian Corporation, to the Public Record, September 1994.
Memorandum: Final Pollutant Loading Estimates for the Pharmaceutical
Manufacturing Industry - Subcategory A/C and B/D Direct and Indirect
Discharging Facilities, from K. Mahsman and M. Willett, Radian
Corporation, to F. Hund, USEPA/EAD, August 31, 1994.
Letter from M. Willett, Radian Corporation, to K. Koon, Versar,
December 15, 1994. :
9-45
-------
-------
SECTION 10
COSTS OF TECHNOLOGY BASES FOR REGULATIONS
10.1
Introduction
Previous sections have described the respective BPT, BCT, BAT, NSPS, PSES, and PSNS
technology options that were considered as the bases of regulations for the
pharmaceutical manufacturing industry. This section presents the estimated engineering
costs associated with installing and operating each of these technology bases. These
costs are calculated to determine the overall economic impact on the industry of
complying with each regulatory option.
The following information is discussed in this section:
• Section 10.2 discusses the costing methodology;
• Section 10.3 discusses cost modeling and summarizes cost estimating
assumptions and design bases for the technologies that make up the
regulatory options; and
• Section 10.4 presents the cost estimates by regulatory option.
10.2
Costing Methodology
To accurately determine the impact of the proposed effluent limitations guidelines and
standards on the pharmaceutical manufacturing industry, it is necessary to calculate costs
associated with regulatory compliance. A cost model was developed to represent each of
the regulatory options under BPT, BCT, BAT, PSES, PSNS, and NSPS. The cost model
is used to calculate costs for each option based on the treatment technologies used as the
basis for that option. These costs are estimates of actual compliance costs; however, the
10-1
-------
regulations do not require that a facility install or possess the technologies specified as
the bases, but only that the appropriate limitations be met.
The Agency has selected a facility-by-facility approach to costing as opposed to a model
facility approach, because of the variability of processes and resultant wastewaters among
pharmaceutical manufacturing facilities. Detailed facility information was available from
responses to the Detailed Questionnaire, which was used to characterize the wastewater
and assess existing treatment technologies at each facility. It should be noted, however,
that in certain instances, engineering assumptions regarding facility operations were
made, or industry average data were used when facility-specific information were not
available. Thus, for any given facility, the costs estimated may deviate from those that
would actually be experienced by the facility. However, since these assumptions were
based on industry-wide data, the resulting estimates are considered accurate when
evaluated on an industry-wide, aggregate basis.
When practical and appropriate, facilities were given credit for existing treatment on site,
based on an evaluation of the following criteria:
• Biological treatment system aeration capacity (in million gallons);
• Clarifier overflow rate (in gallons per minute per square foot);
• Presence of adequate equalization treatment;
• Presence of steam stripping or steam stripping with distillation
treatment that achieved adequate removal of organic compounds;
and
• Presence of cyanide destruction treatment - this credit was given
wholly or partially based on comparison to the treatment system
selected as the technology basis.
These treatment credits were used to develop cost estimates for system upgrades instead
of new systems where appropriate. At facilities that currently meet the proposed
10-2
-------
limitations associated with a regulatory option, no compliance costs beyond necessary
additional monitoring were estimated.
10.2.1
Cost Model Structure
The model used to calculate wastewater treatment costs was developed based on
research into various existing costing approaches and use of customized computer
software tools. The model consists mainly of a series of technology modules, each of
which calculates the costs associated with a particular treatment technology. These
modules can be combined as appropriate to assemble each of the various regulatory
options. A more detailed discussion of the cost model and its origins is given in
Section 10.3.
Operation and maintenance (O&M) and capital costs were calculated by the model for
each technology and then summed for all technologies at each facility. The facility
capital and O&M costs were combined and totaled by subcategory and discharge type
(e.g. Subcategory A and C - indirect discharger).
Annual O&M costs consist of all costs related to operating and maintaining the
treatment system for a period of one year. Sources for O&M costs primarily included
literature references and engineering judgement (typically used in the case of estimating
required operator hours). O&M costs typically include the following:
• Chemical usage;
• O&M labor;
• Removal, transportation, and disposal of any waste solids, sludges,
solvents, or other waste products generated by the treatment system;
• Any required treatment unit performance monitoring not related to
actual compliance monitoring (e.g., breakthrough monitoring •
between beds of the GAC system); and
10-3
-------
• Utilities, such as electricity and steam, required to run the treatment
system.
Table 10-1 presents the O&M unit costs most commonly used by the model and includes
references for the origin of each cost.
Capital costs consist of direct and indirect costs associated with purchase and installation
of wastewater treatment equipment. Primary sources for the capital costs were vendor
quotes and literature references. Table 10-2 presents the unit capital costs most
commonly used by the model and includes references for the origin of each cost.
Typically, direct capital costs include the following:
• Purchase and installation of treatment equipment;
• Purchase and installation of piping, instrumentation, pumps, and
other ancillary equipment;
• Electrical hookups;
• Any required site preparation (e.g., excavation);
• Construction of buildings or other structures; and
• Land purchase.
In addition to direct capital costs, indirect costs are also included in the estimate of total
capital cost. Indirect capital costs typically include engineering costs and contractor's
fees.
For each technology, it is assumed that ancillary direct capital costs and required indirect
capital costs can be accounted for by using a factor related to purchased and installed
capital cost. Table 10-3 lists these factors for all applicable treatment technologies.
10-4
-------
Because all facility-specific information in the questionnaire database is from 1990, all
costs are adjusted to 1990 dollars. This adjustment allows direct comparison between
reported financial data and costs for each facility. Costs are adjusted using the Marshall
and Swift 1990 annual index (915.1) and the index value for the year in which the costs
were originally reported using the following formula:
AC = OC(915.1/OCI)
(10-1)
where: AC = Adjusted cost, $
OC = Original cost, $
OCI = Original cost year index
The wage rate for all required labor to properly operate and maintain the systems
associated with the technology bases was obtained from the U.S National Bureau of
Labor Statistics. In 1990, the average wage rate for all production workers in the Drugs
Manufacturing industry was $12.90 per hour. This rate was then increased by 115% to
account for supervision (15%), and overhead (100%) to arrive at a total rate of $27.74
per hour. The cost for electricity used by various treatment technologies was obtained
from 1990 U.S Department of Energy statistics for Investor-Owned Utilities for
Commercial Facilities. This rate was given as $0.048 per kilowatt-hour. The cost for
steam usage was assumed to be $3.20 per 1,000 pounds of 100 psig steam. This value
was taken from Plant Design and Economics for Chemical Engineers. Peters and
Timmerhaus, Fourth Edition, and represents the high end of the range of costs given for
100 psig steam. These unit costs are listed along with other O&M unit costs in
Table 10-1.
For the cost estimating effort, it was assumed that all Subcategory A and C facilities and
Subcategory B and D direct discharger facilities operate 350 days per year, and that
Subcategory B and D indirect discharger facilities operate 250 days per year. These
assumptions are based on operating modes observed during engineering site visits. It is
10-5
-------
also assumed, because of the nature of the technology, that all biological treatment
systems operate 365 days per year, regardless of subcategory.
10.3
Cost Modeling
10.3.1
Evaluation of Existing Cost Models
Before a costing methodology could be developed, existing cost models were researched
and evaluated to determine which, if any, existing algorithms for costing various
treatment technologies could be used to develop costs for wastewater treatment systems
and treatment system upgrades in the pharmaceutical manufacturing industry. The
following models were initially considered for potential use:
The Wastewater Treatment System Design and Cost Model
(WTSDCM) developed by EPA in the early 1980s for various metal
manufacturing-related industries;
The Cost of Remedial Action model (CORA);
The Remedial Action Cost Engineering and Requirements
(RACER) model;
The Advanced System for Process Engineering (ASPEN);
The Computer Assisted Procedure for the Design and Evaluation of
wastewater Treatment systems (CAPDET); and
The pesticide industry models developed by EPA for pesticide
chemicals manufacturers and pesticide formulators, packagers, and
repackagers, respectively.
The WTSDCM model was eliminated because of the lack of similarity between
pharmaceutical and metal manufacturing industry wastewaters and related treatment
techniques. The CORA model was also eliminated because it had been superseded by
10-6
-------
the more recently developed RACER model. The remainder of the cost models were
considered further.
The RACER model was determined not to be applicable because it was designed to
address remedial treatment activities associated with cleanup of contaminated sites, and
not industrial wastewater treatment. ASPEN was also determined not to be applicable
because, while serving as an excellent process simulation tool, it is not set up to serve the
cost estimating purposes required. It also models only the steam stripping and
distillation treatment technologies included in the basis for the regulatory options.
The remaining models (CAPDET and the pesticide industry models) were determined to
have some appropriate design and costing information, but were not configured properly
to be used directly to cost the pharmaceutical manufacturing industry. Based on this
conclusion, it was determined that the most effective way to model costs for the industry
would be through development of a new cost model.
The resulting cost model is an integrated computer model that uses design and costing
information taken from many sources, including CAPDET and the pesticides industry
models. The cost model includes program files that design and cost all technologies
included as bases for the regulatory options discussed in Section 7.2, and data files that
include all pertinent facility data.
10.3.2
Model Driver
Because the pharmaceutical manufacturing industry cost model (hereafter referred to as
the cost model) is basically a collection of computer "modules" designed to calculate
costs for each of the basic technologies, it was necessary to include a program to
organize the modules and track the costs for the entire industry. This program has been
designated as the model "driver". The model driver performs the following major
functions associated with generating industry costs for each of the regulatory options:
10-7
-------
• Locate and open all necessary input data files;
• Store input data entered by a user of the model;
• Open and run each of the technology modules in the appropriate
order;
• Track all costs and pollutant concentrations generated by the
technology modules; and
• Send tracked costs by subcategory, discharge type, and regulatory
option to a storage file which may be printed or maintained in
electronic form.
The following sections list the major technologies included as modules within the cost
model, and describe the major assumptions and costing methodology used for each.
10.3.3
Advanced Biological Treatment
Advanced biological treatment is used to control BOD5, COD, and TSS and to degrade
various organic pollutants. Biological treatment systems are normally designed based on
BOD5 and TSS loads and desired removal efficiency. Organic pollutant reduction also
occurs through well-operated treatment systems. The installation of extended aeration
activated sludge biological treatment was assumed for cost estimating purposes. As
shown in Table 7-1, activated sludge treatment is the most common biological treatment
used in the pharmaceutical manufacturing industry. All of the facilities that form the
bases for the limitations based on biological treatment use activated sludge biological
treatment on site.
Typically, an extended aeration activated sludge biological treatment system consists of
the following major equipment: •
An equalization basin;
An aeration basin;
A secondary clarifier; and
A sludge handling system, if necessary.
10-8
-------
10.3.3.1
Overview of Costing Methodology
Facilities requiring additional treatment of BOD5, COD, TSS, or ammonia (if applicable)
were costed for installing a biological treatment system capable of removing these
pollutants down to the long-term mean performance concentrations for this technology
that are discussed in Section 8.5. If a facility had no biological treatment on site, a new
treatment system was costed. If a facility had biological treatment on site, an upgrade to
the existing system was costed.
Various types of upgrades were possible for a facility with existing treatment on site. If
additional BOD5 or COD removal was required, an additional aeration basin was
installed in parallel with the existing treatment unit. If additional TSS treatment was
also required, additional clarifiers were installed in parallel with the existing clarifiers.
If a facility required additional TSS treatment only, polymer was added to the existing
clarifiers to enhance settling. If only additional ammonia treatment was required,
surface aerators were added to the existing aeration basin to enhance the growth of
nitrifying microorganisms.
If the costed biological treatment system, whether an upgrade or new system, was
determined to generate excess biological solids, a new sludge handling system was
installed. The following table shows the breakdown between facilities requiring upgrades
and facilities requiring completely new biological treatment systems.
Subcategory
A and C
A and C
Band D
B and D
Discharge
type
Direct
Indirect
Direct
Indirect
Based on BPT Option 2
Upgrades
9
NA
3
NA -
'••- New
Systems
5
NA
2
NA
Already in
compliance
10
NA
9
NA
Total
24
14
! Based on PSES Option 3
: Upgrades
NA
63
NA
NA
: :., New .
Systems
NA
5
NA
NA
Already in
compliance
NA
20
NA
NA
Total
88
111
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10.3.3.2
Design Bases and Assumptions
The design of the aeration basin and secondary clarifier are based on a combination of
relationships and equations developed by Eckenfelder and from field data for suspended
growth biological treatment. Costing equations were taken from CAPDET for
equalization basins, package extended aeration activated sludge units (facility flows less
than 0.5 MGD), full-size extended aeration activated sludge units (flows greater than 0.5
MOD), and circular secondary clarifiers.
Design equations for biological treatment systems were similar for new units and for
upgrades. The following is a list of key design assumptions for costing biological
treatment for pharmaceutical manufacturing facilities:
• Values for key design parameters associated with biological
treatment were established based on subcategory-specific
information obtained from the Detailed Questionnaire. These
values are listed in Table 10-4.
• The retention time for designed clarifiers is 5 hours.
• The retention time for designed equalization basins is 24 hours (if a
new equalization basin is necessary).
• The sludge generated by the biological treatment unit has the
following characteristics:
1% solids in the sludge from the clarifier to the sludge
thickener;
5% solids in the sludge from the thickener to the filter press;
13% solids in filter press cake; and
Sludge density equal to 80 lbs/ft3.
• Generated sludge is thickened, dewatered, and hauled off site for
incineration as a nonhazardous waste.
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Installation of any of the equipment associated with biological
treatment will not require purchase of additional land.
One or more floating surface mixers are necessary for operation of
the equalization basin. (It is assumed that 30 horsepower per million
gallons are required for mixing in the equalization basin.)
Floating surface aerators will be used for ammonia treatment
upgrades, and fix-mounted surface aerators will be used for
treatment of BOD5 and COD.
10.3.3.3
Costing Methodology
Cost equations for purchase and installation of equipment associated with equalization,
aeration, and secondary clarification were obtained from CAPDET. The costs for the
following standard-sized equipment were also obtained from CAPDET: package aeration
plant (100,000 gal/day) and clarification tank (90-foot diameter). The following costs
were obtained from vendors or costing references: chemical unit costs, excavation unit
cost, reinforced concrete installation unit cost, floating surface aerator costs, fixed-
mounted surface aerator costs, sludge thickening tank costs, sludge filter press costs, and
sludge hauling and disposal costs. Tables 10-1 and 10-2 presents all unit costs listed
above.
The following are included in the total capital cost calculated for each facility requiring
biological treatment (all equipment costs include purchase and installation):
• A reinforced, concrete equalization basin (if not already existing at
the facility);
• Floating surface mixers for the equalization basin, if necessary;
• Floating surface aerators in an existing aeration basin for the
nitrification of ammonia, if necessary;
• A reinforced concrete aeration basin, with associated fixed-mounted
surface aerators, if necessary (aeration basins are provided at
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facilities with no existing biological treatment, or where existing
treatment is not adequate);
• A reinforced concrete clarifier, if necessary (clarifiers are provided
at facilities with no existing biological treatment, or where existing
suspended solids removal is not adequate);
• Any earthwork required for site preparation prior to installing the
equalization basin, aeration basin, or clarifier (earthwork includes
the construction of curbs and dikes for secondary containment);
• A platform and pedestrian bridge over the aeration basin;
• Sludge thickening tank(s); and
• Filter press(es) for sludge dewatering. ,
Table 10-3 presents the factors that are used by the cost model to account for ancillary
direct and all indirect capital costs.
The following are included in the total O&M costs calculated for each facility:
O&M labor;
Electricity usage;
Chemical purchases;
Miscellaneous O&M materials and supplies; and
Sludge hauling and incineration.
Table 10-5 lists operation and maintenance labor hour requirements for various activities
associated with biological treatment.
All operation and maintenance hour requirement calculations except those used for
sludge handling were based on assumptions and equations from CAPDET. Sludge
handling labor hour requirements were developed based on engineering judgement
regarding the labor required for operation and maintenance of the filter press or presses.
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Electricity usage was calculated using relationships provided in CAPDET. Electricity
requirement equations for each portion of the biological treatment system are shown
below.
Activity
Package aeration
Full-scale aeration
Clarification
Sludge Handling
Electricity Usage Equation (a)
75,000 (FLOW)
6701.4 (TICA) (b)
7500 , (SA < 1670)
2183.3 (SA)°'ISS3 (1670 < SA < 16,700)
38.4 (SA)0-5818 (SA > 16,700)
None
(a) All equations yield values in kilowatt-hours.
(b) This equation represents operating aerators 90% of the time, every day, year-round.
FLOW - Facility flowrate (MOD).
TICA - Total installed capacity of aeration (horsepower).
SA - Clarifier surface area (ft3).
Miscellaneous O&M material and supply costs are based on factors provided in
CAPDET. These factors are listed for biological treatment operations below.
Activity
Package aeration
Full-size aeration
Clarification
Miscellaneous O&M Cost
1.74 (FLOW)-0-2497
4.225 - 0.9751og (TICA)
1 percent of total clarification purchased
installed equipment costs
and
FLOW - Facility flowrate (MGD)
TICA - Total installed capacity of aeration (horsepower)
Table 10-1 lists unit costs for chemical purchases and sludge hauling and incineration.
10.3.4
Multimedia Filtration
Multimedia filtration is a treatment technology used primarily for the removal of TSS
from wastewater. This technology can be used as an end-of-pipe treatment to remove
10-13
_
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biological or other suspended solids prior to off-site discharge, or as a pretreatment
technology prior to activated carbon treatment or other technologies that may be
adversely affected by high TSS concentrations. Multimedia filtration is considered to be
superior to sand or other single-media filtration technologies due to increased flow
capacity and higher efficiency.
Multimedia filtration was costed for all options that included filtration at facilities where
current TSS concentrations exceeded the long-term mean concentration for filtration.
The physical equipment required for this treatment includes a filtration unit with
multiple filter cells (to allow continuous operation during maintenance of individual
cells), a backwash tank and pump, and all internal piping and electrical controls
associated with operating the treatment unit. For filters with a surface area greater than
400 square feet, the filtration unit and backwash tank are both assumed to be
constructed of reinforced concrete. Package filtration units are installed for facilities
requiring a filter surface area of 400 ft2 or less. Materials of construction vary for
package filtration units.
10.3.4.1 Overview of Costing Methodology
Cost estimates for multimedia filtration units were developed for those facilities with
reported TSS concentrations in the final effluent above the long-term mean
concentrations. No credit was given to facilities for filtration units existing on site unless
they currently achieve the long-term mean performance level associated with filtration.
There were situations where facilities did incur costs for TSS treatment even if they
achieved the long-term mean performance level. This occurred when facilities required
biological treatment as part of a technology option that also included filtration. It was
assumed that the biological system discharged wastewater containing TSS at the long-
term mean concentration associated with biological treatment. This concentration may
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have been higher than the TSS concentration reported in the Detailed Questionnaire for
a particular facility.
10.3.4.2
Design Bases and Assumptions
Design equations for multimedia filtration were taken directly from CAPDET. The
following is a list of key design assumptions associated with costing multimedia filtration
treatment.
Facilities would not be required to purchase additional land to
install this technology;
Package filtration units are installed for facilities requiring a filter
surface area of 400 ft2 or less;
For units requiring greater than 400 ft2 of filter surface area, a
standard unit size of 784 ft2 is used as a basis for purchase cost
equations;
Backwashing is performed, when necessary, at a rate of 20 gpm/ft2
for 10 minutes at a time;
The system is assumed to be gravity flow; and
The hydraulic loading rates used to size the new units are based on
industry averages (3.37 gpm/ft2 for Subcategory A and C facilities
and 2.23 gpm/ft2 for Subcategory B and D facilities).
Table 10-3 presents the factors used by the model to account for ancillary direct and all
indirect costs.
10.3.4.3
Costing Methodology
Costing equations and values were taken from CAPDET and vendor information. The
following unit costs were obtained from CAPDET: package filtration and full-size
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filtration standard unit costs. Unit costs for earthwork and reinforced concrete wall
installation are based on vendor information. Tables 10-1 and 10-2 present all of these
unit costs.
The following are included in the total capital cost calculated for each facility requiring
multimedia filtration treatment:
For Package Filtration
• Earthwork associated with installation of
backwash tank (earthwork includes the
construction of curbs and dikes for
secondary containment);
• Construction of the concrete backwash
tank;
• Purchase of package filter unit; and
• Installation of equipment (assumed by
CAPDET to be 53% of the concrete
installation cost).
For FiiH-Scale Filtration
• Earthwork associated with installation of the
filter unit and backwash tank (earthwork
includes the construction of curbs and dikes
for secondary containment);
• Construction of the concrete filter unit and
concrete backwash tank;
• Purchase of required filtration equipment; and
• Installation of equipment (assumed by
CAPDET to be 53% if the concrete
installation cost).
Factors to account for ancillary direct and all indirect capital costs were taken from
CAPDET, and are listed in Table 10-3.
As mentioned earlier, filters larger than 400 ft2 were costed using 784 ft2 as a standard
size. The equations for calculating the cost of these filters are:
If SAD < 784 ft2
COST - [1.04 (SAD)'-] STANDARD)
100
(10-2)
If SAD > 784 ft2
10-16
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COST = [8.99 (SAD)0-3615]
(STANDARD)
100
(10-3)
where:
COST
SAD
STANDARD
The capital cost of the filter unit, $
The designed filter surface area, ft2
The capital cost of a 784 ft2 filtration unit, $.
The following are included as O&M costs for multimedia filtration treatment:
O&M labor;
Miscellaneous O&M materials (assumed by CAPDET to be equal to
5% of the purchase cost of the filter unit); and
Electricity usage.
Operation and maintenance labor requirements and electricity usage requirements are
based on relationships provided in CAPDET. They are as follows:
Operation labor (hrs) = 80.4 (FLOW)0-572
Maintenance labor (hrs) = 54 (FLOW)0-585
Electricity Usage (Kwh) = 8213 (FLOW)0-972
where:
FLOW = Facility flowrate (MOD).
10.3.5
Polishing Pond Treatment
Polishing pond treatment is used primarily to control TSS in wastewater. BOD5 removal
associated with the settling of suspended solids may also result from this treatment. This
technology is most commonly used as a final end-of-pipe treatment prior to off-site
discharge of wastewater.
10-17
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Costs for polishing ponds were included for all options with polishing pond treatment as
part of the technology basis at facilities where current long-term mean TSS
concentrations exceed the long-term mean for polishing ponds.
The physical equipment required to perform polishing pond treatment includes influent
and effluent structures (both assumed to be reinforced concrete), a pond or surface
impoundment with an engineered, synthetic double liner system, and a groundwater
detection monitoring system. It is assumed for cost estimating purposes that the
installation of polishing ponds would require facilities to comply with all applicable
RCRA regulations for surface impoundments used to manage hazardous waste.
Typically, industrial wastewater treatment systems are excluded from complying with
RCRA regulations. However, since a polishing pond meets the RCRA definition of a
surface impoundment, and pharmaceutical wastewater typically contains listed hazardous
wastes, RCRA hazardous waste regulations are assumed to. apply to polishing ponds.
10.3.5.1 Overview of Costing Methodology
Costs for new polishing ponds were included for all facilities with reported TSS
concentrations above long-term mean concentrations in end-of-pipe wastewater streams.
Cost estimates for all facilities requiring polishing pond treatment included a
groundwater detection monitoring system and a RCRA closure plan. If the facility did
not already have a RCRA Part B Permit (required for operators of surface
impoundments that receive hazardous waste), costs were included for obtaining the
permit.
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10.3.5.2
Design Bases and Assumptions
The system designed and costed by the cost model is based primarily on equations
developed for CAPDET. Important assumptions associated with this design include the
following.
• The hydraulic detention time of the pond is 3 days.
• The depth of the pond is 5 feet.
• The excavation cut and fill volumes are approximately equalized to
minimize the volume of fill required or soil removed from the
construction site.
• Facilities would be able to purchase land contiguous to their existing
facilities to install this treatment. Each facility was assigned a
classification of "urban" or "rural", and purchased land was priced
accordingly.
• Sludge settled in the bottom of the pond is removed once per year,
hauled off site and disposed of by incineration.
• Monitoring wells installed as part of the groundwater detection
monitoring system would be installed at 200-feet intervals around
the perimeter of the pond, with a minimum of four wells installed.
10.3.5.3
Costing Methodology
All design and costing equations for polishing pond treatment were taken from
CAPDET. Unit costs for the following were obtained from vendors: earthwork,
reinforced concrete installation, double liner, monitoring well installation, annual and
semiannual groundwater sampling and analysis, sludge removal, sludge hauling, sludge
disposal, groundwater background concentration determination, groundwater monitoring
plan development, RCRA closure plan development, and RCRA Part B permit
development. Groundwater sampling and analysis costs were calculated based on
compliance with RCRA regulations. Specific costing algorithms can be found in The
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Pharmaceuticals Manufacturing Cost Documentation Reportl. All other unit costs are
presented in Tables 10-1 and 10-2. Land costs were estimated for urban and rural areas,
respectively. A purchase cost of $10,000 per acre was assumed for urban facilities, and
$2,000 per acre was assumed for rural facilities.
Costs for periodic sampling and analysis were scaled depending on the size of the pond.
For pond sizes of one acre or smaller, the base costs listed below were used. For larger
pond sizes, the base costs were multiplied by the number of acres (assuming the next
largest whole number of acres).
Activity/Item
- Background Groundwater Sampling
- Semi-annual Groundwater Monitoring
- Annual Groundwater Monitoring
Cost (1990$)
114,868
57,434
5,210
Unit/Standard Size
per pond
per pond
per pond
The following are included in the total capital cost calculated for each facility requiring
polishing pond treatment:
• Purchase of land;
• Earthwork to prepare the area for pond construction;
• Construction of influent and effluent structures (reinforced
concrete);
• An impermeable double liner system (this system consists of a
synthetic liner underlain by 6 inches of sand containing the leachate
collection system, underlain by another synthetic liner and another 6
niches of sand);
• A groundwater detection monitoring system;
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• A RCRA closure plan; and
• A RCRA Part B permit application, if necessary.
Table 10-3 presents the factors used by the model to account for ancillary direct and all
indirect capital costs.
The following are included in the total O&M costs calculated for each facility:
• O&M labor;
• Yearly groundwater sampling and analysis; and
• Sludge removal hauling and disposal.
Operation and maintenance labor requirements were calculated using assumptions and
equations provided in CAPDET. It was assumed, for flow rates smaller than 0.1 MGD,
that the total O&M labor requirement would be 160 hours per year. At flows of 0.1
MGD or greater, the following equation was used to calculate O&M hours:
where:
O&M Hours = 313.8 (FLOW)0-2925
FLOW = Facility flow rate, MGD
(10-4)
Groundwater sampling and analysis costs were developed based on the estimated cost for
field sampling and vendor quotes for sample analyses.
Sludge removal costs were based on literature references, and sludge disposal costs were
based on vendor quotes. Table 10-1 presents these unit costs.
10.3.6
Cyanide Destruction Treatment
The technology basis for cyanide destruction is hydrogen peroxide treatment. This
technology is used by Facility 30542 and represents the basis of the treatment
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performance data used by EPA to develop the limitation for cyanide. The system
designed and costed by the cost model has a greater degree of control than the system
used by Facility 30542, hi that laboratory analysis of treated batches of wastewater for
cyanide is required prior to discharge. This approach minimizes the potential for
releases of wastewater with cyanide concentrations above the proposed limitations.
Facility 30542 currently uses a qualitative field technique to measure cyanide after
treatment which does not provide the same level of precision and accuracy as the EPA-
approved analytical method.
The cyanide destruction treatment system costed for the pharmaceutical manufacturing
industry includes the following equipment: four pumps (influent, effluent, sodium
hydroxide, and hydrogen peroxide feed pumps), five tanks (pH adjustment, reactor,
hydrogen peroxide feed, sodium hydroxide feed, and treated wastewater storage), two
agitators (for the reactor and pH adjustment tanks), and a pre-engineered building to
house the treatment unit. If the required volumes of the chemical additives were less
than 5.7 gal/day, 55-gallon drums are used for storage instead of storage tanks.
10.3.6.1
Overview of Costing Methodology
Costs for in-plant cyanide destruction treatment were included for all facilities that
reported the presence of cyanide in their wastewater in the Detailed Questionnaire. In-
plant streams are defined as cyanide-bearing wastewater streams prior to dilution with
noncyanide-bearing wastewater. Facilities that had portions of the technology basis for
this treatment already on site were given credit for these elements, and therefore did not
incur costs associated with a complete, new treatment system.
10.3.6.2 Design Bases and Assumptions
Cyanide destruction treatment is based on the reaction of cyanide with hydrogen
peroxide under basic conditions to form ammonia and carbonate ions. Components that
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comprise the treatment system were selected based on the system used by Facility 30542.
The cost estimates generated by the cost model are based on the following treatment
steps:
• Collection of the wastewater in the pH adjustment tank.
• . Addition of sodium hydroxide to raise the pH in the tank.
• Transfer of wastewater to the reactor vessel.
• Addition of hydrogen peroxide to the reactor to treat cyanide,
followed by field cyanide analysis.
• If the batch fails the field analysis, it is reacted again with additional
hydrogen peroxide. If it passes, the wastewater is transferred to the
storage tank for laboratory analysis.
• If the batch fails laboratory analysis, it is returned to the hydrogen
peroxide reaction vessel for additional treatment. If it passes, it is
discharged to the end-of-pipe treatment system (if applicable).
Costs for equipment and chemicals are based on vendor information.
The following key assumptions and design bases were used to cost cyanide destruction
treatment:
• There is adequate land to install the treatment unit at each facility
requiring cyanide destruction;
All equipment is sized based on in-plant flow rate reported for
waste streams containing cyanide; and
Cyanide destruction treatment is operated in a batch mode, with up
to three batches treated per day.
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10.3.6.2
Costing Methodology
The treatment system components were chosen based on the system used by Facility
30542. Unit costs for the following were obtained from vendors or costing reference
manuals: spill containment drum pallets, pumps, tanks, agitators, earthwork for building
installation, pre-engineered building purchase and installation, chemical purchases, and
laboratory and field monitoring. Tables 10-1 and 10-2 present these unit costs.
The following are included in the direct capital cost calculated for each facility requiring
cyanide destruction treatment:
• Tanks for pH adjustment, reaction, storage of hydrogen peroxide,
storage of sodium hydroxide, and storage of treated wastewater prior
to discharge;
• For smaller volumes (less than 5.7 gal/day), 55-gallon drums to
store chemicals used for cyanide destruction, instead of tanks (if
drums are used, drum spill containment pallets are included);
• Pumps for delivering influent wastewater to the system, removing
effluent from the system, delivering hydrogen peroxide to the
reaction tank, and delivering sodium hydroxide to the pH
adjustment tank;
• Agitators in the reaction and pH adjustment tanks;
• Earthwork to prepare the site for installation of a pre-engineered
building (earthwork includes the construction of curbs and dikes for
spill containment); and
• A building to house the cyanide destruction treatment system.
Table 10-3 presents the factors for calculating ancillary direct and all indirect capital
costs.
10-24
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The following are included in the total O&M costs calculated for each facility:
O&M labor (assumed to be 1 hour per day);
Materials and supplies;
Chemical purchases;
Field monitoring for cyanide concentration;
Laboratory monitoring for cyanide concentration; and
Electricity usage.
Maintenance material and supply costs are calculated based on the following
relationships to installed equipment costs: 1% is used for pumps, 2% is used for storage
tanks, and 5% is used for reaction tanks and agitators. Maintenance of pumps is also
assumed to require one hour per day of operator labor.
Field and laboratory monitoring are assumed to occur once per batch for cyanide
destruction treatment. Table 10-1 lists unit costs for cyanide monitoring. Electricity
costs are based on pump usage.
10.3.7
Steam Stripping and Distillation
Steam stripping and distillation are used to treat organic pollutants and ammonia in
wastewater. In a steam stripping column, the wastewater to be treated is introduced
near the top of the column and is allowed to flow downward through the column by
gravity. Steam is simultaneously introduced at the bottom of the column, and flows
countercurrently to the wastewater. In a distillation column, the wastewater feed enters
lower down the column to provide for a rectification section above the feed. In the
rectification section, a portion of the condensed vapors are refluxed to the column to
countercurrently contact the rising vapors. This process concentrates the volatile
components in the overhead stream. In both steam stripping and distillation columns,
organic compounds and ammonia enter the vapor phase as the steam contacts the
wastewater, and are carried out of the top of the column with the steam. The column
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overheads are condensed from vapor to liquid. A portion of the condensed overheads
are returned to the top section of the column as reflux, the remaining portion is disposed
of off-site. If the condensed overheads form an aqueous and organic layer, a decanter is
used so that the portion returned to the column is the aqueous layer, while the portion
disposed of is the organic layer. Treated wastewater exits the column from the bottom.
The following equipment is assumed to be required to perform steam stripping or
distillation: stripping or distillation column, feed preheater/bottoms cooler, steam
condenser, subcooler, decanter, air pollution control device, feed collection and storage
tank, and associated pumps, piping, and instrumentation. Multiple units may be required
for any or all of the equipment listed above, due to high facility flow rates or if multiple
process streams requiring steam stripping or distillation exist at a facility. The air
pollution control device is costed as an acid scrubber if ammonia is present in the waste
stream; otherwise it is costed as a carbon canister. Facilities may find that it is cost
effective to route vents from the steam stripper or distillation unit to an existing
incinerator or other air pollution control system. This approach was not costed as part
of this effort because information on existing air pollution control systems was not
available.
10.3.7.1
Overview of Costing Methodology
Facilities were costed for steam stripping or distillation of all process area wastewater
with concentrations of regulated pollutants above the long-term mean treatment
performance concentrations for the steam stripping and steam stripping with distillation
options, provided in Section 8. Cost estimates are based on the installation of the
technology at an in-plant location. An in-plant location is defined as prior to dilution by
non-process wastewater, commingling with other process wastestreams not containing
regulated pollutants at treatable levels, and any conveyance, equalization, or other
treatment units which are open to the atmosphere.
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Facilities were given credit for steam stripping or distillation on site if an existing column
was used to treat organic pollutants in wastewater to concentrations below the long-term
mean treatment performance concentrations for steam stripping or steam stripping with
distillation. If steam stripping or distillation treatment existed on site that did not treat
organics to. these levels, effluent from the existing column was considered as influent to
the new column to be costed. It may be possible for facilities to improve performance of
existing steam stripping and distillation columns to meet the required levels. However,
the facility-specific information provided in responses to the Detailed Questionnaire was
not adequate to determine if this would be possible for individual cases. Therefore, new
columns were costed for all facilities not meeting the long-term mean treatment
performance concentrations. The modelled compliance costs for facilities able to
optimize their existing steam stripping or distillation column performance will be higher
than actual compliance costs.
Information reported in the Detailed Questionnaire was used to characterize waste
streams at each facility. Facility flow diagrams and process area information were used
to determine how many in-plant process area streams existed at each facility. Quantities
of pollutants discharged to wastewater and flow rate information reported in the
Detailed Questionnaire were used to determine which constituents were present in each
stream and to calculate their respective concentrations.
10.3.7.2
Design Bases and Assumptions
The steam stripping and distillation systems designed and costed by the cost model are
based on achieving sufficient treatment of the least strippable compound present in the
process wastewater stream being treated. Strippability groups were created for the
purpose of establishing the design bases for both steam stripping and steam stripping
with distillation treatment. The Strippability groups contain all regulated compounds and
range from most easily stripped (Group 1) to not strippable at all (Group 8). Table 10-6
lists all regulated compounds by these Strippability groups. The Strippability groups for
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steam stripping with distillation contain all regulated compounds and range from most
easily stripped (Group 1) to not strippable at all (Group 7). Table 10-7 lists all
regulated compounds by these strippability groups.
The least strippable compound is selected for a particular stream based on the following
criteria:
Only compounds with concentrations above the steam stripping or
steam stripping with distillation long-term mean treatment
performance concentration are considered;
Only compounds in the least strippable group (excluding the
nonstrippable group) of any compounds at the facility are
considered; and
Within the least strippable group, the compound with the lowest
Henry's Law Constant is selected.
Design parameters for the steam stripping or distillation column are selected based on
the least strippable compound and its concentration in the process wastewater to be
treated. Key steam stripping and distillation design parameters are:
• K value - the volatility or equilibrium ratio for a contaminant in a
vapor/liquid system at the temperature and pressure of the column.
• Number of equilibrium stages - the number of contact units in a
column within which the concentration of components in the liquid
phase is in equilibrium with the concentration of components in the
vapor phase.
• Steam-to-feed ratio - the volume of steam required to treat a given
volume of wastewater.
Table 10-8 lists the steam stripping design parameters for constituents hi Groups 1
through 7 (no values are given for compounds in Group 8 because they are not
considered treatable by steam stripping). Table 10-9 lists the steam stripping with
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distillation design parameters for constituents in Groups 1 through 6 (no values are given
for compounds in Group 7 because they are not considered treatable by steam stripping
with distillation).
Process simulations were used to assist in establishing the cost module design basis in
two ways:
Process simulations were used to develop process designs that would
achieve the long-term steam stripping or stream stripping with
distillation performance levels discussed in Section 8 for pollutants
in each of the strippability groups; and
Simulations were also used to help estimate a typical K value for
pollutants in each strippability group.
The key process design parameters which must be determined in order to develop
accurate costs for a steam stripping or distillation system are the steam/feed ratio and
the number of equilibrium stages. For each of the cost groups, typical numbers of
equilibrium stages and feed/steam. (L/V) ratios were determined using process
simulations. Tables 10-8 and 10-9 show the stages and L/V used for each group for both
the steam stripping and steam stripping with distillation options.
For Groups 1 through 3, the number of stages and L/V were determined by varying
stages and L/V until the steam stripping or steam stripping with distillation long-term
mean treatment performance concentration could be achieved for the industry average
influent concentration of the least strippable compound in the strippability group. As
Tables 10-8 and 10-9 show, for Groups 4 and above, the number of stages and L/V
ratios were determined as a function of influent concentration of the least strippable
compound in the group.
The model scans all pollutants in each stream at each facility for strippability group and
for concentration. If any pollutants are above the steam stripping or steam stripping with
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distillation long-term mean treatment performance concentration (depending on the
option being costed) and are considered strippable, then treatment is costed for the
stream. Wastewater streams within a facility are considered separately; therefore, a
facility with four in-plant wastewater streams might have four steam stripping or
distillation systems costed. The largest diameter column costed by the model is 15 feet.
This limitation is based on the difficulty associated with transporting larger columns. If a
column larger than 15 feet is required, multiple columns are costed.
It is assumed that facilities requiring steam stripping or steam stripping with distillation
treatment will have adequate space within existing enclosed process buildings.
10.3.7.3
Costing Methodology
Design equations were obtained from engineering texts, ASPEN methodology, and input
from design engineers. Most unit costs were obtained from algorithms found in Peters
and Timmerhaus, Third Edition (12). Others were obtained from vendor quotes. Unit
costs were included in the cost model for the following: packed and tray columns,
storage tanks, condensers, decanters, subcoolers, air pollution control devices, and feed
preheaters. These unit costs were developed using algorithms dependent on multiple
variables, and are presented in the Pharmaceuticals Manufacturing Industry Cost
Documentation Report, which can be found in the Administrative Record for the
rulemaking. The following table shows the purchase costs for the smallest and largest
size of each major component of the distillation treatment unit, as designed and costed
for all pharmaceutical manufacturing facilities that responded to the Detailed
Questionnaire:
10-30
-------
Component
Packed Column
Tray Column
Condenser and Subcooler
Decanter
Acid Scrubber
Feed Preheater
Smallest Unit
Cost
$17,552
$80,274
$3,360
$119
$16,507
$3,361
Size
Diameter =
.10 inches
Height = 17 (ft)
Diameter =
49 niches
Height = 34 (ft)
Surface area =
9.2 (ft2)
Volume =
0.03 (ft3)
Diameter =
10 (inches)
Surface area =
10.1 (ft2)
Largest Unit
Cost
$237,538
$1,185,637
$1,158,535
$32,925
$35,564
$292,097
Size
Diameter =
38 inches
Height = 52 (ft)
Diameter =
175 inches
Height = 87 (ft)
Surface area =
23,893 (ft2)
Volume =
3,788 (ft3)
Diameter =
11 (inches)
Surface area =
8,913 (ft2)
These costs are for individual components only, some systems may require the
installation of multiple components. Pump costs and chemical additive costs were
obtained from vendor quotes. These unit costs are presented in Tables 10-1 and 10-2.
The following are included in the total capital cost calculated for each facility requiring
steam stripping or distillation treatment:
Stainless steel column(s), including either packing or trays (packing
was used for columns with diameters less than 48 niches; trays were
used for larger diameter columns);
Stainless steel feed preheater(s)/bottoms cooler(s) to prepare
influent wastewater for treatment and to maintain an acceptable
temperature in the effluent from the column;
Stainless steel steam condenser(s)/subcooler(s) to convert overheads
from vapor to liquid;
10-31
-------
• Decanter(s) to separate distilled organic compounds from water to
be returned to the column;
• Air pollution control device(s) to remove noncondensible organics
or ammonia, from the vent stream;
• Stainless steel feed collection and storage tanks with capacities
ranging from 12 to 24 hours; and
• Pumps to deliver influent wastewater to the column, refluxed
wastewater back to the column inlet, and sodium hydroxide to the
feed storage tank if pH adjustment is necessary (pH adjustment is
required for streams that contain ammonia; stripping is performed
at a pH of 8 for ammonia-bearing streams).
Stainless steel components were costed because of the corrosion potential of
pharmaceutical manufacturing wastewater. Hastelloy was considered as a construction
material, and may be necessary on a site-specific basis. However, for the purpose of
calculating industry-wide costs, stainless steel was considered the most appropriate
construction material.
Table 10-3 lists the factors that are used by the model to account for ancillary direct and
all indirect capital costs.
The following are included in the O&M costs calculated for each facility:
• O&M labor;
• Steam usage;
• Chilled water usage for the condenser and subcooler;
• Hydrochloric acid addition to the ammonia scrubber (if necessary)
or carbon canister replacement for air pollution control;
• Sodium hydroxide addition, if pH adjustment is necessary;
10-32
-------
Hauling and disposing of waste hydrochloric acid (if any) and waste
solvents decanted froih the column overhead stream;
Miscellaneous O&M materials and supplies (assumed to be equal to
4% of the total capital cost); and
Electricity usage.
O&M labor requirements are based on 12 labor hours per day to properly operate and
maintain the steam stripping or distillation unit. Steam usage is calculated based on the
facility flow rate and the selected steam-to-feed ratio.
Hydrochloric acid usage in the ammonia scrubber is calculated based on the amount of
ammonia in the overhead stream from the column. It is assumed that 20% of the
ammonia removed from the waste stream will be vented to the air pollution control
device, and that the mass (pounds) of hydrochloric acid required will be 2.12 times the
mass of the removed ammonia. The value 2.12 is based on the reaction of hydrochloric
acid with ammonia in the air pollution control device. Carbon canister usage is based on
the total mass of organic compounds removed from the waste stream. Based on ASPEN
simulations, it is assumed that 0.29% of the overheads from the column will be vented to
the air pollution control device. Based on EPA data from air emission studies at
Superfund sites, it is assumed that 10 pounds of carbon will be required for each pound
of organics removed in the air pollution control device.
Sodium hydroxide usage is calculated based on the presence of ammonia in the waste
stream and the flow rate of the stream. Hauling and disposing of waste hydrochloric
acid and waste solvents is based on unit costs displayed in Table 10-1. Electrical usage is
calculated based on pump usage and pump horsepower.
10-33
-------
10.3.8
Activated Carbon Adsorption
Activated carbon adsorption is used to remove organic constituents from wastewater.
The organic constituents bind to sites on the activated carbon as the wastewater passes
through beds containing the treatment medium. These organic constituents can be
measured in bulk as COD. There are two primary types of activated carbon, granular
and powdered. The cost estimates developed for the pharmaceutical manufacturing
industry are based on the use of granular activated carbon (GAC) systems.
The system designed consists of three activated carbon beds operated in series, preceded
by a multimedia filtration unit to capture solids that might prematurely foul the carbon
beds. Multimedia filtration treatment is discussed in Section 10.3.4 and will not be
described further in this section. The three-bed configuration allows for less wasted
activated carbon than a more traditional, two-bed system because the first bed can be
left in operation longer and allow a higher percentage of the activated carbon in the bed
to be used before regeneration is required.
The equipment required to perform GAC treatment is assumed to include:
• An influent holding tank;
• An influent pump;
• Three carbon beds installed in series;
• A backwash pump;
• Two backwash tanks (one for backwash feed, and one for backwash
settling); and
• A pre-engineered building for the three largest GAC systems. It is
assumed that adequate floor space already exists to install the
smaller, drum-based GAC systems.
10-34
-------
10.3.8.1
Overview of Cost Methodology
No credit is given to facilities for having GAC treatment existing on site. All facilities
requiring GAC treatment, based on comparison to long-term mean performance levels
for GAC, are costed for new GAC treatment units.
10.3.8.2
Design Bases and Assumptions
There are four key design parameters for GAC treatment: empty bed residence time,
saturation loading, hydraulic loading rate, and facility flow rate. These parameters are
described below:
Empty bed residence time (EBRT) - the time that the wastewater is
in contact with the activated carbon. The assumed EBRT for all
facilities is 45 minutes.
Saturation loading - the mass of pollutant measured as COD
(pounds) adsorbed per mass of carbon (pounds). This value is
assumed to be 0.09066 pounds of pollutant per pound of carbon for
all facilities. This saturation loading is based on GAC performance
data gathered from the 1984 GAC pilot study.
Hydraulic loading rate - the flow rate of wastewater per GAC bed
surface area (gpm/ft2). This number has been calculated from
industry averages to be approximately 2.5 gpm/ft2 for Subcategory
A and C facilities and 3.0 gpm/ft2 for Subcategory B and D
facilities.
Facility flow rate - This flow rate is used to size all equipment used
by the activated carbon system.
The amount of carbon required over the course of a year for a given facility is calculated
as follows. The reported COD concentration for a facility reported in the Detailed
Questionnaire is compared to the GAC long-term mean performance level (for options
that include advanced biological treatment, the COD concentration after advanced
10-35
-------
biological treatment is compared to the GAC long-term mean performance level). The
difference between the two concentrations is assumed to be the total organic load on the
activated carbon. This concentration difference is converted to a mass using the
reported facility flow rate. The mass and saturation loading are then used to calculate
the total mass of carbon required per year to perform wastewater treatment.
It is assumed that facilities requiring activated carbon treatment have the available space
necessary to implement this treatment technology.
10.3.8.3
Cost Methodology
Unit costs for the following were obtained from vendors: pumps, tanks, GAC systems,
backwash systems, breakthrough monitoring, and carbon regeneration. Unit costs are
provided in Tables 10-1 and 10-2.
The following are included in the total capital cost for each facility requiring GAC
treatment systems (all equipment costs .include purchase and installation):
• Multimedia filtration treatment unit directly upstream of the GAC
unit.
• Feed tank with a 12-hour retention tune for equalizing flow prior to
introduction to the GAC treatment system.
• Feed pump to convey wastewater from the feed tank to the
treatment system.
• The activated carbon treatment beds. Varying sizes of drums or
tanks are used to hold the activated carbon. These units are pre-
engineered with influent and effluent ports to allow easy hook up to
facility piping.
• The backwash system, including two holding tanks and one pump.
The backwash system operates by pumping clean facility water to
the backwash tank, and then pumping water from the tank up
10-36
-------
through the beds (in the opposite direction of normal wastewater
flow) and into the backwash settling tank. Backwash water and
solids are returned to the biological treatment unit, if available. If a
biological system does not exist on site, decanted water is sent to the
head of the treatment works and solids are taken off site for
disposal.
A pre-engineered building to house the activated carbon treatment
system (only required for the three-tank-based systems).
Table 10-3 lists the factors for calculating ancillary direct and all indirect capital costs.
The following are included in the O&M costs calculated for each facility:
• O&M labor;
• Regeneration of spent activated carbon;
• Monitoring for breakthrough between carbon beds;
• Electricity usage; and
• Miscellaneous O&M materials and supplies (assumed to be 4% of
the total capital cost).
Operation and maintenance labor is based on a curve with an assumed maximum
required daily labor requirement of 4 hours (this maximum applies to facilities with flow
rates above 500,000 gal/day). The equation used to calculate labor hour requirements is
as follows:
10-37
-------
LABOR HOUR REQUIREMENTS = [363.23 + (3.2347 x (FLOW)) - /10_5)
(0.0036842 x (FLOW)2)] x (DAYS)
where: FLOW = Facility flow rate, gpm
DAYS = Number of operating days per year.
Regeneration costs for spent carbon and monitoring costs were based on vendor quotes
(33,16). Electricity usage was based on pump usage and pump horsepower.
10.3.9
Contract Hauling
Cost estimates for contract hauling of wastewater were developed for facilities with low
flows. The treatment consists of storing untreated wastewater at the current end-of-pipe
discharge point, and then hauling it off site for incineration. It has been determined that
this approach is more cost-effective than other in-plant or end-of-pipe treatments for
flows below 30 gallons per day.
The equipment required to perform this treatment depends on whether drums or a
storage tank are used to store the wastewater. For drum storage, the only equipment
required is the drums. If a storage tank is used, the equipment includes the tank and a
discharge pump. It is assumed that for each scenario, the facility will have enough
existing space for wastewater storage, requiring no additional land or facility
improvement costs.
10.3.9.1 Overview of Costing Methodology
No credit was given to facilities for existing treatment on site. It was assumed that
contract hauling would be performed at facilities with discharge flows below 30 gal/day
and regulated pollutants at concentrations above the long-term mean treatment
performance, regardless of the existing level of treatment.
10-38
-------
10.3.9.2
Design Bases and Assumptions
The following assumptions were made for costing contract hauling:
Facilities with zero wastewater discharge, no regulated pollutants
reported, or no concentrations of regulated constituents above
Limitations did not incur any costs.
Wastewater from all facilities requiring contract hauling required
incineration.
Any facility with a flow rate greater than 30 gal/day was not
considered.
The incineration facility was assumed to be 500 miles from the
generating facility.
The selection of drums versus a storage tank for on site storage prior to disposal is based
on the on-site storage time required to generate 5,000 gallons of wastewater. If it takes
longer than 45 days to accumulate 5,000 gallons on site (approximately 110 gal/day),
drums are used to store the wastewater. If it takes less than 45 days to generate 5,000
gallons, a storage tank is used instead.
Spill prevention for the dram storage system is provided by including spill prevention
drum pallets for the storage area. These pallets provide a contained space beneath the
drums to collect any leakage or spills.
10.3.9.3
Cost Methodology and Assumptions
Required costs for the following were obtained from vendor information: tanks, pumps,
hauling, incineration, drams, and spill prevention pallets. Tables 10-1 and 10-2 present
these unit costs.
10-39
-------
The following were included in the total capital cost for each facility requiring contract
hauling:
• Storage tank purchase and installation, if necessary (assumed to be
an 11,000-gallon tank); and
• Discharge pump purchase and installation (assumed to be a 70-gpm
pump), if necessary.
The following items are included as O&M costs for contract hauling:
• Drum purchase, if necessary;
• Spill prevention pallet purchase, if necessary;
• Electricity requirements for the pump, if necessary;
• Tank or drum area daily inspection (15 minutes per day);
• Loading and unloading of wastewater for transport;
• Transport of wastewater to the disposal facility (assumed to be 500
miles); and
• Incineration of the wastewater.
10.3.10
Compliance Monitoring
Compliance monitoring costs were calculated for all pharmaceutical manufacturing
facilities that discharge wastewater. Costs represent analytical analysis costs based on
which pollutants were reported in 1990 to be present in a facility's wastewater.
Monitoring may be required in plant, at the end of pipe, or in both locations, depending
on the regulatory option. See Sections 13 through 17 for additional detail on monitoring
locations.
10-40
-------
Costs for monitoring the discharge levels of BOD5, COD, and TSS have not been
included, as no incremental costs above those which the plants are presently incurring
are anticipated. Cyanide monitoring costs are included as part of the cyanide treatment
cost module and are not calculated in the monitoring module. It is assumed that no
additional physical equipment is required to perform monitoring.
10.3.10.1
Overview of Costing Methodology
For the purpose of selecting in-plant or end-of-pipe monitoring, four scenarios related to
regulatory options were considered:
1. Options with no steam stripping or steam stripping with distillation
(no in-plant treatment of organics);
2. Options with in-plant steam stripping or steam stripping with
distillation and no end-of-pipe treatment;
3. Options with in-plant steam stripping or steam stripping with
distillation, and end-of-pipe treatment that does not include
activated carbon treatment; and
4. Options with in-plant steam stripping with distillation and activated
carbon treatment.
The following paragraphs describe the cost estimates for monitoring under each of these
scenarios.
Options With No Steam Stripping or Steam Stripping with Distillation
Regulatory options that did not include any in-plant steam stripping or steam stripping
with distillation treatment were costed for weekly end-of-pipe (EOF) monitoring for
compounds present at the facility and one annual EOF full analytical scan for all
regulated pollutants.
10-41
-------
Options With In-Plant Steam Stripping or Steam Stripping with Distillation and No
End-of-Pipe Treatment
Regulatory options that included in-plant steam stripping or steam stripping with
distillation but no EOF treatment were costed for weekly monitoring at each in-plant
monitoring point for compounds present in that facility stream and full analytical scans
for all regulated pollutants at each in-plant monitoring point annually.
Implementation of the proposed PSES and PSNS options will include standards at both
in-plant and end-of-pipe locations. Insufficient time was available to incorporate this
implementation approach prior to completion of the costs for proposal. This
modification will be addressed in the costs estimates supporting the promulgated
rulemaking.
Options With In-Plant Steam Stripping or Steam Stripping with Distillation and End-
of-Pipe Treatment that Does Not Include Activated Carbon Treatment
Regulatory options that included in-plant steam stripping or steam stripping with
distillation and EOP treatment, not including activated carbon treatment, were costed for
a combination of in-plant and EOP monitoring. Weekly in-plant monitoring was costed
for compounds considered treatable by steam stripping or steam stripping with
distillation in the facility stream(s). Weekly EOP monitoring was costed for compounds
considered not to be treatable by steam stripping or distillation present at the facility.
One annual EOP full analytical scan for all regulated compounds was also costed.
The proposed BAT option for Subcategory A and C operations and the proposed NSPS
options include limitations at the end-of-pipe location only. However, it is likely that
facilities will also incur costs for in-plant monitoring, as they conduct routine internal
monitoring to access whether their steam stripping and distillation system are performing
as intended.
10-42
-------
Options With In-Plant Steam Stripping with Distillation and Activated Carbon
Treatment
Regulatory options that included in-plant distillation and EOF activated carbon
treatment were costed for a combination of in-plant and EOF monitoring. Weekly in-
plant monitoring was costed for compounds considered to be not treatable by activated
carbon. Weekly EOF monitoring was costed for compounds considered to be treatable
by activated carbon. One annual EOF full analytical scan for all regulated compounds'
was also costed.
Under each scenario described above, analytical methods were selected to detect all
compounds reported to be present in facility waste streams.
10.3.10.2
Cost Methodology
There are no capital items associated with compliance monitoring. The only O&M costs
included for this activity are the laboratory analytical costs. It is assumed that the labor
required to perform monitoring sampling is negligible compared to labor requirements
already existing at each facility. It is also assumed that any materials required for
monitoring are already present at the facility or are provided by the laboratory
performing the analyses.
All analytical cost information was provided by vendors of analytical services.
10.4
Engineering Costs by Regulatory Option
Table 10-10 presents a summary of estimated BPT, BCT, BAT, and PSES engineering
costs, broken down by subcategory, discharge type, and regulatory option. Costs shown
include capital and operation and maintenance (including energy usage) costs totaled for
each group of applicable facilities.
10-43
-------
It should be noted that advanced biological treatment costs are incorporated into both
the BPT and BAT costs for direct dischargers. Facilities would install only one
treatment system adequate to comply with both BPT and BAT limitations. Therefore,
the BPT and BAT costs should not be summed as this would create double counting for
the biological treatment costs, rather a facility would incur the BAT costs in complying
with both BAT and BPT.
For NSPS and PSNS, costs were developed using the existing facility information to
model potential new source facilities. NSPS and PSNS costs were developed on an
annualized basis using amortized yearly costs and assuming a Subcategory A and/or C
facility flow rate of 1 MOD and a subcategory B and/or D facility flowrate of 0.1 MOD.
The amortized yearly costs are equal to the sum of amortized capital costs and the yearly
operation and maintenance costs. The capital costs are amortized using the following
equation:
Amortized Capital Cost ($/yr) = Capital Cost ($)
i (1 + i)n
where: i = Interest rate of 0.114
n = Equipment life of 20 years.
Table 10-11 presents a summary of estimated NSPS and PSNS engineering costs on an
amortized yearly basis.
10-44
-------
Table 10-1
/
Operation and Maintenance Unit Costs Used By the Cost Model
Unit Disposal Costs
Activity
Incinerate drums of liquid waste
Dispose of bulk wastewater
Incinerate solvents in bulk
Incineration of waste HCL
Dispose of biological treatment
sludge
Cost (1990 $)
480.10
5.02
140.00
180.00
50.00
Units
55-gallon drum
gallon
ton
ton
ton
Reference
2
(2)
34 '
;
(4)
5 (a)
Unit Hauling Costs
Activity
Haul solvents
Haul drums/bulk wastewater
Haul biological treatment sludge
Cost (1990 $)
29.02
2,626.00
4.05
'. ''" -"Unitsv/; -.I," ;
ton
full load (80 drums or
5,000 gallons bulk liquid)
loaded mile
Reference :
(4)
(2)
6
Unit Chemical Costs
Chemical
NaOH (50%)
H,0, (50%)
Nitrogen (Ammonium Sulfate)
Phosphorous (Phosphoric Acid)
Hydrochloric acid
Polymer
Cost (1990 $)
310.00
0.495
0.013
0.199
395.77 - 482.65
2.25
Units
ton
pound
pound
pound
drum (500 Ibs)
pound
Reference
7
(7)
(7)
(7)
8
9
Miscellaneous Unit Costs
Item
O&M labor rate
Electricity usage fee
Steam
Cost (1990$)
27.74
0.04
3.20
Units
hour
kilowatt-hour
1000 Ibs
Reference
10
11
12
10-45
-------
Table 10-1
(Continued)
Miscellaneous Unit Costs
Item
Sample fee (for off-site disposal)
Drum purchase
Dredge polishing pond sludge
Field cyanide analysis
Laboratory cyanide analysis
Cost (1990$)
322.22
43.66
6.95
0.50
27.50
Units
per load of wastewater
drum
cubic yard
per sample
per sample
Reference
(2)
13
14
15
16
(a) Unit cost was calculated by taking the median of costs reported by pharmaceutical manufacturing facilities for disposing of similar
wastes.
10-46
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Table 10-2
Capital Unit Costs Used by the Cost Model
Construction Unit Costs
Activity
Excavation
Concrete wall installation
Concrete slab installation
Prefabricated building
installation
Impermeable, double liner
installation
Crane rental
Handrail installation
Cost (1990 ••$)
4.81
547.69
120.51
19.51
3.58
98.15
46.91
Units
cubic yard
cubic yard
cubic yard
square foot of
floor space
square foot
hour
Linear foot
Reference
17
18
(18)
19
20
21
22
Purchased, Installed Treatment Equipment Unit Cost
Item
Package biological treatment
plant
Clarifier
Filtration unit
Fix-mounted surface aerator
Pump station pump (large
applications)
Filter press (1 ft3 to 20 ft3)
Sludge Thickening Tank
(100 gal to 500,000 gal)
Cost (1990 $)
67,944
139,610
307,143
33,080
32,110
6,119 to 30,992
1,270 to 79,062
Standard Size
100,000 gal/day
90 ft diameter
784 ft2 of filter
surface area
20 HP
3,000 gpm
per press
per tank
Reference
(22)
(22)
(22)
23
(22)
24
25
Miscellaneous Unit Capital Costs:
Activity/Item
Drum pallet (spill
preventative)
Monitoring well installation
Cost (1990 $)
338.64
4,444
Units/Standard
Size
4-drum pallet
per well
Reference
26
27
10-47
-------
Table 10-2
(Continued)
Miscellaneous Unit Capital Costs
Activity/Item
Closure plan development
Groundwater background
concentration determination
RCRA Part B Permit
Application
Develop a groundwater
monitoring plan
Cost (1990$)
28,393
114,868
118,303 •
7,763
Units/Standard
Size
per polishing pond
per acre of
polishing pond
per polishing pond
per polishing pond
Reference
28
(27)
(28)
(27)
Unit Capital Costs Using Curves or Ranges
Item/ Activity
Small pumps (3 - 27 gpm)
Larger pumps
(50 - 900 gpm)
Carbon steel tanks
(11,000 to 150,'600 gal)
Floating aerators
(20 HP to 100 HP)
Package filtration unit
(SA < 400 ft?)
*
Reaction vessel agitator
(025 to 5.0 HP)
Activated carbon treatment
systems (165 Ibs to 40,000
Ibs of carbon)
Range/Equation
Cost = 45.705 (Q) + 615.24
(Q= flow in gpm)
Cost= 6.09 (Q) + 2,485
(Q = flow in gpm)
Cost = 0.1935(V) + 8814
(V = volume in gallons)
11,698 to 42,662
Cost = 60,034(SA)°-3203
(SA = filter surface area in
square feet)
1,210 to 2,614
495 to 250,000
..; '' ' '": Unite- '.'.';' ;'" '
per pump
per pump
per tank
per aerator
per filter unit
per agitator
per system
• , Reference .':
29
(23)
30
31
(22)
32
33
10-48
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Table 10-3
Factors Used To Calculate Indirect and Ancillary Direct Capital Costs As a
Percentage of Total Purchased and Installed Capital Cost
Technology
Equalization
Package aeration (flow < 0.5 MOD)
Full-size aeration (flow > 0.5 MOD)
Clarification
Multimedia filtration
Polishing pond treatment
Cyanide destruction
Distillation
Activated carbon treatment
Factor .(%)
5
11
11
18
25
11
35
62.5
42
Reference
(22)
(22)
(22)
(22)
(22)
(22)
34
(12)
(2)
10-49
-------
Table 10-4
Constants and Values Used to Model Biological Treatment
Parameter
Temperature
Synthesis oxygen coefficient
Influent VSS/TSS ratio
Nondegradable influent VSS
Clarifier hydraulic loading
Clarifier solids loading
Clarifier polymer addition
Field oxygen transfer
Substrate removal rate
constant (K)
Synthesis yield coefficient
Endogenous decay rate
constant
BOD5 associated with
effluent TSS
COD removed to BOD5
removed ratio
. Subcategory A and
C Value
24.56
1.05
0.65
0.70
400
20
1.5
3.0
11.14
036
0.0
0.23
0.615
Snbcategory B and
D Value
24.56
1.05
0.65
0.70
400
20
1.5
3.0
2.06
0.78
0.0
0.24
0.52
Units
°C
Ib 02/lb BOD5
NA
NA
gal/day/ft2
lb/day/ft2
mg/L
Ib/HP-hr
NA
NA
NA
mg/mg
NA
NA - Not applicable.
Source: Mean values based on information provided in the Detailed Questionnaire.
10-50
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Table 10-5
Operation and Maintenance Labor Hour Calculations
for Biological Treatment
Activity
Package aeration
Full-size aeration
Clarification
Sludge Handling
Type 'of Labor
Operation
Maintenance
Operation
Maintenance
Operation
Maintenance
Operation
Maintenance
Minimum hours
(per year)
1200
640
NA
NA
350
200
NA
NA
Equation(s) for calculating hours
per year
1683 (FLOW)0-14*9
1143 (FLOW)0-2519
242.4 (TICA)0-3731 (TICA < 200)
100 (TTCA)0-5425 (TICA > 200)
106.3 (TICA)0-*031 (TICA < 100)
42.6 (TICA)0-5956 (TICA > 100)
37.1(SA)°-3247
(1,000 < SA < 3,000)
4.0 (SA)0-6020 (SA > 3,000)
30.3 (SA)0-2733
(1,000 < SA < 3,000)
2.05 (SA)0-6098 (SA > 3,000)
1 hour per batch per press for
presses < 6 ft3
2 hours per batch per press for
presses between 6 ft3 and 12 ft3
3 hours per batch per press for
presses larger than 12 ft3
The maximum number of
operation hours per day at any one
faculty is 27.
2 hours per year per press
FLOW - Facility end-of-pipe wastewater treatment flow (MGD).
TICA - Total installed capacity of aeration (horsepower).
SA - Ciarifier surface area (ft2).
NA - Not applicable.
10-51
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Table 10-6
Steam Stripping Strippability Groups for All Regulated Compounds
Compound
n-Heptane
Cyclohexane
Benzene
Chlorobenzene
Chloroform
1,2-Dichloroethane
Diethyl Ether
Isopropyl Ether
Methyl Cellosolve
Methylene Chloride
Xylenes
Ammonia
Chloromethane .
o-Dichlorobenzene
n-Hexane
Toluene
Trichlorofluoromethane
n-Amyl Acetate
n-Butyl Acetate
Diethylamine
Ethyl Acetate
Isobutyraldehyde
Isopropyl Acetate
Methyl Formate
MffiK
Tetrahydrofuran
Triethylamine
Strippability Group
1
2
3
3
3
3
3
3
3
3
3
4
3
3
1
3
2
4
4
4
4
4
4
4
4
4
4
Compound
Amyl alcohol
2-Butanone (MEK)
tert-Butyl alcohol
Dimethylamine
N,N-Dimethylaniline
Formamide
Furfural
Isopropanol
Methylamine
2-Methylpyridine
Acetone
Aniline
n-Butyl alcohol
1,4-Dioxane
Ethanol
n-Propanol
Pyridine
Methanol (Methyl alcohol)
Petroleum naphtha
Acetonitrile
N,N-Dimethylacetamide
N,N-Dimethylformamide
Dimethyl sulfoxide
Ethylene glycol
Formaldehyde
Phenol
Polyethylene glycol 600
Strippability
Group
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
5
7
7
8
8
8
8
8
8
8
8
10-52
-------
Table 10-7
Steam Stripping with Distillation Strippability Groups
for All Regulated Compounds
Compound
n-Heptane
n-Hexane
Cyclohexane
Trichlorofluoromethane
Benzene
Chlorobenzene
Chloroform
Chloromethane
o-Dichlorobenzene
1,2-Dichloroethane
Diethyl Ether
Isopropyl Ether
Methyl Cellosolve
Methylene Chloride
Toluene
Xylenes
Ammonia
n-Amyl Acetate
n-Butyl Acetate
.Diethylamine
Ethyl Acetate
Isobutyraldehyde
Isopropyl Acetate
Methyl Formate
MIBK
Tetrahydrofuran
Triethylamine
Strippability Group
1
1
2
2
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
. 4
4
4
4
4
4
: Compound
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl alcohol
tert-Butyl alcohol
Dimethylamine
N,N-Dimethylaniline
1,4-Dioxane
Ethanol
Formamide
Furfural
Isopropanol
Methylamine -
2-Methylpyridine
n-Propanol
Acetone
Pyridine
Methanol (Methyl alcohol)
Petroleum naphtha
Acetonitrile
N,N-Dimethylacetamide
N,N-Dimethylformamide
Dimethyl sulfoxide
Ethylene glycol
Formaldehyde
Phenol
Polyethylene glycol 600
Strippability
Group
5 '
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
7
7
7
7
7
7
7
7
10-53
-------
Table 10-8
Steam Stripping Design Parameters Established by Strippability Group
StrippabUity
Group
1
2
3
4
5
6
7
8
Concentration of Least
Strippable Contaminant
ALL
ALL
ALL
< 2,000
> 2,000
< 1,000
1,000 < cone. < 5,000
5,000 < cone. < 10,000
10,000 < cone. < 50,000
> 50,000
< 1,000
1,000 < cone. < 5,000
5,000 < cone. < 10,000
> 10,000
< 5,000
5,000 < cone. < 10,000
10,000 < cone. < 20,000
20,000 < cone. < 30,000
> 30,000
NA
K Value
10,219
1874.2
400
44.5
44.5
21.6
21.6
21.6
21.6
21.6
11.5
11.5
11.5
11.5
7.8
7.8
7.8
7.8
7.8
NA
Number of
Equilibrium
Stages
4
4
6
8
10
10
14
14
14
14
14
14
14
14
14
14
14
14
14
NA
Feed-to-
Steam Ratio
12.0
12.0
12.0
12.0
12.0
12.3
12.9
12.1
10.9
9.7
12.0
8.8
7.9
6.8
7.8
6.3
5.5
5.1
4.6
NA
cone. - Concentration in mg/L.
ALL - Compounds in Groups 1, 2, and 3 are considered very strippable; therefore, all expected influent
concentrations can be treated to limitations using the design criteria listed.
NA - Compounds in Group 8 are not considered strippable; therefore, no design parameters are listed.
10-54
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Table 10-9
Steam Stripping with Distillation Design Parameters
Established by Strippability Group
Strippability
Group
1
2
3
4
5
6
7
Concentration of Least
Strippable Contaminant
ALL
ALL
ALL
< 10,000
> 10,000
< = 100
100 < cone. < = 1,000
1,000 < cone. < = 10,000
> 10,000
< = 100
100 < cone. < = 1,000
1,000 < cone. < = 10,000
> 10,000
NA
K
Value
10,219
1874.2
400
31.6
31.6
11.5
11.5
11.5
11.5
7.8
7.8
7.8
7.8
NA
Number of
Equilibrium
Stages
4
4
6
10
10
14
14
14
14
14
14
14
14
NA
Feed-to-
Steam Ratio
12.0
12.0
10.0
10.0
7.5
6.0
5.0
4.0
3.5
4.0
3.3
3.0
2.5
NA
cone. - Concentration in mg/L.
ALL - Compounds in Groups 1, 2, and 3 are considered very strippable; therefore, all expected influent
concentrations can be treated to limitations using the design criteria listed.
NA - Compounds in Group 7 are not considered strippable; therefore, no design parameters are listed.
10-55
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Table 10-10
Summary of BPT, BCT, BAT, and PSES Engineering Costs
Subcategory
AandC
A and C
A and C
A and C
AandC
A and C
AandC
AandC
AandC
AandC
AandC
AandC
AandC
AandC
B andD
B andD
B andD
BandD
B andD
B andD
B andD
B andD
B andD
B andD
AandC
AandC
A and C
A and C
B andD
B andD
B andD
Regulation
BPT
BPT
BPT
BPT
BPT
BCT
BCT
BCT
BCT
BCT
BAT
BAT
BAT
BAT
BPT
BPT
BPT
BCT
BCT
BCT
BAT
BAT
BAT
BAT
PSES
PSES
PSES
PSES
PSES
PSES
PSES
Option
1
2
3
4
5
1
2
3
4
5
1
2
3
4
1
2
3
1
2
3
1
2
3
4
' . 1
2
3
4
1
2
3
Capital Cost ($/yr)
0
14,700,000
21,900,000
37,400,000
44,200,000
0
9,730,000
16,900,000
32,400,000
39,200,000
15,000,000
56,400,000
68,000,000
92,900,000
0
606,000
2,980,000
' ' 0
559,000
2,930,000
644,000
1,740,000
3,000,000
10,300,000
70,800,000
90,100,000
144,000,000
187,000,000
21,000,000
25,400,000
36,000,000
O&M Cost
($/yr)
0
6,940,000
7,380,000
21,700,000
23,300,000
0
2,000,000
2,960,000
16,500,000
19,100,000
8,540,000
35,700,000
58,000,000
114,000,000
0
519,000
754,000
0
449,000
684,000
1,100,000
937,000
1,950,000
3,060,000
46,400,000
82,000,000
106,000,000
178,000,000
7,660,000
14,000,000
60,600,000
10-56
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Table 10-11
Summary of NSPS and PSNS Engineering Costs
Subcategory
AandC
A andC
B andD
B andD
A andC
AandC
B andD
B andD
Regulation
NSPS
NSPS
NSPS
NSPS
PSNS
PSNS
PSNS
PSNS
Option
1
2
1
2
1
2
1
2
Annnalized Costs
($/yr)
4,100,000
14,200,000
218,000
336,000
4,010,000
4,990,000
391,000
454,000
Costs at Set
Flowrate (MGD)
1
1
0.1
0.1
1
1
0.1
6.1
10-57
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REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Radian Corporation. Proposed Pharmaceutical Manufacturing Industry
Cost Documentation Report. Herndon, Virginia, October 1994. Prepared
for the U.S. Environmental Protection Agency.
Radian Corporation. Final Pesticide Formulators, Packagers and
Repackagers Cost and Loadings Report. Herndon, Virginia, March 1994.
Prepared for the U.S. Environmental Protection Agency.
Information submitted by Hoffman-LaRoche to EPA at an October 7, 1993
meeting.
Personal communication with R. Bobal, Hoffman-LaRoche, April 27, 1993.
U.S. EPA. 1990 Pharmaceutical Manufacturing Industry Survey. OMB
No. 2040-0146, September 1991.
Personal communication with Chemical Waste Management, March 29,
1993.
Chemical Marketing Reporter. Issues from June 2, 1990 and December 3,
1990.
Personal communication with Technician at Dubois Chemicals USA, May
13, 1993.
Personal communication with Dave Marturana, Betz Labs, May 3, 1993.
Personal communication with National Bureau of Labor Statistics
representative, March 13, 1992.
Personal communication with Department of Energy representative,
February 18, 1993.
Peters, M.S. and K.D. Timmerhaus. Plant Design and Economics for
Chemical Engineers, Fourth Edition. McGraw-Hill, Inc., New York, New
York, 1990.
Personal communication with NSSI Recovery representative, March 13,
1992.
R. S. Means Co., Inc. Means Site Work Cost Data. 1989.
Personal communication with Rich Davis, Pfeizer Corp., May 4, 1993.
10-58
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16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
Lancaster Laboratories. 1994 Schedule of Services.
Pereira, P.E., et al. 1986 Dodge Construction Systems Costs, McGraw-Hill
Information Systems Company, Princeton, New Jersey.
R.S. Means Co., Inc. Building Construction Cost Data. 1986.
R.S. Means Co., Inc. Means Site Work Cost Data. 1989.
B.C. Jordan Co. Neal Janelle. Surface Impoundment Liner Cost Estimates.
1984.
R.S. Means Co., Inc. Means Site Work Cost Data. 1989.
Harris, R.W., MJ. Cullinane and P.T. Sun, eds. Process Design and Cost
Estimating Algorithms for the Computer Assisted Procedure for Design
and Evaluation of Wastewater Treatment Systems (CAPDET). United
States Army Engineer Waterways Experiment Station, Vicksburg,
Mississippi, 1982. (Prepared for the U. S. Environmental Protection
Agency).
Richardson Engineering Services, Inc. Process Plant Construction
Estimating Standards. 1992.
Personal communication with representative of MET-CHEM Corporation,
March 15, 1993.
Non-Ferrous Metals Forming Rulemaking, Tank Costs. May 1989.
New Pig Corporation. 1992 Catalogue of Equipment Prices.
Engineering costing calculations performed by Barbara Wong, Radian
Corporation, March 10, 1994.
Engineering costing calculations performed by John Vidumsky, Radian
Corporation, March 1994.
Non-Ferrous Metals Forming Rulemaking, Pump Costs. May 1989.
Columbian Tank Company. Installed Tank Unit Costs for 1992.
Personal communication with Jim Gault, Aqua-aerobics, November 4, 1992.
Non-Ferrous Metals Forming Rulemaking, Agitator Costs. May 1989.
Personal communication with Al Roy, Calgon Corporation, March 3, 1993.
10-59
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34.
Non-Ferrous Metals Manufacturing Rulemaking, Components of Total
Capital Investment. May 1989.
10-60
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SECTION 11
REGULATORY OPTIONS SELECTION
11.1
Introduction
This section presents proposed regulatory options for the pharmaceutical manufacturing
industry and discusses the factors considered in determining the selected options for
BPT, BAT, NSPS, PSES, and PSNS. Factors considered included: reduction in pollutant
discharges to the environment, costs to the industry, age of the equipment and facilities
involved, the manufacturing processes used, process changes required, nonwater quality
environmental impacts, engineering aspects of the control technologies, and energy
requirements.
The regulatory options selected provide the technology basis of the effluent limitations
guidelines and standards presented in Sections 13 (BPT), 15 (BAT), 16 (NSPS), and 17
(PSES and PSNS). Selection of the BCT option is determined by the BCT cost test
analysis, which is discussed in Section 14. Owners or operators of facilities subject to
these regulations would not be required to use the specific wastewater treatment
technologies selected by EPA to establish the limitations and standards. Rather, a
facility could choose to use any combination of process changes, water use changes, and
wastewater treatment to comply with the limitations and standards provided that the
limitations and standards are not achieved through prohibited dilution.
Sections 11.2 through 11.6 provide an overview of the regulatory options considered, the
options selected as the bases of the proposed regulation, and the rationale for options
selected under BPT, BAT, NSPS, PSES, and PSNS, respectively.
11-1
-------
112
Effluent limitations guidelines based on the best practicable control technology currently
available are generally based upon the average of the best existing performance, in terms
of treated effluent discharged by facilities in a subcategory. BPT focuses on end-of-pipe
treatment technology and such process changes and internal controls that are common
industry practice. Based on Section 304(b)(l)(B) of the CWA, the factors considered in
assessing BPT include:
• The cost of achieving effluent reductions in relation to the effluent
reduction benefits;
• The age of equipment and facilities involved;
• The process used;
• Process changes required;
• Engineering aspects of the control technologies;
• Nonwater quality environmental impacts (including energy
requirements); and
• Other factors the Administrator deems appropriate.
The BPT limitations proposed for the pharmaceutical manufacturing industry apply to
direct dischargers and are intended to regulate BOD5, COD, TSS, and cyanide. The
Agency is not proposing to change the current BPT effluent limitations set for pH in the
November 17, 1976 interim final regulation for the pharmaceutical manufacturing
industry.
Thirty-one of the 38 direct discharging pharmaceutical manufacturing facilities currently
use on-site activated sludge biological treatment as part of their wastewater treatment
systems. Therefore, the Agency has evaluated this technology in addition to other
11-2
-------
treatment techniques for BODS, COD, and TSS treatment performance. In addition, all
of the BPT regulatory options include treatment for cyanide-bearing wastewaters at
Subcategory A and C direct dischargers. The BPT regulatory options considered by the
Agency are discussed in Section 7.3.2 and are listed below.
Regulatory Option
Control Technology Description
Subcategories A and C
BPT Option 1
BPT Option 2
BPT Option 3
BPT Option 4
BPT Option 5
Current treatment systems (no cost option)
In-plant cyanide destruction, followed by end-of-pipe advanced biological
treatment
In-plant cyanide destruction, followed by end-of-pipe advanced biological
treatment and filtration
In-plant cyanide destruction, followed by end-of-pipe advanced biological
treatment and polishing pond treatment
In-plant cyanide destruction, followed by end-of-pipe advanced biological
treatment, filtration, and polishing pond treatment
Subcategories B and D
BPT Option 1
BPT Option 2
BPT Option 3
Current treatment systems (no cost option)
End-of-pipe advanced biological treatment
End-of-pipe advanced biological treatment and filtration
Analysis of the impacts of these options in terms of reduction in pollutant discharges to
the environment, costs to industry, and nonwater quality environmental impacts
(including energy impacts) are described in Sections 9, 10, and 12, respectively. The
Agency is proposing the options identified as Option 2 for Subcategories A and C and
for Subcategories B and D, based on the comparison of estimated costs to effluent
reduction benefits of each option. For all Subcategories, Option 2 represents the most
appropriate balance of costs and effluent reduction benefits and other factors.
11.3
BAT
Effluent limitations guidelines based on the best available technology economically
achievable represent the best existing economically achievable performance of plants in
11-3
-------
the industrial subcategory. The CWA establishes BAT as the principal national means
of controlling the direct discharge of priority pollutants and nonconventional pollutants
to waters of the United States. Based on Section 304(b)(2)(B) of the CWA, the factors
considered in assessing BAT include:
• The age of equipment and facilities involved;
• The process used;
• Process changes required;
• Engineering aspects of control technologies;
• The cost of achieving effluent reduction;
• Nonwater quality environmental impacts (including energy
requirements); and
• Other factors the Administrator deems appropriate.
The Agency retains considerable discretion in assigning the weight to be accorded these
factors. BAT may include process changes or internal controls, even when these
technologies are not common industry practice.
The BAT regulatory options considered by the Agency are discussed in Section 7.3.4 and
are listed below.
Regulatory Option
Control Technology Description
Subcategories A and C
BAT Option 1
BAT Option 2
BAT Option 3
BAT Option 4
In-plant cyanide destruction, followed by end-of-pipe advanced biological treatment with
nitrification
In-plant steam stripping and cyanide destruction, followed by end-of-pipe advanced biological
treatment
In-plant steam stripping with distillation and cyanide destruction,
advanced biological treatment
In-plant steam stripping with distillation and cyanide destruction,
advanced biological treatment and activated carbon adsorption
followed by end-of-pipe
followed by end-of-pipe
11-4
-------
Regulatory Option
Control Technology Description
Subcategories B and D
BAT Option 1
BAT Option 2
BAT Option 3
BAT Option 4
End-of-pipe advanced biological treatment
In-plant steam stripping followed by end-of-pipe advanced biological treatment
In-plant steam stripping with distillation followed by end-of-pipe advanced
treatment
In-plant steam stripping with distillation followed by end-of-pipe advanced
treatment and granular activated carbon adsorption
biological
biological
Analysis of the impacts of these options in terms of reduction in pollutant discharges to
the environment, costs to industry, and nonwater quality environmental impacts
(including energy impacts) are described in Section 9, 10, and 12, respectively. The
Agency is proposing Option 2 as the proposed technology basis for BAT limitations for
Subcategories A and C. The Agency is proposing Option 1 as the technology basis for
BAT limitations for Subcategories B and D. The Agency's rationale for BAT selection is
discussed below by subcategory.
11.3.1
Subcategories A and C
EPA selected Option 2 as the proposed technology basis for BAT limitations for facilities
with Subcategory A and/or C operations because EPA believes this option represents the
best available technology economically achievable, considering all statutory factors.
The Agency estimated that none of the options would result in any closures or
unemployment. Based on these findings, EPA concluded that all four options are
economically achievable. EPA selected Option 2 because it determined that option
represented the best available technology from among all the economically achievable
options.
The Agency found that the annual incremental increase in electrical power consumption
for all facilities to achieve Option 2 was 13,200 MW. This increase is equivalent to an
increase of approximately 0.25 percent of the pharmaceutical industry's purchased
11-5
-------
electrical energy usage in 1990. Using the industry's 1990 purchased electrical energy
usage on a baseline, the estimated incremental increases for electrical power
consumption for the remaining options were, for Option 3, an increase of 13,800 MW
and, for Option 4, an increase of 17,900 MW. With respect to energy needs associated
with steam generation for steam stripping and distillation, the Agency found that Option
2 would result in 720,000 MW of incremental energy consumption, or approximately an 8
percent increase above the industry's 1990 total energy consumption. For Option 3, EPA
found that 2,220,000 MW of incremental energy consumption, or a 25 percent increase
above the industry's 1990 total energy consumption, would be required.
EPA did not select Option 3 as proposed BAT because of the large increase in energy
consumption associated with this option. This decision is consistent with the CWA's
requirement that EPA take into account energy requirements in selecting BAT. While
steam generation under BAT Option 2 requires a higher energy consumption than the
energy purchased by the industry in 1990, the Agency notes that the potential for solvent
recovery and reuse will off-set these energy expenditures.
It should be noted that in estimating the energy consumption for steam generation
associated with Options 2 and 3, EPA assumed, based on the available detailed
questionnaire data, that very high volumes of wastewater would need to be stripped and
distilled, thus requiring high demands for steam. EPA believes that this assumption is
very conservative, because the Agency assumed from the Detailed Questionnaire
responses that wastewater streams containing high concentrations of volatile organic
pollutants could not be segregated from steams containing minimal or no concentrations
of these pollutants. EPA believes that stream segregation is possible and expects that
more recent data will show that the volume of wastewater that would be subject to steam
stripping and/or distillation is substantially lower than the volume assumed in this
proposal. Lower volumes would result in higher concentrations of the volatile organic
pollutants to be stripped, less steam and thus less energy would be required to strip or
distill such pollutants from low volume, high concentration wastewater.
11-6
-------
The Agency considered other non-water quality environmental impacts of the selected
option including:
The role which the proposed regulation may play in minimization,
recycle, and disposal of characteristic (ignitable) volatile organic
wastes; and
The effect of the options on the current levels of air emissions from
wastewaters.
BAT Options 2 and 3 will generate 52,200 and 61,000 metric tons per year of
condensates, respectively, due to the use of steam stripping and steam stripping with
distillation. The condensates may include both halogenated and nonhalogenated
solvents. Plants may choose to purify these condensates and then recycle/reuse the
purified solvents as raw materials or use the condensate streams as fuel for incinerators
or boilers either on or off-site. In the Agency's costing effort, EPA assumed all
condensates will be disposed of by off-site incineration. The difference in off-site
incineration costs between Options 2 and 3 is about 10 percent and this cost differential
represents a small part of the total costs associated with these options. Therefore, EPA
concluded that the generation of condensates as a result of steam stripping and steam
stripping with distillation does not provide a basis for choosing between these options.
The Agency also considered the effect of the options on the current levels of air
emissions from wastewater. EPA used the WATER? computer model employed by the
EPA Office of Air and Radiation (OAR) in the recently promulgated Hazardous
Organic NESHAP (HON) for the Synthetic Organic Chemical Manufacturing Industry
(SOCMI), in conjunction with the Detailed Questionnaire responses, to evaluate the
1990 levels of air emissions from wastewater for this industry. Direct discharging
facilities with Subcategory A and/or C operations reported in the 1990 questionnaire
that they emit from wastewater a total of 3.2 million pounds/year of volatile organic
pollutants, and the WATER? model projected 14 million pounds/year of those pollutants
11-7
-------
from wastewater. The results of the analyses were used to estimate air emission
increases or decreases for the regulatory options. The Agency estimated that Option 1
would result in a minimal increase in air emissions, while Option 2 and 3 would decrease
air emissions by 5,300 and 6,350 metric tons per year, respectively. Option 4 would
achieve the same air emission reduction as Option 3. In EPA's view, these beneficial
non-water quality environmental impacts militate in favor of selecting a technology
option employing steam stripping or distillation (Options 2, 3, or 4).
The Agency did not find that the age of equipment and facilities involved provided any
basis for choosing among the options. The Agency also evaluated whether the
engineering aspects of the options were compatible with the manufacturing processes
employed and potential process changes at facilities with Subcategory A and/or C
operations. EPA concluded that the engineering aspects of all four options were
compatible with current manufacturing processes and possible process changes at these
facilities, and the results of this evaluation did not provide a basis for selecting an option.
11.3.2
Subcategories B and D
EPA is proposing Option 1 as the technology basis for BAT limitations for facilities with
Subcategory B and/or D operations because, on the basis of the data submitted by the
direct dischargers in these subcategories, EPA determined that this technology basis is
the best available technology economically achievable for these pollutants. In making
the proposed BAT determination, EPA analyzed data for each facility identified through
the 1989 Pharmaceutical Screener Questionnaire and the 1990 Detailed Questionnaire as
engaging in Subcategory B and/or D operations. The results of the screener
questionnaire indicate that, nationwide, 14 pharmaceutical manufacturing plants with
direct discharges engage only in Subcategory B and/or D operations (excluding
Subcategory E research activities). These 14 facilities reported to EPA in response to
the 1990 Detailed Questionnaire that they discharge BOD5, TSS, COD, six solvents and
no priority pollutants. EPA's analysis of the questionnaire data indicates that the total
11-8
-------
nonconventional pollutant loadings discharged, on average, for each facility with
Subcategory B and/or D operations in 1990 was 1,660 pounds/year. In addition, these
14 facilities reported in their questionnaire responses that they emit from wastewater a
total of 170 pounds/year of volatile organic pollutants. Subsequent analysis by EPA
using its WATER? model indicates that these 14 facilities may actually emit closer to
35,000 pounds/year from wastewater. By way of comparison, facilities with Subcategory
A and/or C operations reported in the 1990 questionnaire that they emit from
wastewater a total of 3.2 million pounds/year of volatile organic pollutants, and the
WATER? model projected 14 million pounds/year of those pollutants.from wastewater.
In view of the comparatively small quantities of pollutants reported to be discharged and
emitted from wastewater from the 14 existing facilities with Subcategory B and/or D
operations only, EPA has determined that the chosen technology basis for the proposed
BAT limits is best suited to the type of wastewater the data describe for direct discharges
in these subcategories. Technology options 2, 3, and 4, which incorporate steam
stripping or steam stripping with distillation technologies, are designed to remove large
quantities and many varieties of solvents from process wastewater. They are not optimal
treatment technologies for the type of wastestreams reported by the 14 direct dischargers
in these subcategories.
The Agency estimated that none of the options would result in any closures or
unemployment. Based upon these findings, EPA concluded that all four options are
economically achievable. EPA selected Option 1 because it determined that option
represented the best available technology from among all the economically achievable
options.
In evaluating the non-water quality environmental impacts of the options, specifically
electrical power consumption, the Agency found that the annual incremental increase in
electrical power consumption for all facilities to achieve Option 1 was 265 megawatts
(MW) beyond current usage (the same as for the proposed BPT limits). This is
11-9
-------
equivalent to an increase of approximately 0.005 percent of the pharmaceutical industry's
purchased electrical energy usage in 1990. The incremental increases for electrical
power consumption for the remaining options were: for Options 2 and 3, an increase of
182 MW and 364 MW, respectively, for all facilities for which EPA estimated compliance
costs; and for Option 4 an increase of 911 MW for all facilities for which EPA estimated
compliance costs.
BAT Options 2, 3, and 4 will generate 76 metric tons per year of condensates as a result
of the use of steam stripping or steam stripping with distillation technologies at direct
discharging plants. Based on the small increase in condensate generation associated with
Options 2, 3, and 4 EPA has concluded that the recovery opportunities or incineration
issues prompted by condensate generation do not provide a basis for choosing one of the
technology options as the basis for proposed BAT limitations for facilities with
Subcategory B and/or D operations. The Agency also considered the effect of these four
options on the current levels of air emissions from wastewater at facilities with
Subcategory B and/or D operations. To do this, EPA used the WATER? computer
model to evaluate the 1990 levels of air emissions from wastewater for facilities with
Subcategory B and/or D operations. The results of the analyses were used to estimate
air emission increases or decreases for the regulatory options. The Agency estimates
that Option 1 would result in a minimal increase in air emissions, while Options 2, 3, and
4 would decrease air emissions by 16 metric tons per year. EPA concluded that the
changes from current emission levels are not significant enough to justify selection of
Options 2, 3, and 4.
EPA also concluded that the engineering aspects of all four options were compatible
with current manufacturing processes employed and potential process changes at
facilities with Subcategory B and/or D operations and thus did not provide a basis for
selecting an option. Similarly, the age of equipment and facilities involved did not
provide any basis for selecting among the options.
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The selection of Option 1 as BAT for facilities with Subcategory B and/or D operations
reflects, in large part, EPA's conclusion, based on currently available data, that BPT
level biological treatment can degrade the relatively small load of organic pollutants
generated by these facilities with a low occurrence of air emissions during advanced
biological treatment.
11.4
NSPS
The basis for new source performance standards under Section 306 of the CWA is the
best available demonstrated technology. Industry has the opportunity to design and
install the best and most efficient pharmaceutical manufacturing processes and
wastewater treatment systems at new plants. Accordingly, Congress directed EPA to
consider the best demonstrated alternative processes, process changes, in-plant control
measures, and end-of-pipe wastewater treatment technologies that reduce pollution to
the maximum extent feasible. In response to that directive, and as with the development
of options for the proposed BAT effluent limitations guidelines, EPA considered effluent
reductions attainable by the most advanced and demonstrated process and treatment
technologies at pharmaceutical manufacturing facilities.
The general approach followed by the Agency for developing NSPS options was, where
appropriate, to evaluate the best demonstrated processes for control of priority and
nonconventional pollutants at the process level and best demonstrated end-of-pipe
treatment for control of- conventional pollutants and additional control of certain
nonconventional pollutants. The factors considered in assessing NSPS include:
• The demonstration status of the process and wastewater treatment
technologies;
• The cost of achieving effluent reductions;
• Nonwater quality environmental impacts; and
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• Energy requirements.
The NSPS regulatory options considered by the Agency are discussed in Section 7.3.5
and are listed below.
Regulatory Option
Sabcategories A and C
NSPS Option 1
NSPS Option 2
Subcategories B and D
NSPS Option 1
NSPS Option 2
Control Technology Description
In-plant steam stripping with distillation and cyanide destruction, followed by end-of-pipe advanced
biological treatment
In-plant steam stripping with distillation and cyanide destruction, followed by end-of-pipe advanced
biological treatment and granular activated carbon adsorption
In-plant steam stripping with distillation followed by end-of-pipe advanced biological treatment
In-plant steam stripping with distillation followed by end-of-pipe advanced biological treatment and
granular activated carbon adsorption
11.4.1
Subcategories A and C
EPA selected NSPS Option 1 for Subcategories A and C because EPA has determined
that it is the best available demonstrated control technology for treating and removing
the pollutants of concern for these Subcategories. EPA selected a more stringent NSPS
technology than its chosen BAT technology because new sources have the opportunity to
segregate their process wastewater in such a way as to minimize the amount of
wastewater that will require steam stripping with distillation, thereby reducing the
adverse energy impacts that prevented EPA from selecting this technology as BAT.
EPA considered the potential cost of the proposed NSPS technology for new plants, as
well as the costs associated with Option 2, which EPA did not select. EPA concluded
that costs associated with any option would not be so great as to present a barrier to
entry, because EPA anticipated no economic impacts for existing source Subcategory A
and C plants if they were to implement the proposed NSPS technology. The Agency also
considered energy requirements and other non-water quality environmental impacts when
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comparing the GAC technology (Option 2) with Option 1. EPA concluded that there
would be only a slight difference in the energy requirements associated with Options 1
and 2. There are no significant differences in the other non-water quality environmental
impacts between the two options considered. EPA did not select Option 2 as the
proposed basis for NSPS because EPA does not have sufficient data to quantify the
amount of COD removed after application of steam stripping with distillation technology
and therefore could not determine whether granular activated carbon technology is
appropriate to remove remaining COD loads.
The Agency considered energy requirements and other non-water quality environmental
impacts and found no basis for any different standards than the proposed NSPS for
conventional pollutants.
11.4.2
Subcategories B and D
EPA selected NSPS Option 1 for subcategories B and D. In making this selection, EPA
analyzed all of the questionnaire data supplied by facilities with Subcategory B and/or D
operations and projected the types and volume of volatile organic pollutants that would
be present in treatable levels in process wastewaters from new facilities in these
subcategories. Although the Detailed Questionnaire data indicated that process
wastewater from the 14 direct dischargers contained fewer pollutants in lower
concentrations than the process wastewater of indirect dischargers (therefore justifying
proposed effluent limitations based on advanced biological treatment alone, not
including steam stripping with distillation), EPA has determined that there is no basis to
conclude that data would adequately depict the wastewater characteristics of a new direct
discharger. Thus, EPA relied instead on the entire universe of facilities with Subcategory
B and/or D operations, irrespective of their direct or indirect discharger status, on the
theory that these facilities are more plentiful and hence statistically more significant.
Because the EPA has no basis for concluding that the wastewater characteristics are
related to the manner of discharge, EPA saw no reason to confine its NSPS analysis to
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the 14 existing direct dischargers and to ignore the 67 indirect dischargers that reported
data. In evaluating all of the data available to it for these subcategories from the
Detailed Questionnaire, EPA concluded that the vast majority of facilities with
Subcategory B and/or D operations have process wastewater with a comparatively wide
variety of volatile organic pollutants in comparatively high concentrations, as reported by
67 of the 188 existing indirect discharging plants with Subcategory B and/or D
operations. EPA considers wastestreams of these 67 plants to be more typical of the
wastestreams EPA expects to find in new sources in these subcategories. Therefore,
EPA concluded that the process wastewater of new facilities with Subcategory B and/
or D operations was more likely to resemble the more typical Subcategory B and/or D
wastestreams, not the atypical wastestreams reported by the 14 existing direct dischargers
in those subcategories. Based on that conclusion, EPA selected, as the proposed
technology basis for NSPS for facilities with Subcategory B and/or D operations, in-plant
steam stripping with distillation treatment followed by end-of-pipe advanced biological
treatment, which EPA has concluded represents the best available demonstrated
treatment technology. EPA selected a more stringent NSPS technology than its chosen
BAT technology because new sources have the opportunity to segregate their process
wastewater in such a way as to minimize the amount of wastewater that will require
steam stripping with distillation, thereby reducing the adverse energy impacts that
prevented EPA from selecting this technology as BAT.
EPA considered the potential cost of the proposed NSPS technology for new plants.
EPA concluded that costs associated with either option would not be so great as to
present a barrier to entry. EPA predicted no economic impacts (i.e., closures) for
existing source Subcategory B and D plants if they were to implement the equivalent
technology options considered as possible BAT for those subcategories.
The Agency also considered energy requirements and other non-water quality
environmental impacts when comparing the GAG technology (Option 2) with Option 1.
EPA concluded that there would be only a slight difference in the energy requirements
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associated with Options 1 and 2. There are no significant differences in the other non-
water quality environmental impacts between the two options considered. EPA did not
select Option 2 as the proposed basis for NSPS because EPA does not have sufficient
data to quantify the amount of COD removed after application of steam tripping with
distillation technology and therefore could not determine whether granular activated
carbon technology is appropriate to remove remaining COD loads.
11.5
PSES
Pretreatment standards for existing sources are designed to prevent the discharge of
pollutants which pass through, interfere with, or are otherwise incompatible with the
operation of POTWs. The CWA requires pretreatment for pollutants that interfere with
or pass through POTWs in amounts that would exceed direct discharge effluent
limitations or limit POTW sludge management alternatives, including the beneficial use
of sludges on agricultural lands. The Agency is also requiring pretreatment for
pollutants that pass through POTWs due to the pollutant exhibiting significant
volatilization prior to treatment by a POTW. The transfer of a pollutant to another
media (air) through volatilization does not constitute treatment. PSES are to be
technology-based and analogous to BAT for removal of priority and nonconventional
pollutants.
The PSES regulatory options considered by the Agency are discussed in Section 7.3.6 and
are listed below.
Regulatory Optkm
Subcategories A and C
PSES Option 1
PSES Option 2
PSES Option 3
PSES Option 4
Control Technology Description
In-plant steam stripping and cyanide destruction
In-plant steam stripping with distillation and cyanide destruction
In-plant steam stripping with distillation and cyanide destruction, followed by end-of-pipe
advanced biological treatment
In-plant steam stripping with distillation and cyanide destruction, followed by end-of-pipe
advanced biological treatment and granular activated carbon adsorption
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Regulatory Option
Control Technology Description
Subcategories B and D
PSES Option 1
PSES Option 2
PSES Option 3
In-plant steam stripping
In-plant steam stripping with distillation
In-plant steam stripping with distillation followed by granular activated carbon adsorption
The Agency is also co-proposing two implementation scenarios for the selected PSES
option. Under co-proposal (1), EPA is proposing to regulate all pollutants found to
pass-through or interfere with POTWs as described in EPA's POTW pass-through
analysis described in Section 17. Under co-proposal (2), EPA is proposing to regulate
only highly volatile pollutants at indirect dischargers and is taking comment on the pass-
through analysis for other pollutants of concern. See Section 17 for further discussion of
the two co-proposals.
11.5.1
Subcategories A and C
EPA selected Option 1 for PSES under both co-proposals for Subcategories A and C.
The Agency has evaluated the costs of this option based on co-proposal (1), which is
more expansive, and found that there would be no closures among affected facilities (for
which costs were estimated by EPA) as a result of these costs. Therefore EPA
determined the costs of Option 1 to be economically achievable under either co-
proposal. EPA also found the other options to be economically achievable. EPA
selected Option 1 because it determined that this option represents the best available
technology among all economically achievable options, insofar as it achieves pollutant
reductions necessary to prevent pass-through of volatile organic pollutants, allows for
recovery and recycling of volatile organic pollutants, and reduces non-water quality
environmental impacts caused by air emissions of pollutants from wastewater. The
Subcategory A and/or C indirect discharging facilities reported in their questionnaire
responses that they emit from wastewater a total of 3,850 million pounds/year of volatile
organic pollutants (in contrast to the emissions totaling 3,220 million pounds/year by
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direct dischargers). Subsequent analysis using the WATER? model indicate that these
indirect dischargers may actually emit closer to 17,900 million pounds/year from
wastewater (in contrast to the emissions totaling 14,000 million pounds/year for the
direct dischargers). Although Options 2, 3, and 4 would achieve essentially the same
decrease in the emission of wastewater pollutants to the air as Option 1, the increase in
energy use requirements associated with Options 2, 3, and 4 would be equivalent to an
increase of 31 percent above the 1990 pharmaceutical industry energy use. For this
reason, EPA selected Option 1 over Options 2, 3, and 4.
The Agency also considered age, size, processes, other engineering factors, and non-
water quality environmental impacts in developing the proposed PSES for Subcategories
A and C. The Agency did not identify any basis for establishing different pretreatment
standards based on age, size, processes, or other engineering factors.
11.5.2
Subcategories B and D
EPA also selected Option 1 for PSES under both co-proposals for Subcategories B
and D. In selecting steam stripping as the technology basis for the proposed PSES for
Subcategories B and D, EPA relied upon the 1990 questionnaire data supplied by 188
facilities with Subcategory B and/or D operations that sent their wastewater to POTWs
for treatment. The data supplied by the 188 indirect facilities with Subcategory B and D
operations, show that these facilities discharge BODS, TSS, COD, 18 nonconventional
pollutants and four priority pollutants. EPA's analysis of the questionnaire data indicates
that the total nonconventional and priority pollutant loadings discharged, on average, for
each indirect discharger with Subcategory B and D operations in 1990 was 14,600
pounds/year (in contrast to the average of 1,660 pounds/year reported by the 14 direct
dischargers in these Subcategories). The 188 facilities also reported in their
questionnaire responses that they emit from wastewater a total of 1.5 million
pounds/year of volatile organic pollutants (in contrast to the emissions totaling 170
pounds/year reported by the direct dischargers). Subsequent analysis using the
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WATER? model indicates that these indirect dischargers may actually emit closer to
3.3 million pounds/year from wastewater (in contrast to the emissions totaling 35,000
pounds/yr for the direct dischargers). Based on evaluation of this data, EPA selected
Option 1 as the basis of pretreatment standards for facilities with Subcategory B and D
operations. This technology is designed to remove large quantities and many varieties of
solvents from process wastewater. According to the data supplied by the 188 indirect
dischargers with Subcategory B and D operations, EPA has concluded that the
wastewater characteristic of these facilities—with its comparatively high volume and
concentration of solvents-is well-suited to this form of treatment. In addition, EPA
found that none of the indirect dischargers with Subcategory B and D operations that
would incur costs as a result of the proposed PSES limitations (based on the more
expansive co-proposal (1)) would close as a result of this option. Therefore EPA
determined that the costs of the pollutant reduction achieved by this option under either
co-proposal were economically achievable.'
The Agency considered age, size, processes, other engineering factors, and non-water
quality environmental impacts in developing the proposed PSES for Subcategories B
and D. The Agency did not identify any basis for establishing different pretreatment
standards based on age, size, processes, or other engineering factors. EPA has also
concluded that Option 1 would significantly decrease air emissions and would be
consistent with the Administrator's waste minimization and combustion strategy. EPA
did not choose Option 2 because, although this option would result in approximately the
same decrease in air emissions as Option 1, it would result in a significant increase in
total energy use over that required under Option 1.
11.6
PSNS
Pretreatment standards for new sources are designed to prevent the discharge of
pollutants that pass through, interfere with, or are otherwise incompatible with the
operation of POTWs. The CWA requires pretreatment for pollutants that pass through
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POTWs or limit POTW sludge management alternatives, including the beneficial use of
sludges on agricultural lands.
The development of regulatory options for PSNS is analogous to the development of
options for NSPS, in that the new source has the opportunity to design and install the
best and most efficient pharmaceutical manufacturing processes and wastewater
treatment facilities. Accordingly, Congress directed EPA to consider the best
demonstrated alternative processes, process changes, in-plant control measures, and end-
of-pipe wastewater treatment technologies that reduce pollution to the maximum extent
feasible. In response to that directive, EPA considered effluent reductions attainable by
the most advanced and demonstrated process and treatment technologies at
pharmaceutical manufacturing facilities. The factors considered in assessing PSNS
include:
• The demonstration status of the process and wastewater treatment
technologies;
• The cost of achieving effluent reductions;
• Nonwater quality environmental impacts; and
• Energy requirements.
The PSNS regulatory options considered by the Agency are discussed in Section 7.3.7
and are listed below.
Regulatory Option
Control Technology Description
Subcategories A and C
PSNS Option 1
PSNS Option 2
PSNS Option 3
In-plant steam stripping with distillation and cyanide destruction
In-plant steam stripping with distillation and cyanide destruction, followed by end-of-pipe
advanced biological treatment
In-plant steam stripping with distillation and cyanide destruction, followed by end-of-pipe
advanced biological treatment and granular activated carbon adsorption
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Regulatory Option
Control Technology Description
Subcategories B and D
PSNS Option 1
PSNS Option 2
In-plant steam stripping with
In-plant steam stripping with
distillation
distillation followed by granular activated
carbon adsorption
The Agency is also co-proposing two implementation scenarios for the selected PSNS
option. Under co-proposal 1, EPA is proposing to regulate all pollutants found to pass-
through or interfere with POTWs as described in EPA's POTW pass-through analysis
described hi Section 17. Under co-proposal 2, EPA is proposing to regulate only highly
volatile pollutants at indirect dischargers and is taking comment on the pass-through
analysis for other pollutants of concern. See Section 17 for further discussion of the two
co-proposals.
The Agency selected PSNS Option 1 as the basis of NSPS-for Subcategory A, B, C, and
D operations. Option 1 in all subcategories provides treatment of priority and
nonconventional pollutants by in-plant steam stripping with distillation prior to biological
treatment, which, for indirect dischargers, occurs at the receiving POTW. EPA also
proposes to set standards based on cyanide destruction for cyanide-bearing wastestreams
at new source Subcategory A and/or C operations.
EPA selected a more stringent PSNS technology than its chosen PSES technology
because new sources have the opportunity to segregate their process wastewater in such.
a way as to minimize the amount of wastewater that will require steam stripping with
distillation, thereby reducing the adverse energy impacts that prevented EPA from
selecting this technology as PSES.
EPA considered the cost of the proposed PSNS technologies for new plants based on co-
proposal (1), which is more expansive than co-proposal (2). EPA has concluded that
such costs are not so great as to present a barrier to entry under either co-proposal, as
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demonstrated by the fact that currently operating plants are using these technologies.
The Agency also considered energy requirements and other non-water quality
environmental impacts when comparing the three PSNS technology options for facilities
with Subcategory A and/or C operations and the two PSNS technology options for
facilities with Subcategory B and/or D operations. EPA concluded that there would be
only a slight difference in the energy requirements associated with Options 1, 2, and 3
for Subcategory A and/or C facilities and with Options 1 and 2 for Subcategory B and/
or D facilities. There are no significant differences in the other non-water quality
environmental impacts between the options considered.
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SECTION 12
NONWATER QUALITY ENVIRONMENTAL IMPACTS
12.1
Introduction
Sections 304(b) and 306 of the CWA require EPA to consider the nonwater quality
environmental impacts associated with effluent limitations guidelines and standards. In
accordance with these requirements, EPA has considered the potential effect of the
proposed regulatory options for the pharmaceutical manufacturing industry on energy
consumption, air emissions, and solid waste generation. Sections 12.2, 12.3, and 12.4,
respectively, discuss these nonwater quality environmental impacts. EPA has also
evaluated the potential effect of process wastewater flow rate on these nonwater quality
environmental impacts and a summary of a flow sensitivity analysis is discussed in
Section 12.5. The Agency's preliminary development of air emission standards is
discussed in Section 12.6.
123
Energy Impacts
Energy impacts to the pharmaceutical manufacturing industry from the proposed
regulatory options will include increased electrical usage and increased energy usage in
the generation of steam for steam stripping with and without distillation. These energy
impacts are discussed below in Sections 12.2.1 and 12.2.2.
12.2.1
Electrical Usage
According to the Department of Energy, the pharmaceutical manufacturing industry
purchased approximately 5,404 x 106 kWh of electrical energy in 1990, accounting for
0.7% of the total U.S. industrial electrical energy purchase (756,646 x 106 kWh) in
1990.1 The Agency evaluated the annual incremental increase in electrical power
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consumption expected under each regulatory option for direct dischargers. These
estimated annual incremental increases (in kWh) are shown below.
BAT Option 1
BAT Option 2
BAT Option 3
BAT Option 4
•••••.'. . Increase in Electrical Energy Consumption (kWh)
Subcategory A and C
1.38 x 10s
13.2 x 10s
13.6 x 106
13.6 x 106
Subcategory B and D
0.265 x 10s
0.182 x 10s
0.364 x 106
0.364 x 106
For Subcategory A and C operations, the Agency is proposing BAT Option 2. This
option would increase the electrical power consumption by less than one percent of the
total electrical power purchased in 1990 by the pharmaceutical manufacturing industry.
For Subcategory B and D operations, the Agency is proposing BAT Option 1. This
option would increase the electrical power consumption by less than 0.01 percent of the
total electrical power purchased in 1990 by the industry.
1223
Energy Usage in the Generation of Steam
Of greater impact is the energy usage required to generate steam under the regulatory
options that include either steam stripping or steam stripping with distillation. Steam
stripping and steam stripping with distillation are part of BAT and PSES options
considered for Subcategory A and C direct and indirect dischargers and Subcategory B
and D direct and indirect dischargers. The Agency evaluated the annual incremental
increase in energy usage from steam generation expected under each of these options.
These estimated annual incremental increases (in kWh) are shown below.
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BAT Option 2
BAT Option 3
BAT Option 4
PSES Option 1
PSES Option 2
PSES Option 3
PSES Option 4
Increase in Energy Demand Related to Steam Usage (kWfa)
Subcategory
AandC
Direct
Dischargers
720 x 10s
2,220 x 10s
2,220 x 10s
-
Subcategory
Band D
Direct
Dischargers
1.61 x 106
18.6 x 10s
18.6 x 10s
-
Sabcategory
AandC
Indirect
Dischargers
-
749 x 106
2,760 x 106
2,760 x 106
2,760 x 106
I Subcategory
BandD
Indirect
; Dischargers
-
90.2 x 106
266 x 106
266 x 10s
According to the Department of Energy (1), the pharmaceutical manufacturing industry
purchased approximately 8,981 x 106 kWh of fuel and electric energy in 1990. for
Subcategory A and/or C operations at direct dischargers, the Agency is proposing BAT
Option 2, which would increase the energy consumption for steam generation by an
amount equal to 8 percent of the total fuel and electrical power purchased in 1990. The
Agency is not proposing a BAT option that includes steam stripping for Subcategory B
and/or D operations at direct dischargers. For Subcategory A and/or C operations at
indirect dischargers, the Agency is proposing PSES Option 1 which would increase the
energy consumption for steam generation by an amount equal to 8 percent of the total
fuel and electrical power purchased in 1990. For Subcategory B and/or D operations at
indirect dischargers, the Agency is proposing PSES Option 1, which would increase the
energy consumption for steam generation by an amount equal to one percent of the total
fuel and electrical power purchased hi 1990.
It should be noted, however, that in estimating the energy consumption for steam
generation associated with the steam stripping and steam stripping with distillation
options, EPA assumed that very high volumes of wastewater would need to be stripped
and/or distilled. This assumption was based on the available detailed questionnaire data
and leads to the high requirements for steam. EPA believes that this assumption is very
conservative, because the Agency assumed from the Detailed Questionnaire responses
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that wastewater streams containing high concentrations of volatile organic pollutants
could not be segregated from streams containing minimal or no concentrations of these
pollutants. EPA believes that stream segregation is possible and that the volume of
wastewater that would be subject to steam stripping and distillation is substantially lower
than the volume assumed for these energy use calculations. To assess what impact a
lower wastewater volume treated would have on steam generation requirements, EPA
conducted a flow sensitivity analysis as described in Section 12.5.
Table 12-1 summarizes the estimated increase in energy usage (including electrical power
j
and steam generation) associated with the proposed regulations. Compliance with the
proposed regulations is estimated to increase the industry's energy usage by
approximately 17.5 percent. While the steam generation required under the proposed
regulations requires increased energy consumption, the Agency notes that the potential
for solvent recovery and reuse will help to offset these energy expenditures. In addition,
these estimates are based on steam stripping of 80 to 100 percent of each facility's
process wastewater which the Agency believes could significantly over estimate the steam
generation requirements. The Agency concludes that the effluent reduction benefits
from the proposed regulation exceed the potential adverse impacts from the increase in
energy consumption that is projected.
12.3
Air Emission Impacts
Pharmaceutical manufacturing facilities generate wastewaters that contain varying
concentrations of organic compounds, some of which are listed as Hazardous Air
Pollutants (HAPs) in Title 3 of the Clean Air Act Amendments (CAAA) of 1990.
Table 12-2 lists the HAPs and volatile organic pollutants present in pharmaceutical
manufacturing wastewaters, as reported by facilities responding to the Detailed
Questionnaire (volatile organic pollutants were identified as those constituents that could
be analyzed by standard EPA methods for volatile organics such as gas chromatography
mass spectrometry (GCMS) by analytical method 1624 (40 CFR Part 136) or GC by
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analytical method 8015.2). Prior to discharge, pharmaceutical manufacturing
wastewaters typically pass through a series of collection and treatment units that are
open to the atmosphere. Atmospheric exposure of organic-containing wastewaters can
result in significant volatilization of HAPs, volatile organic pollutants, and other organic
pollutants to the air.
Air emissions of HAPs, volatile organic pollutants, and other organic pollutants may
occur from wastewater collection units such as process drains, manholes, trenches, sumps,
and junction boxes, and from wastewater treatment units such as neutralization and
equalization basins, settling basins, clarifiers, biological treatment units, air and steam
strippers lacking air pollution control devices, and other units that expose wastewater to
the air.
To determine the impact of the proposed regulation on air emissions, the Agency had to
first determine the current amount of organic constituents emitted into the air from
pharmaceutical manufacturing wastewaters. Section 12.3.1 compares the air emissions
estimated by facilities responding to the Detailed Questionnaire with the air emissions
estimated by a WATER? model analysis, an independent fate analysis performed by the
Agency. Section 12.3.2 discusses the regulatory impact on air emissions based on a
comparison of current air emissions from pharmaceutical manufacturing wastewaters to
projected air emissions from pharmaceutical manufacturing wastewaters of facilities
complying with the proposed regulation.
This section also discusses the estimated impact on criteria pollutant emissions in the
generation of steam for regulatory options which include steam stripping and distillation.
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12.3.1 Current Air Emissions Based on Detailed Questionnaire Responses and
WATER? Analysis
In response to Section 3a of the Detailed Questionnaire, entitled "Compound or
Chemical Usage and Disposition," facilities estimated the quantities of virgin chemicals
used and disposed of during manufacturing of pharmaceutical products in calendar year
1990. As part of 'the chemical usage and disposition reporting, facilities were asked to
estimate the amount of virgin chemicals used in pharmaceutical manufacturing
operations that was: 1) emitted into the air from wastewater prior to discharge,
2) degraded and/or destroyed, and 3) discharged to a surface water and/or a POTW.
These three disposition methods summarize the fate, or disposal pathways, of organic
constituents present in pharmaceutical manufacturing wastewaters.
Upon examining responses to the Detailed Questionnaire regarding the fate of
wastewater organic constituents, the Agency suspected that a greater percentage of
wastewater organic constituents are emitted to the air than most facilities reported. The
Agency noted that 20 indirect dischargers that had no on-site wastewater treatment
systems reported a large percentage of wastewater organic constituents degraded and/or
destroyed on site. It is improbable that such high rates of degradation and/or
destruction could be achieved in the absence of any wastewater treatment system, such
as biological treatment or incineration. In addition, some plants with open
impoundments or basins with mechanical agitators or aerators, reported relatively small
percentages of air emissions from wastewater in Table 3-2 of the Detailed Questionnaire.
The responses to the detailed questionnaire also lacked in most cases an indication of
the estimation method used in determining the load discharged as air emissions from
wastewater.
To provide an independent estimate of the partitioning of wastewater organic
constituents (including the HAPs and volatile organic pollutants listed in Table 12-2), the
Agency performed a fate analysis using the WATER? model and data provided by the
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244 pharmaceutical manufacturing facilities that responded to the Detailed
Questionnaire. Facilities were grouped by manufacturing process (Subcategory A and C
or Subcategory B and D) and by type of wastewater discharge (direct or indirect). For
each facility group, the WATER? model was used to estimate the amount of reported
wastewater organic constituents: 1) emitted to the air from wastewater during collection
and treatment, 2) degraded and/or destroyed, or 3) discharged to surface water and/or
POTW. In addition, the WATER? model estimated the amount of reported wastewater
organic constituents disposed of as a result of sludge adsorption. The Detailed
Questionnaire did not have a separate category for sludge adsorption with regard to
organic constituent disposal pathways. Therefore, the responses from facilities did not
differentiate the amount of wastewater organic constituents disposed of as a result of
sludge adsorption from the amount emitted into the air, degraded and/or destroyed, or
discharged to surface water and/or POTW. The amount of wastewater organic
constituents disposed of as a result of sludge adsorption was most likely reported by
facilities under the degraded and/or destroyed disposal category because wastewater
sludge generated is typically incinerated.
The WATER? model uses the chemical properties data from CHEMDAT7, a database
described in the Air Emission Models Report.3 The model determines wastewater
pollutant disposal pathways from the following wastewater treatment units:
Pretreatment;
Primary filter;
Trickling filter;
Equalization;
Aeration 1;
Aeration 2; and
Secondary clarifier.
The wastewater treatment trains used in the WATER? model to simulate the wastewater
treatment trains of the facilities responding to the Detailed Questionnaire consisted of a
combination of the various treatment units listed above. The wastewater pollutant data
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and pollutant loading data used as input for WATER? model analysis were compiled
from facility responses to Section 3a of the Detailed Questionnaire. Information on
treatment unit characteristics used as input for WATER? model analysis were compiled
from facility responses to Section 5 of the Detailed Questionnaire. A complete
description of the WATER? model, the fate analysis, and the assumptions made for the
fate analysis is presented in the May 18, 1994 memorandum entitled WATER? Analysis
of the Fate of Organic Pollutant Loads through Pharmaceutical Facilities 4, located in
the Record for this rulemaking.
Table 12-3 presents the results of the WATER? analysis for direct dischargers, listed by
subcategory, and the corresponding estimates reported by direct dischargers responding
to the Detailed Questionnaire. Table 12-4 presents the results of the WATER? analysis
for indirect dischargers and the corresponding estimates reported by indirect dischargers
responding to the Detailed Questionnaire. For both direct and indirect dischargers, the
results of the WATER? analysis indicate that a significantly higher percentage of
wastewater organic constituents partition to the air than was reported by facilities
responding to the Detailed Questionnaire. For example, Subcategory A and C indirect
dischargers estimated that approximately 90.5 million pounds of constituents present in
pharmaceutical manufacturing wastewaters in 1990 were: 1) emitted into the air from
wastewater, 2) degraded and/or destroyed, or 3) discharged to POTWs. Of this total,
the Subcategory A and C indirect dischargers reported that approximately 4% was
emitted into the air, 59% was degraded and/or destroyed, and 37% was discharged to
POTWs. In comparison, of the 90.5 million pounds of wastewater constituents reported
by facilities, the WATER? model analysis estimated that 20% would be emitted into the
air, 36% would be degraded and/or destroyed, 43% would be discharged to POTWs, and
1% would be disposed of by sludge adsorption.
Overall, a total of 8.5 million pounds of organic pollutants were reported as emitted into
the air in 1990 from pharmaceutical manufacturing wastewaters based on summarized
Detailed Questionnaire responses. The WATER? model estimated that approximately
12-8
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35.2 million pounds of organic pollutants were emitted into the air in 1990 from
pharmaceutical manufacturing wastewaters, four times the estimate reported by facilities
in the Detailed Questionnaire.
12.3.2
Regulatory Impact on Air Emissions
The use of in-plant steam stripping as part of the Agency's proposed regulatory options
will impact air emissions in two ways. First, priority and nonconventional pollutants that
are currently released as air emissions from wastewater at pharmaceutical manufacturing
facilities will be removed and condensed by in-plant steam stripping for recycle, reuse, or
disposal. Second, the generation of steam for steam stripping or steam stripping with
distillation options will result in increased emissions of criteria pollutants (CO, NOX,
VOC, SO2, and particulate matter). EPA's evaluation of these impacts are described in
Sections 12.3.2.1 and 12.3.2.2 below.
12.3.2.1 Reduction in Air Emissions Due to Proposed Regulatory Options
As discussed in Section 11, the Agency is proposing effluent limitations guidelines and
standards for ammonia and organic pollutants based on the following in-plant and end-
of-pipe treatment technologies:
Subcategory
AandC
AandC
B andD
B andD
Discharge Status
Direct
Indirect
Direct
Indirect
Proposed ^^BAT/»SES T^tment Technologies for
Ch^anie PoUlitants
In-plant steam stripping followed by end-of-pipe
advanced biological treatment
In-plant steam stripping
End-of-pipe advanced biological treatment
In-plant steam stripping
12-9
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The Agency estimates that the proposed BAT and PSES options that include in-plant
steam stripping will remove organic pollutants and ammonia currently discharged as air
emissions from wastewater as follows:
Regulatory Option
BAT Option 2
BAT Option 1
PSES Option 1
PSES Option 1
Subcategory
AandC
B and D
AandC
B andD
Estiiniafed Reduction in Air
Emissions (Ibs/yr)
13.5 x 10s
(a)
17.9 x 106 (b)
3.08 x 106 (b)
(a) The Agency expects that application of advanced biological treatment for Subcategory B and D direct
dischargers will result in a minimal increase in air emissions of organic pollutants from wastewater due to the
addition of open aeration under this option.
(b) These reductions assume implementation of PSES co-proposal (1).
These reductions should occur since the proposed technology basis of in-plant steam
stripping is applied at a point prior to dilution of process wastewaters and prior to
exposure of the wastestrearris to the air.
123.2.2
Criteria Pollutant Air Emissions
EPA evaluated the impact of steam generation requirements, under regulatory options
that include in-plant steam stripping and steam stripping with distillation, on criteria
pollutant emissions. To develop this estimate, the total steam generation requirements •
in tons of steam were estimated using the pharmaceutical cost model and it was assumed
that the steam would be generated in industrial boilers with no emission controls. Fifty
percent of the required boiler fuel is assumed to be low sulfur Number 6 fuel oil and the
remaining 50% supplied by natural gas. The calculation of criteria pollutant air
emissions is presented in the December 15, 1994 calculation package entitled Calculation
of Air Emissions Related to Steam Generation.5 Table 12-5 presents an estimate of the
resultant criteria pollutant emissions.
12-10
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For those options proposed as the basis of regulation, the resultant criteria pollutant
emission total is 3,014 tons/yr or 6.03 x 106 Ibs/yr. The Agency concludes that the air
emission and effluent reduction benefits of hazardous air pollutants, priority,
nonconventional, and conventional pollutants far outweigh the potential negative impacts
of increased emissions of criteria air pollutants.
12.4
Solid Waste Impacts
The Agency has evaluated the following solid waste impacts which would be expected
due to the application of the proposed BPT, BCT, BAT, and PSES effluent limitations
guidelines and standards:
The increase in dry sludge generation due to the application of
advanced biological treatment;
The increase in waste solvent generation due to the application of
in-plant steam stripping and in-plant steam stripping with
distillation; and
The increase in waste hydrogen chloride (HC1) due to scrubber
liquor generated by facilities with wastewaters containing ammonia.
These impacts are discussed below in Sections 12.4.1, 12.4.2, and 12.4.4, respectively.
Section 12.4.3 presents an overview of EPA's waste minimization and combustion
strategy including EPA's approach for clean fuels. The Agency is not proposing any
BAT or PSES options which include activated carbon treatment and therefore there are
no solid waste impacts associated with this technology.
12.4.1
Dry Sludge Generation
Based on the responses to the Detailed Questionnaire, pharmaceutical manufacturers
generated approximately 112,000 tons of dry sludge in 1990. Table 12-6 presents the
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amount of sludge (dry basis) generated in 1990 by Subcategory A and/or C and
Subcategory B and/or D direct and indirect dischargers as well as the estimated amount
of additional dry sludge that would be generated by Subcategory A and/or C and
Subcategory B and/or D direct and indirect dischargers facilities complying with the
proposed effluent limitations guidelines.
Compliance with BAT/BPT/BCT is expected to increase the mass of wastewater
treatment sludge generated by Subcategory A and/or C direct dischargers by
5,180 tons/yr, a result of increased solids generation and removal at facilities upgrading
to advanced biological treatment systems. This represents approximately a 14% increase
in the current sludge generation rate of 36,400 tons/yr for Subcategory A and/or C
direct dischargers.
Compliance with BAT/BPT/BCT is expected to increase the mass of wastewater
treatment sludge generated by Subcategory B and/or D direct dischargers by 44 tons/yr,
a result of increased solids generation and removal at facilities upgrading to advanced
biological treatment systems. This represents less than a 2% increase in the current
sludge generation rate of 2,760 tons/yr for Subcategory B and/or D direct dischargers.
Compliance with BAT/BPT/BCT is anticipated to improve the quality of wastewater
treatment sludge by reducing mass loadings of pollutants exported in sludge. The
Agency concludes that there will be no adverse non-water quality environment impacts
regarding sludge management.
No additional sludge is expected to be generated by facilities that discharge directly as a
result of the proposed regulations.
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12.4.2
Waste Solvent Generation
Compliance with BAT for Subcategory A and/or C direct dischargers and compliance
with PSES for Subcategory A and/or C and Subcategory B and/or D indirect dischargers
is expected to increase the amount of waste solvents generated by pharmaceutical
manufacturing facilities as a result of in-plant steam stripping. The amount of waste
solvents recovered as a result of steam stripping by Subcategory A and/or C direct
dischargers would be approximately 57,300 tons/yr or 52,000 metric tons/yr. The
amount of waste solvents recovered as a result of steam stripping by Subcategory A
and/or C and Subcategory B and/or D indirect dischargers would be approximately
63,500 and 6,370 tons/yr, respectively or 57,600 and 5,780 metric tons/yr, respectively.
As discussed previously, the use of in-plant steam stripping would remove a significant
amount of organic pollutants from the wastewater prior to atmospheric exposure of the
wastewater and the subsequent emission of pollutants into the air.
Organic solvent overheads generated under the proposed BAT and PSES options will
create the opportunity for additional solvent recovery or reuse in the pharmaceutical
manufacturing industry. For example, the Agency is aware of at least one
pharmaceutical manufacturer that is currently distilling methanol from a process
wastewater stream and recycling the concentrated methanol overheads back into their
process operation. The Agency is also aware of at least two other pharmaceutical
manufacturers that steam strip their process wastewaters and sell the solvent overheads
for profit. Where possible, facilities would be expected to recover solvents for reuse
within the process or for use in other industrial processes.
The solvent overheads will also have a value associated with their energy
content. The Agency has estimated that the energy value of the solvent overheads
generated under the proposed options will be 77.4 million kWhr/yr for Subcategory A
and/or C direct dischargers. The energy value of the solvent overheads generated by
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Subcategory A and/or C and B and/or D indirect discharging facilities is estimated as
85.7 and 8.6 million kWhr/yr, respectively.
12.43
Waste Minimization and Combustion Strategy
In May 1994, the EPA Administrator announced a Draft Hazardous Waste Minimization
and Combustion Strategy that is pertinent to the pharmaceutical manufacturing industry.
The Draft Strategy provides the central framework for EPA's federal effort to maximize
the source reduction and recycling of hazardous wastes under RCRA. The Draft
Strategy focuses on a number of specific goals, including reducing the amount and
toxicity of hazardous waste that is generated, particularly when such reductions would
benefit more than one environmental medium. The Draft Strategy also encompasses a
number of other features, including public outreach, public involvement and
environmental justice, permitting, enforcement, risk assessments, and good science.6
12.4.3.1
Waste Minimization
The Draft Strategy has both short-term and a longer-term phases. In the short-term,
EPA will address the source reduction and environmentally sound recycling of
halogenated (and metal-bearing) combustible wastes. The longer-term effort will
encompass all RCRA hazardous wastes, taking a more comprehensive approach to how
wastes are generated and managed, and the role waste minimization can play as a
preferred "mode of management" over other forms of waste management (e.g.,
treatment, storage, and disposal). This source reduction (waste minimization) strategy
should reduce the long-term demand for combustion and other waste management
facilities.(6) Section 7.2 presents-EPA's efforts toward increasing opportunities for
source reduction (e.g., process changes) in the pharmaceutical manufacturing industry.
The Agency also has released a draft report by the EPA Office of Solid Waste's
Definition of Solid Waste Task Force. This report, Reengineering RCRA for
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Recycling 7, presents recommendations of the Task Force to improve the regulation of
hazardous waste recycling under RCRA. One of the recommendations of the Task
Force was that provision should be made to exempt "clean" waste-derived fuels from the
regulatory requirements of RCRA for hazardous wastes. "Clean fuels" are fuels with "de
minimis" levels of halogens (primarily chlorine in this case) or toxic metals, especially
fuels that are characteristically hazardous only because of ignitability. EPA will address
the recommendations of the Task Force, including the recommendation on "clean fuels."
In the case of the pharmaceutical manufacturing industry, the volatile organic pollutants
that are generated in the largest quantities are non-halogenated volatile organic
pollutants, including methanol, ethanol, isopropanol, and acetone. Implementation of in-
plant steam stripping technology affords the opportunity to recover these pollutants and
reuse them for their solvent properties. In situations where reuse of solvents is not
practical, these non-halogenated pollutants can potentially be used as "clean fuels" in
industrial boilers, such as those on-site at pharmaceutical manufacturing facilities.
Implementation of in-plant steam stripping also affords the opportunity to recover
halogenated volatile organic pollutants (e.g., methylene chloride) for recycle in the
pharmaceutical manufacturing process. Recovered chlorinated solvents that are not of
sufficient quality for reuse in pharmaceutical manufacturing processes may be sold for
reuse in other industries.
12.4.3.2
Combustion
The Draft Strategy also addresses rigorous controls on hazardous waste combustion
facilities using best available technologies to ensure that these facilities do not impose
unacceptable risk to human health and the environment. EPA's regulatory activities are
scheduled to be directed toward upgrading technical standards for residual wastes and
emissions from hazardous waste combustion facilities, including incinerators, cement
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kilns, light-weight aggregate kilns, and smelter furnaces, as well as boilers and industrial
furnaces.
EPA estimates that approximately 127,000 tons per year or 115,000 metric tons per year
of solvent waste (halogenated and nonhalogenated) would be recovered from in-plant
steam stripping at pharmaceutical manufacturing facilities. Currently there is RCRA-
permitted capacity at commercially available facilities to incinerate in excess of 1 million
metric tons per year of solvents. Therefore, there is adequate capacity at commercial
incinerators to combust the entire mass of solvents assuming that none would be
recovered and recycled. Again, however, it is the Agency's policy, as stated in the Draft
Waste Minimization and Combustion Strategy, that the most appropriate mode of
management for solvents removed from pharmaceutical manufacturing wastewaters by
steam stripping is recycle in the process, recycle at other facilities, or use as "clean fuels"
in boilers.
12.4.4
Waste Hydrogen Chloride Scrubber Liquor
Compliance with BAT for Subcategory A and/or C direct dischargers and compliance
with PSES for Subcategory A and/or C indirect dischargers is expected to increase the
amount of waste hydrogen chloride (HC1) scrubber liquor recovered by pharmaceutical
manufacturing facilities that generate wastewaters containing ammonia. HC1 wet
scrubbers are used to control air emissions from steam strippers used to remove
ammonia from the wastewater. The amount of waste scrubber liquor generated by
Subcategory A and/or C direct dischargers would be approximately 467 tons/yr. The
amount of waste scrubber liquor generated by Subcategory A and/or C indirect
dischargers would be approximately 706 tons/yr.
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12.5
Flow Sensitivity
To evaluate the impact of process wastewater flow on nonwater quality environmental
impacts, EPA evaluated the impact on electricity and steam usage assuming a facility's
process wastewater organic load is contained in a smaller volume of flow. Table 12-7
presents a summary of the flow sensitivity analysis conducted for Subcategory A and/or
C direct dischargers under BAT Option 3 (in-plant steam stripping with distillation
followed by end-of-pipe advanced biological treatment) and Subcategory A and/or C and
B and/or D indirect dischargers under PSES Option 2 (In-plant steam stripping with
distillation). Under this analysis, all process wastewater is treated through end-of-pipe
biological treatment (for direct dischargers) but the organic load is assumed to be
concentrated in a portion of the process wastewater flow for the in-plant steam stripping
with distillation treatment. The flow sensitivity analysis shows that segregation of high
concentration wastewaters from dilute process wastewaters could significantly reduce the
steam generation required under the proposed regulatory options which include in-plant
steam stripping with distillation and in-plant steam stripping.
12.6
Preliminary Development of Air Emission Standards
Title III of the 1990 Clean Air Act Amendments was enacted to reduce the amount of
nationwide emissions of hazardous air pollutants. It comprehensively amended section
112 of the Clean ALT Act (CAA).
Section 112(b) lists the 189 chemicals, compounds, or groups of chemicals deemed by
Congress to be hazardous air pollutants (HAPs). These toxic air pollutants are to be
regulated by national emission standards for hazardous air pollutants (NESHAP).
Section 112(c) requires the Administrator to use this list of HAPs to develop and publish
a list of source categories for which NESHAP will be developed. EPA must list all
known categories and subcategories of "major sources."
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The term major source is defined in paragraph 112(a)(l) to mean any stationary source
or group of stationary sources located within a contiguous area and under common
control that emits or has the potential to emit, considering controls, in the aggregate 10
tons per year (tons/yr) or more of any HAP or 25 tons/yr or more of any combination of
HAPs. The term stationary source, from section 111 of the CAA, means any building,
structure, facility, or installation that emits or may emit any air pollutant. The term area
source, as defined in section 112(a)(2), means any stationary source of HAPs that is not
a major source.
Notice of the initial list of categories of major and area sources of HAPs was published
on July 16, 1992 (57 FR 31576), under authority of section 112(c). This notice listed
pharmaceutical manufacturing as a category of major sources of HAPs. Notice of the
schedule for the promulgation of emission standards for the listed categories, under
authority of section 112(e), was given on December 3, 1993 (58 FR 63941). Under this
notice, emission standards for the pharmaceutical production industry would be
promulgated no later than November 15, 1997.
Section 112(d) of the CAA directs the Administrator to promulgate emission standards
for each category of HAP sources listed under section 112(c). Such standards are
applicable to both new and existing sources and must require the maximum degree of
reduction in emissions of the hazardous air pollutants subject to this section (including a
prohibition on such emissions, where achievable) that the Administrator, taking into
consideration the cost of. achieving such emission reduction, and any non-air quality
health and environmental impacts and energy requirements, determines is achievable for
new and existing sources in the category or subcategory to which such emission standard
applies. See 42 U.S.C. 7412(d)(2).
Section 112(d)(3) provides that the maximum degree of reduction in emissions that is
deemed achievable for new sources shall not be any less stringent than the emission
control that is achieved in practice by the best controlled similar source. For existing
12-18
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sources, the standards may not be less stringent than the average emission limitation
achieved by the best performing 12 percent of existing sources in each category of 30 or
more sources.
Once this minimum control level (referred to as the floor) has been determined for new
or existing sources for a category, the Administrator must set a standard based on
maximum achievable control technology (MACT) that is no less stringent than the floor.
The Administrator may set MACT standards that are more stringent that the floor if
such standards are achievable considering the cost, environmental, and other impacts
listed in section 112(d)(2). Such standards must then be met by all sources within the
category.
EPA is in the early stages of developing the MACT standard for pharmaceutical
facilities; the standards will require the control of several different emission points,
including organic air emissions from wastewater operations: EPA recently promulgated
a similar MACT standard for organic HAP emissions from the Synthetic Organic
Chemical Manufacturing Industry (SOCMI). This rule, often referred to as the
Hazardous Organic NESHAP or HON, was published on April 22, 1994 (59 FR 19402).
On January 7, 1993, EPA published amendments to the Benzene Waste Operations
NESHAP, which controls benzene emissions from wastewater operations based upon
Clean Air Act authority predating the 1990 amendments (40 CFR Part 61 Subpart FF).
The control approach that EPA is considering for the pharmaceutical manufacturing
industry is similar to the approach EPA used in the SOCMI HON and the Benzene
Waste Operations NESHAP to control organic air emissions from wastewater collection
and treatment operations. That approach consists first of identifying a subset of
wastewater streams that require control through a combination of wastewater flow rate
and concentration action levels, and second, the control requirements for these affected
streams. The flow rate and concentration of each wastewater stream would be
12-19
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determined to reflect the characteristics at the point of generation of the wastewater
stream.
The point of generation is defined to be where each individual wastewater stream exits
production process equipment prior to any form of wastewater treatment. The
characteristics of a wastewater stream at the point of generation are used to determine
which streams to control because this is where the organic concentration is the highest
and the flow is the lowest. The use of the point of generation characteristics in this way
results in the identification of the most cost effective streams for control. If the
characteristics of the streams were determined at some point downstream of the point of
generation, there would be losses of organics due to air emissions and an increase in the
wastewater flow rate due to mixing with other wastewater streams, both of which would
result in the subsequent control of the stream being less cost effective. In addition, if
wastewater treatment were allowed before the point of generation, the treatment unit,
such as an air stripper, would not be required to have air emission control.
The flow rate action level is generally expressed as the liters per minute of wastewater
flow. Values of flow rate used in previous regulatory analyses range from 0.02 to 10
liters per minute.
The concentration action level is based on the "volatile organic" concentration of the
wastewater stream rather than the total concentration. EPA has developed a test
method, Method 305 in Appendix A of 40 CFR Part 63, to determine the volatile
organic HAP concentration for use with wastewater MACT standards. The purpose of
this test method is to determine a relative measure of the emission potential of a
typically controlled wastewater stream by measuring essentially all of an organic HAP
compound that is likely to be emitted in significant quantities while measuring essentially
none of an organic HAP compound that is unlikely to be emitted. Previous regulatory
analyses have used an action level of 10,000 ppmw at any flow rate and coupled with a
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range of action levels from 10 to 1,000 ppmw tied to a flow rate cutoff as described
above.
Examples of the use of these action levels in recent rules include the Benzene Waste
Operations NESHAP, which has action levels of 0.02 liters per minute and 10 ppmw
benzene, and the HON, which has a 10,000 ppmw volatile organic HAP concentration
action level at any flow rate coupled with an action level pair of 10 liters per minute and
1,000 ppmw volatile organic HAP concentration.
The control requirements for affected wastewater streams include managing the
identified wastewater streams in controlled units during collection and treatment to
remove or destroy the organics. This control approach includes: 1) suppression or
control of air emissions from the point of wastewater generation to the treatment device
by installing controls on the sewer system, tanks, and containers used to transport the
wastewater; 2) treatment of the wastewater to remove or destroy the organics; 3) control
of air emissions from the treatment device (e.g., the non-condensible air emissions from
the stripper condenser); and 4) control or recycling of the organics removed by the
treatment device (e.g., the condensed residuals collected by the stripper condenser).
The treatment device used as the basis for the HON is a steam stripper, the same device
proposed as the primary technology basis for the proposed pharmaceutical industry
limitations and standards. The HON requirements are performance standards, so that
any device that achieves the desired performance can be used. In addition, the HON
allows several compliance alternatives including the use of open biological treatment
units to treat the wastewater if a controlled collection and treatment system is used up to
the unit and the unit can be demonstrated to achieve the required level of biological
degradation. The HON requires the use of the procedures outlined in Appendix C of 40
CFR Part 63 to demonstrate that the organics are being degraded by the biological
treatment unit and not emitted to the air.
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The CAAA also requires EPA to establish Control Techniques Guideline (CTG)
documents for the states to use to develop volatile organic pollutant emissions control
plans for ozone nonattainment areas. Industrial wastewater, which includes the
pharmaceutical manufacturing industry, is one of the source categories for which EPA is
developing a CTG document (see the draft document entitled "Control of Volatile
Organic Compound Emissions from Industrial Wastewater," EPA-453/D-92-056,
September 1992; available in the record). Based on this guidance, certain states will
write rules for volatile organic pollutant emissions from wastewater operations at
pharmaceutical facilities located in ozone nonattainment areas. These rules are expected
to be similar to the MACT standards, except they would control additional wastewater
streams based on their potential for volatile organic pollutant emissions rather than HAP
emissions. The concentration action level used in the draft CTG is based on the volatile
organic concentration, which is determined by Method 25D in Appendix A of 40 CFR
part 60.
The volatile organic HAP and flow rate action levels for the MACT standard for
pharmaceutical plants have not yet been determined. EPA has conducted a preliminary
analysis of the impacts of a set of control options (action levels) for direct and indirect
dischargers of Subcategory A and C, and Subcategory B and D based on the approaches
used in the HON. EPA emphasizes that this analysis is still preliminary. Wastewater
data from the Detailed Questionnaire responses were used in the analysis; however, a
number of assumptions were made. See the draft document entitled "Control of Volatile
Organic Compound Emissions from Industrial Wastewater," EPA-453/D-92-056,
September 1992, for presentation of the assumptions and methodology used for this
preliminary analysis. During the development of the MACT standard, this analysis will
be refined based on new information and comments from the public.
Tables 12-8 and 12-9 summarize the results of this preliminary analysis. Two sets of
preliminary results are presented based on two ways to evaluate the existing data for
effluent guideline Subcategory A, B, C, and D facilities. The actual results of a rule
12-22
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based on any of the control options could be very different than these preliminary
impacts. Table 12-8 presents results based on applying the controls described above to •
wastewater streams that are equal to or greater than the identified action levels as the
streams were reported in the Detailed Questionnaire responses. This database reflects
the characteristics of combined process area wastewater streams, not the point of
generation of the wastewater. Table 12-9 presents results based on the same criteria, but
the Detailed Questionnaire wastewater data have been disaggregated in an attempt to
simulate the characteristics at the point of generation. This disaggregation was
performed in the manner described in Appendix B of the draft CTG document.
The control options (action levels), which encompass different combinations of volatile
organic HAP (VOHAP) and wastewater stream flow rates, identified in both tables are
ones that were considered in the development of the HON. All of the control options
would require control of any wastewater stream that has 10,000 ppmw or greater volatile
organic HAP concentration. The least stringent control option identified would require
all wastewater streams with a flow of 10 liters per minute or greater and a 1,000 ppmw
or greater volatile organic HAP concentration be equipped with controls. Wastewater
streams below these criteria would not require control. Other more stringent control
options would have lower action levels and require more wastewater streams to be
controlled. The most stringent control option shown would require all streams with a
flow of 1.0 liters per minute or greater and a 100 ppmw or greater volatile organic HAP
concentration be controlled.
The analysis will be refined, and these results, along with other statutory criteria in the
Clean Air Act, will be considered before a MACT standard for the pharmaceutical
manufacturing industry is proposed.
It is the Agency's intent for both the effluent guidelines proposed in this document and
the MACT standards to be proposed at a later date that upon promulgation the in-plant
technology basis of both rules will be applicable to essentially the same high
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concentration low volume process wastewater streams in which the bulk of the volatile
organic pollutants are contained, as represented preliminarily by Tables 12-8 and 12-9.
The practical effect of this approach will be that only a relatively small portion (i.e.,
substantially less than half) of all process wastewaters will require control by a treatment
device (e.g., steam stripping) to achieve both rules. EPA has been informed by the
industry that additional data will be submitted (some data have been submitted) in order
to characterize, m greater detail than available in responses to the Detailed
Questionnaire, the individual process wastewater streams at the point of generation.
This additional data and any other information available to EPA will be considered prior
to promulgation in identifying the small portion of process wastewater streams that
would require control of volatile organic pollutants under both the effluent limitations
guidelines and the MACT standard for this industry.
12-24
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12-25
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Table 12-2
HAPs and Volatile Organic Pollutants Present in Pharmaceutical
Manufacturing Wastewaters
HAPs
Volatile Organic Pollutants
Const.
Code
Chemical Name
Const.
Code
Chemical Name
3
12
15
22
25
35
37
39
62
64
67
77
79
83
87
97
102
105
114
130
136
139
Acetonitrile
Aniline
Benzene
Bis(chloromethyl)ether
2-Butanone (MEK)
Chlorobenzene
Chloroform
Chloromethane
N,N-Dimethylaniline
N,N-Dimethylformamide
1,4-Dioxane
Ethylene glycol
Formaldehyde
Glycol ethers
n-Hexane
Methanol (Methyl alcohol)
Methylene chloride
Methyl isobutyl ketone (MIBK)
Phenol
Toluene
Triethylamine
Xylenes
3
10
11
15
25
26
27
29
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51
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66
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77
84
87
94
97
101
102
103
105
117
118
130
134
139
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n-Amyl acetate
Amyl alcohol
Benzene
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
1,2-Dichloroethane
Diethyl ether
Dimethyl sulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
n-Heptane
n-Hexane
Isopropanol
Methanol
Methyl cellosolve
Methylene chloride
Methyl formate
Methyl isobutyl ketone (MIBK)
n-Propanol
Acetone
Toluene
Trichlorofluoromethane
Xylenes
12-26
-------
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12-29
-------
Table 12-6
Regulatory Impact on Solid Waste Generation.
Current dry
sludge generated
(tons/yr)
BAT/BPT/BCT
Increase in dry
sludge generation
(tons/yr)
BAT/PSES
Increase in waste
solvent
generation
(tons/yr)
BAT/PSES
Increase in waste
HC1 generation
(tons/yr)
Subcategory
A and C
Direct
Dischargers
36,400
5,180
57,300
467
Subcategory
B and D
Direct
Dischargers
2,760
44
Subcategory
A and C
Indirect
Dischargers
68,500
63,500
706
Subcategory
B and D
Indirect
Dischargers
4,630
6,370
12-30
-------
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12-33
-------
REFERENCES
1.
2.
3.
4.
5.
6.
7.
U.S. Department of Commerce. 1990 Annual Survey of Manufacturers,
Statistics for Industry Groups and Industries. M90(AS)-1, March 1992.
Test Methods for Evaluating Solid Waste, Physical/Chemical Methods,
SW-846, 3rd Edition, May 1991.
U.S. EPA, Office of Air Quality Planning and Standards. Hazardous
Waste Treatment, Storage, and Disposal Facilities (TSDF)-Air Emission
Models. EPA-450/3-87-0, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, December 1987.
Memorandum: WATER7 Analysis of the Fate of Organic Pollutant Loads
Through Pharmaceutical Facilities, from Radian Corporation to the Public
Record, May 18, 1994.
Calculation of Air Emissions Related to Steam Generation. Prepared by
R. Sieber, Radian Corporation. December 15, 1994.
U.S. EPA. Draft Hazardous Waste Minimization and Combustion
Strategy. EPA Report No. 530-D-94-002, U.S. Environmental Protection
Agency, Washington, D.C., May 1994.
U.S. EPA, Office of Solid Waste. Reengineering RCRA for Recycling.
U.S. Environmental Protection Agency, Washington, D.C., April 22, 1994.
12-34
-------
SECTION 13
BEST PRACTICABLE CONTROL TECHNOLOGY (BPT)
13.1
Introduction
Effluent limitations guidelines based on the best practicable control technology currently
available establish quantitative limits on the direct discharge of pollutants from existing
industrial point sources. BPT effluent limitations guidelines are based upon the average
of the best existing performance, in terms of treated effluent discharged by facilities of
various sizes, ages, and unit processes within a category or subcategory. BPT effluent
limitations guidelines most commonly focus on the control of conventional and
nonconventional pollutants, but can also control priority pollutants, such as cyanide.
BPT effluent limitations guidelines are based upon the performance of specific
technologies, but do not require the use of any specific technology. BPT effluent
limitations guidelines are applied to individual facilities through NPDES permits issued
by EPA or authorized states under Section 402 of the CWA. The facility then chooses
its own approach to comply with its permit limitations.
In developing BPT, the Agency considers the total cost of applying the technologies in
relation to the effluent reduction benefits to be achieved from the technologies; the size
and age of equipment and facilities; the processes used; the engineering aspects of
applying various types of control techniques; process changes; and nonwater quality
environmental impacts, including energy requirements.
The Agency proposes to establish BPT effluent limitations based on in-plant cyanide
destruction and advanced biological treatment (BPT Option 2) for Subcategories A and
C, and advanced biological treatment (BPT Option 2) for Subcategories B and D, as
discussed in Section 11.
13-1
-------
The following information is discussed in this section:
Section 13.2 reviews the subcategories and the pollutants proposed
to be regulated by BPT and presents the proposed BPT effluent
limitations guidelines; and
Section 13.3 discusses BPT effluent limitations guidelines
implementation with regard to NPDES permits, point of application,
and monitoring and compliance issues.
13.2
Summary of the Proposed BPT Effluent Limitations Guidelines
13.2.1
Regulated Subcategories
BPT effluent limitations guidelines, as discussed in Section 7.3, are proposed for
Subcategories A, B, C, and D. As discussed in Section 4.3, Subcategories A, B, and C
include wastewater discharges resulting from the manufacture of Pharmaceuticals by
fermentation, biological or natural extraction processes, and.chemical synthesis processes,
respectively. Subcategory D includes wastewater discharges resulting from mixing,
compounding, and formulating of pharmaceutical products.
13.2.2
Regulated Pollutants
The proposed BPT effluent limitations guidelines establish BOD5, COD, and TSS
effluent limitations for Subcategories A, B, C, and D. In addition, cyanide is proposed to
be regulated in Subcategory A and C wastewater discharges.
The pH effluent limit, established in the 1976 Final Rule (41 FR 50676) to be the range
of 6.0 to 9.0 standard units for all subcategories, will not be amended. As discussed in
Section 6.5, other conventional pollutants, such as fecal coliform and oil and grease, will
not be regulated under BPT because they are not pollutants of concern for this industry.
13-2
-------
13.2.3
The Proposed BPT Effluent Limitations Guidelines
The proposed BPT effluent limitations guidelines for each subcategory are based on a
combination of long-term mean effluent concentrations and variability factors that
account for day-to-day variation in measured treated effluent concentrations. Long-term
means, discussed in Section 8, are target values that a facility's treatment system should
achieve on a long- term, average basis. The variability factors, discussed in the Statistical
Support Document (1), which is located in the Administrative Record for this
rulemaking, represent the ratio of an elevated value that would be expected to occur
only rarely to the long-term mean. The variability factors are provided in Appendix C of
the Technical Development Document for ease of reference. The purpose of the
variability factor is to allow for variations in effluent concentrations that comprise the
long-term mean. A facility that designs and operates its treatment system to achieve a
long-term mean on a consistent basis should be able to comply with the daily and
monthly limitations in the course of normal operations.
Table 13-1 presents the proposed maximum daily and monthly average BPT effluent
limitations guidelines for end-of-pipe monitoring points for Subcategories A, B, C, and D
based on long-term mean treatment performance concentrations and associated
variability factors.
The limitations for each pollutant were calculated in the following manner. For each
available data set from best-performing advanced biological treatment systems, the long-
term mean concentration was multiplied by the 1-day and 30-day variability factors for
the data set. This resulted in dataset specific limitations. The mean value of the dataset
specific limitations, calculated from all available datasets, was established. The mean
value based on the 1-day variability factor is the BPT maximum limitation for any one
day, the mean value based on the 30-day variability factor is the BPT monthly average
limitation.
•13-3
-------
13.3
Implementation of the BPT Effluent Limitations Guidelines
13.3.1
NPDES Permit
BPT effluent limitations guidelines are applied to individual facilities through NPDES
permits issued by EPA or authorized states under Section 402 of the CWA.
The proposed effluent Limitations guidelines are concentration-based and, as such, do not
regulate wastewater flow. For in-plant effluent limitations, the concentration-based
limitations will apply directly to applicable in-plant streams. For end-of-pipe effluent
limitations, permit writers will use a reasonable estimate of process wastewater discharge
flow and the concentration-based limitations to develop mass-based limitations for the
NPDES permit.
"Process wastewater discharge" is defined by 40 CFR 122.2 to include wastewaters
resulting from manufacture of pharmaceutical products that come in direct contact with
raw materials, intermediate, products, and final products, and surface runoff from the
immediate process area that has the potential to become contaminated. Noncontact
cooling waters, utility wastewaters, general site surface runoff, groundwater, and other
nonprocess water generated on site are specifically excluded from this definition. The
appropriate process wastewater discharge flow to be used when developing mass-based
limitations must be determined by the permitting or control authority on a case-by-case
basis using current information provided by the applicant. In cases where the permit
writer deems the process wastewater discharge flow claimed by industry to be excessive,
he/she may develop a more appropriate process wastewater discharge flow for use in
computing the mass effluent limitations. The permit writer should review the following
items to evaluate whether process wastewater discharge flow is excessive.
Component flows, to ensure that the claimed flows are, in fact,
process wastewater discharge flows as defined by 40 CFR 122.2.
13-4
-------
Plant operations, to ensure that sound water conservation practices
are being followed. Examples include minimization of process water
uses and reuse or recycle of intermediate process waters or treated
wastewaters at the process area and in wastewater treatment
operations (pump seals, equipment and area washdowns, etc.).
The barometric condenser use at the process level. Often,
barometric condensers will generate relatively large volumes of
slightly contaminated water. Replacing barometric condensers with
surface condensers can reduce wastewater volumes significantly and
result in collection of condensates that may be returned to the
process.
To establish an NPDES permit for a direct discharger, the permit writer should
determine the facility's subcategorization and use the corresponding concentration-based
effluent limitations as a basis for developing the mass-based limitations. The permit
writer should then use best professional judgment to determine the facility's annual
average process wastewater discharge flow (i.e., the permit writer should consider only
the sources of "process wastewater discharge," as defined previously, when determining
the annual average process wastewater discharge flow; nonprocess wastewater discharges
should not be included). The annual average flow is defined as the average of daily flow
measurements calculated over at least a year; however, if available, three to five years of
data are preferable to obtain a representation of average daily flow. (2)
If no historical or actual process wastewater flow data exist, the permitting authority is
advised to establish a reasonable estimate of the facility's projected flow that would be
representative during the entire term of the permit. This may include a request for the
facility to measure process wastewater flows for a representative period of time to
establish a flow basis. If a plant is planning significant changes in production during the
effective period of the permit, the permitting authority may consider establishing
multiple tiers of limitations as a function of these production changes. Alternatively, a
permit may be modified during its term, either at the request of the permittee or another
interested party, or on EPA's initiative, to increase or decrease the flow basis in response
13-5
-------
to a significant change in production (40 CFR 124.5, 122.62). A change in production
may be an "alteration" of the permitted activity or "new information" that could provide
the basis for a permit modification (40 .CFR 122.62(a)).
After determining the facility's annual average process wastewater flow, the permit writer
should use the annual average process wastewater discharge flow to convert the end-of-
pipe concentration-based limitations into mass-based limitations. Below is an example of
how to convert a concentration-based limitation into a mass-based limitation: the
conversion of the maximum monthly average discharge of TSS for a hypothetical facility
with Subcategory A and B operations. The facility's average daily wastewater (WW)
generation in gallons per day is as follows:
• 1,000,000 gal/day of Subcategory A pharmaceutical process WW;
• 339,000 gal/day of Subcategory B pharmaceutical process WW;
• 2,718,000 gal/day of noncontact cooling WW; and
• 11,000 gal/day of sanitary WW.
Totalling the amounts listed above, the facility generates approximately 4,068,000 gal/day
of wastewater. To estimate the process wastewater discharge, the permit writer should
review the component flows listed above and determine which wastewater flows can be
deemed process wastewater discharge. In this case, only Subcategory A and B
pharmaceutical process wastewater constitute process wastewater discharge. Allowance
would not be given for noncontact cooling wastewater or sanitary wastewater. Thus, a
reasonable estimate of the process wastewater discharge for this hypothetical facility is
calculated as follows:
Process WW discharge = Subcategory A pharmaceutical process WW + Subcategory
B pharmaceutical process WW
= 1,000,000 GPD + 339,000 gal/day
13-6
-------
= 1,339,000 gal/day
For Subcategory A wastewater discharges, the concentration-based effluent limitation for
the maximum daily discharge of TSS, as presented in Table 13-1, is 318 mg/L. For
Subcategory B wastewater discharges the concentration-based effluent limitation for the
maximum daily discharge of TSS is 80 mg/L. The permit writer would convert these
concentration-based limitations into a mass-based limitation by using the following
equation:
(13-1)
where:
LM
Lc
F
k
mass-based effluent limitation, Ibs/day
concentration-based effluent limitation, mg/L
average Subcategory process wastewater discharge, gal/day
unit conversion factor.
For this example, the unit conversion factor, k, is used to convert from
[(mg/L) x (gal/day)] to (Ibs/day) as follows:
k = (mg/L) x (lL/0.264179gal) x (Ig/lOOOmg) x (lib/453.592g) x (gal/day) = 8.345 x 10
,-6
For the example, the mass-based maximum daily TSS limitation would be calculated
using equation (13-1) as follows:
For Subcategory A process wastewaters:
= (3 18 mg/L TSS) x (1,000,000 gal/day) x 8.345 x 10'6
= 2,654 Ibs/day TSS
13-7
-------
For Subcategory B process wastewaters:
l^ = (80mg/LTSS) x (339,000 gal/day) x 8.345 x 10'6
1^=226 Ibs/day TSS
Thus, the mass-based maximum daily TSS limitation would be the sum of 2,654 Ibs/day
TSS and 226 Ibs/day TSS which is 2,880 Ibs/day TSS.
Limits for other end-of-pipe parameters would be calculated in a similar manner.
Additional detailed guidance on the establishment of permit limitations is available in
the Guidance for Implementing the Pharmaceutical Manufacturing Industry Regulations,
included as Appendix A.
1332
Point of Application
The proposed BPT effluent limitations guidelines for cyanide in wastewater for
Subcategory A and C operations are applicable to the in-plant cyanide-bearing
wastewater streams. The proposed BPT effluent limitations guidelines for BOD5, COD,
and TSS for Subcategory A, B, C, and/or D direct dischargers would be applicable to the
final effluent at the point of discharge to waters of the United States (i.e., end-of-pipe).
13.3.3
Monitoring and Compliance
The proposed BPT effluent limitations guidelines for Subcategory A, B, C, and/or D
direct dischargers require daily monitoring for BOD5, COD, and TSS. For facilities with
Subcategory A and/or C operations, cyanide-bearing wastestreams would require
monitoring on each cyanide destruction treatment batch.
13-8
-------
Compliance with the proposed end-of-pipe effluent limitations guidelines should be
determined by multiplying the measured concentration of a regulated pollutant in the
effluent sample by a conversion factor and the total applicable process wastewater flow
discharged during the effluent sampling period, which is typically 24 hours. Thus, the
mass compliance value should be based on the applicable flow discharged on the day of
sampling, not on the long-term average flow rate that provided the basis for establishing
the permit limitations and standards. The mass compliance value can be determined
using the following equation:
where:
CVM =
PC
F
= PcxFxk
(13-2)
mass compliance value, Ibs/day -
pollutant concentration, mg/L
average applicable process wastewater discharge flow
over 24-hour sampling period, gal/day
unit conversion factor, 8.345 x 10"6.
For example, if analytical data from a 24-hour sampling period for the facility in the
above example demonstrates a TSS concentration of 70 mg/L, and the measured
applicable process wastewater flow discharged for the same 24-hour period is 4.1 million
gallons, then the plant's reported daily mass compliance value of the pollutant, using
Equation 13-2, is 2,395 Ibs/day. Similarly, the monthly average compliance value would
be calculated by averaging the available daily mass compliance values in each calendar
month.
13-9
-------
Table 13-1
Proposed BPT Effluent Limitations Guidelines for Direct Dischargers
Subcategory '
A - Fermentation
Operations
B - Biological and
Natural Extraction .
Operations
C - Chemical Synthesis
Operations
D - Mixing,
Compounding, or
Formulating"
Operations
Pollutant or Pollutant
Property
BODS
COD
TSS
Cyanide
BOD5
COD
TSS
BODj
COD
TSS
Cyanide
BOD5
COD
TSS
Proposed BPT Effluent Limitation for End-of-Pipe
Monitoring Points (a)
Maximum for any one day
(mg/L)
137
1,100
318
0.766
37
145
80
137
1,100
318
0.766
37
145
80
Monthly Average
(mg/L)
58
628
110
0.406
11
60
27
58
628
110
0.406
11
60
27
(a)The proposed BPT limitations for cyanide apply at an in-plant location (i.e., prior to dilution with non-
cyanide-bearing wastestreams).
13-10
-------
REFERENCES
U.S. EPA, Office of Water. Statistical Support Document for the Proposed
Effluent Limitations Guidelines for the Pharmaceutical Manufacturing
Industry. U.S. Environmental Protection Agency, Washington, D.C.,
February 10, 1995.
U.S. EPA, Office of Water. Training Manual for NPDES Permit Writers.
EPA 833-B-93-003, U.S. Environmental Protection Agency, Washington,
D.C., 1993.
13-11
-------
-------
SECTION 14
BEST CONVENTIONAL TECHNOLOGY
14.1
Introduction
Effluent limitations guidelines based on best conventional technology establish
quantitative limits on the direct discharge of conventional pollutants from existing
industrial point sources. In contrast to BPT guidelines, which are based on the average
of the best existing performance by a group of facilities, BCT guidelines are developed
by identifying candidate technologies and evaluating their cost-reasonableness. Effluent
limitations guidelines based upon BCT may not be less stringent than BPT effluent
limitations guidelines. As such, BPT effluent limitations are a "floor" below which BCT
efficient limitations guidelines cannot be established. As discussed below, EPA has
developed a BCT cost test methodology to assist the Agency in determining whether it is
"cost-reasonable" for industry to control conventional pollutants at a level more stringent
than would be required by BPT effluent limitations.
The following information is presented in this section:
Section 14.2 discusses the Agency's general methodology for
detennining BCT effluent limitations for industry;
Section 14.3 reviews the subcategories and pollutants proposed to be
regulated by BCT, describes the application of the general BCT
methodology to the pharmaceutical manufacturing industry, and
presents the proposed BCT effluent limitation guidelines; and
Section 14.4 discusses BCT effluent limitations guideline
implementation.
14-1
-------
143,
General Methodology for BCT Effluent Limitations Development
The July 9, 1986 Federal Register (51 FR 24974) presents the Agency's general
methodology for developing BCT effluent limitations guidelines. BCT effluent
limitations guidelines are based on the performance of the pollution control technology
selected as BCT. As noted in 51 FR 24974, the first step in determining BCT is to
establish that a BCT option is technologically feasible (defined as providing conventional
pollutant control beyond the level of control provided by application of BPT). If a BCT
option is found to be technologically feasible, the Agency applies a two-part BCT cost
test to evaluate the "cost-reasonableness" of the BCT option. The BCT cost test consists
of a POTW test and an industry cost-effectiveness test that the BCT option must pass to
be considered as a basis for BCT effluent limitations guidelines. The results of these
tests along with other industry-specific factors are evaluated to determine BCT. The
POTW cost test, the industry cost-effectiveness test, and the process of BCT
determination are discussed below.
14.2.1
POTW Cost Test
The POTW cost test compares the cost-effectiveness of an industrial treatment system
upgrade to meet the BCT requirements to the benchmark cost-effectiveness of a POTW
upgrade. For a BCT option to pass the POTW cost test, the cost per pound of
conventional pollutant removed by upgrading from BPT to the BCT option at industrial
direct dischargers must be less than the cost per pound of conventional pollutant
removed by upgrading POTWs from secondary treatment to advanced secondary
treatment. Specifically, the upgrade cost to industry must be less than the POTW
benchmark of $0.25 per pound (in 1976 dollars) for industries whose cost per pound is
based on long-term performance data (Tier I POTW benchmark), or must be less than
SO. 14 (hi 1976 dollars) per pound for industries whose cost per pound is not based on
long-term performance data (Tier II POTW benchmark).
14-2
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As noted in 51 FR 24974, the conventional pollutants measured for removal during the
two-part BCT cost test are BOD5 and TSS. Oil and grease may be used along with
BODj and TSS to calculate pollutant removal for BCT options when deemed
appropriate for the industry and technology being evaluated. Fecal coliform and pH are
not included in the calculations because control of these pollutants is not measurable as
"pounds removed". An acceptable interval for controlling pH is evaluated with respect to
the particular processes of a BCT option. Generally, the acceptable pH interval for BCT
will be the same as that for BPT. Maintaining the acceptable interval is an inherent cost
of the BCT option and must be economically achievable and cost-reasonable (51 FR
24974).
14.2.2
Industry Cost-Effectiveness Test
To remain a viable option, a BCT option must also pass an industry cost-effectiveness
test which consists of computing a ratio of two incremental costs. The first increment is
the cost per pound of pollutant load removed by the BCT option relative to BPT; the
second increment is the cost per pound of pollutant load removed by BPT relative to no
treatment (i.e., raw wastewater). The ratio of the two incremental costs (first cost
divided by the second cost) is compared to an industry benchmark. The industry
benchmark is a ratio of two POTW incremental costs: (1) the cost per pound of
pollutant removed for a POTW to upgrade from secondary treatment to advanced
secondary treatment, and (2) the cost per pound of pollutant removed for a POTW to
upgrade from no treatment to secondary treatment. If the first ratio (BCT option to
BPT) is lower than the industry benchmark, the BCT option passes the industry cost-
effectiveness test. The Tier I industry benchmark, for industries whose ratio is based on
long-term performance data, is 1.29. The Tier II industry benchmark, for industries
whose ratio is not based on long-term performance data, is 0.68.
In calculating the ratio of a BCT option to BPT, the Agency will consider any BCT
option cost per pound less than $0.01 to be equivalent to zero costs. The Agency
14-3
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believes that a BCT option with zero cost per pound of pollutant removed satisfies the
Congressional intent for cost-reasonableness.
14.2.3
BCT Determination
BCT is determined by evaluating results of both the POTW test and the industry cost-
effectiveness test as measures of cost-reasonableness. In addition, Section 304 (b)(4)(B)
of the CWA instructs the Agency to consider "other factors deemed appropriate" when
making BCT determinations; other factors are considered on an industry-specific basis.
Generally, BCT is the most stringent technology option (i.e., the technology option that
achieves the greatest pollutant reduction) to pass both parts of the cost test. If all BCT
options for an industry category or subcategory fail either or both of the tests, or if no
BCT option more stringent than BPT is identified, then BCT is set equal to BPT.
The owners or operators of facilities subject to BCT are not required to use the specific
technologies selected by EPA to establish BCT, but may choose to use any combination
of process technologies and wastewater treatment to comply with NPDES permit
limitations derived from BCT effluent limitations guidelines.
14.3
BCT Effluent Limitations Guidelines Development for the Pharmaceutical
Manufacturing Industry
14.3.1
Regulated Subcategories
BCT effluent Mmitations guidelines, as discussed in Section 7.3, are being proposed for
Subcategories A, B, C, and D.
14-4
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14.3.2
Regulated Pollutants
The proposed BCT effluent limitations guidelines establish BOD5 and TSS effluent
limitations. The pH effluent limitation under BCT will be the equivalent of the pH
limitation established by BPT. An effluent limitations guideline for oil and grease will
not be proposed since oil and grease is not normally found in pharmaceutical
manufacturing waste streams.
14.3.3 Application of General BCT Methodology to the Pharmaceutical
Manufacturing Industry
The Agency applied the general methodology for BCT effluent limitations guidelines
development to the pharmaceutical manufacturing industry subcategories. First,
technologically feasible BCT options that provide a greater degree of conventional
pollutant control than BPT were identified. Section 7.3.2 describes the BCT options
evaluated by the BCT determination process. After determining that the BCT options
were technologically feasible, the Agency applied the two-part BCT cost test. The results
of the BCT cost test were used to establish the technology basis for the proposed BCT
effluent limitations guidelines.
The following subsections discuss the BPT baseline established for the two-part BCT cost
test, the BCT options evaluated, the use of the pharmaceutical cost model to generate
costs for this analysis, the two-part BCT cost test results, and the proposed BCT effluent
limitations guidelines for the pharmaceutical manufacturing industry subcategories.
14.3.3.1
BCT Cost Test Baseline
To apply the two-part BCT cost test to the pharmaceutical manufacturing industry, a
baseline technology representing BPT was defined to serve as the comparison point for
the more stringent BCT options. The methodology for BCT determination (as
14-5
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documented in 51 FR 24974) requires that this point of comparison is BPT. As
discussed in Section 13, BPT Option 2, advanced biological treatment, is the proposed
BPT Option for Subcategories A and C and Subcategories B and D. Thus, the baseline
technology used in the two-part BCT cost test is advanced biological treatment.
14.3.3.2
BCT Options
Subcategories A and C
As described in Section 7.3.2, there are five BCT options for Subcategories A and C:
Option 1 = Existing Biological Treatment;
Option 2 = Advanced Biological Treatment;
Option 3 = Option 2 + Effluent Filtration;
Option 4 = Option 2 + Polishing Pond; and
Option 5 = Option 2 + Polishing Pond + Effluent Filtration.
These five BCT options are equivalent to the five BPT options for Subcategories A and
C, except for" cyanide treatment, which is not included under BCT because cyanide is not
a conventional pollutant. BCT Option 1 is equivalent to BPT Option 1 and represents a
no cost, no load removal option. BCT Option 2 is equivalent to the baseline BPT
technology proposed (BPT Option 2) and BCT Option 2 forms the comparison point for
the BCT cost test.
Subcategories B and D
As described in Section 7.3.2, there are three BCT options for Subcategories B and D:
Option 1 = Existing Biological Treatment;
Option 2 = Advanced Biological Treatment; and
Option 3 = Option 2 + Effluent Filtration.
14-6
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These three BCT options are equivalent to the three BPT options for Subcategories B
and D. BCT Option 1 is equivalent to BPT Option 1 and represents a no cost, no load
removal option. BCT Option 2 is equivalent to the baseline BPT technology proposed
(BPT Option 2) and Option 2 thus forms the comparison point for the BCT cost test.
14.3.3.3
Pharmaceutical Manufacturing Cost Model
The Agency used the pharmaceutical manufacturing cost model (described in Section 10)
to calculate baseline (BPT Option 2) conventional pollutant control costs and
corresponding costs for the BCT options. Since BCT options primarily target BOD5 and
TSS reductions, only BOD5 and TSS pollutant control costs were calculated by the cost
model. Annualized conventional pollutant control costs for the baseline and BCT
options were calculated in 1990 dollars using a 11.4% interest rate and a 20-year
equipment lifetime for pollution control equipment.
14.3.3.4
BCT Cost Test Results
Table 14-1 summarizes the results of the two-part BCT cost test. All results are based
on the use of long-term performance (i.e., Tier I) data. Results of the POTW cost test
and the industry cost-effectiveness test are discussed below.
POTW Cost Test Results
Results of the POTW cost test are summarized in the upper portion of Table 14-1. For
Subcategory A and C direct dischargers, BCT Options 3, 4, and 5 failed the POTW cost
test. For Subcategory B and D direct dischargers, BCT Option 3 failed the POTW cost
test.
As an example of POTW test application, consider BCT Option 3 for Subcategory
A and C direct dischargers. The cost of upgrading from the BPT baseline (advanced
14-7
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biological treatment) to BCT Option 3 (advanced biological treatment followed by
effluent filtration) is $1,870,000 per year (in 1990 dollars). The load reduction of BOD5
and TSS achieved by upgrading to BCT Option 3 is 925,000 Ibs/yr. Thus, upgrading
from the BPT baseline to BCT Option 3 results in a ratio of 2.02 $/lb (dollars expended
to pounds of BOD5 and TSS removed). This ratio is greater than the Tier I POTW
benchmark (in 1990 dollars) of 0.56 $/lb. (The POTW benchmark of 0.56 $/lb, expressed
in 1990 dollars, was calculated using the May 1986 promulgated methodology entitled
BCT Benchmarks: Methodology. Analysis and Results for Calculating and Indexing BCT
POTW Benchmarks to Various Years' Dollars *.) Since the cost per pound of pollutant
removed is greater than the POTW benchmark, BCT Option 3 for Subcategory A and C
direct dischargers failed the POTW cost test.
Industry Cost-Effectiveness Test Results
Results of the industry cost-effectiveness test are presented in the lower portion of Table
14-1. For Subcategory A and C direct dischargers, BCT Options 3, 4, and 5 failed the
industry cost-effectiveness test. For Subcategory B and D direct dischargers, BCT
Option 3 failed the industry cost-effectiveness test.
As an example of industry cost-effectiveness test application, consider BCT Option 3 for
Subcategory A and C direct dischargers. From the POTW test, the incremental cost per
pound of pollutant removed associated with upgrading from the BPT baseline to BCT
Option 3 was 2.02 $/lb. • The cost of upgrading from no treatment (i.e., raw wastewater)
to the BPT baseline is $29,100,000 per year (in 1990 dollars). The load reduction of
BODj and TSS achieved by upgrading from no treatment to the BPT baseline is
101,000,000 Ibs/yr. Thus, the incremental cost per pound of pollutant load removed for
Subcategory A and C direct dischargers upgrading from no treatment to the BPT
baseline is 0.29 $/lb. The ratio of these two incremental costs is 6.97 (i.e., 2.02 divided
by 0.29). Since this ratio (6.97) is greater than the industry benchmark of 1.29, BCT
Option 3 failed the industry cost-effectiveness test.
14-8
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14.3.3.5
Conclusions
Based on the results of the two-part BCT cost test and the criteria discussed in Section
14.1.3 for BCT determination, the proposed BCT effluent limitations guidelines for
Subcategory A and C and Subcategory B and D direct dischargers are presented below.
BCT Determination for Subcategories A and C
For Subcategory A and C direct dischargers, BCT Options 3, 4, and 5 failed the two-part
BCT cost test. Therefore, the proposed BCT is established as BCT Option 2, the
equivalent of proposed BPT. As such, the proposed BCT for Subcategories A and C
consists of advanced biological treatment. Table 14-2 presents the proposed BCT
effluent limitations guidelines for Subcategories A and C.
BCT Determination for Subcategory B and D
For Subcategory B and D direct dischargers, BCT Option 3 failed the two-part BCT cost
test. Therefore, the proposed BCT is established as BCT Option 2, the equivalent of
proposed BPT. As such, the proposed BCT for Subcategories B and D consists of
advanced biological treatment. Table 14-3 presents the proposed BCT effluent
limitations guidelines for Subcategory B and D direct dischargers.
14.4
Implementation of the BCT Effluent Limitation Guidelines
The proposed BCT limitations for BOD5 and TSS are equivalent to the proposed BPT
limitations, and would be implemented in a manner similar to that described in Section
13.3.
14-9
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w
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5
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P
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20,800,000
17,500,000
1-^*
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-------
Table 14-2
Proposed BCT Effluent Limitations Guidelines for Subcategory
A and C Discharges
Pollutant
BOD5
TSS
Proposed BCT Effluent Limitations
Maximum for Any One Day
(mg/L)
137
318
Maximum for Monthly Average
(mg/L)
58
110
Table 14-3
Proposed BCT Effluent Limitations Guidelines for Subcategory
B and D Discharges
Pollutant
BOD5
TSS
Proposed BCT Effluent Limitations
Maximum for Any One Day
(mg/L)
37
80
Maximum for Monthly Average
(mg/L):
11
27
14-11
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REFERENCES
1.
U.S. EPA. BCT Benchmarks: Methodology, Analysis, and Results for
Calculating and Indexing BCT POTW Benchmarks to Various Year's
Dollars. U.S. Environmental Protection Agency, Washington, D.C., May
1986.
14-12
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SECTION 15
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)
15.1
Introduction
Effluent limitations guidelines based on the best available technology economically
achievable establish quantitative limits on the direct discharge of priority and
nonconventional pollutants to waters of the United States. These limits are based upon
the performance of specific technologies, but do not specify which technologies must be
used to achieve compliance. BAT effluent limitations guidelines are applied to
individual facilities through NPDES permits issued by EPA or authorized states under
Section 402 of the CWA. Each facility then chooses its own approach to comply with its
permit limitations.
The technology selected by the Agency to define the BAT performance may include end-
of-pipe treatment, process changes, and internal controls, even when these technologies
are not common industry practice. BAT performance is established for groups of
facilities with shared characteristics. Where a group of facilities demonstrates uniformly
inadequate performance in controlling pollutants of concern, BAT may be transferred
from a different subcategory or industrial category. Section 7 provides an overview of
the technologies assessed by the Agency.
The Agency has selected in-plant steam stripping and cyanide destruction followed by
end-of-pipe advanced biological treatment (BAT Option 2) as the technology basis for
the proposed BAT effluent limitations guidelines for Subcategory A and/or Subcategory
C direct dischargers. The Agency has selected end-of-pipe advanced biological treatment
(BAT Option 1) as the technology basis for the proposed BAT effluent limitations
guidelines for Subcategory B and/or Subcategory D direct dischargers. The rationale
behind these selections is discussed hi Section 11.
15-1
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The following information is presented in this section:
Section 15.2 reviews the subcategories and the pollutants proposed
to be regulated by BAT and presents the proposed BAT effluent
limitations guidelines; and
Section 15.3 discusses BAT effluent limitations guidelines
implementation with regard to point of application, NPDES permits,
and monitoring and compliance issues.
Summary of the Proposed BAT Effluent Limitations Guidelines
15.2.1
Regulated Subcategories
Revised BAT effluent limitations guidelines are proposed for Subcategories A, B, C, and
D. As discussed in Section 4.3, Subcategories A, B, and C include wastewater discharges
resulting from the manufacture of pharmaceuticals by fermentation, biological or natural
extraction processes, and chemical synthesis processes, respectively. Subcategory D
includes wastewater discharges resulting from mixing, compounding, and formulating of
pharmaceutical products.
15.2.2
Regulated Pollutants
The proposed BAT guidelines establish effluent limitations for the priority and
nonconventional pollutants listed in Table 15-1 for direct dischargers in Subcategories A,
B, C, and D. In addition, the proposed BAT guidelines establish effluent limitations for
ammonia and cyanide for direct dischargers in Subcategories A and C. Conventional
pollutants are regulated under BPT and BCT and not discussed here.
15-2
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15.2.3
The Proposed BAT Effluent Limitations Guidelines
The proposed BAT effluent limitations guidelines for each subcategory are based on a
combination of long-term mean treatment performance concentrations and variability
factors that account for day-to-day variation in measured treated effluent concentrations.
Long-term mean treatment performance concentrations, discussed in Section 8, are target
values that a facility's treatment system should achieve on a long-term, average basis.
The variability factors, discussed in the Statistical Support Documentl, which is located
in the Record for this rulemaking, represent the ratio of an elevated value that would be
expected to occur only rarely to the long-term mean. The purpose of the variability
factor is to allow for variations in effluent concentrations that comprise the long-term
mean. A facility that designs and operates its treatment system to achieve a long-term
mean on a consistent basis should be able to comply with the daily and monthly
limitations in the course of normal operations.
Tables 15-2 and 15-3 present the proposed maximum daily and monthly average BAT
effluent limitations guidelines for Subcategory A and C operations, and Subcategory B
and D operations, respectively. These proposed limitations were determined by
multiplying the long-term means (LTMs) for each subcategory by the respective
pollutant's 1-day and 4-day variability factors (VFs). Note that a 4-day variability factor
is used for the proposed BAT limitations while a 30-day variability factor is used for the
proposed BPT limitations. This results from the recommended daily monitoring
frequency to show compliance with the proposed BPT BOD5, COD, and TSS limitations
and the weekly monitoring frequency to show compliance with the proposed BAT
limitations.
The proposed regulation for the pharmaceutical manufacturing industry presents
analytical method minimum levels in Section 439.1 (g). These values apply to those
limitations and standards set at ND. For ease of use, the tables presented in this section
15-3
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present the analytical method minimum level in parentheses for those limitations and
standards set at ND.
15.3
Implementation of the BAT Effluent Limitations Guidelines
The proposed BAT effluent limitations are dependent on the type of manufacturing
operations at each pharmaceutical manufacturing facility. The proposed effluent
limitations for wastewater from Subcategory A and C operations are numerically
different than the proposed effluent limitations for wastewater from Subcategory B and
D operations. The proposed BAT Effluent Limitations Guidelines for Subcategory A
and C operations are presented in Table 15-2. The proposed BAT Effluent Limitations
Guidelines for Subcategory B and D operations are presented in Table 15-3.
As noted hi Section 7, EPA is not proposing but is considering use of Best Management
Practices (BMPs) to reduce discharges from leaks and spills of process chemicals and
materials. These materials include organic solvents (some of which are ignitable) that
contribute to air emissions and to effluent discharges and off-specification products which
may upset biological treatment systems. BMPs may offer the opportunity to reduce these
discharges and air emissions while concurrently increasing utilization of consumable
materials. Suggested details on BMPs being considered for the pharmaceutical
manufacturing industry are presented in Appendix B.
15.3.1
Establishing List of Pollutants for Compliance Monitoring
If final effluent limitations are promulgated as proposed, permit limitations would be
established and compliance monitoring required for each regulated pollutant listed on
Table 15-1 generated or used at a pharmaceutical manufacturing facility. Limitations
and routine compliance monitoring would not be required for regulated pollutants not
generated or used at a facility. A determination that regulated pollutants are not
generated or used would be based on a review of all raw materials used and an
15-4
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assessment of all chemical processes used, considering resulting products and by-
products. The determination that a regulated pollutant is not generated or used would
need to be confirmed by annual chemical analyses of wastewater from each monitoring
location. Such confirmation would be provided by an analytical measurement of a non-
detect value.
15.3.2
Point of Application
The proposed BAT limitations for cyanide presented in Table 15-2 are applicable to
those wastewaters from Subcategory A and C operations known or believed to contain
cyanide. Compliance monitoring for cyanide would occur in plant, prior to dilution or
mixing with any non-cyanide-bearing wastewater. In-plant monitoring would be required
to prevent compliance through dilution with non-cyanide-bearing wastewater.
The proposed BAT effluent limitations for ammonia (applicable to Subcategories A and
C), and the organic pollutants listed in Tables 15-2 and Table 15-3 are end-of-pipe
limitations and would be applicable to the final effluent at the point of discharge to
waters of the-United States. This compliance point is identical to the point used to
demonstrate compliance with the proposed BPT effluent limitations guidelines.
EPA also is soliciting comments and data on whether limits for the 12 most strippable
priority and nonconventional organic pollutants should be applied at an in-plant
monitoring point (e.g., following steam stripping and prior to dilution with other process
and non-process wastewaters not containing these pollutants in treatable quantities and
prior to end-of-pipe biological treatment systems). The limits EPA would propose for
this in-plant monitoring point are found in Table 2-8.
15-5
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153.3
Permit Limitations
EPA expects that permit limitations for cyanide at in-plant locations based on the
proposed BAT limitations would be concentration-based, and would not be converted to
a mass basis. Table 15-2 lists these proposed concentration-based limitations, which
apply only to Subcategories A and C. A concentration basis should be used because it
offers a direct benchmark to assess whether the in-plant control technology is achieving
the intended BAT level. In-plant wastestreams that require control may be generated or
treated on a variable, batch basis. In such a setting, mass-based permit limitations are
difficult to establish accurately, and compliance is hindered because the permitted facility
cannot make a direct measurement to determine if its control technology is performing
at the required level. Concentration-based permit limitations eliminate these problems
and offer a direct measure to both the permitting authority and the permitted facility
that BAT performance levels are being achieved.
End-of-pipe permit limitations based on the proposed BAT limitations for ammonia (for
Subcategories A and C) and organic constituents would be mass-based unless the
maximum, for any one day limitation is non-detect (ND). In such a case, the permit
would specify that all measured values should be non-detect values. Non-detect values
are concentration-based measurements reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. The minimum level is the
level at which an analytical system gives recognizable signals and an acceptable
calibration point. Minimum levels for all regulated pollutants are specified in
Table 18-7.
If final effluent limitations are promulgated as proposed, permit writers would use a
reasonable estimate of process wastewater discharge flow and the concentration-based
limitations listed in Table 15-2 to develop mass-based limitations for the NPDES permit.
"Process wastewater discharge" is defined by 40 CFR 122.2 to include wastewaters
resulting from pharmaceutical products manufacturing that come in direct contact with
15-6
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raw materials, intermediate products, and final products, and surface runoff from the
immediate process area that has the potential to become contaminated. Noncontact
cooling waters, utility wastewaters, general site surface runoff, groundwater, and other
nonprocess water generated on site are specifically excluded from this definition. The
appropriate process wastewater discharge flow to be used when developing mass-based
limitations must be determined by the permitting or control authority on a case-by-case
basis using current information provided by the applicant. In cases where the permit
writer deems the process wastewater discharge flow claimed by industry to be excessive,
he/she may develop a more appropriate process wastewater discharge flow for use in
computing the mass-based limitations. The permit writer should review the following
items to evaluate whether process wastewater discharge flow is excessive:
Component flows, to ensure that the claimed flows are, in fact,
process wastewater discharge flows as defined by 40 CFR 122.2.
Plant operations, to ensure that sound water conservation practices
are being followed. Examples include mirdmizing process water
uses and reusing or recycling intermediate process waters or treated
wastewaters at the process area and in wastewater treatment
operations (pump seals, equipment and area washdowns, etc.).
The barometric condenser use at the process level. Often,
barometric condensers will generate relatively large volumes of
slightly contaminated water. Replacing barometric condensers with
surface condensers can reduce wastewater volumes significantly and
result in collection of condensates that may be returned to the
process.
Once the permit writer has reviewed the permit application, best professional judgment
should be used to determine the facility's annual average process wastewater discharge
flow (i.e., the permit writer should consider only the sources of "process wastewater
discharge," as defined previously, when determining the annual average process
wastewater discharge flow; nonprocess wastewater discharges should not be included).
The annual average flow is defined as the average of daily flow measurements calculated
15-7
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over at least a year; however, if available, three to five years of data are preferable to
obtain a representation of average daily flow.2
If no historical or actual process wastewater flow data exist, the permitting authority is
advised to establish a reasonable estimate of the facility's projected flow that is expected
to be representative during the entire term of the permit. If a plant is planning
significant production changes during the effective period of the permit, the permitting
authority may consider establishing multiple tiers of limitations as a function of these
production changes. Alternatively, a permit may be modified during its term, either at
the request of the permittee or another interested party, or on EPA's initiative, to
increase or decrease the flow basis in response to a significant change in production (40
CFR 124.5, 122.62). A change in production may be an "alteration" of the permitted
activity or "new information" that could provide the basis for a permit modification (40
CFR 122.62(a)).
After determining the facility's annual average process wastewater flow, the permit writer
would use this flow to convert the concentration-based limitations into mass-based
limitations for ammonia and organic constituents for control at the end-of-pipe. The
following example shows how a permit writer would establish daily maximum limits for a
facility that generates wastewater from Subcategory B and C operations. The
hypothetical faculty's average daily wastewater generation (gal/day), the constituents in
each stream, and the concentrations (mg/L) of each constituent are shown below.
Wastestream
1
2
3
Wastewater
Source
Subcategory B
Process Flow
Subcategory C
Process Flow
Noncontact
Cooling Water
Flow
(gal/day)
2,000
30,000
10,000
Pollutants
Methanol
Methanol
tert-Butyl Alcohol
Chlorobenzene
None
: Concentration
(mg/L)
250
500
100
2
—
15-8
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To estimate process wastewater discharge flow, the permit writer should review the
component flows listed above and determine which wastewater flows can be deemed
process wastewater discharge. In this example, only Subcategory B and C wastewater
discharges constitute process wastewater discharge flow. Thus, a reasonable estimate of
the process wastewater discharge flow for this example facility is 32,000 gal/day.
The limitations for chlorobenzene, methanol, and tert-butyl alcohol would be applied to
the final effluent. The proposed Subcategory B and Subcategory C maximum daily
limitations for chlorobenzene are both ND. Therefore, the permit limitation for
chlorobenzene would be concentration-based and would be ND for all measurements.
While the maximum daily limitation for methanol is ND for Subcategory C, the proposed
limitation for Subcategory B is 6.60 ^tg/L. A limitation for the combined effluent would
be calculated by using a numerical value equal to the minimum level for the Subcategory
C wastewater. This calculation is shown in the example below.
The concentration-based limitations for methanol and tert-butyl alcohol would be
converted to mass-based limitations using the annual average daily process wastewater
discharge flow, 32,000 gal/day. This conversion can be calculated using the following
equation:
where:
LM
Lc
F
k
mass-based effluent limitation, Ibs/day
concentration-based effluent limitation, mg/L
average process wastewater discharge, gal/day
unit conversion factor, (L x lbs)/(gal x mg).
(15-1)
15-9
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For this example, the unit conversion factor, k, is used to convert from
[(mg/L) x (gal/day)] to (Ibs/day) as follows:
k = (1L/0.264179 gal) x (Ig/lOOOmg) x (llb/453.592g) = 8.345 x W6 (L x lbs)/(gal x mg)
For this example, the mass-based maximum daily limitations for methanol and tert-butyl
alcohol would be calculated using Equation 15-1:
Methanol:
Stream 1 1^ = (6.66 mg/L) x (2,000 gal/day) x 8.345 x 10'6 = 0.11 lbs/da^
Stream 21^ = (3.18 mg/L) x (30,000 gal/day) x 8.345 x 10'6 = 0.80 Ibs/dz
Total I^j = 0.91 Ibs/day methanol
Tert-butyl alcohol:
Stream
^ = (3.98 mg/L) x (2,000 gal/day) x 8.345 x 10'6 = 0.07 Ibs/day
Stream 2 1^ = (0.668 mg/L) x (30,000 gal/day) x 8.345 x 10'6 = 0.17 Ibs/c
Total L^j = 0.24 Ibs/day tert-butylalcohol
Thus, the maximum daily limitations for methanol and tert-butyl alcohol would be 0.91
Ibs/day and 0.24 Ibs/day, respectively. The monthly average limitations would be
calculated in a similar manner and are shown below.
15-10
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Methanol:
Stream 1 1^ = (3.18 mg/L) x (2,000 gal/day) x 8.345 x 10'6 = 0.05 Ibs/day
Stream 21^ = (3.18 mg/L) x (30,000 gal/day) x 8.345 x 10'6 = 0.80 Ibs/day
Total L^ = 0.85 Ibs/day methanol
Tert-butyl alcohol:
Stream
^, = (1.69 mg/L) x (2,000 gal/day) x 8.345 x 10'6 = 0.03 Ibs/day
Stream 21^ = (0.284 mg/L) x (30,000 gal/day) x 8.345 x 10'6 = 0.07 Ibs/day
Total L^ = 0.10 Ibs/day tert-butylalcohol
The monthly average limitations for methanol and tert-butyl alcohol would be
0.85 Ibs/day and 0.10 Ibs/day, respectively.
There are no mass allowances for noncontact cooling water. Additional detailed
guidance on the establishment of permit limitations is available in the Guidance for
Implementing the Pharmaceutical Manufacturing Industry Regulations, included as
Appendix A.
15.3.4
Monitoring and Compliance
Compliance monitoring for ammonia and all regulated organic constituents should be
performed weekly. The list of pollutants for which monitoring would be required
includes all regulated constituents listed in Table 15-1 generated or used in
pharmaceutical manufacturing processes at the facility. Based on the proposed
limitations, monitoring of ammonia and organic constituents generated or used in
pharmaceutical manufacturing processes would occur prior to discharge to waters of the
United States. Monitoring for cyanide based on the proposed cyanide limitations would
be performed prior to commingling or dilution with non-cyanide bearing wastewater.
15-11
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Monitoring should be conducted at a minimum of once for every treated batch of
cyanide-bearing wastewater from Subcategory A and C process operations.
Compliance with the proposed effluent limitations guidelines for cyanide, if finalized,
should be determined by comparing the concentration of cyanide with the daily
maximum concentration-based limitation listed in Table 15-2. The monthly average
concentration should be calculated by averaging the available measurements taken in
each calendar month. Concentrations equal to or less than the concentrations listed in
Table 15-2 would be in compliance.
Compliance with mass-based permit limitations for pollutants monitored prior to
discharge to waters of the United States should be determined by multiplying the
measured concentration of a regulated pollutant in the effluent sample by a conversion
factor and the total wastewater flow at the monitoring location during the effluent
sampling period, which is typically 24 hours. Thus, the mass compliance value should be
based on the total flow discharged on the day of sampling, not on the long-term average
process water flow rate that provided the basis for establishing the permit limitations and
standards. The mass compliance value can be determined using the following equation:
M = Pr x F x k
M C
(15-2)
where:
CVM
PC
F
mass compliance value, Ibs/day
pollutant concentration, mg/L
total wastewater discharge flow through the monitoring point
over 24-hour sampling period, gal/day
unit conversion factor, 8.345 x 10'6 (L x lbs)/(gal x mg).
For example, if analytical data from a 24-hour sampling period for a particular plant
demonstrates a pollutant concentration of 5.0 mg/L, and the measured flow discharged
through the monitoring point for the same 24-hour period is 0.600 million gallons, then
15-12
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the plant's reported daily mass compliance value of the pollutant, using Equation 15-2, is
25.0 Ibs/day. Similarly, the monthly average compliance value would be calculated by
averaging the available daily mass compliance values in each calendar month.
For pollutants where the permit limitations are non-detect values, compliance is
demonstrated by having all concentration-based measurements be below the minimum
level that can be -reliably measured by the analytical method for the pollutant. Minimum
levels for all pollutants proposed to be regulated in this rulemaking are specified in
Table 18-7.
The list of pollutants for which monitoring would be required should be updated based
on consideration of raw material and process changes throughout the facility and an
annual scan for cyanide and all pollutants listed in Table 15-1. After promulgation of a
final rule for this industry, the annual scan should be performed at the compliance
monitoring point(s) to identify any regulated pollutants in the wastewater. Permit
monitoring and compliance should be required at all monitoring locations for all
pollutants detected at any locations.
15-13
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Table 15-1
Pollutants Proposed to be Regulated Under BAT
Priority Pollutants , '" ' .
Benzene
Chlorobenzene
Chloroform
Chloromethane (Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
Nonconyentional Pollutants
Acetone
Acetonitrile
Ammonia (a)
Arayl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Chemical Oxygen Demand (COD)
Cyclohexane
Dicthylaminc
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl Sulfoxide
1.4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Cyanide (a)
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde .
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum naphtha
Polyethylene glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
(a) Ammonia and cyanide are proposed to be regulated in Subcategories A and C only.
15-14
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Table 15-2
Proposed BAT Effluent Limitations for
Subcategory A and C Operations
Pollutant or Pollutant Property
Cyanide
Proposed BAT Effluent Limitations for In-Plant Monitoring Points
Maximum for any 1 day
M?/L
766
Monthly Average
>g/L
406
Pollutant or Pollutant Property
Acetone
Acetonitrile
Ammonia
n-Amyl Acetate
Amyl Alcohol
Aniline
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chemical Oxygen Demand (COD)
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
o-Dichlorobenzene
1,2-Dichloroethane
Proposed BAT Effluent Limitations for End-of-Pipe Monitoring
.:!.'"•• ' ' Points ;:'.' • "-' •:•'"' •• • ' -...' '•
Maximum for any 1 day
pg/L
ND (50)
ND (5,000)
4,850
105
668
10
ND (10)
202
87
ND (500)
668
1,100,000
ND (10)
ND (10)
ND (50)
ND(5)
ND(10)
100
Monthly Average
• •".--. •':' '••'•• /tg/k
ND(50)
ND (5,000)
3,230
45
ND (500)
10
ND(10)
86
37
ND(500)
284
628,000
ND(10)
ND (10)
ND(50)
ND(5)
ND (10)
35
15-15
-------
Table 15-2
(Continued)
Pollutant or Pollutant Property
Diethylamine
Diethyl Ether
Dimethylamine
N,N-Dimethylacetamide
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl Sulfoxide
1,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene Glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Methanol
Methylamine
Methyl Cellosolve
Methyl Formate
Proposed BAT Effluent Limitations for End-of-Pipe Monitoring
Points
Maximum for any 1 day
Atg/L
ND (50,000)
574
ND (50,000)
ND (50)
50
45
ND (20,000)
220
ND (3,180)
105
ND (100,000)
1,480
ND (100,000)
2,670
ND (10)
ND (10)
1,370
ND (200)
87
574
ND (3,180)
ND (50,000)
ND (20,000)
105
Monthly Average
«?/L
ND (50,000)
244
ND (50,000)
ND (50)
50
19
ND (20,000)
94
ND (3,180)
45
ND (100,000)
623
ND (100,000)
1,140
ND (10)
ND(10)
581
ND (200)
37
244
ND (3,180)
ND (50,000)
ND (20,000)
ND (100)
15-16
-------
Table 15-2
(Continued)
Pollutant or Pollutant Property
Methylene Chloride
MIBK
2-Methylpyridine
Petroleum Naphtha
Phenol
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
Proposed BAT Effluent Limitations for End-of-Pipe Monitoring
Points
Maximum for any 1 day
«/L
ND (10)
ND(10)
50
ND (10)
25
4,870
ND (3,180)
10
910
ND (10)
ND(10)
ND (50,000)
ND(10)
Monthly Average
PS/L
ND (10)
ND (10)
50
ND (10)
14
2,070
ND (3,180)
10
264
ND (10)
ND (10)
ND (50,000)
ND (10)
ND - Non-detect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
15-17
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Table 15-3
Proposed BAT Effluent Limitations for
Subcategory B and D Operations
Pollutant or Pollutant Property
Acetone
Acetonitrile
n-Amyl Acetate
Amyl Alcohol
Aniline
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chemical Oxygen Demand (COD)
Chlorobenzene
Chlorofonn
Chloromethane
Cyclohexane
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
N,N-Dimethylacetamide
Dimethylamine
NtN-DimethylaniHne
N,N-Dimethylformamide
Dimethyl Sulfoxide
1,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene Glycol
Proposed BAT Effluent Limitations for End-of-Pipe Monitoring
Points
Maximum for any I day
Mg/L
413
ND (5,000)
3,000
3,980
10
40
202
500
ND (500)
3,980
145,000
ND (10)
22
206
ND (5)
ND (10)
438
ND (50,000)
4,870
ND (50)
ND (50,000)
50
45
ND (20,000)
220
ND (3,180)
3,000
ND (100,000)
Monthly Average
H8/L
178
ND (5,000)
1,280
1,690
10
17
86
500
ND (500)
1,690
59,900
ND (10)
13
87
ND(5)
ND(10)
152
ND (50,000)
2,070
ND(50)
ND (50,000)
50
19
ND (20,000)
94
ND (3,180)
1,280
ND (100,000)
15-18
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Table 15-3
(Continued)
Pollutant or Pollutant Property
Formaldehyde
Form amide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Methanol
Methylamine
Methyl Cellosolve
Methylene Chloride
Methyl Formate
MIBK
2-Methylpyridine
Petroleum Naphtha
Phenol
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamme
Xylenes
Proposed BAT Effluent Limitations for End-of-Pipe Monitoring
Points
Maximum for any 1 day
P8/L
1,480
ND (100,000)
3,000
ND(10)
ND(10)
1,370
1,120
500
4,870
6,660
ND (50,000)
ND (20,000)
1,420
3,000
119
50
40
25
4,870
3,980
10
15,000
40
599
ND (50,000)
ND (10)
Monthly Average
0g/L
623
ND (100,000)
1,280
ND(10)
ND (10)
581
476
500
2,070
ND (3,180)
ND (50,000)
ND (20,000)
• 357
1,280
51
50
17
14
2,070
ND (3,180)
10
4,350
17
322
ND (50,000)
ND (10)
ND - Nondetect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
15-19
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REFERENCES
U.S. EPA, Office of Water. Statistical Support Document for the Proposed
Effluent Limitations Guidelines for the Pharmaceutical Manufacturing
Industry. U.S. Environmental Protection Agency, Washington, D.C.,
February 10, 1995.
U.S. EPA, Office of Water. Training Manual for NPDES Permit Writers.
EPA 833-B-93-003, U.S. Environmental Protection Agency, Washington,
D.C, 1993.
15-20
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SECTION 16
NEW SOURCE PERFORMANCE STANDARDS (NSPS)
16.1
Introduction
The basis for new source performance standards under Section 306 of the CWA is the
best available demonstrated technology. Industry has the opportunity to design and
install the best and most efficient process operations and wastewater treatment systems
at new pharmaceutical manufacturing facilities. Accordingly, Congress directed EPA to
consider the best demonstrated alternative processes, process changes, in-plant control
measures, and end-of-pipe wastewater treatment technologies that reduce pollution to
the maximum extent feasible. In response to that directive, and as with the development
of options for the proposed BAT effluent limitations guidelines, EPA considered effluent
reductions attainable by the most advanced treatment technologies at pharmaceutical
manufacturing facilities.
NSPS establish quantitative limits on the direct discharge of conventional, priority, and
nonconventional pollutants to waters of the United States. These standards are based
upon the performance of specific advanced technologies, but do not specify which
technologies must be used to achieve compliance. NSPS are applied to individual
facilities through NPDES permits issued by EPA or authorized states under Section 402
of the CWA. Each facility then chooses its own approach to complying with its permit
limitations.
NSPS apply to all new sources in the pharmaceutical manufacturing industry. The
NPDES permit regulations define the term "new source" at 40 CFR 122.2 and 122.29.
According to these regulations, to be "new", a source must:
16-1
-------
Be constructed at a site at which no other source is located;
Totally replace the process or production equipment that causes the
discharge of pollutants at an existing source; or
Be a process substantially independent of an existing source at the
same site, considering the extent of integration with the existing
source and the extent to which the new source is engaged in the
same general type of activity as the existing source.
The Agency has selected in-plant steam stripping with distillation and cyanide destruction
followed by end-of-pipe advanced biological treatment (NSPS Option 1) as the
technology basis for the proposed NSPS for Subcategories A and C. The performance
level of the advanced biological treatment system component of NSPS for subcategories
A and C reflects the one best performing advanced biological treatment system at a
facility with both subcategory A and C operations. The Agency has selected in-plant
steam stripping with distillation followed by end-of-pipe advanced' biological treatment
(NSPS Option 2) as the technology basis for the proposed NSPS for Subcategories B and
D. The performance level of the advanced biological treatment system component of
NSPS for Subcategories B and D is the one best performing advanced biological
treatment system of a facility with Subcategory D operations. The rationale behind these
selections is discussed in Section 11.
The following information is presented in this section:
Section 16.2 reviews the subcategories and the pollutants proposed
to be regulated by NSPS and presents the proposed NSPS; and
Section 16.3 discusses NSPS implementation with regard to point of
application, permit limitations, and monitoring and compliance
issues.
16-2
-------
16.2
Summary of the Proposed NSPS
16.2.1
Regulated Subcategories
Revised NSPS are proposed for Subcategories A, B, C, and D. As discussed in Section
4.3, Subcategories A, B, and C include wastewater discharges resulting from the
manufacture of pharmaceuticals by fermentation, biological or natural extraction
processes, and chemical synthesis processes, respectively. Subcategory D includes
wastewater discharges resulting from mixing, compounding, and formulating of
pharmaceutical products.
16.2.2
Regulated Pollutants
The proposed NSPS establish effluent limitations for the conventional, priority, and
nonconventional pollutants listed in Table 16-1 for direct dischargers in Subcategories A,
B, C, and D. In addition, the proposed NSPS establish effluent limitations for cyanide
and ammonia for direct dischargers in Subcategories A and C.
16.2.3
NSPS
The proposed NSPS for each subcategory are based on a combination of long-term mean
effluent values and variability factors that account for day-to-day variation in measured
treated effluent concentrations. Long-term means, discussed in Section 8, are target
values that a facility should achieve on a long-term, average basis. The variability
factors, discussed in the Statistical Support Documentl, which is located in the
Administrative Record for this rulemaking, represent the ratio of an elevated value that
would be expected to occur only rarely to the long-term mean. The variability factors
are also provided in Appendix C of this document for ease of reference. The purpose of
the variability factor is to allow for variations in effluent concentrations that comprise
the long-term mean. A facility that designs and operates its treatment system to achieve
16-3
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a long-term mean on a consistent basis should be able to comply with the daily and
monthly limitations in the course of normal operations.
Table 16-2 presents the proposed maximum daily and monthly average NSPS for in-plant
and end-of-pipe monitoring points for Subcategory A, and C operations. Table 16-3
presents the proposed maximum daily and monthly average NSPS for end-of-pipe
monitoring points for Subcategory B and D operations.
The proposed regulation for the pharmaceutical manufacturing industry presents
analytical method minimum levels in Section 439.1 (g). These values apply to those
limitations and standards set at ND. For ease of use, the tables presented in this section
present the analytical method minimum level in parentheses for those limitations and
standards set at ND.
The pH effluent limit, established in the 1976 Final Rule (41 FR 50676) to be the range
of 6.0 to 9.0 standard units for all subcategories, is not being revised.
16.3
Implementation of NSPS
As noted in Section 7, EPA is not proposing but is considering use of Best Management
Practices (BMPs) to reduce discharges from leaks and spills of process chemicals and
materials. These materials include organic solvents (some of which are ignitable) that
contribute to air emissions and to effluent discharges and of-specification products which
may upset biological treatment systems. BMPs may offer the opportunity to reduce these
discharges and air emissions while concurrently increasing utilization of consumable
materials. Suggested details on BMPs being considered for the pharmaceutical
manufacturing industry are presented in Appendix B.
16-4
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16.3.1
Establishing List of Pollutants for Compliance Monitoring
If final new source performance standards are promulgated as proposed, permit
limitations would be established and compliance monitoring required for each pollutant
listed on Table 16-1 generated or used at a pharmaceutical manufacturing facility.
Limitations and routine compliance monitoring would not be required for regulated
pollutants not generated or used at a facility. A determination that regulated pollutants
are not generated or used would be based on a review of all raw materials used and an
assessment of all chemical processes used, considering resulting products and by-
products. The determination that a regulated pollutant is not generated or used would
need to be confirmed by annual chemical analyses of wastewater from each monitoring
location. Such confirmation would be provided by an analytical measurement of a non-
detect value.
16.3.2
Point of Application
The proposed NSPS for ammonia (applicable to Subcategories A and C) and organic
pollutants listed in Tables 16-2 and Table 16-3 are end-of-pipe standards and would be
applicable to the final effluent at the point of discharge to waters of the United States.
EPA also is soliciting comments and data on whether limits for the 12 most strippable
priority and non-conventional organic pollutants should be applied at an in-plant
monitoring point (e.g., following steam stripping and prior to dilution with other process
and non-process wastewaters not containing these pollutants in treatable quantities and
prior to end-of-pipe biological treatment systems). The limits EPA would propose for
this in-plant monitoring point are found in Table 2-8. The proposed NSPS for cyanide,
presented in Table 16-2, are applicable to Subcategories A and C. Compliance
monitoring for cyanide would occur in plant, prior to dilution or mixing with any non-
cyanide-bearing wastewater. In-plant monitoring would be required to prevent
compliance through dilution with non-cyanide-bearing wastewater.
16-5
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16.3.3
Permit Limitations
If final new source performance standards are promulgated as proposed, permit
limitations for cyanide at in-plant locations should be concentration-based, and would not
be converted to a mass basis. The proposed concentration-based standards for cyanide
are listed hi Table 16-2. A concentration basis should be used because it offers a direct
benchmark to assess whether the in-plant control technology is achieving the intended
NSPS level. In-plant wastestreams that require control may be generated or treated on a
variable, batch basis. In such a setting, mass-based permit limitations are difficult to
establish accurately, and compliance is hindered because the permitted facility cannot
make a direct measurement to determine if its control technology is performing at the
required level. Concentration-based permit limitations eliminate these problems and
offer a direct measure to both the permitting authority and the permitted facility that
NSPS performance levels are being achieved.
Permit limitations for ammonia, conventional, and nonconventional organic pollutants
that EPA proposed to control at end-of-pipe should be mass-based unless the maximum
for any one day limitation is non-detect (ND). In such a case, the permit should specify
that all measured values should be non-detect values. Non-detect values are
concentration-based measurements reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. The minimum level is the
level at which an analytical system gives recognizable signals and an acceptable
calibration point. Minimum levels for all regulated pollutants are specified in Table
18.7.
Permit writers would use a reasonable estimate of process wastewater discharge flow and
the concentration-based standards listed hi Tables 16-2 and 16-3 to develop mass-based
permit limitations for the NPDES permit. Section 15.3.3 presents guidance regarding
how a reasonable estimate of process wastewater discharge flow would be established
after final NSPS are adopted.
16-6
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The following example shows how a permit writer would establish daily maximum limits
for a facility with wastewaters from Subcategories B and C process operations. The
hypothetical facility's average daily wastewater generation (gal/day), the pollutants in
each stream, and the concentrations (mg/L) of each constituent are as follows:
Wastestream
1
2
3
Wastewater
Source
Subcategory B
Process Flow
Subcategory C
Process Flow
Noncontact
Cooling Water
Flow (gal/day)
2,000
30,000
10,000
Pollutants
Methanol
BOD
COD
TSS
Methanol
Aniline
BOD
COD
TSS
None
Concentration
(mg/L)
250
2,100
3,000
250
500
20
800
1,800
130
To estimate process wastewater discharge flow, the permit writer should review the
component flows listed above and determine which wastewater flows can be deemed
process wastewater discharge. In this example, only Subcategory A and B wastewater
discharges constitute process wastewater discharge flow. Thus, a reasonable estimate of
the process wastewater discharge flow for this example facility is 32,000 gal/day.
All limitations would be applied to the final effluent. The concentration-based standards
for methanol and aniline are listed in Tables 16-2 and 16-3 for subcategories C and B,
respectively. Note that they are the same for both subcategories. The standards for
aniline would be converted to mass-based permit limitations using the annual average
16-7
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daily process wastewater discharge flow, 32,000 gal/day. This conversion can be
calculated using the following equation:
where:
LM
LC
F
k
mass-based effluent limitation, Ibs/day
concentration-based effluent limitation, mg/L
average process wastewater discharge, gal/day
unit conversion factor, (L x lbs)/(gal x mg).
(16-1)
For this example, the unit conversion factor, k, is used to convert from
[(mg/L) x (gal/day)] to (Ibs/day):
k = (1 L/0.264179 gal) x (1 g/1000 mg) x (1 lb/453.592 g) = 8.345 x 10'6 [(L x lbs)/(gal x mg) j
For this example, the mass-based maximum daily and monthly average limitations for
aniline would be calculated using Equation 16-1:
Maximum daily:
= (0.010 mg/L) x (32,000 gal/day) x 8.345 x 10'6 [(L x lbs)/(gal x mg)]
= 0.0027 Ibs/day aniline
Monthly average:
= (0.004 mg/L) x (32,000 gal/day) x 8.345 x 10'6 [(L xlbs)/(gal x mg)]
= 0.0011 Ibs/day aniline
The Subcategory B and the Subcategory C maximum daily limitations for methanol are
ND. Therefore, the permit limitation for methanol should be ND for all measurements.
16-8
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The proposed NSPS for BOD5, COD, and TSS would also be applied to the final
effluent at the point of discharge to waters of the United States. An example calculation
of permit limitations for BOD5 follows. The concentration-based standards for BOD5
would also be converted to mass-based permit limitations using Equation 16-1.
However, the concentration-based effluent limitation, L0 for BOD5 would be determined
from the different limitations set for Subcategory B (from Table 16-3) and Subcategory C
(from Table 16-2) wastewaters using the following equation:
where:
Lc
Fc
F
B + C
_(LBxFB)+(LcxFc)
(16-2)
• B + C
combined concentration-based effluent limitations, (mg/L)
concentration-based effluent limitation for Subcategory B
wastewater, mg/L
concentration-based effluent limitation for Subcategory C
wastewater, mg/L
flow of Subcategory B wastewater, gal/day
flow of Subcategory C wastewater, gal/day
flow of Subcategory B wastewater and Subcategory C
wastewater, gal/day.
For this- example, the mass-based maximum daily limitation for BOD5 would be
calculated using Equations 16-1 and 16-2:
BOD: L= f (34 mg/L x
5: LM= f
= 16 Ibs/day BOD5
(*2™i/L * 30.000 gal/day) j x (32,000 gal/day) x (8.345 x
There are no mass allowances for noncontact cooling water. The monthly average
permit limitation for BOD5, and limitations for COD and TSS would be calculated in a
16-9
-------
similar manner. Additional detailed guidance on establishing permit limitations is
available in the Guidance for Implementing the Pharmaceutical Manufacturing Industry
Regulations included as Appendix A.
16.3.4
Monitoring and Compliance
Compliance monitoring for the proposed NSPS for BODS, COD, TSS, and pH, if
finalized, should be performed daily. Similarly, compliance monitoring for ammonia (for
subcategories A and C) and all regulated organic constituents, based on final NSPS, in
wastewater should be performed weekly. The list of pollutants for which EPA proposes
to require monitoring includes all regulated constituents listed in Table 16-1 generated
or used hi pharmaceutical manufacturing processes at the facility. Under the proposed
NSPS, monitoring for BOD5, COD, TSS, pH, ammonia, and organic constituents
generated or used hi pharmaceutical manufacturing processes would occur at the point of
discharge to waters of the United States. Similarly, monitoring for cyanide for
Subcategories A and C would be performed prior to commingling or dilution with non-
cyanide bearing wastewater. If final NSPS for cyanide are promulgated as proposed,
monitoring should be conducted at a minimum of once for every treated batch of
cyanide-bearing wastewater from Subcategory A and C process operations.
Compliance with the standards for cyanide, if promulgated as proposed, should be
determined by comparing the concentration of cyanide with the daily maximum
concentration-based limitation listed in Table 16-2. The monthly average concentration
should be calculated by averaging the available measurements taken in each calendar
month. Concentrations equal to or less than the concentrations listed in Table 16-2
would be hi compliance.
Compliance with mass-based permit limitations for pollutants monitored prior to
discharge to waters of the United States should be determined by multiplying the
measured concentration of a regulated pollutant in the effluent sample by a conversion
16-10
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factor and the total wastewater flow at the monitoring location during the effluent
sampling period which is typically 24 hours. Thus, the mass compliance value should be
based on the total flow discharged on the day of sampling, not on the long-term average
process water flow rate that provided the basis for establishing the permit limitations and
standards. The mass compliance value can be determined using the following equation:
CVM=PCxFxk
where: CVM = mass compliance value, Ibs/day
pollutant concentration, mg/L
CVM
PC
F
total wastewater discharge flow through the monitoring point
over 24-hour sampling period, gal/day
unit conversion factor, 8.345 x 10"6.
For example, if analytical data from a 24-hour sampling period for a particular plant
demonstrates a pollutant concentration of 5.0 mg/L, and the measured flow discharged
through the monitoring point for the same 24-hour period is 0.600 million gallons, then
the plant's reported daily mass compliance value of the pollutant, using Equation 16-3, is
25.0 Ibs/day. Similarly, the monthly average compliance value would be calculated by
averaging the available daily mass compliance values in each calendar month.
For pollutants where the permit limitations are non-detect values, compliance would be
demonstrated by having all concentration-based measurements be below the minimum
level that can be reliably measured by the analytical method for the pollutant. Minimum
levels for all regulated pollutants are specified in Table 18-7.
The list of pollutants for which EPA proposes to require monitoring should be updated
based on consideration of raw material and process changes throughout the facility and
an annual scan for cyanide and all regulated pollutants in Table 16-1. The annual scan
16-11
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should be performed at the compliance monitoring point(s) to identify any regulated
pollutants in the wastewater. Permit monitoring and compliance should be required at
all monitoring locations for all pollutants detected at any locations.
16-12
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Table 16-1
Pollutants Proposed to be Regulated Under NSPS
Conventional Pollutants
BOD5
TSS
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane (Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
Cyanide (a)
Nonconventional Pollutants
Acetone
Acetonitrile
Ammonia (a)
Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl Sulfoxide
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum naphtha
Polyethylene glycol 600
n-Propanol
Pyridine
16-13
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Table 16-1
(Continued)
Nonconventional Pollutants (cont)
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
COD (Chemical Oxygen Demand)
(a) Cyanide and ammonia are proposed to be regulated for Subcategories A and C only.
16-14
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Table 16-2
Proposed NSPS for Subcategory A and C Operations
Pollutant or Pollutant Property
Cyanide
Proposed NSPS for In-Plant Monitoring Points
Maximum for any 1 day
Atg/L
766
Monthly Average
^g/L
406
Pollutant or Pollutant Property
Acetone
Acetonitrile
Ammonia
Amyl Alcohol
n-Amyl Acetate
Aniline
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethyl Sulfoxide
1,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene Glycol
Proposed NSPS for End-of-Pipe Monitoring Points
Maximum for any 1 day
Ag/t
ND (50)
ND (5,000)
4,850
. ND (500)
14
10
ND (10)
144
11
ND (500)
ND (100)
ND (10)
ND (10)
ND(50)
ND (5)
ND (10)
13
ND (50,000)
74
ND (50)
ND (50,000)
50
45
ND (20,000)
ND(50)
ND (3,180)
14
ND (100,000)
Monthly Average
pg/L
ND (50)
ND (5,000)
3,230
ND(500)
6
4
ND(10)
61
ND(5)
ND(500)
ND (100)
ND (10)
ND (10)
ND (50)
ND(5)
ND(10)
ND (10)
ND (50,000)
ND (50)
ND(50)
ND (50,000)
45
19
ND (20,000)
ND(50)
ND (3,180)
ND (10)
ND (100,000)
16-15
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Table 16-2
(Continued)
Pollutant or Pollutant Property
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
MEBK
Methanol
Methylamine
Methyl Cellosolve
Methylene Chloride
Methyl Formate
2-Methylpyridine-
Petroleum Naphtha
Phenol
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
BODj (mg/L)
COD (mg/L)
TSS (mg/L)
Proposed NSPS for Erid-of-Pipe Monitoring Points
Maximum for any 1 day
«/t-
1,480
ND (100,000)
53
ND (10)
ND(10)
304
ND (200)
11
74
ND (10)
ND (3,180)
ND (50,000)
ND (20,000)
ND (10)
ND (100)'
50
ND (10)
25
4,870
ND (3,180)
10
910
ND (10)
ND(10)
ND (50,000)
ND (10)
62
781
87
Monthly Average
Atg/L
623
ND (100,000)
ND (50)
ND (10)
ND (10)
129
ND (200)
ND(10)
32
ND (10)
ND (3,180)
ND (50,000)
ND (20,000)
ND(10)
ND(IOO)
45
ND(10)
14
2,070
ND (3,180)
10
264
ND (10)
ND(10)
ND (50,000)
ND(10)
29
538
43
ND - Nondetect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
16-16
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Table 16-3
Proposed NSPS for Subcategory B and D Operations
Pollutant or Pollutant Property
Acetone
Acetonitrile
n-Amyl Acetate
Amyl Alcohol
Aniline.
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
N,N-Dimethylacetamide
N,N-Dimethylaniline
N,N-Dimethylformamide
Dimethylamine
Dimethyl Sulfoxide
1,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene Glycol
Formaldehyde
Formamide
Furfural
Proposed NSPS for End-ofrPipe Monitoring Points
Maximum for any 1 day
•• • . '/'•'• ' mfc -'.""'.'••'.'•' "
ND (50)
ND (5,000)
14
ND (500)
10
ND (10)
144
11
ND(500)
ND (100)
ND (10)
ND (10)
ND(50)
ND (5)
ND(10)
13
ND (50,000)
74
ND(50)
50
45
ND (50,000)
ND (20,000)
ND (50)
ND (3,180)
14
ND (100,000)
1,480
ND (100,000)
53
'•'•"' Monthly Average
.;•.. • - '' mft*
ND(50)
ND (5,000)
6
ND(500)
4
ND (10)
61
ND(5)
ND (500)
ND (100)
ND(10)
ND(10)
ND(50)
ND (5)
ND (10)
ND'(IO)
ND (50,000)
ND (50)
ND(50)
45
19
ND (50,000)
ND (20,000)
ND(50)
ND (3,180)
ND (10)
ND (100,000)
623
ND (100,000)
ND(50)
16-17
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Table 16-3
(Continued)
Pollutant or Pollutant Property
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
MBBK
Methanol
Methylamine
Methyl Cellosolve
Methyl Formate
Methylene Chloride
2-Methylpyridine
Petroleum Naphtha
Phenol
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofiiran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
BOD5 (mg/L)
COD (mg/L)
TSS (mg/L)
Proposed NSPS for End-of-Pipe Monitoring Points
Maximum for any 1 day ;
*«g/k
ND (10)
ND (10)
304
ND (200)
11
74
ND (10)
ND (3,180)
ND (50,000)
ND (20,000)
ND (100)
ND(10)
50
ND (10)
25
4,870
ND (3,180)
10
910
ND(10)
ND (10)
ND (50,000)
ND (10)
34
.60
40
Monthly Average
0g/L
ND (10)
ND (10)
129
ND (200)
ND(10)
32
ND (10)
ND (3,180)
ND (50,000)
ND (20,000)
ND(IOO)
ND(10)
45
ND (10)
14
2,070
ND (3,180)
10
264
ND(10)
ND (10)
ND (50,000)
ND(10)
10
24
12
ND - Nondetect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
16-18
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REFERENCES
1.
U.S. EPA, Office of Water. Statistical Support Document for the Proposed
Effluent Limitations Guidelines for the Pharmaceutical Manufacturing
Industry. U.S. Environmental Protection Agency, Washington, B.C.,
February 10, 1995.
16-19
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SECTION 17
PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES) AND
PRETREATMENT STANDARDS FOR NEW SOURCES (PSNS)
17.1
Introduction
Pretreatment standards for existing sources are designed to prevent the discharge of
pollutants which pass through, interfere with, or are otherwise incompatible with the
operation of POTWs. The CWA requires pretreatment for pollutants that pass through
POTWs in amounts that would exceed direct discharge effluent limitations or limit
POTW sludge management alternatives, including the beneficial use of sludges on
agricultural lands. EPA also determines that there is pass-through of a pollutant if the
pollutant exhibits significant volatilization prior to treatment by POTWs. Pretreatment
standards are to be technology-based and analogous to the BAT for removal of priority
and nonconventional pollutants.
Section 307(c) of the CWA requires EPA to promulgate pretreatment standards for new
sources at the same time that it promulgates NSPS. New indirect discharging facilities,
like new direct discharging facilities, have the opportunity to incorporate the best
available demonstrated technologies, including process changes, in-plant control
measures, and end-of-pipe wastewater treatment technologies that reduce pollution to
the maximum extent feasible. Pretreatment standards for new sources (see Section 16
for a discussion of the definition of new source) are to be technology-based and
analogous to the NSPS for the removal of priority and nonconventional pollutants.
The owners or operators of facilities subject to PSES or PSNS are not required to use
the specific process technologies and wastewater treatment technologies selected by EPA
to establish the PSES or PSNS, but may choose to use any combination of process
17-1
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technologies and wastewater treatment to comply with permit limitations derived from
the PSES or PSNS.
The Agency has selected in-plant steam stripping and cyanide destruction (PSES
Option 1) as the technology basis for the proposed PSES for Subcategory A and C
operations. The Agency has selected in-plant steam stripping (PSES Option 1) as the
technology basis for the proposed PSES for Subcategory B and D operations. For PSNS,
the Agency has selected in-plant steam stripping with distillation and cyanide destruction
(PSNS Option 1) as the proposed technology basis for the proposed PSNS for
Subcategory A and C operations. The Agency also selected in-plant steam stripping with
distillation (PSNS Option 1) as the proposed PSNS for Subcategory B and D operations.
The rationale behind these selections is discussed in Section 11.
The following information is presented in this section:
Section 17.2 reviews the subcategories regulated by PSES and PSNS,
the results of the Agency's POTW pass-through analysis to
determine pollutants proposed to be regulated by PSES and PSNS,
and presents the proposed PSES and PSNS; and
Section 17.3 discusses PSES and PSNS implementation with regard
to point of application, permit limitations, and monitoring and
compliance issues.
17.2
Summary of the Proposed PSES and PSNS
17.2.1
Regulated Subcategories
Revised PSES and PSNS are proposed for Subcategories A, B, C, and D. As discussed
in Section 4.3, Subcategories A, B, and C include wastewater discharges resulting from
the manufacture of Pharmaceuticals by fermentation, biological or natural extraction
processes, and chemical synthesis processes, respectively. Subcategory D includes
17-2
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discharges resulting from mixing, compounding, and formulating of pharmaceutical
products.
17.2.2
POTW Pass-Through Analysis
Based on currently available data and information, the Agency evaluated POTW pass-
through for those pollutants proposed for regulation as listed in Sections 6.6 and 6.7. In
determining whether a pollutant is expected to pass through a POTW, the Agency
assessed the following:
Whether the pollutant would be volatilized from conveyance
systems, equalization or other treatment units or POTW head works
which are open to the atmosphere;
Whether the nation-wide average percentage of a pollutant removed
by well-operated POTWs achieving secondary treatment is less than
the percentage removed by the BAT model treatment system; or
Whether there are any specific instances of POTW interference,
upset, or pass through known to the Agency as being caused by the
pollutants proposed for regulation.
The uncontrolled transfer of a pollutant from water to air through volatilization does not
constitute treatment. Therefore, the Agency has determined that those pollutants
proposed for regulation that will undergo significant volatilization from conveyance
systems, equalization, or other treatment units or POTW head works that are open to
the atmosphere pass through POTWs and should be regulated by pretreatment
standards. Pollutants with a Henry's Law constant equal to or greater than 2.7 x 10~6
atm/gmole/m3 undergo significant volatilization and are considered to pass through
POTWs for this reason. The list of organic pollutants that EPA has determined pass
through POTWs based on this criteria are shown in Table 17-1,
17-3
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The Agency also made a comparison of the nation-wide average percentage of a
pollutant removed by well-operated POTWs achieving secondary treatment to the
percentage removed by the BAT model treatment systems. Pollutants are considered to
pass through POTWs if the average percentage removal by the BAT model treatment
systems is greater than the average percentage removed by well-operated POTWS. The
Agency evaluated the percentage removed by the BAT model treatment systems using
the Detailed Questionnaire data submitted by direct dischargers and the long-term mean
treatment performance concentrations developed for the BAT treatment technologies as
discussed in Section 8. The major source of the nation-wide average percentage of a
pollutant removed by well-operated POTWs achieving secondary treatment was the
Domestic Sewage Study. (1) The list of organic pollutants that EPA has determined
pass through POTWs based on this criteria are shown in Table 17-1.
The Agency has reviewed responses received from a pharmaceutical outreach
questionnaire sent by EPA/EAD in February 1993 to selected POTWs whose wastewater
influents include pharmaceutical facility sources. These responses were reviewed to
identify pharmaceutical candidate pollutants that may be causing interference, upsets, or
pass-through at POTWs. In addition, data collected by EPA from the Syracuse POTW
and data submitted previously to EPA by the Syracuse POTW were also reviewed for
evidence of pollutants that may cause POTW interference, upset, or pass through. Based
on these reviews, POTW personnel have reported POTW interference or upset by
discharges from pharmaceutical facilities of ammonia, tetrahydrofuran, and dimethyl
sulfoxide.
EPA does not have sufficient data at this time to determine whether acetonitrile,
polyethylene glycol 600, or COD pass through POTWs. Pending collection of additional
data, EPA is not proposing pretreatment standards for acetonitrile, polyethylene glycol
600, or COD at this time. With regard to the priority pollutant cyanide, EPA found that
this pollutant passes through POTWs because the removal of cyanide by the BAT
cyanide destruction system is significantly greater than the documented removals by well-
17-4
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operated POTWs achieving secondary treatment. Ammonia (aqueous) is also considered
to pass through because most POTWs do not have nitrification capability that is part of
the BAT model treatment system and therefore will not achieve as much ammonia
removal as the BAT model treatment system. For a detailed discussion of the Agency's
POTW pass-through analysis see the memorandum entitled, "POTW Pass-Through
Analysis for the Pharmaceutical Manufacturing Industry" (2) which is located in the
Record for this rulemaking.
Based on the pass through analysis, the Agency has arrived at two alternate
determinations of POTW pass-through. The Agency is putting forward two proposals for
PSES and PSNS based on these alternate pass-through determinations. Under co-
proposal (1), based on the data and information currently available, EPA has determined
that the 50 organic pollutants listed in Table 17-1 pass through POTWs. Under co-
proposal (2), the Agency is considering a finding that 33 of the less volatile priority and
nonconventional pollutants do not pass through.. EPA has developed co-proposal (2)
because of concerns expressed by industry representatives that EPA's pass-through
analysis supporting co-proposal (1) may not be correct for some of the 33 less volatile
priority and nonconventional pollutants.
17.2.3
Regulated Pollutants
Co-proposal (1) establishes PSES and PSNS standards for the priority and
nonconventional pollutants listed in Table 17-2 for indirect dischargers in Subcategories
A, B, C, and D. Co-proposal (2) establishes PSES and PSNS standards for the priority
and nonconventional pollutants listed in Table 17-3 for indirect discharges in
Subcategories A, B, C, and D.
The proposed regulation for the pharmaceutical manufacturing industry presents
analytical method minimum levels in Section 439.1 (g). These values apply to those
limitations and standards set at ND. For ease of use, the tables presented in this section
17-5
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present the analytical method minimum level in parentheses for those limitations and
standards set at ND.
There are five organic pollutants that were found to pass through POTWs that are not
treatable by the proposed PSES technology basis of steam stripping or the PSNS
technology basis of steam stripping with distillation. These pollutants are formaldehyde,
N,N-dimethyl formamide, N,N-dimethyl acetamide, ethylene glycol, and dimethyl
sulfoxide and EPA has not proposed pretreatment standards for them at this time. One
technology which might serve as the basis for pretreatment of these five pollutants is
package biological treatment of selected wastestreams. In the proposed rule, the Agency
has solicited data on the performance of this technology or others for treating these five
nonstrippable pollutants. Based on a review of any new treatment performance data
collected or received by the Agency for these pollutants, EPA may develop pretreatment
standards at a later date. PSES and PSNS for these five pollutants are currently
reserved.
17.2.4
PSES and PSNS
The proposed PSES and PSNS for each subcategory are based on a combination of long-
term mean treatment performance concentrations and variability factors that account for
day-to-day variation in measured treated effluent concentrations. Long-term mean
treatment performance concentrations, discussed in Section 8, are target values that a
facility should achieve on a long-term, average basis. The variability factors, discussed in
the Statistical Support Document (3), which is located in the Record for this
rulemaking, represent the ratio of an elevated value that would be expected to occur
only rarely to the long-term mean. The purpose of the variability factor is to allow for
variations in effluent concentrations that comprise the long-term mean. Variability
factors are provided in Appendix C for reference purposes. A facility that designs and
operates its treatment system to achieve a long term mean on a consistent basis should
17-6
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be able to comply with the daily and monthly limitations in the course of normal
operations.
The proposed technology basis, and hence the proposed PSES, are the same for each of
the four pharmaceutical manufacturing subcategories. The same is true for PSNS. The
only difference between Subcategories A and C and Subcategories B and D is the
absence of proposed ammonia and cyanide standards for Subcategories B and D. The
proposed PSES under co-proposal (1) are presented in Table 17-4. The proposed PSES
under co-proposal (2) are presented in Table 17-5. The proposed PSNS under co-
proposal (1) are presented in Table 17-6. The proposed PSNS under co-proposal (2) are
presented in Table 17-7. These proposed standards were determined by multiplying the
long-term mean treatment performance concentrations for the selected treatment
technology bases by the respective 1-day and 4-day variability factors (VFs).
17.3
Implementation of the PSES and PSNS
As noted in Section 7, EPA is not preparing but is considering use of Best Management
Practices (BMPs) to reduce discharges from leaks and spills of process chemicals and
materials. These materials include organic solvents (some of which are ignitable) that
contribute to air emissions and to effluent discharges and off-speciation products which
may upset biological treatment systems. BMPs may offer the opportunity to reduce these
discharges and air emissions while concurrently increasing utilization of consumable
materials. Suggested details on BMPs being considered for the pharmaceutical
manufacturing industry are presented in Appendix B.
17.3.1
Establishing List of Pollutants for Compliance Monitoring
If final PSES and PSNS are adopted as proposed, permit limitations would be
established and compliance monitoring required for each regulated pollutant listed on
Table 17-2 or 17-3 generated or used at a pharmaceutical manufacturing facility
17-7
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(depending upon which co-proposal is promulgated). Limitations and routine
compliance monitoring would not be required for regulated pollutants not generated or
used at a facility. A determination that regulated pollutants are not generated or used
would be based on a review of all raw materials used and an assessment of all chemical
processes used, considering resulting products and by-products. The determination that a
regulated pollutant is not generated or used would need to be confirmed by annual
chemical analyses of wastewater from each monitoring location. Such confirmation
would be provided by an analytical measurement of a non-detect value.
17.3.2
Point of Application
PSES and PSNS under co-proposals (1) and (2) for wastewaters from Subcategory A, B,
C, and D operations are applicable at both in-plant process area discharge points and at
end-of-pipe discharge points, as denoted in Tables 17-4 through 17-7 depending upon the
pollutant being regulated.
The in-plant monitoring points should be placed prior to dilution by nonprocess
wastewater, commingUng with other process wastestreams not containing the regulated
pollutants at treatable levels, and any conveyance, equalization, or other treatment units
which are open to the atmosphere. In-plant monitoring is required to prevent
compliance through dilution by significant wastewater flows from other portions of the
facility that do not contain these pollutants, and to prevent cross-media transfer of these
pollutants from wastewater to the atmosphere during collection, equalization, and POTW
biological treatment. The end-of-pipe monitoring point should be placed prior to
discharge to the POTW sewer system.
The proposed PSES and PSNS for cyanide are applicable to those wastewaters from
Subcategory A and C operations. Compliance monitoring for cyanide should occur in
plant, prior to dilution or mixing with any noncyanide-bearing wastewater. EPA
17-8
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proposes to require in-plant monitoring to prevent compliance through dilution with
noncyanide-bearing wastewater.
17.3.3
Permit Limitations
If final PSES and PSNS are promulgated as proposed, EPA expects that permit
limitations for cyanide and organic constituents at in-plant locations would be
concentration-based, and not converted to a mass basis. Proposed concentration-based
limitations are listed in Tables 17-4 and 17-5 for PSES, and Tables 17-6 and 17-7 for
PSNS. A concentration basis should be used because it offers a direct benchmark to
assess whether the in-plant control technology is achieving the intended PSES and PSNS
levels. In-plant wastestreams that require control may be generated or treated on a
variable, batch basis. In such a setting, mass-based permit limitations are difficult to
establish accurately, and compliance is hindered because the permitted facility cannot
make a direct measurement to determine if its control technology is performing at the
required level. Concentration-based permit limitations eliminate these problems and
offer a direct measure to both the permitting authority and the permitted facility that
PSES and PSNS performance levels are being achieved.
0
Permit limitations for ammonia (for Subcategories A and C) and organic constituents
that are controlled at the final effluent should be mass-based unless the maximum for
any one day limitation is ND. In such a case the permit should specify that all measured
values should be non-detect values.
Non-detect values are concentration-based measurements reported below the minimum
level that can be reliably measured by the analytical method for the pollutant. The
minimum level is the level at which an analytical system gives recognizable signals and
an acceptable calibration point. Minimum levels for all pollutants proposed to be
regulated are specified in Table 18-7.
17-9
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If final PSES and PSNS are promulgated as proposed, permit writers would use a
reasonable estimate of process wastewater discharge flow and the concentration-based
standards listed in Tables 17-4 through 17-7 to develop mass-based permit limitations.
Section 15.3.3 presents guidance regarding how a reasonable estimate of process
wastewater discharge flow would be established after final PSES and PSNS are adopted.
The following example shows how a permit writer would establish daily maximum limits
for a facility with wastewaters from Subcategory C and D process operations. The
hypothetical facility's average daily wastewater generation (gal/day), the pollutants in
each stream, and the concentrations (mg/L) of each constituent are as follows:
; Wastestream
1
2
3
Wastewater
Source
Subcategory C
Process Flow
Subcategory D
Process Flow
Noncontact
Cooling Water
Flow
(gal/day)
20,000
8,000
5,000
Pollutants
Acetone
Pyridine
Toluene
Ethanol
Toluene
None
Concentration
(mg/L)
50
2
5
100
2
—
To estimate process wastewater discharge flow, the permit writer should review the
component flows listed above and determine which wastewater flows can be deemed
process wastewater discharge. In this example, only Subcategory C and D wastewater
discharges constitute process wastewater discharge flow. Thus, a reasonable estimate of
the process wastewater discharge flow for this example facility is 28,000 gal/day.
Under co-proposal (1) for PSES, the limitation for toluene would be applied at in-plant
locations, immediately following treatment of process wastewater streams 1 and 2, prior
to any dilution, commingHng with'other process wastestreams not containing the
regulated pollutants at treatable levels, and any conveyance, equalization, or other
17-10
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treatment units which are open to the atmosphere. The maximum daily limitation for
toluene is concentration-based, and is 0.198 mg/L (from Table 17-4). The monthly
average limitation for toluene is 0.148 mg/L.
The limitations for acetone, ethanol, and pyridine under co-proposal (1) for PSES would
be applied to the final effluent. The concentration-based limitations for these three
pollutants would be converted to mass-based limitations using the annual average daily
process wastewater discharge flow, 28,000 gal/day. This conversion can be calculated
using the following equation:
= Lc x F x K
(17-1)
where:
LM
Lc
F
K
mass-based effluent limitation, Ibs/day
concentration-based effluent limitation, mg/L
average process wastewater discharge, gal/day
unit conversion factor, (L x lbs)/(gal x nag).
For this example, the unit conversion factor, k, is used to convert from [(mg/L) x
(gal/day)] to (Ibs/day) as follows:
K = (mg/L) x
1 L
x
1 Ib
0.264179 gal 1,000 mg 453.592 g
x (gal/day) = 8.345 x 10
,-6
For this example, the mass-based maximum daily and monthly average limitations for
acetone would be calculated using Equation 17-1:
17-11
-------
Maximum daily limitation:
L. = (31.4 mg/L) x (28,000 gal/day) x 8.345 x 10'6 [ L, X lbs ]
M [ gal x mg J
= 7.34 Ibs/day acetone
Monthly average limitation:
= (9.69 mg/L) x (28,000 gal/day) x 8.345 x 10'6 f
L X lbs
gal x mg
= 2.26 Ibs/day acetone
The limitations for ethanol and pyridine can be calculated in a similar manner.
Under co-proposal (2) for PSES, there would be no limitations for acetone, ethanol, and
pyridine, but toluene would-still have in-plant limitations. The limitations for toluene
would be the same as those shown for co-proposal (1) for PSES.
Under co-proposal (1) for PSNS, the limitations for acetone, ethanol, and toluene would
be applied at in-plant locations, immediately following treatment of wastewater streams 1
and 2, prior to any dilution, commingling with other process wastestreams not containing
the regulated pollutants at treatable levels, and any conveyance, equalization, or other .
treatment units which are open to the atmosphere. The maximum daily limitations for
acetone, ethanol, and toluene are concentration-based, and are 1.19 mg/L, 8.69 mg/L,
and 0.184 mg/L, respectively. The monthly average limitations are 0.600 mg/L, 3.22
mg/L, and 0.135 mg/L, for acetone, ethanol, and toluene, respectively (from Table 17-6).
The limitations for pyridine under co-proposal (1) for PSNS would be applied to the
final effluent. The concentration-based limitations for pyridine would be converted to
17-12
-------
mass-based limitations using the annual average daily process wastewater discharge flow,
' 28,000 gal/day. This conversion can be calculated using Equation 17-1 as shown below:
Maximum daily limitation:
= (1.00 mg/L) x (28,000 gal/day) x 8.345 x 10
= 0.23 Ibs/day pyridine
L x Ibs
gal x mg
The monthly average limitation for pyridine would be the same as the maximum daily
limitation, since the concentration standards for the maximum for any one day and the
monthly average are the same.
Under co-proposal (2) for PSNS, there would be no limitations for acetone, ethanol, and
pyridine, but toluene would still have in-plant limitations. The limitations for toluene
would be the same as those shown for co-proposal (1) for PSNS.
There are no mass allowances for noncontact cooling water under PSES or PSNS.
Additional detailed guidance on the establishment of permit limitations is available in
the Guidance for Implementing the Pharmaceutical Manufacturing Industry Regulations,
included as Appendix A.
17.3.4
Monitoring and Compliance
The list of pollutants for which monitoring would need to be performed includes all
constituents from Subcategory A, B, C, and D operations listed in Table 17-2 or 17-3
generated or used by a facility's pharmaceutical manufacturing processes (depending
upon which co-proposal is promulgated). Based on the proposed PSES and PSNS,
monitoring of those constituents generated or used in any pharmaceutical manufacturing
processes at the facility would occur at every in-plant control point. Compliance
17-13
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monitoring for ammonia and all other regulated organic constituents would be
performed at a minimum on a weekly basis. Monitoring for cyanide based on the
proposed cyanide PSES and PSNS would be performed at a minimum of once for every
treated batch of cyanide-bearing wastewater from Subcategory A and C process
operations.
Compliance with the standards for pollutants regulated at in-plant locations, if
promulgated as proposed, would be determined by comparing the concentrations of
those regulated pollutants with the daily maximum concentration-based standards listed
in Tables 17-4 through 17-7. The monthly average concentrations should be calculated
by averaging the available 1-day concentration values in each calendar month. (Since
EPA proposes to require weekly monitoring for nonconventional and priority organic
pollutants, there should be a minimum of four values to average.) Concentrations equal
to or less than the concentrations listed in Tables 17-4 through 17-7 for a particular
pollutant would be in compliance.
Compliance with mass-based permit limitations applicable to the end-of-pipe effluent
should be determined by multiplying the measured concentrations of a regulated
pollutant in the effluent sample by a conversion factor and the total wastewater flow at
the monitoring point during the effluent sampling period, which is typically 24 hours.
Thus, the mass compliance value should be based on the total flow discharged on the
day of sampling, not on the long-term average flow rate that provided the basis for
establishing the permit limitations. The mass compliance value can be determined using
the following equation:
where:
CVM =
PC =
CVM = Pc x F x k
mass compliance value, Ibs/day
pollutant concentration, mg/L
(17-1)
17-14
-------
total wastewater discharge flow through the monitoring point
over 24-hour sampling period, gal/day
unit conversion factor, 8.345 x 10'6.
For example, if analytical data from a 24-hour sampling period for a particular plant
demonstrates a pollutant concentration of 10.0 mg/L, and the measured flow discharged
through the monitoring point for the same 24-hour period is 0.600 million gallons, then
the plant's reported daily mass compliance value of the pollutant, using Equation 17-1, is
50.1 Ibs/day. Similarly, the monthly average compliance value would be calculated by
averaging the available daily mass compliance values in each calendar month.
For pollutants where the permit limitations are non-detect values, compliance would be
demonstrated by having all concentration-based measurements be below the minimum
level that can be reliably measured by the analytical method for the pollutant. Minimum
levels for all pollutants proposed to be regulated are specified in Table 18-7.
The list of pollutants for which EPA proposes to require monitoring should be updated
based on evaluation of raw material and process changes throughout the facility and an
annual scan for all regulated pollutants in Table 17-2 or Table 17-3. The annual scan
should be performed at all in-plant monitoring points, and at the facility end-of-pipe
process wastewater discharge point, to identify any regulated pollutants in the
wastewater. Permit monitoring and compliance should be required at all monitoring
locations for all pollutants detected at any locations.
17-15
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Table 17-1
Organic Pollutants Considered for Regulation
That Pass Through POTWs
Pollutant
Acetone
Acetonitrile
n-Amyl acetate
Amyl alcohol
Aniline
Benzene
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Chlorobenzene
Chloroform
Chloromethane
(Methyl chloride)
Cyclohexane
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Diethylamine
Diethyl ether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylaniline
N,N-Dunethylformamide
Dimethyl sulfoxide
1,4-Dioxane
Ethanol-
Ethyl acetate
Passes Through. Based on
Volatilization Potential
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Passes Through Based on
Evaluation of % POTW Removal
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
17-16
-------
Table 17-1
(Continued)
Pollutant
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methylene chloride
Methyl formate
Methyl isobutyl ketone (MIBK)
2-Methylpyridine
Petroleum naphtha
Phenol
Polyethylene glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
Passes Through Based on
Volatilization Potential
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X -
X
X
X
X
Passes Through Based on
Evaluation of % POTW Removal
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
17-17
-------
Table 17-2
Pollutants Proposed to be Regulated Under
PSES and PSNS Co-Proposal (1)
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane (Methyl chloride)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2-Dichloroethane
Methylene Chloride
Toluene
Cyanide (a)
Nonconventional Pollutants
Acetone
Ammonia (a)
Amyl acetate
Amyl alcohol
Aniline
2-Butanone (MEK)
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Cyclohexane
Diethylamine
Diethyl ether
Dimethylamine
N,N-Dunethylaniline
1,4-Dioxane
Ethanol
Ethyl acetate
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl cellosolve
Methyl formate
2-Methylpyridine
Methyl isobutyl ketone (MIBK)
Petroleum naphtha
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
Xylenes
(a) EPA proposes to regulate cyanide and ammonia for Subcategories A and C only.
17-18
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Table 17-3
Pollutants Proposed to be Regulated Under
PSES and PSNS Co-Proposal (2)
Pollutant
Ammonia (a)
Benzene
CMorobenzene
Chloroform
Chloromethane
Cyanide (a)
Cyclohexane
n-Heptane
n-Hexane
Methyl Cellosolve
Methylene Chloride
Toluene
Trichlorofluoromethane
Xylenes
(a) EPA proposes to regulate ammonia and cyanide for Subcategories A and C only.
17-19
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Table 17-4
Proposed PSES for Subcategory A, B, C, and D
Operations - Co-Proposal (1)
Pollutant or Pollutant Property
Benzene
Chlorobenzene
Chloroform
Chloromethane
Cyanide (a)
Cyclohexane
n-Heptane
n-Hexane
Methyl Cellosolve
Methylene Chloride
Toluene
Trichlorofluoromethane
Xylenes
Proposed PSES for In-Plant Monitoring Points
Maximum For any 1 day
«A-
796
796
ND (10)
796
766
796
796
796
ND (20,000)
809
198
796
796
Monthly Average
0g/L
268
268
ND (10)
268
406
268
268
268
ND (20,000)
279
148
268
268
Pollutant or Pollutant Property
Acetone
Ammonia (a)
n-Amyl Acetate
Amyl Alcohol
Aniline
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
o-Dichlorobenzene
Proposed PSES for End-of-Pipe Monitoring Points
Maximum for any 1 day
0g/L
31,400
12,900
23,900
607,000
10,900,000
1,440,000
23,900
10,900,000
607,000
23.WO
Monthly Average
Atg/L
9,690
10,900
8,050
205,000
3,690,000
430,000
8,050
3,690,000
205,000
, 8,050
17-20
-------
Table 17-4
(Continued)
Pollutant or Pollutant Property
1,2-Dichloroethane
Diethylamine
Diethyl Ether
Dimethylamine
N,N-Dimethylaniline
1,4-Dioxane
Ethanol
Ethyl Acetate
Form amide
Furfural
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Methanol
Methylamine
Methyl Formate /
MIBK
2-Methylpyridine
Petroleum Naphtha
n-Propanol
Pyridine
Tetrahydrofuran
Triethylamine
Proposed PSES for End-of-Pipe Monitoring Points
Maximum for any 1 day
Mg/L
23,900
ND (50,000)
23,900
607,000
607,000
10,900,000
2,200,000
23,900
607,000
607,000
23,900
597,000
23,900
23,900
11,700,000
607,000
23,900
23,900
607,000
10,900,000
2,790,000
1,000
9,210
ND (50,000)
Monthly Average
«/L
8,050
ND (50,000)
8,050
205,000
205,000
3,690,000
784,000
8,050
205,000
205,000
8,050
198,000
8,050
8,050
3,800,000
205,000
8,050
8,050 .
205,000
3,690,000
941,000
1,000
3,360
ND (50,000)
ND - Nondetect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
(a)
- EPA proposes to regulate cyanide and ammonia for Subcategories A and C only.
17-21
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Table 17-5
Proposed PSES for Subcategory A, B, C, and D
Operations - Co-Proposal (2)
Pollutant or Pollutant Property
Benzene
Chlorobenzene
Chloroform
Chloromethane
Cyanide (a)
Cyclohexane
n-Heptane
n-Hexane
Methyl Cellosolve
Methylene Chloride
Toluene
Trichlorofluoromethane
Xylenes
Proposed PSES for In-Plant Monitoring Points
Maximum for any 1 day
Pg/k
796
796
ND (10)
796
766
796
796
796
ND (20,000)
809
198
796
796
Monthly Average
0g/L
268
268
ND (10)
268
406
268
268
268
ND (20,000)
279
148
268
268
Pollutant or Pollutant Properly
Ammonia (a)
Proposed PSES for End-of-Pipe Monitoring Points
Maximum for and 1 day
Atg/L
12,900
Monthly Average
/*g/k
10,900
ND - Nondetect - A concentration-based measurement reported below the minim urn level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented hi parentheses
corresponding to an analytical method applicable to the respective pollutant.
(a) - EPA proposes to regulate cyanide and ammonia for Subcategories A and C only.
17-22
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Table 17-6
Proposed PSNS for Subcategory A, B, C, and D
Operations - Co-Proposal (1)
Pollutant or Pollutant Property
Acetone
Amyl Alcohol
Benzene
n-Butyl Alcohol
tert-Butyl Alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyanide (a)
Cyclohexane
Diethylamine
Diethyl Ether
Dimethylamine
Ethanol
Formamide
n-Heptane
n-Hexane
Isopropanol
Methanol
Methylamine
Methyl Cellosolve
Methylene Chloride
Methyl Formate
n-Propanol
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
Proposed PSNS for la-Plant Monitoring Points
Maximum for any 1 day
Atg/L
1,190
8,690
573
8,690
8,690
573
ND (10)
573
766
573
ND (50,000)
2,230
ND (50,000)
8,690
ND (100,000)
573
573
8,690
8,320
ND (50,000)
ND (20,000)
809
2,230
8,690
184
573
ND (50,000)
573
Monthly Average
/tg/L
600
3,220
212
3,220
3,220
212
ND (10)
212
406
212
ND (50,000)
826
ND (50,000)
3,220
ND (100,000)
212
212
3,220
ND (3,180)
ND (50,000)
ND (20,000)
279
826
3,220
135
212
ND (50,000)
212
17-23
-------
Table 17-6
(Continued)
Pollutant or Pollutant Property
Ammonia (a)
n-Amyl Acetate
Aniline
2-Butanone (MEK)
n-Butyl Acetate
o-Dichlorobenzene
1,2-Dichloroethane
N.N-Dimethylaniline
1,4-Dioxane
Ethyl Acetate
Furfural
Isobutyraldehyde
Isopropyl Acetate
Isopropyl Ether
MIBK
2-Methylpyridine
Petroleum Naphtha
Pyridine
Tetrahydrofuran
Proposed PSNS for End-of-Pipe Monitoring Points
Maximum for any 1 day
*«g/L
12,900
2,230
8,690
161,000
2,230
2,230
2,230
8,690
8,690
2,230
8,690
2,230
2,230
2,230
2,230
8,690
8,690
1,000
9,210
Monthly Average
Atg/L
10,900
826
3,220
57,900 '
826
826
826
3,220
3,220
826
3,220
826
.826
826
826
3,220
3,220
1,000
3,360
ND - Nondetect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
(a) - EPA proposes to regulate cyanide and ammonia for Subcategories A and C only.
17-24
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Table 17-7
Proposed PSNS for Subcategory A, B, C, and D
Operations - Co-Proposal (2)
Pollutant or Pollutant Property
Benzene
Chiorobenzene
Chloroform
Chloromethane
Cyanide (a)
Cyclohexane
n-Heptane
n-Hexane
Methyl Cellosolve
Methylene Chloride
Toluene
Trichlorofluoromethane
Xylenes
Proposed PSNS for In-Plant Monitoring Points
Maximum for any 1 day
0g/L
573
573
ND(10)
573
766
573
573
573
ND (20,000)
809
184
573
573
Monthly Average
/*g/L
212
212
ND(10)
212
406
212
212
212
ND (20,000)
279
135
212
212
Pollutant or Pollutant Property
Ammonia (a)
Proposed PSNS for End-of-Pipe Monitoring Points
Maximum for any 1 day
f*/L
12,900
Monthly Average
Mg/L
10,900
ND - Nondetect - A concentration-based measurement reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Minimum levels are presented in parentheses
corresponding to an analytical method applicable to the respective pollutant.
(a) - EPA proposes to regulate cyanide and ammonia for Subcategories A and C only.
17-25
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REFERENCES
U.S. EPA, Office of Water Regulations and Standards. Report to
Congress on the Discharge of Hazardous Wastes to Publicly Owned
Treatment Works. U.S. Environmental Protection Agency, Washington,
D.C., February 1986.
Memorandum: POTW Pass-Through Analysis for the Pharmaceutical
Manufacturing Industry, from Mary Willett, Radian Corporation, to Frank
Hund, U.S. EPA, October 1994.
U.S. EPA, Office of Water. Statistical Support Document for the Proposed
Effluent Limitations Guidelines for the Pharmaceutical Manufacturing
Industry. U.S. Environmental Protection Agency, Washington, D.C.,
February 10, 1995.
17-26
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SECTION 18
ANALYTICAL METHODS
18.1
Regulatory Background
Section 304(h) of the Clean Water Act directs EPA to promulgate guidelines establishing
test procedures (analytical methods) for analyzing pollutants. These test procedures are
used for filing applications and for compliance monitoring under the National Pollutant
Discharge Elimination System (NPDES) found at 40 CFR Parts 122.41(j)(4) and
122.21(g)(7), and for the pretreatment program found at 40 CFR 403.7(d). Promulgation
of these methods is intended to standardize analytical methods within specific industrial
categories and across industries.
EPA has promulgated analytical methods for monitoring pollutant discharges at 40 CFR
Part 136, and has promulgated methods for analytes specific to given industrial categories
at 40 CFR Parts 400 to 480. In addition to the methods developed by EPA and
promulgated at 40 CFR Part 136, certain methods developed by others1, have been
incorporated by reference into 40 CFR Part 136. Methods not promulgated or
incorporated by reference at 40 CFR Part 136 are being proposed for inclusion in
40 CFR Part 439 to support regulation of the discharges from the pharmaceutical
manufacturing industry. For this proposed rule, EPA intends to regulate the
conventional pollutants, BODS and TSS; certain priority pollutants (toxic pollutants); and
certain nonconventional pollutants that are not identified as priority pollutants or
conventional pollutants as identified in Section 6. Table 18-1 lists the priority pollutants,
conventional pollutants, and nonconventional pollutants proposed for regulation along
with their Chemical Abstracts Service Registry Numbers (CASRNs).
'For example, the American Public Health Association publishes Standard Methods for the Examination of Water and Wastewater.
18-1
-------
Section 18.2 describes the analytical methods used by EPA for gathering data on waste
streams produced by the pharmaceutical manufacturing industry. Section 18.3 provides a
description of the analytical methods proposed for compliance monitoring of
pharmaceutical manufacturing industry wastewaters.
18.2
Analytical Methods Used By EPA For Data Gathering
The Agency acquired data on the presence and concentration of approximately 400
analytes during 18 sampling episodes and pilot studies conducted during a 10-year period
from May of 1983 to October of 1993. The data collected during these studies and
information acquired from the Detailed Questionnaire form the basis for regulation of
the analytes listed in Table 18-1 and are used to establish the analytical methods and the
effluent guidelines for these substances. In the following paragraphs, each method used
for data gathering is described; promulgated methods will be referenced. Any
modifications to the referenced methods for individual analytes are also described.
18.2.1
Conventional Pollutants and COD
Conventional pollutants and COD were determined using the EPA methods listed in 40
CFR Part 136.(1) Table 18-2 lists these methods.
18.2.2
Priority Pollutants
Table 18-3 lists the analytical methods used to determine the presence and concentration
of the priority pollutants proposed for regulation. Methods 1624, 1625, 335.2, and 335.3
are promulgated methods (2) and are not further described here.
18-2
-------
18.2.3
Nonconventional Pollutants
Table 18-4 lists the analytical methods used to determine the presence and concentration
of the nonconventional pollutants proposed for regulation. Methods 1624, 1625, 8015
(3), and 350.2 (1) are promulgated methods and not further described here.
Modification of a promulgated method is indicated in the "Notes" column; these method
modifications are described in Sections 18.2.3.1 through 18.2.3.3. EPA did not perform
analytical testing for 16 of the nonconventional pollutants listed in Table 18-4 (indicated
by "No EPA Analysis" in the method column).
18.2.3.1
Methods 1624 and 1625; Reverse Search
Qualitative analysis of pollutants using gas chromatography/mass spectrometry (GC/MS)
is performed in one of three ways. The primary method of identification uses an
authentic standard. The GC/MS system is calibrated and the mass spectrum and
retention time for each standard are stored in a user-created library. A pollutant is
positively identified when its retention time and mass spectrum agree with the laboratory
retention time and spectrum. The second method of qualitative analysis, reverse search,
can be used when authentic standards are not available and the pollutant was not
identified by the method described above. The unknown pollutant is considered
identified if its retention time and mass spectrum agree with those specified in the
method. The third method of qualitative analysis produces a list of analytes called
"tentatively identified compounds (TICs)." For chromatographic peaks that have not
been identified by comparison to an authentic standard and for which reverse search is
unsuccessful, the background corrected spectrum at the peak maximum is compared with
spectra in the NIST2/EPA/NIH Mass Spectral File.(4) Tentative identification is
established when the spectrum agrees with one from this file.
' National Institute of Standards and Technology.
18-3
-------
Quantitative analysis of pollutants using GC/MS is performed in one of four ways using
the extracted ion current profile (EICP) areas. The preferred method of quantitation is
applicable to pollutants for which authentic standards and labeled analogs are available.
(A labeled analog is a compound in which one or more of the constituent atoms has
been replaced with a stable isotope such as deuterium or carbon-13.) In this method,
the GC/MS system is calibrated and the analyte concentration is determined using an
isotope dilution technique. A second, method can be used when authentic standards are
available, but labeled analogs are not. In this case, the GC/MS instrument is calibrated
and the pollutant concentration is determined by using an internal standard technique.
For reverse search pollutants, compound concentrations are determined by using known
response factors. For TICs, pollutant concentration is determined using the sum of the
EICP areas relative to the sum of the EICP areas of the nearest eluted internal standard.
18.2.3.2
Method 1624; Hot Purge
Analyses were performed as specified in Method 1624 with the following exception. If
the solids content of the sample was known or determined to be less than one percent,
stable isotopically labeled analogs of the compounds of interest were added to a five-
milliliter sample and the sample was purged with an inert gas at 40 °C in a chamber
designed for water samples. If the solids content was greater than one percent, five
milliliters of reagent water and the labeled analogs were added to a five-gram aliquot
and the. mixture was purged at 40°C in a chamber designed for soil or water samples. In
the purging process, the volatile compounds are transferred from the aqueous phase into
the gaseous phase and trapped on a sorbent column. After purging is completed, the
trap is back flushed and rapidly heated to desorb the compounds for GC/MS analysis.
18-4
-------
18.2.3.3 Method 80153; Hot Purge
Analyses were performed as specified, in Method 8015 using the purge and trap sample
introduction (Method 5030) with the following exception. An inert gas was bubbled
through the solution at 40 °C, instead of the temperature specified in Method 8015, and
the volatile components were transferred from the aqueous phase to the vapor phase.
The vapor was swept through a sorbent column where the volatile components were
trapped. After purging was completed, the sorbent column was heated and backflushed
with inert gas to desorb the volatile components onto the chromatographic column.
18.3
Methods Proposed For Monitoring
Promulgated methods exist for all of the conventional pollutants and the priority
pollutants. Seven nonconventional pollutants (COD, ammonium hydroxide (ammonia as
N), acetone, 2-butanone, diethylether, p-dioxane, and a-picoline) have promulgated
analytical methods. The Agency will require the use of these promulgated methods,
newly developed Method 1665 for a-picoline, or equivalent methods4, for purposes of
compliance monitoring by the pharmaceutical manufacturing industry. Table 18-5 lists
these pollutants and the promulgated analytical methods.
EPA has developed analytical procedures for all of the nonconventional pollutants that
do not have methods published in 40 CFR Part 136. Two nonconventional pollutants
that were considered for regulation for which analytical methods have not been
developed are bis(chloromethyl)ether and dimethylcarbamyl chloride. These substances
are rapidly hydrolyzed in aqueous solution and therefore cannot be detected in
3 Neither Method 8015 nor other SW-846 methods are promulgated at 40 CFR 136 for NPDES compliance monitoring purposes.
Method 8015 was used in this initial screening of the pharmaceutical manufacturing industry.
4 Alternate and equivalent test procedures are defined in 40 CFR 136.3(a). 136.4, and 136.5; in the preamble to promulgation of the
40 CFR 136, Appendix A methods (49 FR 43234); and in the text of the 40 CFR 136 Appendix A methods.
18-5
-------
wastewater analyses. The Agency is, therefore, not proposing these pollutants for
regulation but will monitor concentrations of their hydrolysis products (formaldehyde (5)
and dimethylamine (6), respectively). The half-life for bis(chloromethyl)ether in water
has been reported as 10-38 seconds.(7)
Table 18-6 lists those pollutants for which new analytical methods have been developed
and provides a reference to those methods.(8) The pharmaceutical manufacturing
industry will be allowed to use these methods for compliance monitoring.
18.3.1 Methods Development for Monitoring of Pharmaceutical Manufacturing
Industry Effluents
Many of the non-conventional pollutants that may be released from the pharmaceutical
manufacturing industry are not included in methods previously promulgated for
monitoring effluents from other industries. For this reason it has been necessary to
develop methods for these pollutants. Many of the pharmaceutical manufacturing
industry effluents present difficult analytical challenges. Some are amenable to
extraction from aqueous solution and can be analyzed by GC/MS after extraction and
concentration. Method 1665 has been developed for these analytes. Others may be
concentrated by purging from aqueous solution and trapping in a column containing
sorbent material. For these substances, purge-and-trap followed by GC/MS analysis as
described in Method 1666 was developed. Some highly water soluble pharmaceutical
manufacturing industry analytes, however, cannot be extracted from aqueous solution and
cannot be efficiently purged from water. For this reason, it was necessary to develop a
direct aqueous injection gas chromatography (GC) option for Method 1666. in some
cases, a GC with a flame ionization detector (GC/FID) provides better performance
than GC/MS for the non-purgeable, water soluble analytes. Method 1671, using
GC/FID was developed for these analytes. Formaldehyde is not extractable from water
and cannot be readily analyzed by either purge-and-trap GC/MS or direct aqueous
injection. For this reason a separate approach, Method 1667 utilizing derivatization
18-6
-------
followed by high pressure liquid chromatography (HPLC), was developed for
formaldehyde and the other aldehydes included in the pharmaceutical manufacturing
industry analyte list. Poly(ethylene glycbl)-600 (PEG-600) is a mixture of ethylene glycol
oligomers with a molecular weight centered around 600 Da. GC/MS analysis was
attempted for this pollutant without success. At 200 parts-per-million (ppm), under
conditions used for Method 1665, constituents of PEG-600 were not detected. At 2000
ppm constituents of PEG-600 were detected by the GC/MS system, but with an
extremely low response that was not suitable for quantitation. At higher concentrations,
damage to the analytical system is likely. For these reasons, Method 1673, a
derivatization/HPLC method, was developed for PEG-600. Methods 1665, 1666, 1667,
1671 and 1673 are briefly described below. A complete description of the methods can
be found in the Methods Compendium.(8)
18.3.1.1
Method 1665
Method 1665 entitled "Semi-Volatile Organic Compounds Specific to the Pharmaceutical
Manufacturing Industry by Isotope Dilution GC/MS" is proposed for compliance
monitoring by the pharmaceutical manufacturing industry. The method is based upon
Method 1625, Revision C.
Using Method 1665 the percent solids content of a sample is determined and stable
isotopically labeled analogs of the compounds of interest are added to the sample. If the
solids content of the sample is less than one percent, a one liter sample is extracted at
pH 12-13 with methylene chloride using continuous extraction techniques. If the solids
content is greater than one percent but less than 30 percent, the sample is diluted to one
percent solids with reagent water, ultrasonically homogenized, and extracted as described
for a sample with less than one percent solids. If the solids content is greater than 30
percent, the sample is extracted using ultrasonic techniques.
18-7
-------
Each extract is dried over anhydrous sodium sulfate, concentrated to a volume of five
milliliters, cleaned up using gel permeation chromatography (GPC), if necessary, and
concentrated. Extracts are concentrated to one rnilliliter if GPC is not performed, and
to 0.5 rnilliliter if GPC is performed. An internal standard is added to the extract, and
an aliquot of the extract is injected into the gas chromatograph. The compounds are
separated on the GC and detected by a mass spectrometer.
Analyte concentrations for substances with labeled analogs are determined by
comparison of the extracted ion current profile (EICP) areas with those of the labeled
analogs. Concentrations of analytes without labeled analogs are determined by
comparison of EICP areas with an internal standard.
18.3.1.2
Method 1666
Method 1666 entitled "Volatile Organic Compounds Specific to the Pharmaceutical
Manufacturing Industry by Isotope Dilution GC/MS" is proposed for compliance
monitoring by the pharmaceutical manufacturing industry. The method is based, in part,
upon Method 1624, Revision C. The method description is separated into two parts; the
first part describes the purge-and-trap technique, and the second part describes direct
aqueous injection.
Method 1666 - Purse-and-Trap
The percent solids content of the sample is determined. If the solids content is known or
determined to be less than 1 percent, stable isotopically labeled analogs of the
compounds of interest are added to a 5-milliliter (mL) sample and the sample is purged
with an inert gas at 45 degrees Celsius in a chamber designed for soil or water samples.
In the purging process, the volatile compounds are transferred from the aqueous phase
into the gaseous phase where they are passed into a sorbent column and trapped. For
higher solids samples, five grams of solid is weighed into the purging device and five mL
18-8
-------
of reagent water and the stable isotopically labeled analogs are added before purging.
After purging is completed, the trap is backflushed and heated rapidly to desorb the
compounds into a gas chromatograph where they are separated and detected by a mass
spectrometer. The labeled compounds .serve to correct the variability of the analytical
technique.
Method 1666 - Direct Aqueous Injection
The percent solids content of the sample is determined. If the solids content is known or
determined to be less than 1 percent, stable isotopically labeled analogs of the
compounds of interest are added to a sample. If the solids content of the sample is
greater than one percent, five mL of reagent water and the labeled compounds are
added to a 5-gram aliquot of sample. The mixture is sonicated in a centrifuge tube with
little or no headspace for five minutes. During this period the native analytes and
labeled analogs will equilibrate between the solid and aqueous phases. In some cases,
additional sonification may be necessary to establish equilibrium.
If necessary, the low solids sample may be centrifuged for clarification. High solids
samples will be centrifuged to provide a clear supernate. An aliquot of the aqueous
solution (or supernate) is injected into the GC/MS system. The compounds are
separated by the GC and detected by the mass spectrometer. The labeled compounds
serve to correct the variability of the analytical technique.
18.3.1.3
Method 1667
Method 1667 entitled "Formaldehyde, Isobutyraldehyde, and Furfural by Derivatization
and High Pressure Liquid Chromatography" is proposed for compliance monitoring by
the pharmaceutical manufacturing industry. This method is based on draft Method
8315.(3)
18-9
-------
For pharmaceutical manufacturing industry wastes comprised of solids or for aqueous
wastes containing significant amounts of solid material, the aqueous phase, if any, is
separated from the solid phase and stored for later analysis. If necessary, the particle
size of the solids in the waste is reduced. Twenty-five grams of the solid phase is
extracted with 500 rnilliliters of extraction fluid5. The extraction fluid employed is a
function of the alkalinity of the solid phase of the waste. Following extraction, the
aqueous extract is separated from the solid phase by filtration employing a glass fiber
filter.
If compatible (i.e., multiple phases will not form on combination), the initial aqueous
phase of the pharmaceutical manufacturing industry waste is added to the aqueous
extract, and these liquids are analyzed together. If incompatible, the liquids are analyzed
separately and the results are mathematically combined to yield a volume-weighted
average concentration.
A measured volume of aqueous sample or an appropriate amount of solids leachate is
buffered to pH = 5 and derivatized with 2,4-dinitrophenylhydrazine (DNPH), using
either a solid sorbent or methylene chloride derivatization/extraction option. If the solid
sorbent option is used, the derivative is extracted using solid sorbent cartridges, followed
by elution with ethanol. If the methylene chloride option is used, the derivative is
extracted with methylene chloride, the methylene chloride extracts are concentrated
using the Kuderna-Danish procedure and solvent exchanged into methanol prior to high
pressure liquid chromatographic analysis. Liquid chromatographic conditions are utilized
that permit the separation and measurement of the derivatized pharmaceutical
manufacturing industry analytes in the extract by absorbance detection at 365
nanometers.
1 A proportionally smaller amount of extraction fluid is used it' Ics-s solid phase is available.
18-10
-------
Quantitation of the pharmaceutical manufacturing industry analytes is performed by an
external standard technique. Known concentrations of the pharmaceutical manufacturing
industry analytes are carried through the derivatization/extraction procedure and peak
areas at 365 nanometers measured. The peak areas of the standards are plotted against
concentration of the original aldehydes and the samples quantified by comparison to the
standards. Precision and accuracy of the procedure is assured by use of careful quality
assurance and quality control techniques including analysis of initial precision and
recovery standards and ongoing precision and accuracy samples. Matrix spike and matrix
spike duplicate analyses are performed, when appropriate.
18.3.1.4
Method 1671
Method 1671 "Volatile Organic Compounds Specific to the Pharmaceutical
Manufacturing Industry by GC/FID" is proposed for compliance monitoring by the
pharmaceutical manufacturing industry. The method was developed because some of the
non-purgeable, water-soluble pharmaceutical manufacturing industry analytes did not
perform well in GC/MS investigations.
For aqueous samples, one or more internal standard is added to a 5 mL aliquot. If the
solids content of the sample is known or determined to be greater than 1 percent, 5 mL
of reagent water is added to a 5 gram sample along with the internal standard(s). This
mixture is sonicated for five minutes in a centrifuge tube and the resulting equilibrated
sample centrifuged. An appropriate amount of aqueous solution or supernate is injected
into the GC/FDD system. Identification is based on gas chromatographic retention time
and quantitation is performed by an internal standard technique. Precision and accuracy
of the Method is assured by use of careful quality assurance and quality control
techniques including analysis of blanks, use of calibration solutions, and matrix spike and
matrix spike duplicate analysis.
18-11
-------
18.3.1.5
Method 1673
Method 1673 entitled "Poly(ethylene glycol)-600 by Derivatization and High Pressure
Liquid Chromatography" is proposed for compliance monitoring by the pharmaceutical
manufacturing industry. Derivatization of the PEG-600 polymeric mixture with a
substance that absorbs in the ultraviolet (UV) provides increased sensitivity over other
methods of determination and allows quantitation at one part-per-million.
?
This method has been developed for aqueous samples and is not, in its present form,
applicable to solids or sludges. One liter of aqueous sample is placed into a liquid-liquid
extractor and a known quantity of surrogate is added. Extraction with dichloromethane
is carried out for an 18-hour period. The dichloromethane extracts are dried over
anhydrous sodium sulfate, evaporated to a small volume and dried again. The water-free
extract is derivatized using 3,5-dinitrobenzoyl chloride and pyridine. The derivatized
extract is treated with water to hydrolyze excess derivatization reagent. The extract is
diluted with diethyl ether (ether), washed with acid and base, and the ether evaporated.
The remaining is solvent exchanged with acetonitrile/water and chromatographed on a
reverse-phase C18 column with a solvent gradient of 40% acetonitrile/water to 100%
acetonitrile. Detection is performed at 254 nanometers. The PEG-600 derivative is
identified by its retention tune relative to that of the surrogate and quantified by external
standard techniques. Derivatized samples must be stored at 4°C in an amber container
and analyzed within 96 hours of preparation.
Because PEG-600 is a mixture of poly(ethylene glycol) oligomers (polymers containing
relatively few structural units), the exact nature of PEG-600 samples from various
manufacturers and different batches from a single manufacturer may vary. For this
reason, concentrations of PEG-600 in a specific waste stream are best determined when
standards are prepared using the same batch of PEG-600 in use by the pharmaceutical
manufacturer at the time of discharge to the waste stream under analysis. Where it is
not possible to obtain a discharge-specific PEG-600 standard, adequate results can be
18-12
-------
obtained by use of a PEG-600 standard that is not related to the pharmaceutical
manufacturing waste stream under analysis and careful definition of an "elution range"6
for PEG-600 in both external standards and samples.
18.3.1.6
Modified ASTM Method D3695-88
ASTM Method D3695-88 entitled "Standard Test Method for Volatile Alcohols in Water
by Direct Aqueous-Injection Gas Chromatography" (9), modified as described below, is
proposed as an alternative to Method 1671 .for compliance monitoring for methanol,
ethanol, and n-propanol in the pharmaceutical manufacturing industry. This modified
Method is proposed because it may offer lower quantitation limits than proposed
Method 1671 for these alcohols under some circumstances. Because ASTM methods in
general, and ASTM Method D3695-88 in particular, do not incorporate the quality
assurance/quality control standards found in methods used for filing applications and
compliance monitoring under the NPDES, ASTM Method D3695-88 is modified by
incorporation of certain of these quality control/ quality assurance procedures and their
respective numerical standards and limits described in Method 1671. The following
procedures and corresponding Section in Method 1671 are incorporated into ASTM
Method D3695-88 for purposes of analyses pursuant to NPDES permits:
Operation of a formal quality assurance program (Section 9.1);
Analysis of a matrix spike (MS) and a matrix spike duplicate (MSD)
and adherence to the relative percent difference (RPD) standard
listed and the recovery limits found in Table 3 (Section 9.3);
Analysis of blanks (Section 9.4);
Initial precision and accuracy, limited to methanol, ethanol, and n-
propanol using the acceptance criteria found in Table 3
(Section 9.5);
sAn "elution range" is defined as a characteristic period of time during which the derivatized PEG-600 elutes from the
chromatographic column. This range should encompass at least W) percent of the PEG-600 derivative in both the standard and sample.
18-13
-------
Analysis of field replicates (Section 9.7);
Record keeping (Section 9.8); and
Ongoing accuracy, using the acceptance criteria found in Table 3
(Section 13.1).
18.4
Tables 18-1 through 18-7 provide additional information for each of the analytes
proposed for the pharmaceutical manufacturing industry. Table 18-1 provides the list of
analytes proposed for regulation with their chemical abstracts service registry numbers.
Tables 18-2, 18-3, and 18-4 provide the analytical methods used for determination of
conventional pollutants (and COD), priority pollutants, and nonconventional pollutants,
respectively, in the studies leading up to the proposed rule supported by this document.
Table 18-5 provides a list of the pharmaceutical manufacturing industry analytes with
promulgated analytical methods while Table 18-6 provides a list of nonconventional
pharmaceutical manufacturing industry analytes and the methods proposed for their
determination. Table 18-7 provides a list of the pharmaceutical manufacturing industry
analytes along with their respective minimum levels (MLs). In some cases, more than
one ML is provided for an analyte in this table when more than one proposed method
may be used for its determination.
18-14
-------
Table 18-1
Pollutants Proposed for Regulation
Proposed Pollutant
CASRN
Conventional Pollutants
Biological Oxygen Demand (BOD5)
pH
Total suspended nonfilterable solids (TSS)
C-002
C-006
C-009
(a)
(a)
(a)
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane
Cyanide, Total
o-Dichlorobenzene
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
71-43-2
108-90-7
67-66-3
74-87-3
57-12-5
95-50-1
107-06-2
75-09-2
108-95-2
108-88-3
Nonconventional Pollutants
Acetone
Acetonitrile
Ammonia (Ammonium hydroxide)
Amyl acetate
Amyl alcohol
Aniline
2-Butanone
n-Butyl acetate
67-64-1
75-05-8
1336-21-6
628-63-7
71-41-0
62-53-3
78-93-3
123-86-4
18-15
-------
Table 18-1
(Continued)
Proposed Pollutant
n-Butyl alcohol
tert-Butyl alcohol
Chemical Oxygen Demand (COD)
Cyclohexane
Diethylamine
Diethylether
N.N-Dimethylacetarnide
Dimethylamine
N,N-Dimethylaniline
N,N-Dimethylfonnamide
Dimethylsulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane (b)
n-Hexane (b)
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropylether
CASRN
71-36-3
75-65-0
C-004 (a)
110-82-7
109-89-7
60-29-7
127-19-5
124-40-3
121-69-7'
68-12-2
67-68-5
123-91-1
64-17-5
141-78-6
107-21-1
50-00-0
75-12-7
98-01-1
142-82-5
110-54-3
78-84-2
67-63-0
108-21-4
108-20-3
18-16
-------
Table 18-1
(Continued)
Proposed Pollutant
Methanol
Methylamine ,
Methyl cellosolve (2-methoxyethanol)
Methyl formate
Methylisobutyl ketone
2-Methylpyridine (a-picoline)
Petroleum naphtha (b)
Poly(ethylene glycol)-600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
m-Xylene
o-Xylene
p-Xylene
CASRN
67-56-1
74-89-5
109-86-4
107-31-3
108-10-1
109-06-8
8030-30-6
25322-68-3
71-23-8
110-86-1
109-99-9
75-69-4
121-44-8
108-38-3
95-47-6
106-42-3
(a) These are synthetic CASRNs designed for use with the Environmental Monitoring Methods Index (EMMI).
(b) Petroleum naphtha concentration will be estimated as the sum of the concentrations of n-pentane, n-hexane, and n-heptane.
18-17
-------
Table 18-2
Analytical Methods Used for Determination of
Conventional Pollutants and COD
Pollutant (Synthetic CASRN)
BOD5 (C-002)
COD (C-004)
pH (b)(C-006)
TSS (C-009)
Method
405.1
410.1, 410.2,
410.3 (a), 410.4
150.1
160.2
(a) May be used in saline waters.
(b) The Agency is not reproposing pH limitations under BPT, but the previously promulgated method is listed here for convenience.
18-18
-------
Table 18-3
Analytical Methods Used for Determination of Priority Pollutants
Priority Pollutant (CASRN)
Benzene (71-43-2)
Chlorobenzene (108-90-7)
Chloroform (67-66-3)
Chloromethane (74-87-3)
Cyanide, Total (57-12-5)
o-Dichlorobenzene (95-50-1)
1,2-Dichloroethane (107-06-2)
Methylene chloride (75-09-2)
Phenol (108-95-2)
Toluene (108-88-3)
Method
1624
1624
1624
1624
335.2, 335.3
1625
1624
1624
1625
1624
18-19
-------
Table 18-4
Analytical Methods Used for Determination of Nonconventional Pollutants
Nonconventional Pollutant (CASRN)
Acetone (67-64-1)
Acetonitrile (75-05-8)
Ammonium hydroxide (1336-21-6)
n-Amyl acetate (628-63-7)
n-Amyl alcohol (71-41-0)
Aniline (62-53-3)
2-Butanone (78-93-3)
n-Butyl acetate (123-86-4)
n-Butyl alcohol (71-36-3)
tert-Butyl alcohol (75-65-0)
Cyclohexane (110-82-7)
Diethylamine (109-89-7)
Diethylether (60-29-7)
N,N,-Dimethylacetamide (127-19-5)
Dunethylamine (124-40-3)
N,N-DimethylanUine (121-69-7)
N,N-Dimethylfonnamide (68-12-2)
Dimethylsulfoxide (67-68-5)
1,4-Dioxane (123-91-1)
Ethanol (64-17-5)
Method
1624
1624
350.2
No EPA Analysis
No EPA Analysis
1625
1624
No EPA Analysis
1624
8015
8015
1624
8015
8015
No EPA Analysis
No EPA Analysis
1624
No EPA Analysis
No EPA Analysis
No EPA Analysis
1625
No EPA Analysis
1624
1624
8015
8015
Notes
Reverse search
Hot purge
Hot purge
Direct injection (a)
Hot purge
Hot purge
Direct injection (a)
Reverse search
Hot purge
Hot purge
Direct injection (a)
18-20
-------
Table 18-4
(Continued)
Nonconventional Pollutant (CASRN)
Ethyl acetate (141-78-6)
Ethylene glycol (107-21-1)
Formaldehyde (50-00-0)
Formamide (75-12-7)
Furfural (98-01-1)
n-Heptane (142-82-5)
n-Hexane (110-54-3)
Isobutyraldehyde (78-84-2)
Isopropanol (67-63-0)
Isopropyl acetate (108-21-4)
Isopropylether (108-20-3)
Methanol (67-56-1)
Methylamine (74-89-5)
Methyl cellosolve (109-86-4)
Methyl formate (107-31-3)
Methylisobutyl ketone (108-10-1)
2-Methylpyridine (109-06-8)
Petroleum naphtha (8030-30-6)
Polyethylene glycol 600 (25322-68-3)
Method
8015
No EPA Analysis
HPLC
No EPA Analysis
No EPA Analysis
1624
1624
No EPA Analysis
1624
8015
8015
8015
1624
8015
8015
1624
8015
8015
No EPA Analysis
No EPA Analysis
8015
1624
1625
1624
No EPA Analysis
Notes
Direct injection (a)
Region IX method
(precursor to method
8315)
Reverse search
Reverse search
Hot purge
Hot purge
Direct injection (a)
Direct injection (a)
Hot purge
Hot purge
Direct injection (a)
Hot purge
Hot purge
Direct injection (a) •
Direct injection (a)
Reverse search
Reverse search
18-21
-------
Table 18-4
(Continued)
Nonconventional Pollutant (CASRN)
n-Propanol (71-23-8)
Pyridine (110-86-1)
Tetrahydrofuran (109-99-9)
Trichlorofluoromethane (75-69-4)
Triethylamine (121-44-8)
m-Xylene (108-38-3)
o-Xylene (95-47-6)
p-Xylene (106-42-3)
Method
1624
8015
8015
1625
1624
1624
1624
1624
1624
1624
Notes
Hot purge
Hot purge
Direct injection (a)
Reverse search
Reverse search
Reverse search
Reverse search
Reverse search
Reverse search
Reverse search
(a) Two sample introduction techniques are listed in the method: 5020 is direct injection of a headspace sample and 5030 is purge and
trap. The former method was used here.
18-22
-------
Table 18-5
Pollutants From the Pharmaceutical Manufacturing Industry
With Promulgated Analytical Methods
Pollutant (CASRN)
Acetone (67-64-1)
Ammonia (Ammonium
hydroxide) (1336-21-6)
Benzene (71-43-2)
BOD5 (C-002) (a)
2-Butanone (78-93-3)
Chlorobenzene (108-90-7)
Chloroform (67-66-3)
Chloromethane (74-87-3)
COD (C-004) (a)
Cyanide, Total (57-12-5)
o-Dichlorobenzene (95-50-1)
1,2-Dichloroethane (107-06-2)
Diethylether (60-29-7)
1,4-Dioxane (123-91-1)
Methylene chloride (75-09-2)
pH (b) (C-006) (a)
Phenol (108-95-2)
a-Picoline (2-
Methylpyridine)(109-06-8)
Toluene (108-88-3)
TSS (C-009) (a)
Promulgated Analytical
Method
1624B
350.1, 350.2, 350.3
(Ammonia as N)
1624B
405.1
1624B
1624B
1624B
1624B
410.1, 410.2, 410.3, 410.4
335.2, 335.3
1625B
1624B
1624B
1624B
1624B
150.1
1625B
1625B
1624B
160.2
Reference
40 CFR 136, Appendix A
40 CFR Part 136
40 CFR 136, Appendix A
40 CFR Part 136
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR Part 136
40 CFR Part 136
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR Part 136
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR 136, Appendix A
40 CFR Part 136
(a) These are synthetic CASRNs designed for use with the Environmental Monitoring Methods Index (EMMI).
(b) The Agency is not reproposing pH limitations under BPT, but the previously promulgated method is listed here for convenience.
18-23
-------
Table 18-6
Nonconventional Pharmaceutical Manufacturing Industry Pollutants and
Proposed Analytical Methods
Nonconventional Pollutant (CASRN)
Acetonitrile (75-05-8)
n-Amyl acetate (628-63-7)
n-Amyl alcohol (71-41-0)
Aniline (62-53-3)
n-Butyl acetate (123-86-4)
n-Butyl alcohol (71-36-3)
tert-Butyl alcohol (75-65-0)
Cyclohexane (110-82-7)
Diethylamine (109-89-7)
N,N-Dimethylacetamide (127-19-5)
Dimethylamine (124-40-3)
N,N-Dimethylaniline (121-69-7)
N,N-Dimethylformamide (68-12-2)
Dimethylsulfoxide (67-68-5)
Ethanol (64-17-5)
Ethyl acetate (141-78-6)
Ethylene glycol (107-21-1)
Formaldehyde (50-00-0)
Proposed Analytical Method
1666
1671
1666
1666
1665
1666
1666
1666
1666
1666
. • 1671
1665
1666
1671
' 1665
1665
1666
1671
1666
1671
Modified ASTM
D3695-88
1666
1666
1671
1667
18-24
-------
Table 18-6
(Continued)
Nonconventional Pollutant (CASRN)
Formamide (75-12-7)
Furfural (98-01-1)
n-Heptane (a) (142-82-5)
n-Hexane (a) (110-54-3)
Isobutyraldehyde (78-84-2)
Isopropanol (67-63-0)
Isopropyl acetate (108-21-4)
Isopropylether (108-20-3)
Methanol (67-56-1)
Methylamine (74-89-5)
Methyl cellosolve (2-methoxyethanol)( 109-86-4)
Methyl formate (107-31-3)
Methylisoburyl ketone (108-10-1)
2-Methylpyridine (a-picoline)( 109-06-8)
Petroleum naphtha (a) (8030-30-6)
Polyethylene glycol 600 (25322-68-3)
n-Propanol (71-23-8)
Proposed Analytical Method
1666
1671
1666
1667
. 1666
1666
1666
1667
1666
1666
1666
1666
1671
Modified ASTM -
D3695-88
1666
1671
1666
1671
1666
1666
1665
1666
1673
1666
1671
Modified ASTM -
D3695-88
18-25
-------
Table 18-6
(Continued)
Nonconventional Pollutant (CASRN)
Pyridine (110-86-1)
Tetrahydrofuran (109-99-9)
Trichlorofluoromethane (75-69-4)
Triethylamine (121-44-8)
m,p-Xylene (108-38-3 and 106-42-3)(b)
o-Xylene (95-47-6)
Proposed Analytical Method
1665
1666
1666
1666
1671
1666
1666
(a) Petroleum naphtha concentration will be estimated as the sum of the concentrations of n-pentane, n-hexane, and n-heptane.
(b) m-Xylenc and p-xylene elute together and are indistinguishable in the analytical system.
18-26
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Table 18-7
Proposed and Promulgated MLs for Pharmaceutical
Manufacturing Industry Pollutants
Proposed Pollutant
Proposed or
Promulgated
Analytical Method
ML*
units/Liter0
Conventional Pollutants
Biological Oxygen Demand (BOD5)
pH
Total suspended nonfilterable solids (TSS)
405.1
150.1
160.2
2mgd
NA
4mg6
Priority Pollutants
Benzene
Chlorobenzene
Chloroform
Chloromethane
Cyanide, Total
o-Dichlorobenzene
1,2-Dichloroethane
Methylene chloride
Phenol
Toluene
1624B
1624B
1624B
1624B
335.2
335.3
1625B
1624B
1624B
1625B
1624B
10 Mg
lOpg
10 Mg
50 ^
20 Mgf
5/*gg
10 Mg
10 Mg
10 ng
10 Mg
10 Mg
Nonconventional Pollutants
Acetone -\ /
Acetonitrile
Ammonia (Ammonium hydroxide)
Amyl acetate
Amyl alcohol
1624B
1666
1671
350.1
350.2
350.3
1666
1666
50 Mg
5 mg
50 mg
10 n£
50 Mg5
30 ^
$Mg
500 Mg
18-27
-------
Table 18-7
(Continued)
Proposed Pollutant
Aniline
2-Butanone
n-Butyl acetate
n-Butyl alcohol
tert-Butyl alcohol
Chemical Oxygen Demand (COD)
Cyclohexane
Diethylamine
Diethylether
N,N-Dimethylacetamide
Dimethylamine
N,N-Dimethylam'line
N,N-Bimethylformamide
Dimethylsulfoxide
1,4-Dioxane
Ethanol
Ethyl acetate
Proposed or
Promulgated
Analytical Method
1665
1624B
1666
1666
1666
410.1
410.2
410.3
410.4
1666
1666
1671
1624B
1665
1666
1671
1665
1665
1666
1671
1624B
1666
1671
Modified ASTM
D3695-88
1666
ML*
units/Liter6
2/*g
50 Mg
5 jig
500 Mg
100 Mg
NA
NA
NA
NA
5/tg
200 mg
50 mg
50 Mg
50 Mg
200 mg
50 mg
10 Mg
5/*g
100 mg
20 mg
50 Mg
20 mg
50 mg
lmgh
10 Mg
18-28
-------
Table 18-7
(Continued)
Proposed Pollutant
Ethylene glycol
Formaldehyde
Formamide
Furfural
n-Heptane (b)
n-Hexane (b)
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropylether
Methanol
Methylamine
Methyl cellosolve (2-methoxyethanol)
Methyl formate
Methylisobutyl ketone
2-Methylpyridine (a-picoline)
n-Pentane (b)
Proposed or
Promulgated
Analytical Method
1666
1671
1667
1666
1671
1666
1667
1666
1666
1666
1667
1666
1666
1666
1666
1671
Modified ASTM
D3695-88
1666
1671
1666
1671
1666
1666
1625B
1665
1666
ML*
units/Liter"
200 mg
100 mg
50 Mg
1000 mg
100 mg
500 Mg
50 Mg
10 Mg
10 ^g
10 Mg
50 Mg
200 Mg
10 Mg
SM§
50 mg
50 mg
Img"
200 mg
50 mg
50 mg
20 mg
100 Mg
10 Mg
50 Mg
$Mg
10 Mg
18-29
-------
Table 18-7
(Continued)
Proposed Pollutant
Petroleum naphtha (b)
Poly(ethylene glycol)-600
n-Propanol
Pyridine
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
m,p-Xylene
o-Xylene
Proposed or
Promulgated
Analytical Method
1666
1673
1666
1671
Modified ASTM
D3695-88
1665
1666
1666
1666
1671
1666
1666
ML*
units/Liter0
30 Mg
1 mg
20 mg
50 mg
lmgh
5f*g
20 Mg
10 Mg
200 mg
50 mg
10 Mg
5^g
(a) The minimum level at which the entire analytical system shall give a recognizable signal and acceptable
calibration points, taking into account method-specific sample and injection volumes. The ML is often
calculated as 3.18 times the method detection limit (MDL). The ML was promulgated in 1984 at 40 CFR
Part 136, Appendix A.
(b) Petroleum naphtha concentration will be estimated as the sum of the concentrations of n-pentane, n-
hexane, and n-heptane.
(c) Units are either milligrams (mg) per liter or micrograms (Mg) per liter. NA indicates that an ML is not
applicable or that no ML is given in the method listed.
(d) "[Established by the requirement for a minimum DO [dissolved oxygen] depletion of 2 mg/L."
(e) This is the lower end of the "practical range of the determination."
(f) The method is stated to be "sensitive to about 0.02 mg/L."
(g) This is the lower end of the "applicable range."
(h) The method states that the analytes can be "detected quantitatively in water and waste water at a
minimum detection limit of 1 mg/L."
18-30
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REFERENCES
1. U.S. Environmental Protection Agency, Environmental Monitoring Systems
Laboratory. Methods for Chemical Analysis of Water and Wastes. EPA-600/4-
79-020, Cincinnati, Ohio, Revised March 1983 and 1979 where applicable.
2. 40 CFR Part 136, and 40 CFR Part 136, Appendix A.
3. U.S. Environmental Protection Agency. Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods, Second Edition, as amended (1984). EPA
Publication SW-846. NTIS Document No. PB87-120-291.
4. U.S. National Bureau of Standards, National Standard Reference Data System.
Mass Spectral Tape Format. 1979, and later attachments.
5. Tou, J.C. Journal of Physical Chemistry, 78(11):1096-1098, 1974.
6. Queen, A. Kinetics of the Hydrolysis of Acyl Chlorides in Pure Water. Can. J.
Chem. 45:1619 - 29 (1967).
7. Howard, Philip H. Handbook of Environmental Fate and Exposure Data. Vol. I.
Lewis Publishers, Inc., Chelsea, Michigan, 1989. p. 92.
8. U.S. Environmental Protection Agency. Analytical Methods for the
Determination of Pollutants in Pharmaceutical Manufacturing Industry
Wastewater. U.S. EPA Publication No. EPA-821-B-94-001, February, 1995.
9. "Standard Test Method for Volatile Alcohols in Water by Direct Aqueous-
Injection Gas Chromatography." 1994 Annual Book of ASTM Standards, Volume
11.02 (Water (II)). ASTM, 1916 Race Street, Philadelphia, PA 19103-1187.
18-31
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SECTION 19
GLOSSARY
Pharmaceutical Screener Questionnaire - A short questionnaire distributed by EPA to
all known pharmaceutical facilities in June of 1989 in order to identify plants which
manufacture pharmaceutical products.
Detailed Questionnaire - The 1990 Pharmaceutical Manufacturing Survey. A
questionnaire sent by EPA to certain facilities in the pharmaceutical manufacturing
industry in September 1991 to gather technical and financial information. The
questionnaire was sent to those facilities likely to be affected by promulgation of revised
effluent limitations guidelines, pretreatment standards, and new source performance
standards for this industry.
Administrator - The Administrator of the U.S. Environmental Protection Agency.
Agency - The U.S. Environmental Protection Agency.
Annual average - The mean concentration, mass loading, or production-normalized mass
loading of a pollutant over a period of 365 consecutive days (or such other period of
time determined by the permitting authority to be sufficiently long to encompass
expected variability of the concentration, mass loading, or production-normalized mass
loading at the relevant point of measurement).
Average monthly discharge limitation - The highest allowable average of "daily
discharges" over a calendar month, calculated as the sum of all "daily discharges"
measured during the calendar month divided by the number of "daily discharges"
measured during the month.
Backwashing - The operation of cleaning a multimedia filter by reversing the flow of
water or liquid that is being filtered.
Batch operation - A pharmaceutical manufacturing operation consisting of a series of
operating units which process predetermined specific amounts of materials and carry the
process to completion before starting another cycle.
Bench-scale operation - Laboratory testing of materials, methods, or processes on a small
scale, such as on a laboratory worktable.
BAT - The best available technology economically achievable, as described in Section
304(b)(2) of the Clean Water Act.
19-1
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BCT - The best conventional pollutant control technology, as described in Section
304(b)(4) of the Clean Water Act.
BMP or BMPs - Best management practice(s), as described in Section 304(e) of the
Clean Water Act.
Biological and natural extraction - The chemical and physical extraction of
pharmaceutically active ingredients from natural sources such as plant roots and leaves,
animal glands, and parasitic fungi. The process operations involving biological and
natural extraction define Subcategory B (40 CFR 439, Subpart B).
BOD5 - Five-day biochemical oxygen demand. A measure of biochemical decomposition
of organic matter hi a water sample. It is determined by measuring the dissolved oxygen
consumed by microorganisms to oxidize the organic contaminants in a water sample
under standard laboratory conditions of five days and 20°C. BOD5 is not related to the
oxygen requirements in chemical combustion.
Boiler - Any enclosed combustion device that extracts useful energy in the form of steam
and is not an incinerator.
BPT - The best practicable control technology currently available, as described hi Section
304(b)(l) of the Clean Water Act.
CAA - Clean Air Act. The Air Pollution Prevention and Control Act (42 U.S.C. 7401 et.
seq.), as amended, inter aha, by the Clean Air Act Amendments of 1990 (Public Law
101-549, 104 Stat. 2399).
Chemical synthesis - The process(es) of using a chemical reaction or a series of chemical
reactions to manufacture pharmaceutically active ingredients. The chemical synthesis
process operations define Subcategory C (40 CFR 439, Subpart C).
CFR - Code of Federal "Regulations, published by the U.S. Government Printing Office.
A codification of the general and permanent rules published hi the Federal Register by
the Executive departments and agencies of the federal government. The Code is divided
into 50 titles which represent broad areas subject to federal regulation. Each title is
divided into chapters which usually bear the name of the issuing agency, and each
chapter is divided into parts covering specific regulatory areas. Citations of the Code jof
Federal Regulations include title, part, and section number (e.g., 40 CFR 1.1 - title 40,
part 1, and section 1).
Clarifler - A treatment unit designed to remove suspended materials from wastewater
typically by sedimentation.
19-2
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Closed vent system - A system that is not open to the atmosphere and is composed of
piping, ductwork, connections, and, if necessary, flow-inducing devices that transport gas
or vapor from an emission point to a control device or back into the process.
CN - Abbreviation for total cyanide.
COD - Chemical oxygen demand (COD) - A nonconventional bulk parameter that
measures the total oxygen-consuming capacity of wastewater. This parameter is a
measure of materials in water or wastewater that are biodegradable and materials that
are resistant (refractory) to biodegradation. Refractory compounds slowly exert demand
on downstream receiving water resources. Certain of the compounds measured by this
parameter have been found to have carcinogenic, mutagenic, and similar adverse effects,
either singly or in combination. It is expressed as the amount of oxygen consumed by a
chemical oxidant in a specific test.
Combustion device - An individual unit of equipment, including but not limited to, an
incinerator or boiler, used for the thermal oxidation of organic hazardous air pollutant
vapors.
Condensate - Any material that has condensed from a gaseous phase into a liquid phase.
Continuous discharge - Discharge that occurs without interruption throughout the
operating hours of the facility.
Continuous operation - A pharmaceutical manufacturing operation which may consist of
a series of operating units which continuously process materials.
Controlled-release discharge - A discharge that occurs at a rate that is intentionally
varied to accommodate fluctuations in receiving stream assimilative capacity or for other
reasons.
Conventional pollutants - The pollutants identified in Section 304(a)(4) of the Clean
Water Act and the regulations thereunder (i.e., biochemical oxygen demand (BOD5),
total suspended solids (TSS), oil and grease, fecal coliform and pH).
CWA - Clean Water Act. The Federal Water Pollution Control Act Amendments of
1972 (33 U.S.C. 1251 et seq.), as amended, inter alia, by the Clean Water Act of 1977
(Public Law 95-217) and the Water Quality Act of 1987 (Public Law 100-4).
Daily discharge - The discharge of a pollutant measured during any calendar day or any
24-hour period that reasonably represents a calendar day for purposes of sampling. For
pollutants with limitations expressed in units of mass, the daily discharge is calculated as
the total mass of the pollutant discharged over the day. For pollutants with limitations
19-3
-------
expressed in other units of measurement, the daily discharge is calculated as the average
measurement of the pollutant over the day.
Direct discharger - A facility that discharges or may discharge treated or untreated
process wastewaters, non-contact cooling waters, or nonprocess wastewaters (including
stormwater runoff) into waters of the United States.
Effluent - Wastewater discharges.
Effluent limitation - Any restriction, including schedules of compliance, established by a
State or the Administrator on quantities, rates, and concentrations of chemical, physical,
biological, and other constituents which are discharged from point sources into waters of
the United States, the waters of the contiguous zone, or the ocean.
Emission - Passage of air pollutants into the atmosphere via a gas stream or other
means.
Emission point - Any location within a source from which air pollutants are emitted,
including an individual process vent, an opening within a wastewater collection and
treatment system, or an open piece of process equipment.
EOF (end-of-pipe) effluent - Final plant effluent discharged to waters of the United
States or to a POTW.
EOF (End-of-pipe) treatment - End-of-pipe treatment facilities or systems used to treat
process wastewaters, nonprocess wastewaters (including stormwater runoff) after the
wastewaters have left the process area of the facility and prior to discharge. End-of-pipe
treatment generally does not include facilities or systems where products or by-products
are separated from process wastewaters and returned to the process or directed to air
emission control devices.
EPA - The U.S. Environmental Protection Agency.
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. Process operations that utilize fermentation to manufacture pharmaceutically
active ingredients define Subcategory A (40 CFR 439, Subpart A).
FR - Federal Register, published by the U.S. Government Printing Office, Washington,
D.C. A publication making available to the public regulations and legal notices issued
by federal agencies. These include Presidential proclamations and Executive Orders and
federal agency documents having general applicability and legal effect, documents
required to be published by act of Congress and other federal agency documents of
19-4
-------
public interest. Citations of the Federal Register include volume number and page
number (e.g., 55 FR 12345).
General Provisions - General Provisions for national emission standards for hazardous
air pollutants and other regulatory requirements pursuant to Section 112 of the CAA as
amended November 15, 1990. The General Provisions, to be located in Subpart A of
Part 63 of Title 40 of the Code of Federal Regulations, codify procedures and criteria to
implement emission standards for stationary sources that emit (or have the potential to
emit) one or more of the 189 chemicals listed as hazardous air pollutants in Section
112(b) of the CAA as amended in 1990. EPA published the NESHAP General
Provisions in the Federal Register on March 16, 1993 (59 FR 12408). The term General
Provisions also refers to the General Provisions for the effluent limitations guidelines
and standards to be located at 40 CFR 439.
HAP - Hazardous Air Pollutant. Any of the 189 chemicals listed under Section 112(b) of
the CAA.
Incinerator - An enclosed combustion device that is used for destroying organic
compounds. Auxiliary fuel may be used to heat waste gas to combustion temperatures.
Any energy recovery section present is not physically formed into one manufactured or
assembled unit with the combustion section; rather, the energy recovery section is a
separate section following the combustion section and the two are joined by ducts or
connections carrying flue gas.
Indirect discharger - A facility that discharges or may discharge wastewaters into a
publicly owned treatment works (POTW).
Individual drain system - The system used to convey process wastewater streams from
the pharmaceutical manufacturing process equipment or tank, or process wastewater
collection and treatment system unit. The term includes all process drains and junction
boxes, together with their associated sewer lines and other junction boxes, manholes,
sumps, and lift stations. The individual drain system shall be designed to segregate the
vapors within the system from other drain systems. A separate storm sewer system,
which is a dram and collection system designed and operated for the purpose of
collecting storm runoff at a facility, and which is segregated from all other individual
drain systems, is excluded from this definition.
In-plant control technologies - Controls or measures applied within the manufacturing
process to reduce or eliminate pollutant and hydraulic loadings as well as technologies
applied directly to wastewater generated by manufacturing processes such as steam
stripping and cyanide destruction.
19-5
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In-plant monitoring point - A monitoring point placed prior to dilution by non-process
wastewater, commingling with other process wastestreams not containing the regulated
pollutants at treatable levels, and any conveyance, equalization, or other treatment units
which are open to the atmosphere.
In-plant monitoring point for cyanide - A monitoring point for cyanide which occurs in
plant, prior to dilution or mixing with any noncyanide-bearing wastewater.
IU - Industrial User. Synonym for "Indirect Discharger."
Junction box - A manhole access point to a wastewater sewer system or a lift station.
LTM - Long-term mean. For purposes of the effluent guidelines,- average pollutant
levels achieved over a period of time by a facility, subcategory, or technology option.
These LTMs were used in developing the limitations and standards for the proposed
regulation.
MACT - Maximum Achievable Control Technology. Technology basis for the national
emission standards for hazardous air pollutants.
Major source - As defined in Section 112(a) of the CAA, a major source is any
stationary source or group of stationary sources located within a contiguous area and
under common control that emits or has the potential to emit, considering controls, in
the aggregate 10 tons per year or more of any hazardous air pollutant or 25 tons per
year or more of any combination of hazardous air pollutants.
Maximum daily discharge limitation - The highest allowable daily discharge of a
pollutant measured .during a calendar day or any 24-hour period that reasonably
represents a calendar day for purposes of sampling.
Methyl cellosolve - A trademark name for ethylene glycol monomethyl ether (q.v.).
Mg - Megagram. One million (106) grams, or one metric ton.
Metric ton - One thousand (103) kilograms (abbreviated as kkg), or one megagram. A
metric ton is equal to 2,204.5 pounds.
Minimum level - The level at which an analytical system gives recognizable signals and
an acceptable calibration point.
Mixing, compounding, or formulating - Process through which pharmaceutically active
ingredients are put in dosage forms. Processes involving mixing, compounding, or
formulating define Subcategory D (40 CFR 439, Subpart D).
19-6
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Modification - As defined in Section 112(a) of the CAA, a modification is any physical
change in, or change in the method of operation of, a major source which increases the
actual emissions of any hazardous air pollutant emitted by such source by more than a de
minimis amount or which results in the emission of any hazardous air pollutant not
previously emitted by more than a de minimis amount.
NESHAP - National Emission Standard for Hazardous Air Pollutants. Emission standard
promulgated under Section 112(d) of the CAA for hazardous air pollutants listed in
Section 112(b) of the CAA.
New Source - As defined in 40 CFR 122.2, 122.29, and 403.3 (k), a new source is any
building, structure, facility, or installation from which there is or may be a discharge of
pollutants, the construction of which commenced (1) for purposes of compliance with
New Source Performance Standards, after the promulgation of such standards being
proposed today under CWA section 306; or (2) for the purposes of compliance with
Pretreatment Standards for New Sources, after the publication of proposed standards
under CWA section 307(c), if such standards are thereafter promulgated in accordance
with that section.
Noncontinuous or intermittent discharge - Discharge of wastewaters stored for periods
of at least 24 hours and released on a batch basis.
Nonconventional pollutants - Pollutants that are neither conventional pollutants nor toxic
pollutants listed at 40 CFR Section 401.
Nondetect value - A concentration-based measurement reported below the minimum
level that can reliably be measured by the analytical method for the pollutant.
Nonwater quality environmental impact - An environmental impact of a control or
treatment technology, other than to surface waters.
NPDES - The National Pollutant Discharge Elimination System authorized under Section
402 of the CWA. The CWA requires NPDES permits for discharge of pollutants from
any point source into waters of the United States.
NRDC - Natural Resources Defense Council.
NSPS - New source performance standards. This term refers to standards for new
sources under Section 306 of the CWA.
Outfall - The mouth of conduit drains and other conduits from which a plant's effluent
discharges into receiving waters.
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Pharmaceutically active ingredient - Any substance considered to be an active ingredient
by Food and Drug Administration regulations (21 CFR 210.3(6)(7)).
Pilot-scale - The trial operation of processing equipment which is the intermediate stage
between laboratory experimentation and full-scale operation in the development of a
new process or product.
Point of generation - The location where the process wastewater stream exits the
pharmaceutical process equipment.
Point source category - A category of sources of water pollutants that are included within
the definition of "point source" in Section 502(14) of the CWA.
Pollutant (to water) - Chemical constituent; dredged spoil, solid waste, incinerator
residue, filter backwash, sewage, garbage, sewage sludge, munitions, chemical wastes,
biological materials, certain radioactive materials, heat, wrecked or discarded equipment,
rock, sand, cellar dirt, and industrial, municipal, and agricultural waste discharged into
water. See CWA Section 502(6); 40 CFR 122.2.
POTW or POTWs - Publicly owned treatment works, as defined at 40 CFR 403.3(o).
Pretreatment standard - A regulation specifying industrial wastewater effluent quality
required for discharge to a POTW.
Priority pollutants - The toxic pollutants listed in 40 CFR Part 423, Appendix A.
Process changes - Alterations in process operating conditions, equipment, or chemical
use that reduce the formation of chemical compounds that are pollutants and/or
pollutant precursors.
Process emission point - A gas stream that contains hazardous air pollutants discharged
during operation of process equipment. Process emission points include gas streams that
are discharged directly to the atmosphere, discharged to the atmosphere via vents or
open process equipment, or after diversion through a product recovery device.
Process unit - A piece of equipment, such as a chemical reactor or fermentation tank,
associated with pharmaceutical manufacturing operations.
Process wastewater - Any water that, during manufacturing or processing, comes in direct
contact with or results from the production or use of any raw material, intermediate
product, finished product, by product, or waste product. Process wastewater includes
surface runoff from the immediate process area that has the potential to become
contaminated. Noncontact cooling waters, utility wastewaters, general site surface runoff,
19-8
-------
groundwater, and other water generated on site that are not process wastewaters are
specifically excluded from this definition.
Process wastewater collection system - A piece of equipment, structure, or transport
mechanism used in conveying or storing a process wastewater stream. Examples of
process wastewater collection system equipment include individual drain systems,
wastewater tanks, surface impoundments, and containers.
Process wastewater stream - When used in connection with CAA obligations, any HAP-
containing liquid' that results from either direct or indirect contact of water with organic
compounds.
Process water - Water used to dilute, wash, or carry raw materials, and any other
materials used in pharmaceutical manufacturing processes.
Product - Completed material ready for sale or intra-company off-site transfer.
PSES - Pretreatment standards for existing sources of indirect discharges, under Section
307(b) of the CWA.
PSNS - Pretreatment standards for new sources of indirect discharges, under Section
307(b) and (c) of the CWA.
RCRA - Resource Conservation and Recovery Act of 1976, as amended (42 U.S.C. 6901,
et seq.).
Research - Bench-scale activities or operations used in research and/or product
development of a pharmaceutical product. The Research operations define
Subcategory E (40 CFR 439, Subpart E).
SIC - Standard Industrial Classification. A numerical categorization system used by the
U.S. Department of Commerce to denote segments of industry. An SIC code refers to
the principal product, or group of products, produced or distributed, or to services
rendered by an operating establishment. SIC codes are used to group establishments by
the primary activity in which they are engaged.
Source category - A category of major or area sources of hazardous air pollutants.
Source reduction - The reduction or elimination of waste generation at the source,
usually within a process. Any practice that: 1) reduces the amount of any hazardous
substance, pollutant, or contaminant entering any waste stream or otherwise released
into the environment (including fugitive emissions) prior to recycling, treatment, or
disposal; and 2) reduces the hazards to public health and the environment associated
with the release of such substances, pollutants, or contaminants.
19-9
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Stationary source - Any building, structure, facility, or installation that emits or may
emit any air pollutant. See CAA Section lll(a)(3).
TSS - Total suspended solids.
Toxic pollutants - the pollutants designated by EPA as toxic hi 40 CFR Part 401.15.
Also known as priority pollutants.
TWF - Toxic weighting factor.
VF - Variability factor. The daily variability factor is the ratio of the estimated 99th
percentile of the distribution of daily values divided by the expected value, or mean, of
the distribution of the daily data. The monthly variability factor is the estimated 95th
percentile of the monthly averages of the data divided by the expected value of the
monthly averages.
Waters of the United States - The same meaning set forth in 40 CFR 122.2.
Zero discharge - No discharge of wastewater to waters of the United States or to a
POTW.
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APPENDIX A
GUIDANCE FOR IMPLEMENTING THE
PHARMACEUTICAL MANUFACTURING INDUSTRY REGULATIONS
1.0
INTRODUCTION
This appendix is intended to serve as an aid in implementing the Pharmaceutical
Manufacturing Industry Point Source Category Effluent Limitations Guidelines,
Pretreatment Standards and New Source Performance Standards. This appendix
presents the development of permit limitations for several hypothetical plants that
illustrate by example how the proposed pharmaceutical manufacturing industry effluent
limitations guidelines and standards are to be implemented.
Five permit case studies are presented:
Case 1: BPT and BAT limitations for a multiple subcategory facility.
Case 2: PSES for a multiple subcategory facility.
Case 3: NSPS for a multiple subcategory facility.
Case 4: PSNS for a multiple subcategory facility.
Case 5: • BPT and BAT limitations for a facility with pharmaceutical
manufacturing and organic chemicals manufacturing
operations.
The examples presented here have been selected to cover direct and indirect dischargers
as well as new and existing sources. Special circumstances have been built into each
example to illustrate how a permit writer would be advised to handle these cases. The
plants presented here may not represent an average cross section of the industry, but
they have been selected for their illustrative value.
A-l
-------
As discussed in the body of the Technical Development Document (TDD), the
Pharmaceutical Manufacturing Industry effluent limitations guidelines and standards are
concentration based and adhere to the "building block" concept. Each regulated
wastestream in an outfall is assigned a mass-based discharge allowance based on a
calculation of its applicable concentration-based limitation and annual average flow. The
sum of the allowances is the total mass discharge allowance for the outfall. The
examples that follow assume some familiarity with the "building block" concept as well as
familiarity with the material presented in the pharmaceutical manufacturing industry
preamble, proposed regulations, and main body of the TDD.
Mass limitations for unregulated process wastewater streams and dilution streams at
direct discharging facilities are established by the NPDES permit authority using best
professional judgement (BPJ). Mass limitations for unregulated process wastewater
streams and dilution streams at indirect discharging facilities are established by the
Control Authority (see 40 CFR 403.12(a), and 40 CFR 403.3) by using the combined
wastestream formula (see 40 CFR 403.6(e)(i), (ii)).
The following reference is recommended to complement this document:
• "Training Manual for NPDES Permit Writers," U.S. Environmental
Protection Agency, Office of Water, Washington, D.C., EPA833-B-
93-003, March 1993.
Permit limits are generally expressed in terms of allowable mass (in units of pounds or
kilograms) of pollutant per day. However, the pharmaceutical industry regulations are
concentration based. To convert the concentration-based limitations to mass-based
limitations an accurate determination of the annual average process wastestream flows
will have to be determined by the permit writer. The following discussion is designed to
aid the permit writer in this process.
A-2
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1.1
Calculation of Annual Average Process Wastewater Discharge
"Process wastewater discharge" is defined by 40 CFR 122.2 to include wastewaters
resulting from manufacture of pharmaceutical products that come in direct contact with
raw materials, intermediate products, and final products, and surface runoff from the
immediate process area that has the potential to become contaminated. Noncontact
cooling waters, utility wastewaters, general site surface runoff, groundwater, and other
nonprocess water generated on site are specifically excluded from this definition. The
appropriate process wastewater discharge flow for each stream to be used when
developing mass-based limitations must be determined by the permitting or control
authority on a case-by-case basis using current information provided by the applicant. In
cases where the permit writer deems the process wastewater discharge flow claimed by
industry to be excessive, he/she may develop a more appropriate process wastewater
discharge flow for use in computing the mass-based permit limitations. The permit
writer should review the following items to evaluate whether process wastewater
discharge flow is excessive: •
• The component flows to ensure that the claimed flows are, in fact,
process wastewater discharge flows as defined by 40 CFR 122.2.
The plant operations to ensure that sound water conservation
practices are being followed. Examples include minimization of
process water uses and reuse or recycle of intermediate process
waters or treated wastewaters at the process area and in wastewater
treatment operations (pump seals, equipment and area washdowns,
etc.)
Barometric condenser use at the process level. Often, barometric
condensers will generate relatively large volumes of slightly
contaminated water. Replacing barometric condensers with surface
condensers can reduce wastewater volumes significantly and result in
collection of condensates that may be returned to the process.
A-3
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To establish a NPDES permit for a direct discharging facility, the permit writer should
determine which subcategories the facility's operations fall within and use the
corresponding concentration-based effluent limitations as a basis for developing the
mass-based limitations. The permit writer should then determine the facility's annual
average process wastewater discharge flow (i.e., the permit writer should consider only .
the sources of "process wastewater discharge," as defined previously, when determining
the annual average process wastewater discharge flow; nonprocess wastewater discharges
should not be included). The annual average flow is defined as the average of daily flow
measurements calculated over at least a year (1); however, if available, multiple years'
data are preferable to obtain a representation of average daily flow.
The permit writer is advised to establish, for each point source discharge, a single
estimate of the regulated long-term average daily flow measurements based on three to
five years of facuity data. (1) In the event that no historical data or actual process
wastewater flow data exist (such as for a new source), the permit writer is advised to
establish a reasonable estimate of the facility's projected flow. This may include a
request for the facility to measure process wastewater flows for a representative period
of time to establish a flow basis. The permit writer is advised to establish a flow rate
that is expected to be representative during the entire term of the permit. If a plant is
planning significant changes in production during the effective period of the permit, the
permittmg authority may consider establishing multiple tiers of limitations as a function
of these changes. Alternatively, a permit may be modified during its term, either at the
request of the permittee, permitter, or another party, or on EPA's initiative, to increase
or decrease the flow basis in response to a significant change in production (40 CFR
124.5, 122.62). A change in production may be an "alteration" of the permitted activity
or "new information" that would provide the basis for a permit modification (40 CFR
122.62(a)).
A-4
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1.2
Calculation of Mass-Based Permit Limitations
After determining the facility's annual average process wastewater flow, the permit writer
should use the annual average process wastewater discharge flow to convert
concentration-based limitations into mass-based limitations. The following equation can
be used by the permit writer to convert a concentration-based limitation into a mass-
based limitation:
Lm = Lc x F x kj
where:
LM
Lc
F
mass-based effluent limitation, Ibs/day
concentration-based limitation, mg/L
average process wastewater discharge, gal/day
unit conversion factor, (L x lbs)/(gal x mg).
For this example, the unit conversion factor, kt is used to convert from
[(mg/L) x (gal/day)] to (Ibs/day) as follows:
k =-
1L
x.
lg
X
lib
0.264179 gal 1,000 mg 453.592 g
= 8.345 xlO'6x
Lxlb
gal x mg
If the concentration based limitations are expressed as jwg/L, the unit conversion factor
k2 can be used to convert from [(/ig/L) x (gal/day)] to (Ibs/day) as follows:
1 L
x
X
1 Ib
0.264179 gal 1,000,000 jig 453.592 g
= 8.345 x 10-9 x
Lx Ib
gal x/ig
A-5
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2.0
CASE STUDY 1, BPT AND BAT EFFLUENT LIMITATIONS FOR A
MULTIPLE SUBCATEGORY FACILITY
Plant A is an existing multiple subcategory, direct discharging pharmaceutical
manufacturing facility. A wastewater flow schematic for this facility is presented in
Figure A-l.
2.1
BPT Effluent Limitations
The revised BPT effluent limitations guidelines establish new BOD5, COD, and TSS
effluent limitations for Subcategory A, B, C, and D operations at direct discharging
facilities. The pH effluent limit, established in the 1976 final rule to be in the range of
6.0 to 9.0 standard units for all subcategories, will not be amended. The BPT effluent
limitations for Subcategory E bench-scale operations, established in the 1983 final rule,
will not be amended. As discussed in Section 6.2 of the TDD, the other conventional
pollutants, such as fecal coliform and oil & grease, will not be regulated by BPT for the
pharmaceutical manufacturing point source category.
The proposed effluent limitations guidelines are concentration-based and, as such, do not
regulate wastewater flow. The permit writer must use a reasonable estimate of process
wastewater discharge flow and the concentration-based limitations to develop mass-based
limitations for the NPDES permit. Table 13-1 of the TDD presents the proposed
maximum daily and monthly average BPT effluent limitations for Subcategory A, B, C,
and D operations at direct discharging facilities.
The limitations for BOD5, COD, and TSS will be applied to the final effluent. An
example calculation of the BPT maximum for any one day and monthly average BOD5
limitations for this facility is shown in 2.1.1 and 2.1.2.
A-6
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2.1.1
Maximum Effluent Limitations for Any One Day
The first step in establishing permit limitations is to determine the types of wastestreams
(i.e., regulated process, unregulated process, and dilute). The flow breakdown for Facility
A would look like this:
Waste Stream
Flow (gal/day)
1. Fermentation Operations
2. Product Recovery
3. In-plant Scrubbers for Chemical
Synthesis
4. Chemical Synthesis
5. Mixing, Formulating, and Packaging
6. Boiler Slowdown
7. Research and Development
8. Noncontact Cooling Waters
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
1,330,000
55,000
30,000
105,000
10,000
150
40
1,300,000
2,830,190
1,530,040
0
1,300,150
(Regulated, Sub. A)
(Regulated, Sub. A)
(Regulated, Sub. C)
(Regulated, Sub. C)
(Regulated, Sub. D)
(Dilute)
(Regulated, Sub. E)*
(Dilute)
*For monthly average limitations only
Under BPT, streams 1, 2, 3, 4, 5, and 7 are considered regulated wastestreams as effluent
limitations have been established for fermentation operations (Subcategory A), chemical
synthesis operations (Subcategory C), formulating operations (Subcategory D), and
research operations (Subcategory E). Air pollution control wastewaters are considered
process wastewaters corresponding to the Subcategory operations the air pollution control
devices control. We have assumed the permit writer has sufficient information to
A-8
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determine that the noncontact cooling waters do not have treatable levels of BPT
pollutants.
Table 13-1 of the TDD presents the proposed maximum daily and monthly average BPT
effluent limitations for Subcategory A, B, C, and D operations at direct discharging
facilities. Daily maximum limitations have not been promulgated for Subcategory E
operations. Monthly average limitations for Subcategory E operations have been
promulgated and are presented in 40 CFR §439.52. (2). Since maximum limitations for
any one day have not been promulgated for Subcategory E operations, wastestream 7 has
been considered an unregulated wastestream in the calculation of daily maximum
limitations. The total BPT maximum allowable discharge for any one day can be
calculated by determining the mass discharge allowance using the combined wastestream
formula (CWF) shown below:
where:
MT
M,
N
EH
X
FT-FD
N
N
Alternative mass limit for the pollutant in the combined
wastestream (mass per day).
Treatment standard for the pollutant in the regulated stream
i (mass per day)
Average daily flow (at least 30 day average) of the regulated
stream i
Average daily flow (at least 30 day average) of dilute
wastestream(s) entering the combined treatment system
Average daily flow (at least 30 day average) through the
combined treatment facility (including regulated, unregulated,
and dilute wastestreams)
Total Number of regulated streams
A-9
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In this example, the previously listed variables are calculated as follows:
MI
M2
M2
M3
M3
M4
M4
M5
M5
FT =
FD =
F2
F3 =
F4
F5 =
= l>115 lbs
day
Mass limit of BOD5 in stream 1
139.7 mg/L x 1,330,000 gal/day x 8.345 x 10'6 =
1,550.5 Ibs/day
Mass limit of BOD5 in stream 2
139.7 mg/L x 55,000 gal/day x 8.345 x lO'6 = 64.1 Ibs/day
Mass Limit of BOD5 in stream 3
139.7 mg/L x 30,000 gal/day x 8.345 x 10'6 = 35.0 Ibs/day
Mass limit of BOD5 in stream 4
139.7 mg/L x 105,000 gal/day x 8.345 x 10'6 =
122.4 Ibs/day
Mass Limit of BOD5 in stream 5
36.5 mg/L x 10,000 gal/day x 8.345 x 10'6 = 3.0 Ibs/day
M7 = Mg = 0 (since these streams are considered dilution or
unregulated process wastewater)
Total flow = 2,830,190 gpd
Dilution flow = 1,330,150
Flow in stream 1 = 1,330,000
Flow in stream 2 = 55,000
Flow in stream 3 = 30,000
Flow in stream 4 = 105,000
Flow in stream 5 = 10,000
x
2,830,190 gpd - 1,300,150 gpd =
1,530,000 gpd
!]
Therefore, maximum day effluent limitations for BOD5 in the combined wastestream
would be 1,775 Ibs/day.
COD and TSS maximum day effluent limitations can be calculated in a similar manner.
2.13
Monthly Average Effluent Limitations
As mentioned previously, monthly average limitations for Subcategory E operations are
not being amended from the 1983 final rule. These limitations are presented in 40 CFR
§439.52(2). According to the 1983 final rule, the monthly average mass of BOD5 shall
A-10
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reflect not less than 90 percent reduction of BOD5 multiplied by a variability factor of
3.0. However, a facility shall not be required to attain a monthly average BOD5 effluent
limitation of less than 45 mg/L. Assuming this facility has a concentration of 200 mg/L
of BOD5 from Subcategory E operations, a 90 percent reduction would be required,
making the monthly average limitation 20 mg/L. After multiplying by a variability factor
of 3.0, the monthly average effluent limitation for BOD5 from Subcategory E operations
is 60 mg/L. This limit is added to the monthly average limitations from the other
subcategories to determine the total monthly average effluent limitation for BOD5.
The total monthly average BPT BOD5 limitations can be calculated as follows:
Stream 1 (Sub. A): (57.8 mg/L x 1,330,000 gal/day x 8.345 x 1Q-6) = 641.5 Ibs/day
Stream 2 (Sub. A): (57.8 mg/L x 55,000 gal/day x 8.345 x 10'6) = 26.5 Ibs/day
Stream 3 (Sub. C): (57.8 mg/L x 30,000 gal/day x 8.345 x 10'6) = 14.5 Ibs/day
Stream 4 (Sub. C): (57.8. mg/L x 105,000 gal/day x 8.345 x lO"6) = 50.6 Ibs/day
Stream 5 (Sub. D): (11.2 mg/L x 10,000 gal/day x 8.345 x lO"6) = 0.9 Ibs/day
Stream 7 (Sub. E): (60 mg/L x 40 gal/day x 8.345 x 10'6) = 0.02 Ibs/day
Total = 734 Ibs BOD5/day
The monthly average effluent limitation for BOD5 in the combined wastestream would
be 734 Ibs/day.
This monthly average limitation is compared to the average of all daily mass discharge
amounts in a calendar month to determine facility compliance.
COD and TSS monthly average effluent limitations can be calculated in a similar
manner.
A-ll
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2.2
BAT Effluent Limitations
Tables 15-2 and 15-3 of the TDD present the proposed maximum daily and monthly
average BAT effluent limitations guidelines for Subcategories A and C, and
Subcategories B and D, respectively. BAT for ammonia and the organic pollutants listed
in these tables are applicable to the final effluent discharged to the waters of the United
States.
BAT limitations for cyanide are presented in Table 15-2 of the TDD, and are applicable
to those wastewaters from Subcategory A and C operations known or believed to contain
cyanide. Compliance monitoring for cyanide should occur in-plant, prior to dilution or
mixing with any non-cyanide bearing wastewater. In-plant monitoring is required to
prevent compliance through dilution with non-cyanide bearing wastewaters.
We will assume that facility A has provided the permit writer with an accurate
characterization of its process wastestreams by means available such as solvent use and
disposition data, and analytical scans of each stream. Permit limitations should be
established and compliance monitoring required for each regulated pollutant listed on
Table 15-1 generated or used at a pharmaceutical manufacturing facility. Limitations
and routine compliance monitoring are not required for regulated pollutants not
generated or used at a facility. A determination that regulated pollutants are not
generated or used should be based on a review of all raw materials used, and an
assessment of all chemical processes used, considering resulting products and by-
products. The determination that a regulated pollutant is not generated or used must be
confirmed by annual chemical analyses of wastewater from each monitoring location.
Such confirmation is provided by an analytical measurement of a non-detect value.
A-12
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The following presents a summary of the regulated pollutants expected to be found in
this facility's wastestreams:
Stream
1
2
3
4
5
6
7
Subcategory
A
A
C
C
D
N/A
E
Flow (gal/day)
1,330,000
55,000
30,000
105,000
10,000
150
40
Pollutant
Methylene chloride, cyclohexane,
acetone
Methylene chloride, methanol,
acetone
Methanol
Methylene chloride, acetone,
methanol, aniline
Aniline, cyclohexane
No BAT pollutants
No organic pollutants
Based on the above data, permit limitations are established for methylene chloride,
cyclohexane, acetone, methanol, and aniline. All of these pollutants are listed in Table
15-1 of the TDD.
While Subcategory E bench-scale research wastewater is unregulated for the organic
pollutants listed in streams 1-5 according to the definition in the General Pretreatment
Regulations, Control Authorities have the authority to determine whether unregulated
streams should be considered dilution under 40 CFR §403.6(d). Since organic pollutants
were not found to be present in Subcategory E wastewater in this example, this
wastestream is considered here as dilution water and no mass allowances for this
wastewater will be given.
A-13
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2.2.1
BAT Maximum Limitations for Any One Day
As shown in Tables 15-2 and 15-3 of the TDD, cyclohexane has a maximum daily
limitation of non-detect (ND) for A, B, C, and D subcategories. Methylene chloride,
acetone, and methanol have maximum daily limitations of ND in Subcategories A and C
and a maximum daily numerical limitation in Subcategory D. Aniline has a maximum
daily numerical limitation in A, B, C, and D subcategories.
The Subcategory A, C, and D maximum daily limitations for cyclohexane are all ND.
Non-detect values are concentration-based measurements reported below the minimum
level that can be reliably measured by the analytical method for the pollutant.
Therefore, the permit limitation for cyclohexane should specify ND for all
measurements. Any concentration measurements greater than the ND value for the
pollutant are considered out of compliance.
The limitations-for methylene chloride, acetone, and methanol for Subcategories A and
C are ND. However, these pollutants have a numerical limitation for Subcategory D.
Since monitoring points for organic pollutants under BAT are at end-of-pipe locations
and Subcategory A, C, and D wastewater will most likely be combined at this location, a
mass limitation for the combined wastestream can be determined by using the numerical
value of the minimuni level for these pollutants to determine the Subcategory A and C
portion of the mass limitation.
The total BAT maximum allowable discharge for methanol for any one day can be
calculated by determining the mass discharge allowance for each individual process
stream and summing, as shown below.
Stream 1 (Sub. A): (3,180 /*g/L x 1,330,000 gal/day x 8.345 x 10'9) = 35.3 Ibs/day
Stream 2 (Sub. C): (3,180 /xg/L x 55,000 gal/day x 8.345 x 10'9) = 1.46 Ibs/day
Stream 3 (Sub. C): (3,180 /*g/L x 30,000 gal/day x 8,345 x 10'9) = 0.80 Ibs/day
A-14
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Stream 4 (Sub. C): (3,180 jtg/L x 105,000 gal/day x 8.345 x 10'9) = 2.79 Ibs/day
Stream 5 (Sub. D): (6,660 /*g/L x 10,000 gal/day x 8.345 x 10'9) = 0.56 Ibs/day
Total = 40.9 Ibs/day
Total Facility Maximum Day Discharge for Methanol = 40.9 Ibs/day
Maximum day effluent limitations for acetone and methylene chloride can be calculated
in a similar manner.
Aniline has a numerical limitation for all subcategories. The concentration-based
limitations in Tables 15-2 and 15-3 of the TDD should be converted to maximum day
mass-based limitations as shown below:
Stream 1 (Sub. A): (10 /tg/L x 1,330,000 x 8.345 x 10'9) = 0.11 Ibs/day
Stream 2 (Sub. A): (10 jwg/L x 55,000 x 8.345 x 10'9) = 0.0046 Ibs/day
Stream 3 (Sub. C): (10 /*g/L x 30,000 x 8.345 x 10'9) = 0.0025 Ibs/day
Stream 4 (Sub. C): (10 /tg/L x 105,000 x 8.345 x 10'9) = 0.0088 Ibs/day
Stream 5 (Sub. D): (10 /*g/L x 10,000 x 8.345 x 10'9) = 0.0008 Ibs/day
Total = 0.13 Ibs/day
Total Facility Maximum Day Discharge for Aniline = 0.13 Ibs/day
It -will be critical in this example to monitor the plant effluent at monitoring Point A; prior
to dilution with non-contact cooling waters. The limitations for most pollutants are based
on treating the pollutant to levels near or below the analytical minimum level. Achieving
such levels in part through dilution is not considered treatment and is not acceptable.
22.2
BAT Monthly Average Limitations for Organic Pollutants
The monthly average limitations for cyclohexane are ND for all subcategories, just like
the cyclohexane maximum daily limitations. Section 2.2.1 explains how these
concentration-based limitations are implemented.
A-15
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The published monthly average limitations for methanol are ND for all subcategories.
However, since the maximum daily limitation for Subcategory D is not ND,
measurements above the minimum level are permitted. Within the course of a month,
the average value of all measurements should be equal to or less than the minimum
level of 3,180 /*g/L. The corresponding monthly average mass-based limitation for this
concentration is shown below.
Stream 1 (Sub. A): (3,180 ^g/L x 1,330,000 gal/day x 8.345 x 10'9) = 35.3 Ibs/day
Stream 2 (Sub. A): (3,180 jtig/L x 55,000 gal/day x 8.345 x 10'9) = 1.46 Ibs/day
Stream 3 (Sub. C): (3,180 ^g/L x 30,000 gal/day x 8.345 x 10'9) = 0.80 Ibs/day
Stream 4 (Sub. C): (3,180 pg/L x 105,000 gal/day x 8.345 x 10'9) = 2.79 Ibs/day
Stream 5 (Sub. D): (3,180 pg/L x 10,000 gal/day x 8.345 x 10'9) = 0.27 Ibs/day
Total = 39.8 Ibs/day
Monthly average discharge limitation for Methanol = 39.8 Ibs/day
The monthly average for methylene chloride and acetone for Subcategories A and C are
ND. These pollutants have numerical limitations for Subcategory D. This same scenario
is described in Section 2.2.1. Using the methodology explained in Section 2.2.1, the
monthly average limitations for methylene chloride are shown below:
Stream 1 (Sub. A): (10 pg/L x 1,330,000 gal/day x 8.345 x 10'9) = 0.11 Ibs/day
Stream 2 (Sub. A): (10 /*g/L x 55,000 gal/day x 8.345 x 10'9) = 0.0046 Ibs/day
Stream 3 (Sub. C): (10 jtg/L x 30,000 gal/day x 8.345 x 10'9) = 0.0025 Ibs/day
Stream 4 (Sub. C): (10 pg/L x 105,000 gal/day x 8.345 x 10'9) = 0.0088 Ibs/day
Stream 5 (Sub. D): (357 pg/L x 10,000 gal/day x 8.345 x 10'9) = 0.03 Ibs/day
Total = 0.16 Ibs/day
Monthly average discharge limitation for methylene chloride = 0.16 Ibs/day
Monthly average limitations for acetone can be calculated in the same manner.
A-16
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The monthly average limitations for aniline are the same as the daily maximum
limitations for aniline in all subcategories. Calculation of corresponding mass-based
limitations are shown in Section 2.2.1.
A-17
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3.0
CASE STUDY 2, PSES FOR A MULTIPLE SUBCATEGORY FACILITY
Facility B is an existing multiple subcategory indirect discharging pharmaceutical plant.
A wastewater flow schematic for this facility is presented in Figure A-2.
3.1
PSES Permit Limitations
Two scenarios -will be presented for PSES, the first will apply under co-proposal 1 and
the second will apply under co-proposal 2. Co-proposal 1 for Subcategories A and C sets
in-plant standards for 13 pollutants and end-of-pipe standards for 33 pollutants. Co-
proposal 2 for Subcategories A and C sets in-plant standards for 13 pollutants, but has
no end-of-pipe standards except for ammonia. Cyanide and ammonia are not regulated
in Subcategories B and D. Co-proposal 1 for Subcategories B and D sets in-plant
standards for 12 pollutants and end-of-pipe standards for 32 pollutants. Co-proposal 2
for Subcategories B and D sets in-plant standards for 12 pollutants, but has no end-of-
pipe standards.
3.2
PSES Permit Limitations for Co-Proposal 1
Table 17-4 of the TDD presents the proposed daily maximum and monthly average
PSES for Subcategories A, B, C, and D. The proposed standards are concentration-
based and, as such, do not regulate wastewater flow. Organics being controlled under
PSES have been divided into two groups, one list for organics to be controlled in-plant,
and a second list of less volatile organics that are controlled at the end-of-pipe.
PSES for cyanide is presented in Table 17-4 of the. TDD as well, and are applicable to
those wastewaters from Subcategories A and C operations known or believed to contain
cyanide. Compliance monitoring for cyanide should occur in-plant, prior to dilution or
mixing with any non-cyanide bearing wastewater. In-plant monitoring is required to
prevent compliance through dilution with non-cyanide bearing wastewaters.
A-18
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-------
The first step in establishing permit limitations is to determine the types of wastestreams
(i.e., regulated process, unregulated process, and dilute). The flow breakdown for
Facility B would look like this:
Waste Stream
Flow (gal/day)
1. Administration
2. Chemical synthesis
3. Mixing, Formulating, and Packaging
4. Boiler Blowdown
5. Pilot-Scale Chemical Synthesis
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
5,000
55,000
30,000
100
200
(Dilute)
(Regulated, Sub. C)
(Regulated, Sub. D)
(Dilute)
(Regulated, Sub. C)
90,300
85,200
0
5,100
Streams 2, 3, and 5 are considered regulated process wastestreams because effluent
limitations have been established for chemical synthesis operations (Subcategory C) and
mixing, formulating, and packaging operations (Subcategory D). Note for this example
that in the proposed regulation pilot-scale chemical synthesis wastewaters are regulated
as normal manufacturing process wastewater, not as research (Subcategory E)
wastewater.
We will assume that Facility B has provided the permit writer with an accurate
characterization of its process wastestreams by means available such as evaluation of
solvent use and disposition data, and has performed analytical scans of each stream.
Permit limitations should be established and compliance monitoring required for each
regulated pollutant listed on Table 17-2 generated or used at a pharmaceutical
manufacturing facility. Limitations and routine compliance monitoring are not required
for regulated pollutants not generated or used at a facility. A determination that
A-20
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regulated pollutants are not generated or used should be based on a review of all raw
materials used and an assessment.of all chemical processes used, considering resulting
products and by-products. The determination that a regulated pollutant is not generated
or used must be confirmed by annual chemical analyses of wastewater from each
monitoring location. Such confirmation is provided by an analytical measurement of a
non-detect value.
The following presents a summary of regulated pollutants found in this facility's
wastestr earns:
Stream
1
2
3
4
5
Subcategory
N/A
C
D
N/A
C
Flow (gpd)
5,000
55,000
30,000
100
200
Pollutant
No PSES pollutants
Acetone, chloroform,
toluene, cyanide
Acetone, isopropanol,
toluene
No PSES pollutants
Chloroform, toluene
Based on the above data, permit limitations are established for acetone, chloroform,
cyanide, isopropanol, and toluene. All of these pollutants are listed in Table 17-4 of the
TDD.
3.2.1
PSES Maximum Limitations for Any One Day
The limitations for both chloroform and toluene would be applied to process wastewater
streams 2, 3, and 5, at in-plant location points B, C, and D, prior to any dilution,
commingling with other treated wastestreams, and any equalization or treatment units
which are open to the atmosphere. (These monitoring points are shown at in-plant
A-21
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locations after steam stripping. Although steam stripping is the basis for the regulated
concentrations, it does not have to be the technology used at the facility.) These
maximum daily limitations would be concentration-based, and are ND and 198 /*g/L
(from Table 17-4) for chloroform and toluene, respectively. Non-detect (ND) values are
concentration-based measurements reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Therefore, the permit
limitation for chloroform should specify ND for all measurements. Any concentration
measurements greater than the ND value for the pollutant are considered out of
compliance.
PSES effluent limitations for cyanide should also be applied in-plant. The cyanide
standards are applicable to wastewaters from Subcategories A and C operations that
contain cyanide. Therefore, the concentration-based limitations for cyanide will apply to
process wastestream 2 at point A prior to dilution or mixing with any non-cyanide
bearing wastewater. The maximum daily limitation for cyanide is 766 jtg/L (from Table
17-4).
The limitations for both acetone and isopropanol would be applied at end-of-pipe
location point E.
A-22
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The total maximum allowable discharge for acetone for any one day can be calculated by
determining the mass discharge allowance using the combined wastestream formula
(CWF) shown below:
where:
MT
M;
F,
FD
FT
N
N
EH
X
FT-FD
N
Alternative mass limit for the pollutant in the combined
wastestream (mass per day).
Pretreatment standard for the pollutant in the regulated
stream i (mass per day)
Average daily flow (at least 30 day average) of the regulated
stream i
Average daily flow (at least 30 day average) of dilute
wastestream(s) entering the combined treatment system
Average daily flow (at least 30 day average) through the
combined treatment facility (including regulated, unregulated,
and dilute wastestreams)
Total Number of regulated streams
A-23
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In this example, the previously listed variables are calculated as follows:
M2
M2
M3
M3
Ms
M5
FT
FD
F2
F3
F5
M4 = 0 (since these streams are considered dilution water)
Mass limit for acetone in stream 2
31,400 fig/L x 55,000 gpd x 8.345 x 10'9 = 14.4 Ibs/day
acetone
Mass limit for acetone in stream 3
31,400 pg/L x 30,000 gpd x 8.345 x 10'9 = 7.86 Ibs/day
acetone
Mass limit for acetone in stream 5
31,400 Aig/L x 200 gpd x 8.345 x 10'9 = 0.05 Ibs/day
acetone
Total flow = 90,300 gpd
Dilution flow = Ft + F4 = 5,1000 gpd
Flow in stream 2 = 55,000 gpd
Flow in stream 3 = 30,000 gpd
Flow in stream 5 = 200 gpd
,, = 22.3 libs ("90,300 gpd-5,100 gpd] = 22.3 libs
^ day [ 85,200 gpd \ day
Total facility maximum discharge of acetone for any one day = 22.31 Ibs/day.
Maximum day effluent limitations for isopropanol can be calculated in a similar manner.
3.2.2
PSES Monthly Average Limitations for Organic Pollutants
The monthly average discharge limitations for chloroform and toluene are ND and 148
/ig/L, respectively. These limitations would be applied to process wastewater streams 2,
3, and 5 at in-plant location points A, B, and C, prior to any dilution, commingling with
other treated wastestreams, and any equalization or treatment units which are open to
the atmosphere.
A-24
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The monthly average discharge standard for cyanide is 406 jig/L. This standard will be
applied to process wastestream 2 at point A prior to dilution or mixing with any non-
cyanide bearing wastewater.
The monthly average discharges for acetone and isopropanol can be calculated by
determining the mass discharge allowance using the CWF presented in Section 3.2.1.
To determine the monthly average limitations for acetone, the variables listed in Section
3.2.1 are calculated as follows:
M2
M2
M3
M3
Ms
M5
FT
FD
F2
M4 = 0 (since these streams are considered dilution water)
Mass limit for acetone in stream 2
9,690 pg/L x 55,000 gal/day x 8.345 x 10'9 = 4.45 Ibs/day
acetone
Mass limit for acetone in stream 3
9,690 Aig/L x 30,000 gal/day x 8.345 x 10'9 = 2.43 Ibs/day
acetone
Mass limit for acetone in stream 5
9,690 pg/L x 200 gal/day x 8.345 x 10'9 = 0.02 Ibs/day
acetone
Total flow = 90,300 gpd
Dilution flow = Fx + F4 = 5,1000 gpd
Flow in stream 2 = 55,000 gpd
Flow in stream 3 = 30,000 gpd
Flow in stream 5 = 200 gpd
6.90 Ibs x f 90,300 gpd -5,100 gpd] = 6.90 Ibs
day [ 85,200 gpd J day
The monthly average discharge limitation for acetone is 6.90 Ibs/day. Monthly average
limitations for isopropanol can be calculated in a similar manner.
A-25
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3.3
PSES Effluent Limitations for Co-Proposal 2
Co-proposal 2 sets in-plant limitations for the 13 pollutants listed in Table 17-5 of the
TDD. There are not end-of-pipe standards for any pollutants under this co-proposal
except ammonia. Facility B would have no limitations for acetone and isopropanol
under this co-proposal, but would still have in-plant limitations for chloroform, cyanide,
and toluene. The limitations for chloroform, cyanide, and toluene would be the same as
those shown for co-proposal 1.
A-26
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4.0
CASE STUDY 3, NSPS FOR A MULTIPLE SUBCATEGORY FACILITY
Facility C is a multiple subcategory direct discharging pharmaceutical facility built after
this rule is promulgated and in effect. A wastewater flow schematic for this facility is
presented in Figure A-3.
4.1
NSPS Effluent Limitations
Tables 16-2 and 16-3 of the TDD present the proposed daily maximum and monthly
average NSPS for Subcategories A and C, and Subcategories B and D, respectively.
NSPS for ammonia and the organic pollutants listed in these tables are applicable to the
final effluent discharged to the waters of the United States.
The proposed standards are concentration-based and, as such, do not regulate
wastewater flow. The permit writer must use a reasonable estimate of process
wastewater discharge flow and the concentration-based standards to develop mass-based
standards for the NPDES permit.
NSPS for cyanide is presented in Table 16-2 of the TDD as well, and are applicable to
those wastewaters from Subcategories A and C operations known or believed to contain
cyanide. Compliance monitoring for cyanide should occur in-plant, prior to dilution or
mixing with any non-cyanide bearing wastewater. In-plant monitoring is required to
prevent compliance through dilution with non-cyanide-bearing wastewaters.
A-27
-------
O
CHEMICAL
SYNTHESIS #1
/ N 35.000 ood ^
W *
Non-contact Cooling
^
JOO.OOO gpd r
O
ID
O
O
D
O
V-
D
£
05
JC
O
00
O)
3
8
d
-------
The first step in establishing permit limitations is to determine the types of wastestreams
(i.e., regulated process, unregulated process, and dilute). The flow breakdown for Facility
C would look like this:
Waste Stream
Flow (gal/day)
Outfall #001
1. Chemical Synthesis
2. Biological Extraction
3. Boiler Blowdown
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
35,000
30,000
150
(Regulated, Sub. C)
(Regulated, Sub. B)
(Dilute)
65,150
65,000
0
150
Outfall #002
1. Non-Contact Cooling
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
550,000
550,000
0
0
550,000
Streams 1 and 2 are considered regulated wastestreams because effluent limitations have
been established for chemical synthesis operations (Subcategory C) and biological
extraction operations (Subcategory B).
We will assume that Facility C has provided the permit writer with accurate
characterization of its process wastestreams by means available such as projected solvent
use and disposition data, and analytical scans of each stream. Permit limitations should
be established and compliance monitoring required for each regulated pollutant listed on
Table 16-1 generated or used at a pharmaceutical manufacturing facility. Limitations
A-29
-------
and routine compliance monitoring are not required for regulated pollutants not
generated or used at a facility. A determination that regulated pollutants are not
generated or used should be based on a review of all raw materials used and an
assessment of all chemical processes used, considering resulting products and by-
products. The determination that a regulated pollutant is not generated or used must be
confirmed by annual chemical analyses of wastewater from each monitoring location.
Such confirmation is provided by an analytical measurement of a non-detect value.
The following presents a summary of the regulated pollutants expected to be found in
this faculty's wastestream:
Stream
I
2
3
Subcategory
C
B
N/A
Flow (gpd)
35,000
30,000
150
Pollutant
Methylene chloride,
tetrahydrofuran, acetone,
methanol, toluene, BOD5,
COD, TSS
Methanol, tetrahydrofuran,
BODS, COD, TSS
No NSPS pollutants
Based on the above data, permit writers would use reasonable estimates of the process
wastewater discharge flow and the concentration-based standards in Tables 16-2 and 16-3
to develop limitations for methylene chloride, tetrahydrofuran, acetone, methanol, and
toluene in the NPDES permit. Permit limitations would also be established for BOD5,
COD, and TSS.
A-30
-------
4.2
NSPS Maximum Limitations for Any One Dav
As shown in Tables 16-2 and 16-3, methylene chloride, acetone, methanol, and toluene
have maximum daily limitations of ND for all subcategories. Non-detect (ND) values
are concentration-based measurements reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Therefore, the permit
limitation for methylene chloride, acetone, methanol, and toluene should specify ND for
all measurements. Any concentration measurements greater than the ND value for the
pollutant are considered out of compliance.
Tetrahydrofuran has a numerical limitation for all subcategories. The concentration-
based limitations in Tables 16-2 and 16-3 should be converted to maximum daily mass-
based limitations as shown below:
Stream 1 (Sub. C): (910 pg/L x 35,000 gal/day x 8.345 x 10'9)
Stream 2 (Sub. B): (910 Mg/L x 30,000 gal/day x 8.345 x 10'9)
Total = 0.50 Ibs/day
0.27 Ibs/day
0.23 Ibs/day
Stream 3 is considered a dilution stream, and therefore does not receive a discharge
mass allowance. The total facility maximum day discharge limitation for tetrahydrofuran
is 0.50 Ibs/day.
The limitations for BOD5, COD, and TSS would also be applied to the final effluent.
The total NSPS maximum for any one day discharge for BOD5 can be calculated by
summing the allowable mass discharges for each process stream as follows:
Stream 1 (Sub. C): (62 mg/L x 35,000 gal/day x 7.345 x 10'6) = 18.1 Ibs/day
Stream 2 (Sub. B): (34 mg/L x 30,000 gal/day x 7.345 x lO"6) = 8.5 Ibs/day
Total = 26.6 Ibs/day BOD5
A-31
-------
The total facility maximum discharge of BOD5 for any one day is 26.6 Ibs/day.
Maximum day effluent limitations for COD and TSS can be calculated in a similar
manner.
4.3
NSPS Monthly Average Limitations
Maximum for any one day and monthly average limitations for methylene chloride,
acetone, methanol, and toluene are ND. Therefore, the permit limitations for these
pollutants should specify ND for all measurements.
The total NSPS monthly average discharge limitation for tetrahydrofuran can be
calculated as shown below.
Stream 1 (Sub. C): (264 pg/L x 35,000 gal/day x 8.345 x 10'9)
Stream 2 (Sub. B): (264 /xg/L x 30,000 gal/day x 8.345 x 10'9)
Total = 0.15 Ibs/day
0.08 Ibs/day
0.07 Ibs/day
Stream 3 is considered a dilution stream, and therefore does not receive a discharge
mass allowance. The monthly average discharge limitation for tetrahydrofuran is 0.15
Ibs/day.
The total NSPS monthly average discharge limitation for BOD5 can be calculated as
follows:
Stream 1 (Sub. C): (29 mg/L x 35,000 gal/day x 8.345 x 10'6)
Stream 2 (Sub. B): (10 mg/L x 30,000 gal/day x 8.345 x 10'6)
Total = 11.0 Ibs/day BOD5
8.47 Ibs/day
2.50 Ibs/day
The monthly average discharge limitation for BOD5 is 11.0 Ibs/day. Monthly average
effluent limitations for COD and TSS can be calculated in a similar manner.
A-32
-------
5.0
CASE STUDY 4, PSNS FOR A MULTIPLE SUBCATEGORY FACILITY
Facility D is a multiple subcategory indirect discharging pharmaceutical facility built after
this rule is promulgated and in effect. A wastewater flow schematic for this facility is
presented in Figure A-4.
5.1
PSNS Effluent Limitations
Two scenarios are presented for PSNS. The first would apply under co-proposal 1 and
the second would apply under co-proposal 2. Co-proposal 1 for Subcategories A and C
sets in-plant standards for 28 pollutants and end-of-pipe standards for 19 pollutants.
Co-proposal 2 for Subcategories A and C sets in-plant standards for 13 pollutants, but
has no end-of-pipe standards except for ammonia. In Subcategories B and D cyanide
and ammonia are not regulated. Co-proposal 1 for Subcategories B and D sets in-plant
standards for 27 pollutants and end-of-pipe standards for 18 pollutants. Co-proposal 2
for Subcategories B and D sets in-plant standards for 12 pollutants.
5.2
PSNS Effluent Limitations for Co-Proposal 1
Table 17-6 of the TDD presents the proposed daily maximum and monthly average
PSNS for Subcategories A, B, C, and D. The proposed standards are concentration-
based and, as such, do not regulate wastewater flow. Organics being controlled under
PSNS have been divided into two groups, one list for organics to be controlled in-plant,
and a second list of less volatile organics that are controlled at the end-of-pipe.
PSNS for cyanide is presented in Table 17-6 of the TDD as well, and are applicable to
those wastewaters from Subcategories A and C operations known or believed to contain
cyanide. Compliance monitoring for cyanide should occur in-plant, prior to dilution or
mixing with any non-cyanide bearing wastewater. In-plant monitoring is required to
prevent compliance through dilution with non-cyanide bearing wastewaters.
A-33
-------
I
< <
ULJ
•
5.000gpd
LU
< i§
.32
D: "
ffi
Sarttaiy
Q
"O
D
.O
"5
CD
O
05
O
CD
0)
-------
The first step in establishing permit limitations is to determine the types of wastestreams
(i.e., regulated process, unregulated process, and dilute). The flow breakdown for Facility
D would look like this:
Waste Stream
Outfall #001
1. Administration (Sanitary)
2. Chemical Synthesis #1
3. Mixing, Formulating, and Packaging
4. Boiler Slowdown
5. Research and Development
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
Flow (gal/day)
5,000
55,000
1,500
150
50
(Dilute)
(Regulated, Sub. C)
(Regulated, Sub. D)
(Dilute)
(Unregulated, Sub. E)
61,700
56,500
50
5,150
Outfall #002
1. Non-Contact Cooling
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
1,000
1,000
0
0
1,000
Streams 2 and 3 are considered regulated process wastestreams because effluent
limitations have been established for chemical synthesis operations (Subcategory C) and
mixing, compounding and formulating operations (Subcategory D). Thus, a reasonable
estimate of the process wastewater discharge flow for this example facility is 56,500
gal/day.
A-35
-------
Stream 5 is considered an unregulated process wastestream because effluent limitations
for organic pollutants have not been established for research and development
operations (Subcategory E).
We will assume that Facility D has provided the permit writer with accurate
characterization of its process wastestreams by means available such as projected solvent
use and disposition data, and analytical scans of each stream. Permit limitations should
be established and compliance monitoring required for each regulated pollutant listed on
Table 17-2 generated or used at a pharmaceutical manufacturing facility. Limitations
and routine compliance monitoring are not required for regulated pollutants not
generated or used at a facility. A determination that regulated pollutants are not
generated or used should be based on a review of all raw materials used and an
assessment of all chemical processes used, considering resulting products and by-
products. The determination that a regulated pollutant is not generated or used must be
confirmed by annual chemical analyses of wastewater from each monitoring location.
Such confirmation is provided by an analytical measurement of a non-detect value.
The following presents a summary of the regulated pollutants expected to be found in
this facility's wastestreams:
Stream
" 1
2
3
4
5
Subcategory
N/A
C
D
N/A
E
Flow (gpd)
5,000
55,000
• 1,500
150
50
Pollutant
No PSNS pollutants
Methylene chloride,
tetrahydrofuran, ammonia,
methanol, cyanide
Methanol, tetrahydrofuran
No PSNS pollutants
Ammonia
A-36
-------
Based on the above data, permit limitations are established for methylene chloride,
tetrahydrofuran, ammonia, methanol, and cyanide. All of these pollutants are listed in
Table 17-6.
5.2.1
PSNS Maximum Limitations for Any One Day
The limitations for both methanol and methylene chloride would be applied at in-plant
location point B, prior to any dilution, commingling with other treated wastestreams, and
any equalization or treatment units which are open to the atmosphere. In this example,
they would be applied to wastestreams 2 and 3. These maximum daily limitations would
be concentration-based, and are 8,320 ^tg/L and 809 jtg/L (from Table 17-6) for
methanol and methylene chloride, respectively. In-plant monitoring is required to
prevent compliance through dilution and by cross-media transfer of these pollutants from
wastewater to the atmosphere during collection, equalization, and end-of-pipe biological
treatment.
PSNS effluent limitations for cyanide should also be applied in-plant. The cyanide
standards are applicable to wastewaters from Subcategories A and C operations that
contain cyanide. Therefore, the concentration-based limitations for cyanide will apply to
process wastestream 2 at point A, prior to dilution or mixing with any non-cyanide
bearing wastewater. The maximum daily limitation for cyanide is 766 /wg/L (from Table
17-6).
PSNS for ammonia and tetrahydrofuran would be applied to the facility effluent at point
C. The concentration-based standards contained in Table 17-6 would be converted to
mass-based
A-37
-------
permit limitations. These mass-based limitations can be calculated using the CWF
shown below:
where:
MT
M,
F,
FD
Ft
N
N
EH
i=l
X
F -F
rT CD
N
£*
i=l
Alternative mass limit for the pollutant in the combined
wastestream (mass per day)
Pretreatment standard for the pollutant in the regulated
stream i (mass per day)
Average daily flow (at least 30 day average) of the regulated
stream i
Average daily flow (at least 30 day average) of dilute
wastestream(s) entering the combined treatment system
Average daily flow (at least 30 day average) through the
combined treatment facility (including regulated, unregulated,
and dilute wastestreams)
Total number of regulated streams
To determine the mass-based limitation for ammonia, the previously listed variables are
calculated as follows:
Mt = M3 = M4 = Ms = 0 (since these streams are considered either
dilution water, or unregulated process
wastewater with respect to ammonia)
M2
M2
Mass limit for ammonia in stream 2
12,900 jtg/L x 55,000 gal/day x 8.345 x 10'9 = 5.92 Ibs/day
ammonia
Wastestream 1 (sanitary wastewater) and wastestream 4 (boiler blowdown) are
considered dilution water. Wastestream 3 (wastewater from formulating and packaging,
Subcategory D) is also considered dilution water for the purpose of calculating ammonia
limitations, because ammonia is not regulated in Subcategory D, and ammonia is not
present in wastestream 3 at this facility. Wastestream 5 (wastewater from research
operations, Subcategory E) is considered unregulated process wastewater, because the
A-38
-------
facility has made a demonstration (based on analysis of wastewater samples) that
ammonia is expected to be present in this wastewater at treatable concentrations.
Therefore:
FT
FD
F2
Total flow = 61,700 gpd
Dilution flow = Fl + F3 + F4 = 6,650 gpd
55,000 gpd
day
61,700 gpd - 6,650 gpd } _ 5.93 Ibs
55,000 gpd
day
ammonia
To determine the mass-based limitation for tetrahydrofuran, the previously listed
variables are calculated as follows:
M2
M2
M3
M3
M5
M4 = 0 (since these streams are considered dilution water)
Mass limit for tetrahydrofuran in Stream 2
9,210 pg/L x 55,000 gal/day x 8.345 x 10'9 = 4.23 Ibs/day
Mass limit for tetrahydrofuran in stream 3
9,210 jttg/L x 1,500 gal/day x 8.345 x 10'9 = 0.12 Ibs/day
0 (since this wastestream is unregulated)
While Subcategory E wastewater is unregulated for the pollutant tetrahydrofuran
according to the definition in the General Pretreatment Regulations, Control Authorities
have the authority to determine whether unregulated streams should be considered
dilution under 40 CFR § 403.6(d). Since tetrahydrofuran was not found to be present in
Subcategory E wastewater in this example, this wastestream is considered here as
dilution water.
M,-
FT
FD
F2
F3
4.35 Ibs
day
x
Total flow = 61,700 gpd
Dilution flow =
55,000 gpd
1,500 gpd
+ F4 + F5 = 5,200 gpd
'61,700 gpd - 5,200 gpd'
56,500 gpd
= 4.35 Ibs/day tetrahydrofuran
A-39
-------
Total facility maximum day discharge limitations for ammonia and tetrahydrofuran are
5.93 Ibs/day and 4.35 Ibs/day, respectively.
5.2.2
PSNS Monthly Average Limitations
The monthly average discharge standards for methanol and methylene chloride are ND
and 279 jcg/L, respectively. These standards would be applied to process wastewater
streams 2 and 3 at point B, prior to any dilution, commingling with other treated
wastestreams, and any equalization or treatment units which are open to the atmosphere.
Note that the published monthly average standard for methanol is ND. However, since
the maximum for any one day standard is not ND, measurements above the minimum
level are permitted. Within the course of a month, the average value of all
measurements should be equal to or less than the minimum level of 3,180
The monthly average discharge standard for cyanide is 406 /*g/L. This standard will be
applied to process wastestream 2 at point A, prior to dilution or mixing with any non-
cyanide bearing wastewater.
The monthly average discharges for ammonia and tetrahydrofuran should be applied at
end-of-pipe location point C and can be calculated by using the CWF shown in Section
5.2.1 of this example. The following variables would be calculated to determine the
ammonia monthly average discharge limitation.
Mt = M3 = M4 = M5 = 0
M2 = 10,900 pg/L x 55,000 gal/day x 8.345 x 10'9 = 5.00 Ibs/day
ammonia
FT = Total flow = 61,700 gpd
FD = Dilution flow = Fl + F3 + F4 = 6,650 .gpd
F2 = 55,000 gpd
A-40
-------
61,700 gpd - 6,650 gpd ] _ 5.00 Ibs
day
55,000 gpd
J
day
ammonia
The monthly average for tetrahydrofuran is calculated similarly and is shown below:
Mj = M4 = M5 = 0
M2 = 3,360 Mg/L x 55,000 gal/day x 8.345 x 10'9 = 1.54 Ibs/day
tetrahydrofuran
M3 = 3,360 Atg/L x 1,500 gal/day x 8.345 x 10'9 = 0.042 Ibs/day
tetrahydrofuran
FT = 61,700 gpd
FD = Fj + F4 + Fs = 5,200 gpd
F2 = 55,000 gpd
F3 = 1,500 gpd
„ L581bs x f 61,700 gpd -5,200 gpd 1 = L581bs tetrahydrofuran
^
day
56,500 gpd
day
The monthly average discharge limitations for ammonia and tetrahydrofuran are
5.00 Ibs/day and 1.58 Ibs/day, respectively.
5.3
PSNS Effluent Limitations for Co-Proposal 2
Co-proposal 2 sets in-plant limitations for the 13 pollutants listed in Table 17-7 of the
TDD. There are no end-of-pipe limitations for any pollutants except ammonia under
this co-proposal. Facility D would have no limitations for methanol and tetrahydrofuran
under this co-proposal, but would still have in-plant limitations for cyanide and
methylene chloride, and an end-of-pipe limitation for ammonia. The limitations for
these three pollutants would be the same as those shown for co-proposal 1.
A-41
-------
6.0
CASE STUDY 5, BPT AND BAT EFFLUENT LIMITATIONS FOR A
MULTIPLE INDUSTRIAL CATEGORY FACILITY
Facility E is a direct discharging manufacturing facility with operations in two industrial
categories. Pharmaceuticals as well as bulk organic chemicals are produced at this
facility. A wastewater flow schematic for this facility is presented in Figure A-5.
6.1
BPT Effluent Limitations
The revised BPT effluent limitations guidelines establish new BODS, COD, and TSS
effluent limitations for Subcategory A, B, C, and D direct discharging facilities. As
described in Case Study 1, the pH effluent limit will not be amended, and other
conventional pollutants will not be regulated by BPT for the pharmaceutical
manufacturing point source category.
The proposed effluent limitations and guidelines are concentration-based and, as such,
do not regulate wastewater flow. The permit writer must use a reasonable estimate of
process wastewater discharge flow and the concentration-based limitations to develop
mass-based limitations for the NPDES permit. Table 13-1 of the TDD presents the
proposed maximum daily and monthly average BPT effluent limitations for Subcategory
A, B, C, and D direct discharging facilities.
The limitations for BOD5, COD, and TSS will be applied to the final effluent at
monitoring point B. An example calculation of the BPT maximum day and monthly
average BOD5, COD, and TSS limitations for this facility is as follows.
A-42
-------
a LU
^3
Is
-&
Slowdown
1,000 gpd
LU . VJ
3381
^155
^ ^ z &
Qi>S
^o^§
5.000 gpd
ll|l^
^> 7S ^ i
105.000 gpd
LLJ
'O
£
5
.o
"o
en
<
-------
6.1.1
Maximum Effluent Limitations for Any One Day
The first step in establishing permit limitations is to determine the types of wastestreams
present The flow breakdown for facility E would look like this:
Waste Stream
1. Fermentation
3. Chemical Synthesis
4. Bulk Organic Chemicals
5. Chemical Synthesis
6. Boiler Blowdown
Total Wastewater Flow:
Total Regulated Process:
Total Unregulated Process:
Total Dilute:
2. Noncontact Cooling Water
(added after monitoring point B)
Flow (gal/day)
500,000
80,000
105,000
5,000
1,000
691,000
690,000
0
1,000
100,000
(Regulated,
(Regulated,
(Regulated,
(Regulated,
(Dilute)
(Dilute)
Sub. A)
Sub. C)
OCPSF)
Sub. C)
Streams 1, 3, 4, and 5 are considered regulated wastestreams as effluent limitations have
been established for fermentation operations (Subcategory A), chemical synthesis
operations (Subcategory C), and OCPSF bulk organic chemical operations. (3)
Table 13-1 of the TDD presents the proposed maximum daily and monthly average BPT
effluent limitalions for Subcategories A and C. 40 CFR §414.71 presents the proposed
maximum daily and monthly average BPT effluent limitations for bulk organic chemical
OCPSF wastewaters. (3) The total BPT maximum for any one day discharge for BOD5
can be calculated as follows:
A-44
-------
Stream 1 (Sub. A): (139.7 mg/L x 500,000 gal/day x 8.345 x 10'6) = 582.9 Ibs/day
Stream 3 (Sub. C): (139.7 mg/L x 80,000 gal/day X 8.345 x 10'6) = 93.3 Ibs/day
Stream 4 (OCPSF): (92 mg/L x 105,000 gal/day x 8.345 x 10'6) = 80.6 Ibs/day
Stream 5 (Sub. C): (139.7 mg/L x 5,000 gal/day x 8.345 x lO'6) = 5.8 Ibs/day
Total = 763 Ibs BODs/day
TSS maximum day effluent limitations can be calculated in a similar manner.
Proposed maximum daily and monthly average COD effluent limitations for
Subcategories A and C are also presented in Table 13-1. However, COD is not
regulated in wastewater from chemical synthesis operations at OCPSF facilities. (3) In
cases where OCPSF wastewaters are combined with pharmaceutical wastewaters and
treated in a central unit, the maximum daily limitation for COD can be calculated by
determining the mass discharge allowance using the CWF shown below:
where:
MT
M;
F,
FD
FT
N
N
N
Alternative mass limit for the pollutant in the combined
wastestream (mass per day).
Treatment standard for the pollutant in the regulated stream
i (mass per day)
Average daily flow (at least 30 day average) of the regulated
stream i
Average daily flow (at least 30 day average) of dilute
wastestream(s) entering the combined treatment system
Average daily flow (at least 30 day average) through the-
combined treatment facility (including regulated, unregulated,
and dilute wastestreams)
Total Number of regulated streams
A-45
-------
In this example, the previously listed variables are calculated as follows:
M2 = M4 = M6 = 0
M,
M3
M3
Ms
M5
FT
FD
(since these streams are considered dilution or
unregulated process wastewater)
Mass limit for COD in stream 1
1,100 mg/1 x 500,000 gal/day x 8.345 x 10'6 =
4,589.75 Ibs/day
Mass limit for COD in stream 3
1,100 mg/L x 80,000 gal/day x 8.345 x 10"6 =
734.36 Ibs/day
Mass limit for COD in stream 5
1,100 mg/L x 5,000 gal/day x 8.345 x 1Q-6 = 45.90 Ibs/day
Total flow = 791,000 gpd
Dilution flow = F6 = 1,000 gpd
Flow in stream 1 = 500,000 gpd
Flow in stream 3 = 80,000 gpd
Flow in stream 5 = 5,000 gpd
_ 5,370 Ibs x [691,000 gpd -1,000 pgdl = fi 34 lbg/dft CQD
^ day |_ 585,000 gpd J
Total facility discharge limitation for any one day for COD is 6,334 Ibs/day.
6.12
Monthly Average Effluent Limitations
Monthly average limitations for BOD5 can be calculated as shown below:
Stream 1 (Sub. A): (57.8 mg/L x 500,000 x 8.345 x lO"6) = 241.2 Ibs/day
Stream 3 (Sub. C): (57.8 mg/L x 80,000 x 8.345 x 10"6) = 38.6 Ibs/day
Stream 4 (OCPSF): (34 mg/L x 105,000 x 8.345 x lO"6) = 29.8 Ibs/day
Stream 5 (Sub. C): (57.8 mg/L x 5,000 x 8.345 x lO"6) = 2.4 Ibs/day
Total = 312 Ibs BOD5/day
TSS monthly average effluent limitations can be calculated in a similar manner.
A-46
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The monthly average limitations for COD can be determined by using the CWF from
Section 6.1.1. The following variables should be changed from those listed in Section
6.1.1:
628 mg/L x 500,000 gal/day x 8.345 x W6 = 2,620.33
Ibs/day
628 mg/L x 80,000 gal/day x 8.345 x lO'6 = 419.25 Ibs/day
628 mg/L x 5,000 gal/day x 8.345 x 10'6 = 26.20 Ibs/day
M, =
M3 =
M5 =
j, = 3,066 Ibs
day
Total facility monthly average discharge limitation for COD is 3,616 Ibs/day.
6.2
BAT Effluent Limitations
Tables 15-2 and 15-3 of the TDD present the proposed maximum daily and monthly
average BAT effluent limitations guidelines for Subcategories A and C, and
Subcategories B and D, respectively.
We will assume that Facility E has provided the permit writer with an accurate
characterization of its process wastestreams by means available such as solvent use and
disposition data, and analytical scans of each stream. Permit limitations should be
established and compliance monitoring required for each regulated pollutant listed on
Table 15-1 generated or used at a pharmaceutical manufacturing facility. Limitations
and routine compliance monitoring are not required for regulated pollutants not
generated or used at a facility. A determination that regulated pollutants are not
generated or used should be based on a review of all raw materials used and an
assessment of all chemical processes used, considering resulting products and by-
products. The determination that a regulated pollutant is not generated or used must be
confirmed by annual chemical analyses of wastewater from each monitoring location.
Such confirmation is provided by an analytical measurement qf a non-detect value.
A-47
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The following presents a summary of the regulated pollutants expected to be.found in
this facility's wastestreams:
Stream
1
2
3
4
5
6
Subcategory
A
N/A
C
OCPSF
C
N/A
Flow (gal/day)
500,000
100,000
80,000
105,000
5,000
1,000
Pollutant
Methylene chloride
Methanol
Toluene
None
Cyanide
Aniline
Methylene chloride
Methanol
Aniline
Methylene chloride
Methanol
None
Concentration
(mg/L)
100
1,000
700
None
50
500
200
100
100
150
250
None
Based on the above data, permit limitations would be established for aniline, methanol,
methylene chloride, and toluene.
6.2.1
BAT Maximum Limitations for Any One Day
The limitations for all organic pollutants listed would be applied to the final effluent at
monitoring point B. The Subcategories A and C maximum daily limitations for niethanol
are ND (from Table 15-2). Therefore, the permit limitation for methanol is
concentration-based and should be ND for all measurements. Non-detect (ND) values
are concentration-based measurements reported below the minimum level that can be
reliably measured by the analytical method for the pollutant. Therefore, the permit
limitation for methanol should specify ND for all measurements. Any concentration
measurements greater than the ND value for the pollutant are considered out of compliance.
A-48
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BAT effluent limitations for cyanide should be applied in-plant. The cyanide standards
are applicable to wastewaters from Subcategories A and C operations that contain
cyanide. Therefore, the concentration-based limitations for cyanide will apply to process
wastestream 3 at point A, prior to dilution or mixing with any non-cyanide bearing
wastewater. The maximum daily limitation for cyanide is 766 ^g/L (from Table 15-2).
The allowable mass discharge of methylene chloride for any one day can be calculated as
follows. Streams 2 and 6 are dilution water in this example.
BAT Maximum Day Effluent Limitation For Methylene Chloride
Methylene chloride is present and regulated in both pharmaceutical and OCPSF bulk
chemicals wastewater. We are assuming Facility E produces more than five million
pounds of OCPSF chemicals per year, and have applied the methylene chloride daily
limitation for OCPSF wastewaters listed in 40 CFR §414.91 as shown below. (3) The
limitations for methylene chloride for Subcategories A and C are ND. However,
methylene chloride has a numerical limitation for OCPSF regulations. (3) Since
monitoring points for organic pollutants under BAT are at end-of-pipe locations and all
process wastewaters will be combined at this location, a mass limitation for the combined
wastestream can be determined by using the numerical value of the minimum level of
this pollutant to determine the Subcategory A and C portion of the mass limitations.
Stream 1 (Sub. A): (10 jug/L x 800,000 x 8.345 x 10'9) = 0.042 Ibs/day
Stream 3 (Sub. C): (10 pg/L x 80,000 x 8.345 x 10'9) = 0.007 Ibs/day
Stream 4 (OCPSF): (89 ^g/L x 105,000 x 8.345 x 10'9) = 0.078 Ibs/day
Stream 5 (Sub. C): (10 jig/L x 5,000 x 7.345 x 10'9) = 0.0004 Ibs/day
Total = 0.127 Ibs/day
The total maximum day discharge for methylene chloride is 0.127 Ibs/day.
A-49
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BAT Maximum Day Effluent Limitation For Aniline
Aniline is present in streams 3 and 4 but is not regulated in wastewater from chemical
synthesis operations at OCPSF facilities (stream 4). In cases where OCPSF wastewaters
are combined with pharmaceutical wastewaters and treated as a central unit, the
maximum daily limitations for aniline can be calculated by determining the mass
discharge allowance using the CWF shown in Section 6.1.1. The following variables
should be changed from those listed in Section 6.1.1:
M3
M5
l(Vg/L x 500,000 gal/day x 8.345 x 10'9 = 0.042 Ibs/day
10/zg/L x 80,000 gal/day x 8.345 x 10'9 = 0.007 Ibs/day
10/ig/L x 5,000 gal/day x 8.345.x 10'9 = 0.0004 Ibs/day
= 0.0494 Ibs x [691,000 gpd-1,000 gpd] = Q Q58 lbg/day
n
day |_ 585,000 gpd J
The faculty maximum discharge limitation for any one day for aniline is 0.0058 Ibs/day.
BAT Maximum Day Effluent Limitation for Toluene
The limitations for toluene for Subcategories A and C are ND. However, toluene has a
numerical Mmitation for OCPSF regulations. (3) Since monitoring points for organic
pollutants under BAT are at end-of-pipe locations and all process wastewater will be
combined at this location, a mass limitation for the combined wastestream can be
determined by using the numerical value of the minimum level of this pollutant to
determine the Subcategory A and C portion of the mass Limitations.
Stream 1 (Sub. A): (10 /tg/L x 500,000 x 8.345 x 10'9) = 0.042 Ibs/day
Stream 3 (Sub. C): (10 pg/L x 80,000 x 8.345 x 10'9) = 0.007 Ibs/day
Stream 4 (OCPSF): (80 pg/L x 105,000 x 8.345 x 10'9) = 0.070 Ibs/day
Stream 5 (Sub. C): (10 jtg/L x 5,000 x 8.345 x 10'9) = 0.0004 Ibs/day
Total = 0.12 Ibs/day toluene
The faculty maximum discharge limitation for any one day for toluene is 0.12 Ibs/day.
A-50
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6.2.2
BAT Monthly Average Limitations For Organic Pollutants
Monthly average limitations for methanol are ND, the same as they were for maximum
daily limitations. Thus, the permit limitations for methanol should be ND for all
measurements.
The monthly average discharge standard for cyanide is 406 /*g/L. This standard will be
applied to process wastestream 3 at point A, prior to dilution or mixing with any non-
cyanide bearing wastewater.
BAT Monthly Average Limitation for Methylene Chloride
The monthly average limitations for methylene chloride can be calculated in the same
manner as the daily maximum limitations. These calculations are shown below:
Subcategories A and C allowable discharge:
10 jtg/L x (500,000 gpd + 80,000 gpd + 5,000 gpd) x 8.345 x 10'9 = 0.049 Ibs/day
OCPSF Bulk Chemicals Subcategory:
40 pg/L x 105,000 gpd x 8.345 x 10'9 = 0.035 Ibs/day
Total = 0.084 Ibs/day
The monthly average discharge limitation for methylene chloride is 0.084 Ibs/day.
BAT Monthly Average Limitation For Aniline
The monthly limitations for aniline are the same as the daily maximum limitations shown
in Section 6.1.2.
A-51
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BAT Monthly Average Limitation for Toluene
The monthly average limitations for toluene can be calculated in the same manner as the
daily maximum limitations. These calculations are shown below:
Subcategories A and C allowable discharge:
10 ftg/L X (500,000 gpd + 80,000 gpd + 5,000 gpd) x 8.345 x 10'9 = 0.049 Ibs/day
OCPSF Bulk Chemicals Subcategory:
26 jtg/L X 105,000 gpd x 8.345 x 10'9 = 0.023 Ibs/day
Total = 0.072 Ibs/day toluene
The monthly average discharge limitation for toluene is 0.072 Ibs/day.
A-52
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1.
2.
3.
REFERENCES
U.S. EPA, Office of Water. Training Manual for NPDES Permit Writers.
EPA 833-B-93-003, U.S. Environmental Protection Agency, Washington,
D.C., 1993.
U.S. EPA. Pharmaceutical Manufacturing Point Source Category Effluent
Limitations Guidelines, Pretreatment Standards, and New Source
Performance Standards; Proposed Regulation, 40 CFR Part 439, FRL
2229-3, Federal Register, November 26, 1982.
U.S. EPA. Plastics, and Synthetic Fibers Effluent Limitations Guidelines,
Pretreatment Standards, and New Source Performance Standards; 40 CFR
Part 414.
A-53
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APPENDIX B
BEST MANAGEMENT PRACTICES
FOR THE
PHARMACEUTICAL MANUFACTURING INDUSTRY
1.0
INTRODUCTION AND BACKGROUND
Section 304(e) of the CWA gives the Administrator the authority to publish regulations,
in addition to the effluent limitations guidelines and standards, to control plant site
runoff, spillage or leaks, sludge or waste disposal, and drainage from raw material
storage that the Administrator determines are associated with or ancillary to the
industrial manufacturing or treatment process of the regulated point source category and
that she (he) determines may contribute significant amounts of pollutants to waters of
the United States.
EPA is not proposing in the proposed rules best management practices (BMPs) pursuant
to Section 304(e) of the Clean Water Act. However, EPA is soliciting comment on
whether BMPs are applicable to the pharmaceutical industry and, if so, what they should
include. See section XIII of the preamble for solicitation of data and comments,
solicitation number 31.0. BMPs established under Section 304(e) may be different from
effluent limitations guidelines and standards principally because BMPs are specific
requirements for conduct, not performance standards.
When EPA sets technology-based effluent limits, those limits may be achieved by any
technology a discharger chooses. However, when EPA establishes BMPs under Section
304(e) of the CWA, and those BMPs are incorporated into a discharger's permit, the
discharger must perform those specific BMPs. The fact that a discharger had met all its
technology-based effluent limits would not be a defense, if the discharger were charged
with a permit violation for failing to perform its BMPs.
B-l
-------
BMPs for the pharmaceutical manufacturing industry, which might include spill
prevention, control provisions, and other aspects to prevent the release of raw materials,
solvents, and process chemicals to wastewaters, would control the release of constituents
listed in sections 307(a) and 311(e) of the CWA, such as methylene chloride, toluene,
chloroform, and chloromethane (methyl chloride).
Information currently available to the Agency indicates that the following are activities
and problems that can occur at pharmaceutical manufacturing plants that may be
controlled by BMPs.
• Spills of solvents.
• Operator error resulting in dropped batches.
• Spilled or mishandled product or intermediate from internal
transport operations.
• Failure of storage tank level indicators resulting in overfilling and
spillage.
• Lack of dikes or berms in chemical storage areas.
• Use of drum storage which can result in poor housekeeping
practices.
• Reaction vessel "burps" which release product and intermediate
materials to roof vents. Rain then picks the pollutants released by
the "burps" which are then released to stormwater.
• Material losses during tank truck loading and unloading operations.
• Complicated piping systems that increase the probability of operator
error.
• Presence and use of floor drains that are used to dispose of spills to
the sewer instead of a more controlled cleanup.
B-2
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The above activities and accidents tend to discharge slug loads to the sewer systems
which can cause interference, pass-through, or endanger worker safety at an on-site
treatment facility or POTW. EPA is evaluating whether control over the above
situations is adequately provided by the proposed effluent limitations guidelines and
standards and the General Pretreatment Regulations, or if Best Management Practices
specific to the Pharmaceutical Manufacturing Industry are warranted.
In 1986, the Domestic Sewage Study (DSS) found that categorical pretreatment
standards were not always effective in handling accidental spills or irregular high strength
batch discharges.
On July 24, 1990, the Agency promulgated amendments to the general pretreatment and
NPDES regulations to enhance the control of toxic pollutant and hazardous waste
discharges to POTWs (55 FR 30082). One of the amendments, 40 CFR 403.8(f)(2)(v),
specifically addresses slug discharges. It provides that POTWs with approved
pretreatment shall evaluate, at least once every two years, whether each significant
industrial user (defined in 40 CFR 403.3(t)) needs a plan to control slug discharges. For
the purposes of this provision, a slug discharge is any discharge of a non-routine, episodic
nature, including but not limited to an accidental spill or a non-customary batch
discharge. If a POTW decides that a slug control plan is needed, CFR 403.8(f)(2)(v)
provides that the plan shall contain, at a minimum, the following elements:
Description of discharge practices, including non-routine batch
discharges;
Description of stored chemicals;
Procedures for immediately notifying the POTW of slug discharges,
including any discharge that would violate a prohibition under 40
CFR 403.5(b), with procedures for follow-up written notification
within five days;
B-3
-------
If necessary, procedures to prevent adverse impact from accidental
spills, including inspection and maintenance of storage areas,
handling and transfer of materials, loading and unloading
operations, control of plant site run-off, worker training, building of
containment structures or equipment, measures for containing toxic
organic pollutants (including solvents), and/or measures and
equipment for emergency response.
This provision sets forth only the minimal federal requirements for slug control plans.
All POTWs (not just those required to establish federally approved pretreatment
programs) may require such plans of any industrial user (not just significant industrial
users) as necessary. Such plans could complement the provisions of BMPs.
B-4
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2.0
POTENTIAL BMPs FOR THE PHARMACEUTICAL MANUFACTURING
INDUSTRY
Preparation and implementation of BMP plans for the pharmaceutical manufacturing
industry would primarily involve spill prevention and control. The BMP plan should
contain the following key elements:
(1) Engineering analyses;
(2) Engineered controls and containment;
(3) Work practices;
(4) Preventive maintenance;
(5) Dedicated monitoring and alarm systems;
(6) Surveillance and repair programs; and
(7) Employee training.
The BMP plan should be prepared in accordance with good engineering practice. If the
BMP plan calls for additional industry practices, facilities, equipment, procedures, or
methods, not fully operational, the details of the installation and the operational start-up
should be explained. The principal objective of the BMP plan should be to prevent
losses and spills of process materials and solvents from equipment items in
pharmaceutical manufacturing service; the secondary objectives should be to contain,
collect, and recover at the immediate process area1, or otherwise control, those spills
and losses that do occur, and to minimize atmospheric emissions of volatile organic
pollutants. The complete BMP plan should contain the elements described below.
'Immediate process area - The location at the facility where pharmaceutical chemical synthesis; fermentation;
natural or biological extraction; mixing, compounding, and formulating; and pharmaceutical research facilities
are located, generally the battery limits of the aforementioned processes. "Immediate process area" includes
pharmaceutical manufacturing storage and spill control tanks located at the facility, whether or not they are
located in the immediate process area.
B-5
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2.1
Engineering Analyses
The BMP plan should be approved and signed by the facility manager. The plan should
be based on a detailed engineering review of the pharmaceutical manufacturing
operations, including but not limited to the following equipment and associated
procedures: process equipment, storage tanks, pipelines and pumping systems, material
transfer equipment, loading and unloading facilities, and other appurtenant equipment in
pharmaceutical manufacturing service. The review should determine the magnitude and
routing of potential leaks, spills and intentional releases during the following periods of
operation:
Process start-ups and shut downs;
Response to off-specification batches;
Maintenance;
Storm events;
Power failures; and
Normal operations.
23,
Engineered Controls and Containment
The BMP plan should also contain a detailed engineering review of existing
pharmaceutical manufacturing containment facilities for the purpose of determining
whether there is adequate capacity for collection and storage of anticipated intentional
manufacturing diversions and sufficient contingency for collection and containment of
spills, based upon good engineering practice. The review should consider whether
adequate engineering control is provided on process and material handling area drains to
prevent slug loads of process material from being intentionally or inadvertently released
to the waste treatment or sewer system. The engineering review should also consider:
(1) The need for process wastewater diversion facilities to protect end-
of-pipe wastewater treatment facilities from adverse effects of
pharmaceutical manufacturing spills and diversions;
B-6
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(2) The potential for contamination of storm water from the immediate
process areas;
(3) The extent to which segregation and/or collection and treatment of
contaminated storm water from the immediate process areas is
appropriate; and
(4) The potential to reduce atmospheric emissions of volatile organic
pollutants where engineered controls and containment are found to
be inadequate by the detailed engineering review.
The BMP plan should specify specific required upgrades and improvements and provide
a firm schedule for implementing such improvements and upgrades.
2.3
Work Practices, Preventive Maintenance, and Dedicated Monitoring and
Alarm Systems
The BMP plan should specify the implementation .of preventive maintenance practices,
standard operating procedures, work practices, engineered controls and monitoring
systems to prevent manufacturing losses and to divert pharmaceutical manufacturing
process wastewaters (e.g. dropped batches) to containment facilities such that the
diverted or spilled materials may be returned to the process or metered to the
wastewater treatment system. Other standard operating procedures that should be
considered include the use of tank level alarms, and associated preventive maintenance
programs to ensure that alarms are functioning properly, to avoid overfilling tanks.
2.4
Surveillance and Repair
The BMP plan should include a program of regular visual inspections (at least once per
operating shift) of equipment items in pharmaceutical manufacturing service and a
program for repair of leaking equipment items. The repair program would encompass
immediate repairs when possible and tagging for repair during the next maintenance
outage those leaking equipment items that cannot be repaired during normal operations.
B-7
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The owner or operator of the facility should also establish conditions under which
production will be curtailed or halted to repair leaking equipment items or prevent
manufacturing losses. The repair program should include tracking repairs over time to
identify those equipment items where upgrade or replacement may be warranted based
upon frequency and severity of leaks or failures. The owner or operator should maintain
logs showing the date leaks were detected, the type of pharmaceutical manufacturing
process, an estimate of the magnitude of the leak, the date of first attempt at repair, and
the date of final repair. The logs should be maintained at the facility for review by the
Regional Administrator or his designee during normal working hours.
2.5
Employee Training
An important aspect of the BMP would be a program of initial and refresher training of
operators, maintenance personnel, and other technical and supervisory personnel who
have responsibility for operating, maintaining, or supervising the operation and
maintenance of equipment items and systems in pharmaceutical manufacturing service.
At a minimum the training would cover the use of engineered controls and containment,
work practices, preventive maintenance procedures, monitoring and alarm systems, and
surveillance and repair aspects of the BMP. Refresher training should be conducted
annually. The training would be documented and records of training would be
maintained at the facility for review by the Regional Administrator or his designee
during normal working hours.
The BMP plan should also specify a program of "boards of review" to evaluate each spill
not contained at the immediate process area and any intentional diversion of
pharmaceutical manufacturing material not contained in the immediate process area.
The boards of review should be conducted as soon as practicable after the event and
should be attended by the involved process operators, maintenance personnel, process
engineering personnel, and supervisory personnel and environmental control staff. A
brief report should be prepared for each board of review. The report should describe
B-8
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the equipment items involved, the circumstances leading to the incident, the effectiveness
of the corrective actions taken, and plans to develop changes to equipment and operating
and maintenance practices to prevent recurrence. Reports of the boards of review
should be included as part of the annual refresher training.
The BMP plan should also include a program to review any planned modifications to the
pharmaceutical manufacturing facilities and any construction activities in the
pharmaceutical manufacturing areas before these activities commence. The purpose of
the reviews should be to ensure that pharmaceutical manufacturing spill prevention and
control is considered as part of the planned modifications and that construction and
supervisory personnel are aware of and can avoid possible manufacturing upsets,
including spills, during manufacturing modification or construction.
B-9
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Appendix C
Variability Factors Associated with Proposed Limitations
for the Pharmaceuticals Manufacturing Industry
Final Appendix C
7 April 1995
0406-01.ip
C-l
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Table C-l
Variability Factors Associated with BPT Limitations
Pollutant or
Pollutant Property
BODS
COD
TSS
Cyanide
Subcategories A and C
1-day
3.31
2.25
3.96
3.25
30-day
1.37
1.29
1.39
1.72*
Subcategories B and D
1-day
5.07
3.31
4.60
-
30-day
1.55
1.35
1.47
- •
* 4-day variability factor.
Final Appendix C
7 April 1995
-------
Table C-2
Variability Factors Associated with BAT Limitations
Pollutant or Pollutant Property
Acetone
Acetonitrile
Ammonia
n-Amyl Acetate
Amyl Alcohol
Aniline
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chemical Oxygen Demand (COD)
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
Cyanide
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
Dimethylamine
N,N-Dimethylacetamide
N,N-Dimethylaniline
N,N-Dimethy]form amide
Dimethyl Sulfoxide
1,4-Dioxane
Ethanol
Ethyl Acetate
Subcategories A and C
1-day
3.65
3.98
1.89
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
2.25
3.98
2.21
3.98
3.98
3.25
3.98
6.83
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
2.47
3.98
4-day
1.57
1.69
1.26
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.29
1.69
1.32
1.69
1.69
1.72
1.69
2.37
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.34
1.69
Subcategories B and D
1-day
3.65
3.98
-
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.31
3.98
2.21
3.98
3.98
-
3.98
6.83
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
2.47
3.98
4-day
1.57
1.69
-
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.35
1.69
1.32
1.69
1.69
-
1.69
2.37
1,69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.34
1.69
Final Appendix C
7 April 1995
0406-01.ip
C-3
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Table C-2
(Continued)
Pollutant or Pollutant Property
Ethylene Glycol
Formaldehyde
Fonnamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Methanol
Methylamine
Methyl Cellosolve
Methyl Formate
Methylene Chloride
MEBK
2-Methylpyridine
Petroleum Naphtha
Phenol
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
Subcategories A and C
1-day
3^98
4.31
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
6.66
3.98
3.98
3.98
15.92
3.98
3.98
3.98
2.50
3.98
3.98
3.98
12.27
3.98
2.73
3.98
3.98
4-day
1.69
1.82
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
2.34
1.69
1.69
1.69
4.01
1.69
1.69
1.69
1.37
1.69
1.69
1.69
3.55
1.69
1.47
1.69
1.69
Subcategories B and D
1-day
3.98
4.31
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
6.66
3.98
3.98
3.98
15.92
3.98
3.98
3.98
2.50
3.98
3.98
3.98
12.27
3.98
2.73
3.98
3.98
4-day
1.69
1.82
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
2.34
1.69
1.69
1.69
4.01
1.69
1.69
1.69
1.37
1.69
1.69
1.69
3.55
1.69
1.47
1.69
1.69
Final Appendix C
7 April 1995
0406-01.ip
C-4
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Table C-3
Variability Factors Associated with NSPS
Pollutant or Pollutant Property
Acetone
Acetonitrile
Ammonia
n-Amyl Acetate
Amyl Alcohol
Aniline.
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
Cyanide
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
Dimethylamine
N,N-Dimethylacetamide
N,N-Dimethylaniline
N,N-Dknethylformamide
Dimethyl Sulf oxide
1,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene Glycol
Formaldehyde
Formamide
Subcategories A and C
1-day
3.65
3.98
1.89
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
2.21
3.98
3.98
3.25
3.98
6.83
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
2.47
3.98
3.98
4.31
3.98
4-day
1.57
1.69
1.26
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.32
1.69
1.69
1.72
1.69
2.37
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.34
1.69
1.69
1.82
1.69
Subcategories B and D
I-day
3.65
3.98
-
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
•3.98
2.21
3.98
3.98
-
3.98
6.83
3.98
3.98
3.98
3.98
3.98
3.98
3.98
3.98
2.47
3.98
3.98
4.31
3.98
4-day
1.57
1.69
-
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.32
1.69
. 1.69
-
1.69
2.37
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.69
1.34
1.69
1.69
1.82
1.69
Final Appendix C
7 April 1995
0406-01.ip
C-5
-------
Table C-3
(Continued)
Pollutant or Pollutant Property
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Metihanol
Methylamine
Methyl Cellosolve
Methyl Formate
Methylene Chloride
MBBK
2-Methylpyridine
Petroleum Naphtha
Phenol
Polyethylene Glycol 600
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
BODj
COD
TSS
Subcategories A and C
1-day
3.98
3.98
3.98
3.98
3.98
3.98
3.98
6.66
3.98
3.98
3.98
15.92
3.98
3.98
3.98
2.50
3.98
3.98
3.98
12.27
3.98
2.73
3.98
3.98
3.08
1.88
2.87
4-day
1.69
1.69
1.69
1.69
1.69
1.69
1.69
2.34
1.69
1.69
1.69
4.01
1.69
1.69 • •
1.69
1.37
1.69
1.69
1.69
3.55
1.69
1.47
1.69
1.69
1.43
1.29
1.42
Subcategories B and D
1-day
3.98
3.98
3.98
3.98
3.98
3.98
3.98
6.66
3.98
3.98
3.98
15.92
3.98
3.98
3.98
2.50
3.98
3.98
3.98
12.27
3.98
2.73
3.98
3.98
5.32
3.50
5.06
4-day
1.69
1.69
1.69
1.69
1.69
1.69
1.69
2.34
1.69
1.69
1.69
4.01
1.69
1.69
1.69
1.37
1.69
1.69
1.69
3.55
1.69
1.47
1.69
1.69
1.58
1.39
1.52
Final Appendix C
7 April 1995
0406-01.ip
C-6
-------
Table C-4
Variability Factors Associated with PSES
Pollutant or Pollutant Property
Acetone
Ammonia
n-Amyl Acetate
Amyl Alcohol
Aniline
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
Cyanide
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
Dimethylamine
N,N-Dimethylaniline
1,4-Dioxane
Ethanol
Ethyl Acetate
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyr aldehyde
Subcategories A and C
1-day
10.45
1.31
7.95
7.95
7.95 .
7.95
11.87
7.95
7.95
7.95
7.95
7.95
7.95
7.95
3.25
7.95
7.95
7.95
7.95
7.95
7.95
7.95
6.27
7.95
7.95
7.95
7.95
7.95
7.95
4-day
3.23
1.10
2.68
2.68
2.68
2.68
3.54
2.68
2.68
2.68
2.68
.2.68
2.68
2.68
1.72
2.68
2.68
2.68
2.68
2.68
2.68
2.68
2.23
2.68
2.68
2.68
2.68
2.68
2.68
Subcategories B and D
1-day
10.45
--
7.95
7.95
7.95.
7.95
11.87
7.95
7.95
7.95
7.95
7.95
7.95
7.95
~
7.95
7.95
7.95
7.95
7.95
7.95
7.95
6.27
7.95
7.95
7.95
7.95
7.95
7.95
4-day
3.23
~
2.68
2.68
2.68
2.68
3.54
2.68
2.68
2.68
2.68
2.68
2.68
2.68
-
2.68
2.68
2.68
2.68
2.68
2.68
2.68
2.23
2.68
2.68
2.68
2.68
2.68
2.68
Final Appendix C
7 April 1995
0406-01.ip
C-7
-------
Table C-4
(Continued)
Pollutant or Pollutant Property
Isopropanol
Isopropyi Acetate
Isopropyl Ether
Methanol
Methylamine
Methyl Cellosolve
Methyl Formate
Methylene Chloride
MIBK:
2-Methylpyriduie
Petroleum Naphtha
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
Subcategories A and C
1-day
7.82
7.95
7.95
8.48
7.95
7.95
7.95
8.09
7.95
7.95
7.95
7.95
7.95
5.97
1.98
7.95
7.95
7.95
4-day
2.60
2.68
2.68
2.76
2.68
2.68
2.68
2.79
2.68
2.68
2.68
2.68
2.68
2.18
1.48
2.68
2.68
2.68
Subcategories B and D
1-day
7.82
7.95
7.95
8.48
7.95
7.95
7.95
8.09
7.95
7.95
7.95
7.95
7.95
5.97
1.98
7.95
7.95
7.95
4-day
2.60
2.68
2.68
2.76
2.68
2.68
2.68
2.79
2.68
2.68
2.68
2.68
2.68
2.18
1.48
2.68
2.68
2.68
Final Appendix C
7 April 1995
0406-01.ip
C-8
-------
Table C-5
Variability Factors Associated with PSNS
Pollutant or Pollutant Property
Acetone
Ammonia
n-Amyl Acetate
Amyl Alcohol
Aniline
Benzene
2-Butanone (MEK)
n-Butyl Acetate
n-Butyl Alcohol
tert-Butyl Alcohol
Chlorobenzene
Chloroform
Chloromethane
Cyclohexane
Cyanide
o-Dichlorobenzene
1,2-Dichloroethane
Diethylamine
Diethyl Ether
Dimethylamine
N,N-Dimethylaniline
1,4-Dioxane
Ethanol
Ethyl Acetate
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyr aldehyde
Subcategories A and C
1-day
3.07
1.31
5.72
5.72
5.72
5.72
6.24
5.72
5.72
5.72
5.72
5.72
5.72
5.72
3.25
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
4-day
1.54
1.10
2.12
2.12
2.12
2.12
2.24
2.12
2.12
2.12
2.12
2.12
2.12
2.12
1.72
2.12
2.12
2.12
, 2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
Subcategories B and D
I-day
3.07
-
5.72
5.72
5.72
5.72
6.24
5.72
5.72
5.72
5.72
5.72
5.72
5.72
-
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
5.72
4-day
1.54
-
2.12
2.12
2.12
2.12
2.24
2.12
2.12
2.12
2.12
2.12
2.12
2.12
-
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
2.12
Final Appendix C
7 April 1995
0406-01.ip
C-9
-------
Table C-5
(Continued)
Pollutant or Pollutant Property
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Methanol
Methylamine
Methyl Cellosolve
Methyl Formate
Methylene Chloride
MIBK
2-Methylpyridine
Petroleum Naphtha
n-Propanol
Pyridine
Tetrahydrofuran
Toluene
Trichlorofluoromethane
Triethylamine
Xylenes
Subcategories A and C
1-day
5.72
5.72
5.72
5.48
5.72
5.72
5.72
8.09
5.72
5.72
5.72
5.72
5.72
5.97
1.84
5.72
5.72
5.72
4-day
2.12
2.12
2.12
2.06
2.12
2.12
2.12
2.79
2.12
2.12
2.12
2.12
2.12
2.18
1.35
2.12
2.12
2.12
Subcategories B and D
1-day
5.72
5.72
5.72
5.48
5.72 .
5.72
5.72
8.09
5.72
5.72
5.72
5.72
5.72
5.97
1.84
5.72
5.72
5.72
4-day
2.12
2.12
2.12
2.06
2.12
2.12
2.12
2.79
2.12
2.12
2.12
2.12
2.12
2.18
1.35
2.12
2.12
2.12
Final Appendix C
7 April 1995
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