United States Industrial Environmental Research EPA-600/2-79-019i
Environmental Protection Laboratory December 1979
Agency Research Triangle Park NC 27711
Research and Development
Source Assessment:
Textile Plant Wastewater
Toxics Study, Phase II
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Mention of trade names or commercial products does
not constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-79-019J
December 1979
Source Assessment:
Textile Plant Wastewater Toxics Study,
Phase II
by
J. R. Klieve and G. D. Rawlings
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
Contract No. 68-02-1874
Task No. 33
ROAPNo. 21AXM-071
Program Element No. 1AB015
EPA Project Officer: Max Samfield
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
PREFACE
The Industrial Environmental Research Laboratory (IERL) of the
U.S. Environmental Protection Agency (EPA) has the responsibility
for insuring that pollution control technology is available for
stationary sources to meet the requirements of the Clean Air act,
the Federal Water Pollution Control Act, and solid waste legisla-
tion. If control technology is unavailable, inadequate, or
uneconomical, then financial support is provided for the develop-
ment of the needed control techniques for industrial and extrac-
tive process industries. The Chemical Processes Branch of the
Industrial Processes Division of IERL has the responsibility for
investing tax dollars in programs to develop control technology
for a large number of operations (more than 500) in the chemical
industries.
Monsanto Research Corporation (MRC) has contracted with EPA to
investigate the environmental impact of various industries which
represent sources of pollution in accordance with EPA's respon-
sibility as outlined above. Dr. Robert C. Binning serves as MRC
Program Manager in this overall program entitled "Source Assess-
ment," which includes the investigation of sources in each of
four categories: combustion, organic materials, inorganic mate-
rials, and open sources. Dr. Dale A. Denny of the Industrial
Processes Division at Research Triangle Park serves as EPA Pro-
ject Officer. Reports prepared in this program are of three
types: Source Assessment Documents, State-of-the-Art Reports,
and Special Project Reports.
Source Assessment Documents contain data on emissions from spe-
cific industries. Such data are gathered from the literature,
government agencies, and cooperating companies. Sampling and
analysis are also performed by the contractor when the available
information does not adequately characterize the source emis-
sions. These documents contain all of the information necessary
for IERL to decide whether emissions reduction is required.
State-of-the-Art Reports include data on emissions from specific
industries which are also gathered from the literature, govern-
ment agencies, and cooperating companies. However, no extensive
sampling is conduced by the contractor for such industries.
Results from such studies are published as State-of-the-Art
Reports for potential utility by the government, industry, and
others having specific needs and interests.
111
-------
Special projects provide specific information or services which
are applicable to a number of source types or have special
utility to EPA but are not part of a particular source assess-
ment study. This special project report, "Source Assessment:
Textile Plant Wastewater Toxics Study, Phase II," was prepared to
examine the level of toxicity (as measured by results of bioassay
tests) and specific toxic pollutant removal attained by selected
tertiary treatment systems treating secondary effluents from
textile plants. Dr. Max Samfield of the Chemical Processes
Branch at IERL-RTP served as EPA Task Officer.
The initial report in the project, "Source Assessment: Textile
Plant Wastewater Toxics Study, Phase I" (EPA 600/2-78-004h), was
prepared to provide chemical and toxicological data on secondary
influent and effluent at 23 textile plants, and it served as a
screening study for Phase II.
IV
-------
ABSTRACT
This study, sponsored by the EPA, was concerned with BATEA for
the textile manufacturing industry. The purpose was to examine
the level of removal of specific toxic pollutants and toxicity
(as measured by results of bioassay tests) attained by selected
tertiary systems treating secondary effluents from textile plants,
Tertiary treatment systems consisting of unit processes arranged
in various ways were ranked according to their apparent capabili-
ties for removal of specific toxic pollutants and toxicity. The
unit processes employed included flocculation/sedimentation,
multimedia filtration with and without precoagulation, granular
activated carbon adsorption, and ozonation. These unit opera-
tions were mobile and, thus, taken to numerous textile plants for
evaluation.
The assessment of the treatment systems was based on both
specific toxic pollutant analysis data and bioassay data gathered
at eight textile plant locations where the treatment systems
were tested. Samples collected from secondary and tertiary
effluent streams were analyzed for specific toxic pollutants and
submitted for the following bioassay analyses: freshwater
ecology series (fathead minnow, bluegill, Daphnia, and algae),
microbial mutagenicity, and cytotoxicity. For comparison, plant
intake waters were also analyzed for specific toxic pollutants.
Based on apparent specific toxic pollutant removal and toxicity
removal, multimedia filtration-activated carbon was the best
system. Tertiary treatment systems whose effluents contained a
high level of residual coagulant appeared to be more detrimental
to water quality, based on bioassay tests, than those systems
which did not use coagulants. In addition, ozonation appeared
to add toxic metals to the wastewater being treated.
This report was submitted in partial fulfillment of Contract 68-
02-1874 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. This report
covers a period from August 1977 to May 1979.
v
-------
CONTENTS
Preface iii
Abstract v
Figures viii
Tables ix
Abbreviations xiii
1. Introduction 1
2. Summary 3
3. Results and Recommendations 10
4. Scope of Work 12
Background 12
Program objective 15
Project organization - phase II 15
Spectra analysis 16
5. Sampling Procedures 18
6. Chemical Analysis Procedures 21
Introduction 21
Analytical procedures 21
7. Bioassay Procedures 29
Introduction 29
Procedures 32
8. Analytical and Bioassay Results 38
Introduction 38
Plant data 42
9. Data Interpretation 86
Introduction 86
Toxic organic removal capabilities 87
Toxic metals removal capabilities 87
Total cyanide removal capabilities 89
Toxicity removal capabilities 89
Other observations. 91
Overview 92
10. Results of Spectra Analysis of Phase I Samples ... 94
Total organic concentration 94
Phase I priority pollutants 95
Other organic compounds identified 95
References 121
Appendix 123
Glossary 126
Conversion Factors and Metric Prefixes 127
VII
-------
FIGURES
Number Paqe
1 Tertiary treatment systems 3
2 Seven tertiary treatment modes initially
selected for "best available technology"
evaluation 13
3 Overall program approach to determine BATEA. . . 15
4 MRC bottle label used for sample
identification 20
5 Chemical analysis logistics - laboratories and
analysis procedures index 22
6 Analytical scheme for volatile organics
analysis 23
7 Sample processing scheme for the analysis of the
base/neutral and acid fractions of semi-
volatile organics 24
8 Sample processing scheme for pesticide and PCB
analysis 25
9 Bioassay logistics - laboratories and bioassay
procedures index 29
10 Candidate wastewater treatment system studied
at plant A 43
11 Candidate wastewater treatment system studied
at plant C 49
12 Candidate wastewater treatment system studied
at plant W 54
13 Candidate wastewater treatment system studied
at plant S 59
14 Candidate wastewater treatment system studied
at plant P 64
15 Candidate wastewater treatment system studied
at plant N 69
16 Candidate wastewater treatment system studied
at plant V 74
17 Candidate wastewater treatment system studied
at plant T 80
Vlll
-------
TABLES
Number Page
1 Bioassay Studies Conducted in Phase II 5
2 Required Sample Containers and Preservatives . . 19
3 Procedure used in Analyzing Other Pollutants . . 28
4 CHO-K1 Clonal Cytotoxicity Test 37
5 Tertiary Treatment Systems Used at Specific
Pilot Plant Sites 39
6 Minimum Determinable Concentrations for Organic
Toxic Pollutants 41
7 Plant A Organic Toxic Pollutants Detected. ... 44
8 Plant A Inorganic Toxic Pollutants Detected. . . 45
9 Plant A Other Pollutants Detected 46
10 Plant A Bioassay Results 47
11 Plant A Effluent Descriptions 48
12 Plant C Organic Toxic Pollutants Detected. ... 50
13 Plant C Inorganic Toxic Pollutants Detected. . . 50
14 Plant C Other Pollutants Detected 51
15 Plant C Bioassay Results 52
16 Plant C Effluent Descriptions 53
17 Plant W Organic Toxic Pollutants Detected. ... 55
18 Plant W Inorganic Toxic Pollutants Detected. . . 55
19 Plant W Other Pollutants Detected 56
20 Plant W Bioassay Results 57
21 Plant W Effluent Descriptions 58
22 Plant S Organic Toxic Pollutants Detected. ... 60
23 Plant S Inorganic Toxic Pollutants Detected. . . 60
24 Plant S Other Pollutants Detected 61
25 Plant S Bioassay Results 62
26 Plant S Effluent Descriptions 63
IX
-------
TABLES (continued)
Number
27 Plant P Organic Toxic Pollutants Detected. ... 64
28 Plant P Inorganic Toxic Pollutants Detected. . . 65
29 Plant P Other Pollutants Detected 66
30 Plant P Bioassay Results 67
31 Plant P Effluent Descriptions 68
32 Plant N Organic Toxic Pollutants Detected. ... 69
33 Plant N Inorganic Toxic Pollutants Detected. . . 70
34 Plant N Other Pollutants Detected 71
35 Plant N Bioassay Results 72
36 Plant N Effluent Descriptions 73
37 Plant V Organic Toxic Pollutants Detected. ... 75
38 Plant V Inorganic Toxic Pollutants Detected. . . 76
39 Plant V Other Pollutants Detected 77
40 Plant V Bioassay Results 78
41 Plant V Effluent Descriptions 79
42 Plant T Organic Toxic Pollutants Detected. ... 81
43 Plant T Inorganic Toxic Pollutants Detected. . . 82
44 Plant T Other Pollutants Detected 83
45 Plant T Bioassay Results 84
46 Plant T Effluent Descriptions 85
47 Concentration of Methylene Chloride-Extractable
Organics in Filtered Secondary Effluents ... 94,
48 Phase I Priority Pollutants in Secondary
Effluents 96
49 Plant A: Other GC/MS Organic Compounds in
Secondary Effluent 98
50 Plant B: Other GC/MS Organic Compounds in
Secondary Effluent ....... 99
51 Plant C: Other GC/MS Organic Compounds in
Secondary Effluent 100
52 Plant D: Other GC/MS Organic Compounds in
Secondary Effluent 101
53 Plant E: Other GC/MS Organic Compounds in
Secondary Effluent 102
x
-------
TABLES
Number Page
1 Bioassay Studies Conducted in Phase II 5
2 Required Sample Containers and Preservatives . . 19
3 Procedure used in Analyzing Other Pollutants . . 28
4 CHO-K1 Clonal Cytotoxicity Test 37
5 Tertiary Treatment Systems Used at Specific
Pilot Plant Sites 39
6 Minimum Determinable Concentrations for Organic
Toxic Pollutants 41
7 Plant A Organic Toxic Pollutants Detected. ... 44
8 Plant A Inorganic Toxic Pollutants Detected. . . 45
9 Plant A Other Pollutants Detected 46
10 Plant A Bioassay Results 47
11 Plant A Effluent Descriptions 48
12 Plant C Organic Toxic Pollutants Detected. ... 50
13 Plant C Inorganic Toxic Pollutants Detected. . . 50
14 Plant C Other Pollutants Detected 51
15 Plant C Bioassay Results 52
16 Plant C Effluent Descriptions 53
17 Plant W Organic Toxic Pollutants Detected. ... 55
18 Plant W Inorganic Toxic Pollutants Detected. . . 55
19 Plant W Other Pollutants Detected 56
20 Plant W Bioassay Results 57
21 Plant W Effluent Descriptions 58
22 Plant S Organic Toxic Pollutants Detected. ... 60
23 Plant S Inorganic Toxic Pollutants Detected. . . 60
24 Plant S Other Pollutants Detected 61
25 Plant S Bioassay Results 62
26 Plant S Effluent Descriptions 63
IX
-------
TABLES (continued)
Number Pac
27 Plant P Organic Toxic Pollutants Detected. ... 64
28 Plant P Inorganic Toxic Pollutants Detected. . . 65
29 Plant P Other Pollutants Detected 66
30 Plant P Bioassay Results 67
31 Plant P Effluent Descriptions 68
32 Plant N Organic Toxic Pollutants Detected. ... 69
33 Plant N Inorganic Toxic Pollutants Detected. . . 70
34 Plant N Other Pollutants Detected 71
35 Plant N Bioassay Results 72
36 Plant N Effluent Descriptions 73
37 Plant V Organic Toxic Pollutants Detected. ... 75
38 Plant V Inorganic .Toxic Pollutants Detected. . . 76
39 Plant V Other Pollutants Detected 77
40 Plant V Bioassay Results 78
41 Plant V Effluent Descriptions 79
42 Plant T Organic Toxic Pollutants Detected. ... 81
43 Plant T Inorganic Toxic Pollutants Detected. . . 82
44 Plant T Other Pollutants Detected 83
45 Plant T Bioassay Results 84
46 Plant T Effluent Descriptions 85
47 Concentration of Methylene Chloride-Extractable
Organics in Filtered Secondary Effluents ... 94
48 Phase I Priority Pollutants in Secondary
Effluents 96
49 Plant A: Other GC/MS Organic Compounds in
Secondary Effluent 98
50 Plant B: Other GC/MS Organic Compounds in
Secondary Effluent 99
51 Plant C: Other GC/MS Organic Compounds in
Secondary Effluent 100
52 Plant D: Other GC/MS Organic Compounds in
Secondary Effluent 101
53 Plant E: Other GC/MS Organic Compounds in
Secondary Effluent 102
-------
TABLES (continued)
Number Page
54 Plant F: Other GC/MS Organic Compounds in
Secondary Effluent 103
55 Plant G: Other GC/MS Organic Compounds in
Secondary Effluent 104
56 Plant H: Other GC/MS Organic Compounds in
Secondary EFfluent 105
57 Plant J: Other GC/MS Organic Compounds in
Secondary Effluent 106
58 Plant K: Other GC/MS Organic Compounds in
Secondary Effluent 107
59 Plant L: Other GC/MS Organic Compounds in
Secondary Effluent 108
60 Plant M: Other GC/MS Organic Compounds in
Secondary Effluent 109
61 Plant N: Other GC/MS Organic Compounds in
Secondary Effluent 110
62 Plant P: Other GC/MS Organic Compounds in
Secondary Effluent Ill
63 Plant R: Other GC/MS Organic Compounds in
Secondary Effluent 112
64 Plant S: Other GC/MS Organic Compounds in
Secondary Effluent 113
65 Plant T: Other GC/MS Organic Compounds in
Secondary Effluent 114
66 Plant U: Other GC/MS Organic Compounds in
Secondary Effluent 115
67 Plant V: Other GC/MS Organic Compounds in
Secondary Effluent 116
68 Plant W: Other GC/MS Organic Compounds in
Secondary Effluent 116
69 Plant X: Other GC/MS Organic Compounds in
Secondary Effluent 117
70 Plant Y: Other GC/MS Organic Compounds in
Secondary Effluent 118
71 Plant Z: Other GC/MS Organic Compounds in
Secondary Effluent 119
XI
-------
TABLES (continued)
Number Page
A-l Volatile Pollutant Analysis Fractions 123
A-2 Base Neutral Extractable Compounds 124
A-3 Acid Extractable Compounds 124
A-4 Pesticides and PCB's 125
A-5 Metals and Other Compounds 125
XI1
-------
ABBREVIATIONS
AA
ATM I
BATEA
BOD 5
CHO-K1
COD
DNA
EC
ECso
EPA
GC
GC/MS
HLI
ICAP
K-D
LCso
MRC
MS
PCB
PCS
SIM
TDS
TSS
atomic absorption
American Textile Manufacturers Institute
best available technology economically
achievable
5-day biochemical oxygen demand, mg/Z
Chinese Hampster Ovary - designation K-l
chemical oxygen demand, mg/£
deoxyribonucleic acid
electron capture detector on a gas chromatograph
effective concentration at which 50% of the test
species reach the desired effect, % effluent
Environmental Protection Agency
gas chromatograph
gas chromatography/mass spectroscopy
Howard Laboratories, Incorporated
inductively coupled argon plasma
Kuderna-Danish
lethal concentration which causes 50% mortality
in the test species, % effluent
Monsanto Research Corporation
mass spectrometer
polychlorinated biphenyls
Pollution Control Science
selected ion mode
total dissolved solids, mg/£
total suspended solids, mg/S,
Xlll
-------
SECTION 1
INTRODUCTION
The Industrial Environmental Research Laboratory - RTF (IERL/RTP)
of the U.S. Environmental Protection Agency (EPA) is currently
engaged in a joint study with the American Textile Manufacturers
Institute (ATMI; EPA Grant No. 804329) to determine the best
available technology economically achievable (BATEA) for textile
plant wastewaters. A total of 23 textile mills representing 8
textile processing categories and having well-operated secondary
wastewater treatment facilities were selected by EPA and ATMI for
the BATEA study. For that study, 2 mobile wastewater treatment
pilot plants were constructed to gather technical data to identify
the best available technology applicable to the 23 plants. The
grant study focused on only a limited number of so-called criteria
pollutants; i.e., 5-day biochemical oxygen demand, chemical
oxygen demand, color, sulfides, total suspended solids, phenol,
and pH.
On 7 June 1976 the U.S. District Court of Washington, D.C.,
issued a consent decree (resulting from Natural Resources Defense
Council, et al. vs. Train) requiring EPA to enhance development
of effluent standards. The court mandate focused federal water
pollution control efforts on potentially toxic and hazardous pol-
lutants. In response to the consent decree EPA developed a list
of 129 specific compounds (known either as toxic or priority
pollutants) that the agency agreed to consider during the stand-
ards setting process. Based on the consent decree, EPA-IERL/RTP
decided to conduct a study parallel to the ATMI/EPA Grant Study
of the textile industry. The objective of the IERL/RTP study was
to determine both the removal efficiencies for the 129 consent
decree specific toxic pollutants and the reduction in toxicity,
as measured by bioassay tests, by the tertiary treatment technol-
ogies being investigated under the original grant study. Monsanto
Research Corporation (MRC) conducted this toxics study under
contract 68-02-1874.
The overall wastewater toxicity study, was divided into two
phases. The first, covered by an initial MRC report, "Source
Assessment: Textile Plant Wastewater Toxics Study, Phase I"
(EPA 600/2-78-004h), established a baseline data base concerning
toxicity and level of toxic pollutants present in raw wastewater
and secondary effluents at 23 textile plants. The data were used
to screen the 23 plants and to select those plants with secondary
-------
effluents of highest toxicity for further study under Phase II.
Based on recommendations by the EPA IERL/HERL - RTF Bioassay
Subcommittee, the following ten plants were recommended for
Phase II study (listed in order of decreasing toxicity): N, A,
W, C, T, V, L, S, P, and R. As the ATMI/EPA Grant Study preceded,
two of the ten plants (Plants L and R) were dropped from the pro-
gram due to scheduling difficulties, and thus were eliminated from
the MRC Phase II scope of work.
The second phase of the effort, covered in this report, deter-
mined the reduction in specific toxic pollutant concentrations
and in toxicity by the mobile pilot plant tertiary treatment
systems. Only those plants selected in the first phase of the
study were investigated.
Covering the second phase of the toxics study, this report
describes sampling, chemical analysis, and bioassay procedures
used. Chemical analyses of intake water, secondary effluents,
and tertiary effluents are presented for the eight locations
visited by the mobile pilot plants. Bioassay data are presented
only for secondary and tertiary effluents.
The tertiary treatment systems are ranked according to their
apparent specific toxic pollutant and toxicity removal capabili-
ties. Other trends apparent in the data are also discussed.
Another activity associated with Phase II involved the Phase I
organic data. Analysis of the organic compounds in the secondary
effluent of the Phase I samples indicated that the organic
priority pollutant species only accounted for 1% to 3% by weight
of the total mass of organics. Therefore, EPA decided to re-
examine the original instrumental data, which were stored on
magnetic tape, and to identify as many of the other organic com-
pounds as possible. This report also discusses the results of
that study.
-------
SECTION 2
SUMMARY
The purpose of this Phase II study was to determine reduction in
toxicity (as measured by results of bioassay tests) and specific
toxic pollutant concentrations achieved by the tertiary treatment
systems under investigation in the ATMI/EPA Grant Study (Grant
No. 804329). In this study, tertiary.treatments of secondary
effluents from eight textile plants in the United States were
evaluated. In all, eight tertiary treatment systems as defined
in Figure 1 were investigated. In the text of this report, treat-
ment system types are identified by the type number defined in
Figure 1. Samples of secondary effluent and effluents from each
unit operation of the various tertiary treatment systems were
analyzed for the 129 consent decree specific toxic pollutants and
were also submitted for the following bioassay toxicity tests:
freshwater ecology series (algae, Daphnia, fathead minnow and/or
bluegill), microbial mutagenicity, and cytotoxicity. In addition,
the samples were analyzed for various metals and nutrients not
TYPE 1 :
TYPE 2:
TYPE 3:
TYPE 4:
TYPES:
TYPE 6:
TYPE 7:
TYPES:
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
TERTIARY PILOT PLANT OPERATIONS
SEDIMENTATION
• COAGULANT -
ADDITION
• MULTIMEDIA
FILTRATION
• COAGULANT -
ADDITION
COAGULANT -
ADDITION
MULTIMEDIA •
FILTRATION
MULTIMEDIA
FILTRATION
COAGULANT -
ADDITION
-ROCCULATION/
SEDIMENTATION
-MULTIMEDIA
FILTRATION
"ROCCULATION/
SEDIMENTATION
GRANULAR
ACTIVATED CARBON
OZONATION
FLOCCULATION/ •
SEDIMENTATION
•MULTIMEDIA
FILTRATION
•MULTIMEDIA-
FILTRATION
—— GRANULAR
ACTIVATED CARBON
• TERTIARY PILOT PLANT OPERATIONS
Figure 1. Tertiary treatment systems.
-------
appearing on the consent decree toxic pollutant list. Samples of
the intake water were collected at each textile plant and analyzed
for the 129 consent decree specific toxic pollutants and various
other metals, but they were not submitted for bioassay tests.
Separate composited samples of textile plant intake water, secon-
dary effluent, and tertiary effluents were collected manually over
a 24-hr period. Sampling began when the tertiary treatment
system under investigation at each plant were operated under
steady-state conditions. Samples were chemically preserved,
stored in ice at 4°C, and shipped by air freight or delivered by
the sampling crew to the various laboratories for appropriate
chemical analyses and bioassay studies.
Most of the 129 specific toxic pollutants in textile plant intake
water, secondary effluent, and tertiary effluent samples (totaling
44 samples) were analyzed by Monsanto Research Corporation (MRC).
The EPA analytical protocol divides the 129 specific toxic pollu-
tants into 5 fractions for analysis: volatile compounds, base/
neutral compounds, acid compounds, pesticides and polychlorinated
biphenyls (PCB's), and metals. EPA recommended that laboratories
not acquire analytical standards for 2,3,7,8-tetrachlorodibenzo-
p-dioxin (TCDD) because of its extreme toxicity. Asbestos was not
analyzed due to the presence of interfering fibrous materials in
textile wastewaters. Analytical procedures followed those recom-
mended by EPA.
Seven organic toxic pollutants were found in the secondary efflu-
ent from at least one textile plant in concentrations greater than
10 Mg/£. The 10 yg/£ was selected as a concentration which is
well above analytical detection limits and above probable levels
of contamination. These include bis(2-ethylhexyl) phthalate, 1,2-
dichlorobenzene, 1,2,4-trichlorobenzene, toluene, methylene
chloride, di-n-butyl phthalate, and total phenol. However, the
presence of bis(2-ethylhexyl) phthalate, methylene chloride, and
di-n-butyl phthalate in the samples could have originated from
contamination by the materials of which the pilot plant was con-
structed. Except for mercury, selenium, and thallium, all inor-
ganic toxic pollutants were found in at least one textile plant
secondary effluent in concentrations greater than 10 yg/£ (or the
detection limit).
Secondary and tertiary effluent samples were also submitted for
static bioassay studies. Table 1 briefly defines the purpose of r
each bioassay test used in the Phase II program. Procedures used
in conducting the algal, Daphnia, and fish assays were based on
protocols developed by the U.S. Environmental Protection Agency.
-------
TABLE 1. BIOASSAY STUDIES CONDUCTED IN PHASE II
Bioassay test system
Indicator organisms
Purpose of test
Freshwater algal assay
Freshwater static bioassay
Microbial mutagenicity
Ul
Cytotoxicity
Selenastrum oapricoimutwn
Pi-mephales prome'las
(fathead minnow)
Daphnia magna
(daphnid)
Lepomis macrochirus
(bluegill)
Salmonella typhimuri-wn (Ames test)
(strains TA1535, TA1538, TA1538,
TA98, TA100)
Escheriahia eoli (pol A test)
(strains W3110, p3478)
Chinese hamster ovary cells
To detect potential toxicity to
aquatic plants.
To detect potential toxicity to
organisms in aquatic environments.
To determine if a chemical mutagen
(possibly a carcinogen) is present.
These microbial strains were
selected because of their sensitiv-
ity to various classes of chemical
compounds.
To measure metabolic impairment and
death in mammalian cells. These
primary cell cultures have some
degree of metabolic repair capability.
-------
Of the eight secondary effluents submitted for algal bioassay,
six were toxic when compared to a control while five of the
eight secondary effluents produced acute Daphnia toxicity in
bioassay studies. Acute toxicity to bluegill fish was detected
only twice although bluegill bioassays were conducted on only
two of the eight secondary effluents, and acute toxicity to
fathead minnows was detected with only three secondary effluents
although only seven were tested.
Microbial mutagenicity was determined with both the Ames test and
the pol A test. The Ames test uses mutant strains of Salmonella
while the pol A test used in the Phase II study employs
Escherichia coli. Cytotoxicity was determined using Chinese
hamster ovary cells (CHO-K1) . No mutagenicity or cytotoxicity was
found in any of the secondary effluent or tertiary effluent
streams tested.
The analytical and bioassay data were then used to identify posi-
tive and negative results which might be expected in applying
various technologies to further treat secondary effluents from
textile mills. In most cases, additional research would be
required to adequately confirm the preliminary results identified
in this study. Toxic organic analyses yielded little information
regarding relative effectiveness of the various tertiary treatment
systems in reducing toxic organic pollutant concentrations since
the secondary effluent from only two plants contained toxic
organic pollutants other than those which may have resulted from
contamination, in concentrations greater than 10
Toxic metals were found to some extent in virtually all wastewater
streams analyzed. Multimedia filtration, multimedia filtration
followed by activated carbon adsorption, and f locculation/sedi-
mentation followed by activated carbon adsorption were most
effective in reducing levels of toxic metals. Multimedia filtra-
tion with precoagulation and ozonation proceeded by multimedia fil-
tration were least effective in removing toxic metals. Toxic
metals appeared to be added by ozonation.
Cyanide was effectively removed by multimedia filtration followed
by both activated carbon adsorption and ozonation. Multimedia
filtration alone was ineffective in removing cyanide.
Multimedia filtration and multimedia filtration followed by
activated carbon adsorption appeared to be best at removing acute
toxicity (as measured by bioassay tests) . Results of the Phase
II study also indicated that tertiary treatment systems that left
high levels of residual aluminum or iron from coagulation in
their effluents generally increased the toxicity of the waste-
water, as compared with treatment systems whose effluents con-
tained lower levels. In addition, systems employing cationic
polymer coagulation were generally detrimental to water quality
in terms of acute toxicity to algae.
-------
The demonstrated capabilities of eight treatment systems to
remove toxic pollutants and toxicity, as measured by bioassay
tests, are listed as follows:
• Removal of Toxic Organic Compounds
Insufficient data on which to base conclusions.
• Removal of Toxic Metals
Best Removal Ability
Multimedia filtration; flocculation/sedi-
mentation followed by multimedia filtration;
multimedia filtration followed by activated
carbon
Intermediate Removal Ability
Sedimentation; flocculation/sedimentation;
flocculation/sedimentation followed by
multimedia filtration and activated carbon
Least Removal Ability
Multimedia filtration with precoagulation;
multimedia filtration followed by ozonation
• Removal of Cyanide
Best Removal Ability
Multimedia filtration followed by activated
carbon; multimedia filtration followed by
ozonation
Intermediate Removal Ability
Sedimentation; flocculation/sedimentation;
multimedia filtration with precoagulation;
flocculation/sedimentation followed by
multimedia filtration; flocculation/sedi-
mentation followed by multimedia filtra-
tion and activated carbon
Least Removal Ability
Multimedia filtration
-------
• Removal of Acute Toxicity
Best Removal Ability
Multimedia filtration; multimedia filtration
followed by activated carbon
Intermediate Removal Ability
Sedimentation; flocculation/sedimentation
followed by multimedia filtration; multi-
media filtration followed by ozonation;
flocculation/sedimentation followed by
multimedia filtration and activated carbon
Least Removal Ability
Flocculation/sedimentation; multimedia
filtration with precoagulation
• Composite
Best Removal Ability
Multimedia filtration followed by
activated carbon
Intermediate Removal Ability
Sedimentation; flocculation/sedimentation;
multimedia filtration; flocculation/sedi-
mentation followed by multimedia filtration;
multimedia filtration followed by ozonation;
flocculation/sedimentation followed by multi-
media filtration and activated carbon
Least Removal Ability
Multimedia filtration with precoagulation
The final activity of the Phase II study was to re-examine the
gas chromatograph/mass spectrometer (GC/MS) spectra from the
organic priority pollutant analysis of the Phase I secondary
effluent samples, stored on magnetic tape, and identify as many
organic compounds as possible.
-------
The magnetic tapes were collected and individual sample spectra
examined for major ion fragments. Using the elution time and
three principal ions, specific organic compounds were identified.
Their estimated percent abundance was calculated based on peak
areas as compared to compounds of known concentration. It was
not possible to quantify the concentrations because the GC/MS
could not be set up to duplicate the instrumental conditions
used 1 year earlier when the data were originally collected.
Analysis of the spectra found organic compounds common to the
textile industry such as chlorobenzenes, C9 to C2o aliphatic
(paraffinic and olefinic) hydrocarbons, benzoic acid, soaps, and
chlorophenols. Methylene chloride, found in moderate concentra-
tions, was present principally due to laboratory contamination.
Triphenyl phosphine, triphenyl phosphine oxide, and triphenyl
phosphine sulfide, which are detergent derivatives, were detected
in varying amounts and may be present due to residues on the
sampling bottles or laboratory glassware. Further analysis of
the data indicated some extraction carryover effects; i.e., the
same organic species were found in both the base/neutral fraction
and the acid fraction.
-------
SECTION 3
RESULTS AND RECOMMENDATIONS
The data presented in this report can be used to identify pre-
liminary positive and negative results which might be expected in
applying various technologies to further treat secondary effluents
from textile mills. In most cases, additional research would be
required to adequately confirm these preliminary results obtained
in this study. The preliminary results are summarized below:
1. Only seven organic toxic pollutants in excess of 10
were seen in any of the secondary effluents of the eight
textile plants. However, three of the compounds may
have, resulted from contamination.
2. Since few organic pollutants were presented in the
wastewater streams, this data provided minimal unit
operations performance information.
3. Eleven inorganic toxic pollutants were seen in at least
one of the eight secondary effluents in levels greater
than 10 yg/H (or the detection limit) .
4. Of the eight tertiary treatment systems tested, multi
media filtration followed by granular activated carbon
adsorption demonstrated the best overall toxic pollutant
and toxicity removal capability, as determined by inorganic
toxic pollutant analyses and bioassays.
5. Of the eight treatment systems tested, multimedia
filtration with precoagulation demonstrated the worst
over all toxic pollutant and toxicity removal capability,
as determined by inorganic toxic pollutant analyses and
bioassays.
6. Tertiary treatment systems that left high levels of
residual inorganic coagulant in their effluents generally
increased the toxicity of the wastewater, as compared
with treatment systems whose effluents contained lower
levels.
7. Systems employing cationic polymer coagulation increased
the toxicity of the wastewater being treated, as measured
by acute algal bioassays.
10
-------
8. None of the secondary effluents or tertiary effluents gave a
positive response in the mutagenicity or cytotoxicity tests.
9. The freshwater algal assay was the most sensitive bioassay
test used in the Phase II program. The•Daphnia assay was
second most sensitive.
Based on the preliminary results listed above, the following
recommendations can be made:
1. Coagulation as a tertiary tratement technology should be
further investigated in terms of its effect upon water
quality, as measured by bioassays. It appears that when the
coagulant is not adequately removed from the wastewater
stream following its use, water quality, as measued by bio-
assays, is adversely affected.
2. Since freshwater algal and Daphnia bioassays were the more
sensitive bioassays, these tests should be considered first
as a means to characterize the toxicity of textile mill
wastewaters.
Based on the results of re-examining the Phase I priority pollu-
tant data base, it is obvious that many organic compounds other
than specific priority pollutants are present. Therefore, in a
total environmental assessment study, the analytical scheme must
have provisions for a more comprehensive analysis scheme than
just looking for 129 specific compounds.
11
-------
SECTION 4
SCOPE OF WORK
BACKGROUND
To understand the nature and purpose of the textile wastewater
toxics program, it is first necessary to briefly review the
events which led up to this study.
In June 1974 the U.S. Environmental Protection Agency's Effluent
Guidelines Division set forth guidelines for the degree of
effluent reduction attainable through the application of the
"Best Practicable Control Technology Currently Available" and the
"Best Available Technology Economically Achievable" which must be
achieved by existing textile manufacturing (SIC 22) point sources
by 1 July 1977 and 1 July 1983, respectively (1). However, on
1 October 1974 the textile manufacturing industry represented by
the American Textile Manufacturers Institute, Northern Textiles
Association, and Carpet and Rug Institute filed a petition with
the U.S. Fourth Circuit Court of Appeals asking for a review of
the proposed 1983 effluent guidelines. Grounds for the suit were
that the BATEA had not been demonstrated for the textile manufac-
turing industry. As a result, ATMI and EPA filed a joint motion
for delay of the petition, stating that additional information
would be developed through a cooperative grant study by ATMI and
EPA's Industrial Environmental Research Laboratory.
The objective of the ATMI/EPA Grant Study was to gather enough
technical and economic data to determine the BATEA for reducing
criteria pollutants from textile wastewaters. Criteria pollutants
for the textile industry include 5-day biochemical oxygen demand
(BOD5), chemical oxygen demand (COD), color, sulfide, pH,
chromium, phenol, and total suspended solids (TSS).
(1) Gallup, J. D. Development Document for Effluent Limitations
Guidelines and New Source Performance Standard for the
Textile Mills Point Source Category. EPA-440/l-74-022a
(PB 238 832), U.S. Environmental Protection Agency,
Washington, D.C., June 1974. 246 pp.
12
-------
To evaluate the best available technology, two mobile pilot
plants were constructed and operated by ATMI's .contractor,
Engineering Science, Inc. This stategy allowed for real-time,
flowthrough treatability studies. Each pilot plant contained 5
tertiary wastewater treatment unit operations; 1 pilot plant was
scheduled to visit 12 textile plants and the other to visit 11.
An additional tertiary treatment technology was laboratory
tested.
Treatment operations in each mobile unit include a reactor/
clarifier (using combinations of alum, lime, ferric chloride,
and anionic and cationic polyelectrolytes), two multimedia
filters, three granular activated carbon columns, ozonation, and
dissolved air flotation. Using these six operations, ATMI and
EPA initially selected seven treatment modes for evaluation
(Figure 2).
MODE A:
MODE B :
MODE C :
MODE D :
MODE E:
(OPTIONAL)
MODE F:
MODEG:
REACTOR/CLARIFIER
MULTIMEDIAFILTER
MULTIMEDIA FILTER
OZONATOR
REACTOR/CLARIFIER
MULTIMEDIA FILTER
GRANULAR ACTIVATED CARBON COLUMNS
OZONATOR
•MULTIMEDIA FILTER — GRANULAR ACTIVATED
CARBON —-OZONATOR
COAGULATION---MULTIMEDIA FILTER
DISSOLVED AIR FLOTATION
Figure 2. Seven tertiary treatment modes initially selected
for "best available technology" evaluation.
Each of the seven treatment modes was to be individually set up,
and operational and pollutant data collected over a 2-day to
3-day period. Based on those data, the "best" system, referred
to as the "candidate mode," was to be set up for 2 weeks of
operational evaluation. These data were then to be forwarded for
economic evaluation.
Prior to pilot plant field testing, a second EPA regulatory event
occurred and formed the basis for the toxicity study. On
7 June 1976, the U.S. District Court of Washington, D.C., issued
a consent decree (resulting from Natural Resources Defense
Council et al. vs. Train) requiring EPA to accelerate development
of effluent standards for 21 industrial point sources, -including
textile manufacturing. Among other requirements, the Court's
mandate focused federal water pollution control on potentially
toxic and hazardous chemical compounds. The original consent
13
-------
decree required that "65 classes" of chemical compounds be
analyzed in wastewater samples. Recognizing the difficulty of
analyzing for all chemical species present in each category of
compounds, EPA developed a surrogate list of 129 specific com-
pounds representative of the classes of compounds listed in the
consent decree. These compounds are referred to as "toxic
pollutants" or "priority pollutants" and are divided into several
fractions for sampling and analytical purposes as shown in the
appendix. EPA also developed a sampling and analytical proce-
dures manual to be used as a laboratory guide for toxic pollut-
ant assessment (2).
The consent decree obligates EPA to identify which toxic pollut-
ants are present in industrial wastewaters and to determine the
ability of various wastewater treatment technologies to remove
toxic pollutants. Therefore, EPA with ATMI's cooperation
decided to conduct a separate, but parallel, .study with the EPA/
ATMI Grant Study designed to measure toxic pollutants. Also,
since the consent decree focused on the issue of wastewater
toxicity, ATMI agreed to have samples collected for bioassay
testing in order to have a complete and comprehensive wastewater
characterization data base. Therefore, the bioassay testing
program established by EPA for evaluating the reduction in
toxicity of water samples by control technologies was integrated
into the program (3). Thus, the overall EPA-IERL/RTP textile
program consists of two separate projects, each with different
activities, running parallel in time, but converging towards
the same goal: determination of the best available technology
economically achievable for textile wastewaters (Figure 3).
(2) Draft Final Report: Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority Pollutants.
U.S. Environmental Protection Agency, Cincinnati, Ohio,
April 1977. 145 pp.
(3) Duke, K. M., M. E. Davis, and A. J. Dennis. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment Biolog-
ical Tests for Pilot Studies. EPA-600/7-77-043 (PB 268 484),
U.S. Environmental Protection Agency, Research Triangle Park,
North Carolina, April 1977. 114 pp.
14
-------
ATMI/EPA
GRANT STUDY
DETERMINE
BATEA
'FOR CRITERIA
POLLUTANTS
MRC/EPA
WASTEWATER
TOXICITY
STUDY
PHASE I:
TECHNOLOGY
STUDY
BAT-
DETERMINATION
OF BATEA
FOR TEXTILE
WASTEWATERS
DETERMINE
REMOVAL
'OF TOXICITY
BY BATEA
PHASE I: .. PHASE 11:
PREENGINEERING1—'X TOXICITY
SCREENING J™>/ REDUCTION
STUDY | V\ BY BAT
Figure 3. Overall program approach to determine BATEA.
PROGRAM OBJECTIVE
The fundamental objective of the textile wastewaters program
conducted by MRC in conjunction with the EPA is to determine the
reduction in toxicity and toxic pollutant concentrations achieved
by the tertiary treatment systems under investigation in the
ATMI/EPA Grant Study. To evaluate the reduction in toxicity in
a cost-effective manner for the MRC/EPA project, a two-phase
approach was developed. Phase I was designed to collect baseline
toxicity and toxic pollutant data on secondary effluents from 23
selected textile plants and to rank the plants in descending
order of toxicity. Data obtained in the Phase I study are
reported in "Source Assessment: Textile Plant Wastewater Toxics
Study, Phase I" (4). Phase II was designed to determine the
level of toxicity and toxic pollutant removal attained by the
tertiary treatment systems in the ATMI/EPA Grant Study at only
those plants with relatively high secondary effluent toxicity, as
determined in Phase I.
PROJECT ORGANIZATION - PHASE II
The major effort of the Phase II MRC/EPA tertiary treatment
assessment study was devoted to the collection, chemical analysis,
and biological toxicity testing of single, 24-hr composited
wastewater samples from mobile tertiary treatment pilot plants
(4) Rawlings, G. D. Source Assessment: Textile Plant Waste-
water Toxics Study, Phase I. EPA-600/2-78-004h, U.S. Envi-
ronmental Protection Agency, Research Triangle Park, North
Carolina, March 1978. 153 pp.
15
-------
located at eight3 textile mills. In addition, samples of intake
water were collected for chemical analysis.
Under the Phase II program, wastewater samples were collected by
MRC (for subsequent toxic pollutant analyses and bioassay) during
the last 2 wk of pilot plant operation at each site. The pilot
plants were operated by Engineering Sciences, Inc., who monitored
certain criteria pollutants for BATEA evaluation of the tertiary
treatment systems. During the MRC sampling period, the pilot
plants were operated under steady-state conditions when "candidate"
modes of operation were studied. "Candidate" modes of operation
were defined as tertiary treatment systems, each consisting of
various treatment technologies, which appeared to be most promis-
ing in improving secondary effluent quality to meet suggested
BATEA guideines, as determined by Engineering Science, Inc.,
based on initial screening studies conducted prior to the
last two weeks of operation.
The MRC wastewater samples were shipped immediately after collec-
tion to various analytical and bioassay laboratories, including
MRC's Dayton Laboratory. Laboratories involved in the analysis
and bioassay work are discussed in Section 6 and 7. Data from
chemical analyses and bioassays were then assembled and evaluated
by MRC. Both phases of the textile wastewater toxics study were
directed by Dr. Max Samfield of the Chemical Processes Branch,
IERL/RTP, EPA. For the Phase II program, Dr. Gary D. Rawlings of
MRC served as contract manager and Mr. Jeffrey R. Klieve of MRC
served as principal investigator.
SPECTRA ANALYSIS
For this portion of the project, magnetic tapes storing all the
chromatograms of the Phase I secondary effluent samples were
collected and loaded on the HP 5934 Data System. Individual
samples were then accessed and the total ion chromatograph for
each was displayed on the data system screen.
The major compound identification search strategy involved
accessing major ions and determining when (scan number) they
eluted from the GC during the 40-min run for each compound. When
the elution time was identified, the computer would display all
aAfter completion of Phase I, 10 textile mill sites were
recommended for Phase II studies. Two of the recommended sites
were eliminated from the ATMI/EPA Grant Study, and thus from
Phase II of the MRC/EPA wastewater toxics study. Therefore,
the Phase II toxics study was conducted at only eight sites.
16
-------
ions produced at that time. Using the three major ions and their
relative intensities, the compound was identified by data listed
in Reference 5.
The estimated percent abundance of the compound was determined
based on the peak areas of the dominant ion fragments and does
not take into account different response ratios for different
organic compounds. The data serve as an indication of bulk
composition.
(5) Eight Peak Index of Mass Spectra, Vol. Ill, Second Edition,
Table 3 (Part 1). Mass Spectrometry Data Centre, AWRE,
Aldermaston, Reading, United Kingdon, 1974. 1933 pp.
17
-------
SECTION 5
SAMPLING PROCEDURES
Samples of intake water, secondary effluent, and various tertiary
effluents were collected for subsequent toxic pollutant analyses
and bioassay at each of the eight sites of the Phase II toxics
study. The sampling was conducted by MRC personnel during one
24-hr period occurring during the last 2 wk of pilot plant
operation. During these last 2 wk, the pilot plant was operated
under steady-state conditions when pilot plant studies were
conducted to assess "candidate" modes of operation. Selected
unit operations were generally run in series during this period.
Prior to the last 2 wk, the unit operations contained in the
pilot plant trailer had been operated individually for short
periods of time in order to screen the unit processes for further
study during the candidate phase.
For analyses other than volatile toxic pollutants, sets of time-
proportional, manually composited samples were taken over a
24-hr period from each water stream subjected to the MRC sampling/
analysis program. Aliquots making up composite samples of
secondary and tertiary effluents were taken once per hour, while
aliquots making up composite samples of intake water were
generally taken every 3 hr. Therefore, each composite sample of
secondary or tertiary effluent was made of 24 aliquots of equal
size, and each composite sample of intake water was generally
made of 8 aliquots of equal size.
For volatile toxic pollutant analyses, three grab samples were
taken from each effluent stream. Each of the grab samples was
hermetically sealed immediately after sample collection. Gener-
ally, one grab sample of each stream was taken during each of the
three working shifts (8 a.m. to 4 p.m., 4 p.m. to 12 p.m., 12 p.m.
to 8 a.m.). The three individual samples were then composited
in the laboratory for a single analysis.
In collecting the samples extreme care was taken to assure the
samples did not come into contact with materials which might
induce contamination. At each point, a separate 3-gal Teflon®-
lined stainless steel bucket or l-£ glass beaker was used to
collect the aliquot. The aliquot was then transferred to a 5-gal
glass jug which was filled over a 3-hr period. Every 3 hr the
sample collected in the jug was distributed to the various
sample bottles listed in Table 2 (except samples for volatile
18
-------
TABLE 2. REQUIRED SAMPLE CONTAINERS AND PRESERVATIVES
Analysis
number
Analysis fraction
Container, per
sampling point
Preservatives required
1 Volatile organics (including
direct injectables)
2 Semivolatile organics (base/
neutral, acid, pesticide,
and PCB's), TSS, and color
3 Metals
4 Fish/Daphnia bioassay
5 Algae bioassay
6 Microbiological bioassays
7 Cyanide (total)
8 Phenol (total) and COD
9 Ammonia and nitrate
10 Total phosphate
11 Sulfide
Three 40-ml glass vials w/Teflon- Keep at 4°c
lined septa
One 4-5, amber glass pharmaceutical Keep at 4°C
job w/TefIon-lined cap
One 500-ml plastic bottle
Four to six 20-£ cubitainers
One 20-£ cubitainer
One 20-5, cubitainer of
secondary effluent,
One l-£ amber glass bottle
of other effluents
One 500-ml plastic bottle
One l-£ amber glass bottle
One 500-ml plastic bottle
One 500-ml plastic bottle
One 500-ml plastic bottle
In the lab, add 5 ml
of redistilled nitric
acid, keep at 4°C
Keep at 4°C
Keep at 4°C
Keep at 4°C
Adjust pH >12 w/lON
sodium hydroxide,
keep at 4°C
4 ml of cone sulfuric
acid, keep at 4°C
2 ml of cone sulfuric
acid, keep at 4°C
Keep at 4°C
2 ml zinc acetate
-------
organics analyses). Care was always taken to insure that the
sample remained homogeneous while in the bucket, beaker, or jug.
Proper preservatives (listed in Table 2) were added to the sample
bottles immediately after the distribution from the 5-gal jug
(i.e., 2 hr after the first aliquot was taken).
Prior to sampling, all glass sample bottles were cleaned thorough-
ly with strong acid (50% sulfuric acid + 50% nitric acid), rinsed
with distilled water, and heated in a glass annealing oven at
400°C for at least 30 min. Once the glass bottles cooled to room
temperature, Teflon-lined caps were applied. Plastic bottles
were cleaned thoroughly by washing in nitric acid and rinsing
several times with distilled water. Once in the field, all
containers were rinsed with the appropriate sample water. Labels
as shown in Figure 4 were filled out and affixed to the appropri-
ate sample bottles prior to sampling. Once applied to the
bottle, the label was covered with clear tape to prevent damage
from water.
Job
Sample or Run No.
Sample Location
Type of Sample
Analyze for
Preservation_
Comments
Log No. Date_
Initials
Figure 4. MRC bottle label used for sample identification.
At the completion of the 24-hr sampling effort, sample containers
were checked to insure proper sample preservation, and bottle
caps were sealed to the bottles to prevent sample leakage during
shipment. All glass bottles were then wrapped with packing
material. Sample containers were packed in ice chests filled with
wet ice to maintain the sample temperature at 4°C. Sample chests
were then transported to the appropriate laboratory for chemical
analysis or bioassay either by commercial air freight or in the
sampling van.
20
-------
SECTION 6
CHEMICAL ANALYSIS PROCEDURES
INTRODUCTION
Chemical pollutants analyzed under the Phase II program included
most of the pollutants on the toxic pollutant list (see the
appendix) and other pollutants which were analyzed while anal-
yzing for the toxic pollutants, analyzed to assess bioassay
results, or analyzed as required by parallel studies. Various
laboratories performed analyses during the program; they are
shown in Figure 5. Analyses for criteria pollutants were
performed for MRC by Pollution Control Science, Inc. (PCS) and
Howard Laboratories, Inc. (HLI) in the Dayton, Ohio area, while
most toxic pollutant analyses were conducted by MRC in-house.
As shown in Figure 5, toxic pollutant compounds are categorized
into a number of analysis fractions. The fractions include
volatile compounds (including direct injectables), base/neutral
extractable compounds, acid extractable compounds, pesticides,
PCB's, total phenol, metals, and total cyanide. Base/neutral
extractable compounds, acid extractable compounds, pesticides,
and PCB's are grouped together as semivolatile compounds.
Still under development, procedures for the analysis of toxic
pollutants require further verification and validation. There-
fore, the data presented in Section 8, which were obtained by
the procedures presented in this section, serve only to indicate
toxic pollutant type and general concentrations.
ANALYTICAL PROCEDURES
Volatile Organic Toxic Pollutants
Toxic pollutants in this category were analyzed at the Dayton
Laboratory of MRC by an analysis procedure designed by EPA to
determine the concentration of those chemical species which are
amenable to the Bellar purge and trap method (2). Sets of
hermetically sealed 45-ml glass vials, which were collected
from each of the Phase II sampling points, were composited in the
laboratory and split into two fractions. One of the fractions
was analyzed, and the other served as a backup sample. Figure 6
provides a simplified diagram of the analytical scheme used for
volatile organics analysis in the Phase II program.
21
-------
WATER SAMPLING
MRC
SECTIONS
BIOASSAY
SECTION 7
TOXIC POLLUTANTS
ORGANICS
- VOLATILES
(INCLUDING
DIRECT INJECTABLES)
MRC
•SEMI VOLATILES
(BASE/NEUTRALS. ACIDS,
PESTICIDES. PCB'S)
MRC .
— TOTAL PHENOL
PCS3ORHLIb
CHEMICAL ANALYSES
SECTION 6
INORGANICS
METALS BY I CAP""
MONSANTO CO. -ST. LOUIS
METALS BY AAd
MRC
CYANIDE
PCS OR HLI
3POLLUTANTS CONTROL SCIENCE, INC.
bHOWARD LABORATORIES.INC.
CINDUCTIVELY COUPLED ARGON PLASMA
dATOMIC ABSORPTION
OTHER POLLUTANTS
— METALS BY I CAP
MONSANTO CO. -ST. LOUIS
— AMMONIA
PCS OR HLI
— NITRATE
PCS OR HLI
— PHOSPHATE
PCS OR HLI
— SULFIDE
HLI
— COD
MRC, PCS, OR HLI
— TSS
PCS
— COLOR
PCS
— pH
BIONOMICS -WAREHAM
— SALINITY
BIONOMICS-WAREHAM
'—SPECIFIC CONDUCTANCE
BIONOMICS-WAREHAM
Figure 5. Chemical analysis logistics - laboratories
and analysis procedures index.
22
-------
SPARGE 5-m/SAMPLE
WITH HaiUM
ONTO TENAX-SILICA TUBE
Figure 6. Analytical scheme for volatile organics analysis.
An internal standard, 1,4-dichlorobutane, was added to 5 ml of
the composited wastewater sample, which was subsequently sparged
with helium onto a Tenax-GC silica-packed sample tube.
Analyses were completed using a Hewlett-Packard 5981 gas
chromatograph/mass spectrometer (GC/MS) with a 5934 data system.
Sample tubes were heated to 180°C over a 1-min period. They were
held at that temperature for 4 min to desorb the compounds onto
a Carbowax 1500 column held at -40°C. For compounds with
boiling points below room temperature, cryogenic trapping at -4°C
(liquid nitrogen cooling) provided better reproducibility of
retention time that did the suggested protocol temperature of
30°C. After desorption, the GC column temperature was raised at
8°C/min to 170°C.
Qualitative identification of a compound was made using the three
criteria listed in the protocol (2): 1) retention time must
coincide with known retention times, 2) three characteristic
masses must elute simultaneously, and 3) intensities of the
characteristic masses must stand in the known proper proportions.
Quantitation of volatile organics was made using response ratios
to the 1,4-dichlorobutane internal standard.
Direct injectables (acrolein and acrylonitrile) were analyzed by
injecting a 5-pfc aliquot of the volatile organics sample directly
onto a Tenax-GC column of a gas chromatograph interfaced with a
computer-controlled quadrupile mass spectrometer. The GC/MS were
23
-------
used in the selected-ion mode
enhanced sensitivity.
(SIM) to provide selectivity and
Semivolatile Organic Toxic Pollutants
Semivolatile organic toxic pollutants were also analyzed at MRC-
Dayton Laboratory with procedures designed by EPA (2). Figure 7
depicts the sample processing scheme used for analyzing the base/
neutral and acid fractions. Two liters of the wastewater sample
were made alkaline (pH >11) using sodium hydroxide, then extracted
three times using methylene chloride. The remaining aqueous
phase was collected and acidified (pH <2) with hydrochloric acid,
after which the organic acids were extracted with methylene
chloride. Both methylene chloride extracts (one containing base/
neutral organics, and the other containing organic acids) were
dried on a column of anhydrous sodium sulfate. The dried
extracts were then concentrated to 1.0 m£ with a Kuderna-Danish
(K-D) evaporator. Resultant solutions were spiked with deuterated
anthracene, sealed in septum-capped vials, and stored at 4°C
until analyzed. Gas chromatographic/mass spectrometric analyses
were performed using SP 2250 and Tenax-GC columns for base/neutral
and acid samples, respectively (2).
ADJUST SAMPLE pH TO
pH > 11
W /SODIUM HYDROXIDE
METHYLENE CHLORIDE
EXTRACTION
BASES & NEUTRALS/PESTICIDES ACIDS (PHENOLS) ..UNEXTRACTABLES
BOTTOM LAYER
TOP LAYER
DRIED ON
ANHY. SODIUM SULFATE
CHANGE pH < 2
W/HYDROCHLORICACID
CONCENTRATED
KUDERNA-DANISH
EVAPORATOR TO 1 ml
METHYLENE CHLORIDE
EXTRACTION
GC/MS
IDENTIFICATION &
QUANTITATION
Figure 7.
Sample processing scheme for the analysis of the base/
neutral and acid fractions of Semivolatile organics.
24
-------
The sample processing scheme used for pesticides and PCB's is
shown in Figure 8. One liter of the wastewater sample was
adjusted to a pH of 6.5 to 7.5 using 50% sodium hydroxide or con-
centrated hydrochloric acid. Pesticides and PCB's were extracted
into a 15% methylene chloride/85% hexane solution which was
separated and back extracted with acetonitrile to remove inter-
fering compounds. Acetonitrile extract was chromatographed on
two SP 2250 columns employing electron capture (EC) detection.
Verification of pesticides and PCB's present was effected using
an SP 2100 column.
15% METHYLENE CHLORIDE/
85% HEXANE EXTRACTION
ORGANIC PHASE
ACETONITRILE
PARTITION FOR CLEANUP'
GC/EC SCREEN
(FURTHER CLEANUP ?)
NO
YES
NO
,
FLORISIL COLUMN
CHROMATOGRAPHY
GC/EC RESCREEN
(FURTHER CLEANUP ?)
JYES
GC/EC QUANTITATION
ON FIRST COLUMN
SILICIC ACID
CHROMATOGRAPHY
GC/EC VERIFICATION
ON SECOND COLUMN
Figure 8. Sample processing scheme for pesticide and PCB analysis
Total Phenol
In addition to specific phenolic compounds analyzed in the semi-
volatile toxic pollutant analysis scheme, total phenol was also
measured. Determinations of total phenol concentrations were
made by two laboratories during the Phase II program; Pollution
Control Science, Inc. of Miamisburg, Ohio made the determinations
25
-------
in the early stages of the program, and Howard Laboratories, Inc.
of Dayton, Ohio made them in the latter stages. Both laboratories
used the chloroform extraction method following distillation
[Standard Methods 510A and 510B (5)].
Inorganic Toxic Pollutants (Including Cyanide)
In addition to organic toxic pollutants, the toxic pollutant
list given in the appendix includes 13 metals (measured as
the total metal), total cyanide, and asbestos.
The following nine toxic pollutant metals were analyzed by
Monsanto Company in St. Louis, Missouri by the ICAP excitation
technique: antimony, beryllium, cadmium, chromium, copper, lead,
nickel, silver, and zinc. Via the ICAP technique, simultaneous
multielement determinations are made of trace metal concentrations
at the sub-mg/Jl level in solutions. The basis of this method is
atomic emission. Excitation energy is supplied by coupling a
nebulized sample with high temperature argon gas which has been
passed through a powerful radio-frequency field. Emitted light is
simultaneously monitored at 22 wavelengths corresponding to 22
different elements.
Since four of the toxic pollutant metals are not amenable to
analysis by ICAP techniques, they were analyzed by standard atomic
absorption (AA) techniques at MRC's Dayton Laboratory. The four
metals are arsenic, mercury, selenium, and thallium. Procedures
for AA analysis of these four metals are found in Standard Method
301A (6). Arsenic alone was analyzed during early stages of the
Phase II program, since mercury, selenium, and thallium were not
found in samples resulting from Phase I investigations (4).
However, a parallel program to Phase II, undertaken part way
through the Phase II study, required analysis of the other three
AA metals, and thus the analytical results for mercury, selenium,
and thallium are available for later pilot plant sites investi-
gated in the Phase II study.
Total cyanide was analyzed using the colorimetric method
following distillation [Standard Methods 413B and 413D (5)] by
Pollution Control Science, Inc. of Miamisburg, Ohio during
initial stages of the Phase II program, and by Howard Labora-
tories, Inc. of Dayton, Ohio during the later stages.
As in Phase I of the program asbestos was not analyzed in the
Phase II program.
(6) Standard Methods for the Examination of Water and Wastewater,
Fourteenth Edition. American Public Health Association,
Washington, D.C., 1976. 874 pp.
26
-------
Other Pollutants
As mentioned earlier, pollutants other than toxic pollutants were
analyzed in many cases during the Phase II program. Some
analyses are available when they were cogenerated with some toxic
pollutant analyses. Metals analyzed by ICAP which do not appear
on the toxic pollutant list given in the appendix are examples.
Some analyses (ammonia, nitrate, phosphate) were conducted to aid
in interpreting bioassay results. Salinity, pH, and specific
conductance were determined in conjunction with bioassay studies
by EG&G International, Inc., while other analyses (COD, TSS,
color, pH, sulfide) were required for studies parallel to the
Phase II study.
Metals were determined via the ICAP technique by Monsanto Company
in St. Louis, Missouri as discussed previously in this section.
Table 3 (1, 6, 7) exhibits methodologies and laboratories used to
conduct the other analyses.
(7) Manual of Methods for Chemical Analysis of Water and Wastes.
EPA-625/6-76-003a (PB 259 973), U.S. Environmental Protection
Agency, Cincinnati, Ohio, 1976. 317 pp.
27
-------
TABLE 3. PROCEDURE USED IN ANALYZING OTHER POLLUTANTS
Pollution Control Science, Inc.
Analysis
Ammonia
Nitrate
Phosphate
Method
Nesslerization
preceded by
distillation
Brucine method
Ascorbic acid
method
Reference
Standard Methods 41 8A
and 418D (6)
Standard Method 419D
(6)
Standard Method 425F
C61
EG&G, Bionomics Aquatic
Howard Laboratories, Inc. Toxicology Laboratory
Method
Selective ion electrode
method
Nitrate electrode method
Stannous chloride method
preceded by persulfate
Reference Method Reference
Methods for Chemical
Analysis of Water
and Wastes, p. 165 (6)
Standard Method 419B
(6)
Standard Methods 425CIII
and 425E (6)
CO
Sulfide
COD
TSS
Color (ADMI)
Total nonfilterable
residue dried at
103-105°C
ADMI color value
pH
Salinity
Specific
conductivity
digestion
Orion direct measurement
method, model 94-16
electrode
Oxygen demand (chemical) Standard Method 508 (6)
Standard Method 208C
(6)
Development Document
for Effluent Limita-
tions Guidelines and
New Source Perform-
ance Standards for
Textile Mills-Appendix
A (1)
Glass electrode
technique
Refractometry with
American Optical
refractometer
Conductivity with
Yellow Springs
instrument
model 33
Standard Method
424 (6)
Standard Method
205 (6)
-------
SECTION 7
BIOASSAY PROCEDURES
INTRODUCTION
In addition to chemical analyses, a series of bioassay tests were
conducted to assess toxicity removal capabilities of the tertiary
treatment systems. In toxicity testing, organisms will integrate
the synergistic and antagonistic effects of all the effluent
components over the duration of exposure. Therefore, analyses of
specific components cannot totally be related to toxicity, and
toxicity testing must be performed. In Phase II, acute toxicity
to various freshwater animal and plant species, microbiological
mutagenicity, and cytotoxicity were determined. Table 1,
repeated here for reader convenience, briefly defines the purpose
of each of the bioassay tests. The laboratories performing
various bioassay tests through the Phase II program are shown
in Figure 9.
CAPRICORNUTUM
BIONOMICS-
PENSCACOLA
(FATHEAD MINNOW)
BIONOMICS -
WAREHAM
CHO-K1TEST
MRC
MACROCHIRUS
IBLUEGIUI
BIONOMICS -
WAREHAM
Figure 9.
Bioassay logistics - laboratories and
bioassay procedures index.
29
-------
TABLE 1. BIOASSAY STUDIES CONDUCTED IN PHASE II
Bioassay test system
Indicator organisms
Purpose of test
Freshwater algal assay
Freshwater static bioassay
u>
o
Microbial mutagenicity
Cytotoxicity
Selenastrum capriaornutum
Pimephales pvomelas
(fathead minnow)
Daphn-ia magna
(daphnid)
Lepomis maaroehirus
(bluegill)
Salmonella typh-i-murium (Ames test)
(strains TA1535, TA1538, TA1538,
TA98, TA100)
Eseheriahia coli. (pol A test)
(strains W3110, p3478)
Chinese hamster ovary cells
To detect potential toxicity to
aquatic plants.
To detect potential toxicity to
organisms in aquatic environments.
To determine if a chemical mutagen
(possibly a carcinogen) is present.
These microbial strains were
selected because of their sensitiv-
ity to various classes of chemical
compounds.
To measure metabolic impairment and
death in mammalian cells. These
primary cell cultures have some
degree of metabolic repair capability.
-------
Acute toxicity tests were used in Phase II to determine the level
of toxic agent in secondary or tertiary effluent that produced an
adverse effect on a specified percentage of test organisms (algae,
fathead minnow, bluegill, or Daphnia) in a short period of time.
The most common acute toxicity test is the acute mortality test.
Experimentally, 50% effect is the most reproducible measure of
the toxicity of a toxic agent to a group of test organisms
during a convenient, reasonably useful exposure time period.
Thus, the acute mortality test is a statistical estimate of the
LCso, which is the median concentration of toxicant in dilution
water, that is lethal to 50% of the test organisms during
continuous exposure for a specified period of time. However, the
effective concentration (ECso)/ the concentration at which growth
rate was 50% of a control, was determined when algae were used.
The terms median lethal concentration (LC5o) and median effective
concentration (EC5o) are consistent with the widely used terms
median lethal dose (LDso) and median effective dose (EDso),
respectively. "Concentration" refers to the amount of toxicant
per unit volume of test solution; "dose" refers to the measured
amount of toxicant given to the test organism.
Microbial mutagenicity bioassays were used in Phase II to deter-
mine if chemical mutagens were present in the secondary and
tertiary effluents. Two bioassays were used to test these
effluents. The Salmonella typhimurium assay (Ames test), using
the five strains TA98, TA100, TA1535, TA1537, and TA1538, and the
Escheriehia ooli pol A+/~ assay using the p3478 and w3110 strains,
were used by MRC to evaluate the effluents. Both assays included
the Aroclor 1254-induced rat liver S-9 fraction for metabolic
activation.
The S. typhimuvium assay (Ames test) has proven to be 85% to 90%
accurate in detecting mutagens (8). The assay as developed by
Dr. Bruce N. Ames (9) uses the mutant strains of Salmonella which
are histidine dependent. A minimal amount of histidine is added
to the system to allow a background growth of the bacteria. If
a mutation occurs, the bacteria revert back to the wild type, a
histidine-independent strain, and these revertants grow into
visible colonies during incubations. A test is then scored by
(8) McCann, J., E. Choi, E. Yamasaki, and B. N. Ames. Detection
of Carcinogens as Mutagens in the Salmonella/Microsome Test:
Assay of 300 Chemicals. Proceedings of the National Academy
of Science, 72:5135-5139, 1975.
(9) Ames, B. N., J. McCann, and E. Yamasaki. Methods for Detect-
ing Carcinogens and Mutagens with the SalmonsZZa/Mammalian-
Microsome Mutagenicity Test. Mutation Research, 31:347-364,
1975.
31
-------
counting the number of spontaneous revertant colonies on the
control plates and the plate treated with the sample. A sample
is considered to be mutagenic if the increase in the number of
revertants on the plate with samples is at least two times that
of the control and a dose response is exhibited.
The E. ooli pol A / assay as described by Slater, et al. (10)
determines DNA damage by the use of the w3110 and p3478 strains,
which are DNA repair-proficient and -deficient, respectively.
Substances that affect the DNA of the E. ooli inhibit the growth
of the repair-deficient strain. This results in a zone of
inhibition or no growth, whereas the proficient strain shows no
inhibition. Some compounds may be toxic to both strains, result-
ing in zones of inhibition with both strains. The test is then
scored by comparison of the inhibition of the two strains.
Cytotoxicity (cell toxicity) assays were performed to measure
quantitatively any cellular metabolic impairment and death
resulting from exposure in vitro to secondary and tertiary
effluent samples. The clonal cytotoxicity assay for acute
toxicity using Chinese hamster ovary cells (CHO-Kl) was selected
to test the secondary and tertiary effluents. MRC has developed
this in vitro clonal assay using the CHO-Kl cells (11) . This
assay was used because of the sensitivity and reproducibility of
the system.
The CHO cytotoxicity assay determines acute toxicity through the
number of colonies formed after a 6-day incubation with the
sample. A precise number of cells are plated, and only those
cells that replicate into visible colonies are scored as
survivors. The number of colonies of the control flask is
compared to the number on the flask with sample, and the percent
survival is determined.
PROCEDURES
Algal Assay
Immediately after collection, effluent samples were shipped to
EG&G, Bionomics Marine Research Laboratory in Pensacola, Florida,
where they were stored at 4°C until testing began. Culture and
test procedures generally followed protocols developed by the
the EPA (3).
(10) Slater, E. E., M. D. Anderson, and H. S. Rosenkranz. Rapid
Detection of Mutagens and Carcinogens. Cancer Research,
31:970-973, 1971.
(11) Wininger, M. T., F. A. Kulik, and W. D. Ross. In Vitro
Clonal Cytotoxicity Assay Using Chinese Hamster Ovary Cells
(CHO-Kl) for Testing Environmental Chemicals. In Vitro,
14 (4) :381, 1978.
32
-------
An inoculum of Selenastrum capriaornutum was added to each of the
test flasks, which contained varying concentrations of the second-
ary or tertiary effluents in dilution water. The test flasks
were then incubated at 24 ± 1°C under 4,300 lux illumination.
After 7, 12, and 14 days of exposure, a portion of the algal
suspension was removed from each flask and filtered through a
Millipore® filter, (BD, 0.6 ym). The filter was then dried at
90°C, cooled in a desiccator to room temperature, and weighed.
The percent change in dry cell weight concentration of the
sample as compared to a control was calculated after 7, 12, and
14 days of exposure. The concentration of secondary or tertiary
effluent at which the percent change in dry cell weight was 50%
that of the control (EC5o) was then determined.
Daphnia Assay
Effluent samples were shipped to the Aquatic Toxicology Labora-
tory of EG&G, Bionomics Marine Research Laboratory at Wareham,
Massachusetts, where they were stored at 4°C until tested.
Daphnia magna (<24 hr old) used in the test were from laboratory
stocks cultured at EG&G, Bionomics. Procedures used were based
on protocols established by the EPA (3).
Two independent tests involving two different series of concen-
trations were generally performed through the study. A prelimin-
ary (range-finding) test was performed to define the narrower
range of concentrations to be used in a subsequent definitive
test. Mortality data derived from the definitive test were used
to calculate a median lethal concentration (LC5o) and its 95%
confidence limit utilizing least squares regression analysis.
The LC50 is the calculated nominal concentration of the test
compound in diluent water which produces 50% mortality in the
test animal population at the stated times of exposure.
The static toxicity tests were conducted in 250-mJl beakers which
contained 150 m£ of test solution. For each test concentration,
the appropriate amount of the effluent was introduced into the
required volume of diluent water to total 500 m£ to 750 mi, and
mixed with a magnetic stirrer. This solution was then divided
into three 150-m£ aliquots in triplicate beakers to provide
replicate exposure treatments. The remaining 50 m£ were used for
0-hr dissolved oxygen (DO), specific conductance, alkalinity,
total hardness, and pH determinations. Five daphnids were
randomly assigned to each test vessel within 30 min after the
effluent was added for a total of 15 daphnids per concentration.
A control, consisting of the same dilution water and conditions
but with no effluent, was established. All test vessels were
maintained at constant temperature, and occasionally the test
solutions had to be aerated. Dissolved oxygen, temperature, and
pH were monitored through each test.
33
-------
Fish Assay (Fathead Minnow and Bluegill)
Effluent samples were shipped to the Aquatic Toxicology Laboratory
of EG&G, Bionomics Marine Research Laboratory at Wareham,
Massachusetts, where they were stored at 4°C until tested. Fat-
head minnows (Pimephales promelas) were obtained from a commercial
fish supplier in Missouri, and bluegills (Lepomis macrochirus)
were obtained from a commercial fish supplier in Connecticut.
Upon receipt at the Bionomics lab, fish were held until use (a
minimum of 14 days) in a l,700-& raceway coated with epoxy paint.
During this time period, all fish were fed a dry pelleted food
daily, ad libitum, and ground liver weekly except during 48 hr
prior to testing. There was less than a 2% mortality observed
during this 2-day period.
Procedures used for the fish bioassay were based on protocols
developed by the EPA (3). The toxicity test was conducted in
19.6-£ glass jars which contained 15 £ of test solution. The
effluent was mixed with diluent water to provide the appropriate
percentage concentrations. A control jar containing the same
dilution water and maintained under the same conditions as test
concentrations, but containing no secondary or tertiary effluent,
was established. Test solution temperatures were controlled by
a system designed to maintain test temperatures at 22 ± 1°C.
Test solutions generally were not aerated. Ten fish were randomly
distributed to each test jar within 3 hr after the test solutions
were mixed. During the toxicity determination, the pH, tempera-
ture, and DO concentration of test solutions were measured at
0, 24, 48, 72, and 96 hr in the control, high, middle, and low
test concentrations. The specific conductance, total hardness
and alkalinity were measured in the control, high, middle, and
low test concentrations at 0 hr. The concentrations tested and
the corresponding mortality data derived from the toxicity test
were used to establish 24-, 48-, 72- and 96-hour median lethal
concentrations (LCso) and 95% confidence intervals. The LC50 is
defined as the concentration (nominal or measured) of the test
compound in diluent water which causes 50% mortality in the test
animal population at the stated exposure interval.
Determination of Mutagenicity
The effluent samples were shipped to MRC and stored at 4°C until
tested. The samples were filter sterilized through 0.45-ym and
0.22-ym filters before application to the bioassay system. When
streaked on nutrient agar, the samples exhibited bacterial
contamination. The five strains of Salmonella (TA98, TA100,
TA1535, TA1537, and TA1538) were obtained from Dr. Bruce Ames of
the University of California. The strains are kept at -80°C and
a scraping made each day to grow an overnight nutrient broth
culture. The stock cultures are routinely checked for their
genotypic characteristics and the presence of the plasmid.
34
-------
For each experiment, the following solutions, listed in the order
of addition, were added to a sterile 15 mm x 85 mm culture tube
placed in a 45°C water bath:
• 2.00 mi of 0.6% agar (containing 0.05 mM histidine and
0.05 mM biotin)
• 0.10 mH of indicator organisms
• 0.50 m£ of metabolic activation mixture
• 0.01 to 1.0 mX, of the effluent sample
The metabolic activation mixture used for each experiment
consisted of:
• 1.0 m£ of S-9 rat liver fraction
• 0.2 m£ of magnesium chloride (0.4 M) and potassium
chloride (1.65 M)
• 0.10 m£ of glucose-6-phosphate (1 M)
• 0.4 mJl of nicotine adenine dinucleotide phosphate (4 yM)
• 5.0 ma of sodium phosphate (0.2 M, pH 7.4)
• 3.3 mH of water
The mixture in top agar with or without the metabolic activation
mixture was vortexed and poured onto minimal agar plates. The
plates consisted of the following, per milliliter:
15 g agar
20 g glucose
0.2 g of magnesium sulfate
2 g of citric acid monohydrate
10 g of potassium phosphate dibasic
3.5 g of sodium ammonium phosphate
After the top agar mixture solidified, the plates were inverted
and incubated at 37°C for 48 hr. The number of revertant
colonies was then counted with a 3M Colony Counter.
All samples were run in duplicate at five dosages, with and with-
out metabolic activation. Positive and negative controls were
run with all samples. The positive controls included 2-
aminoanthracene, 2-nitrofluorene, and sodium nitrite.
The E. ooli pol A ' strains were stored at -80°C. Inoculums
from the frozen stocks were grown overnight at 37°C with shaking
in a liquid medium supplemented with 5 yg of thymine per mi (10).
For each test plate, 2 mH of top agar in a 16 mm x 85 mm tube was
held at 45°C. To the 0.6% top agar, O.lmA overnight bacterial
culture was added. This was mixed and poured onto
35
-------
plates. After the soft agar solidified, a sterile disc was
placed in the center of the plate and the appropriate amount of
filter-sterilized effluent was added to the disc. The plates
were incubated at 37°C for 16 hr and then scored. The zone of
toxicity or inhibition was measured on each plate. Several
concentrations were tested for each sample.
Positive and negative controls were run along with all samples.
The positive control was ethylmethanesulfonate. Larger zones of
inhibition were observed with the DNA repair-deficient strain
(p3478).
Determination of Cytotoxicity
The samples were filter sterilized through 0.45-ym and 0.22-ym
filters prior to application to the test flask. All samples were
kept at 4°C until tested. Samples were run at 5 to 7 concentra-
tion levels using approximately 300 to 500 cells that had been
plated on the previous day. After incubation at 37°C for 6 days
to 7 days, the media and sample were removed and the cells were
fixed, stained, and counted with a Fisher counter. The data were
entered into the laboratory computer to obtain the mean, standard
deviation, and percent survival of each sample versus controls.
Positive and negative controls were run with all samples. The
positive control was cadmium chloride. All samples were run in
triplicate at 5 concentrations. A detailed procedure for this
assay is given in Table 4.
36
-------
TABLE 4. CHO-K1 CLONAL CYTOTOXICITY TEST
Cell line: Chinese hamster ovary epithelial cells ATCC No. CCL 61
Medium: F-12 GIBCO No. H-17 10.8 g/m£
Sodium hydrogen carbonate
10% Fetal calf serum, virus, mycoplasma screened
GIBCO No. 629
Incubation: 37°C, 5% C02, Saturated humidity
Samples: 6 Controls (blank)
5 to 7 Concentrations of test compound in triplicate
5 Concentrations of- a positive toxic control in
triplicate
Test procedure
To stock CHO-K1, add 5 ml 0.25% trypsin at 37°C for 5 min.
Shake cells and add to centrifuge tube.
Add 5 m& media to flask, shake, and add to centrifuge tube.
Centrifuge 5 min at 1,200 G and pour off liquid, retaining cells.
Add 10 m£ medium, shake, centrifuge 5 min, pour off medium.
Add 10 mH medium, shake.
Make hemocytometer count of trypsinized cells.
Dilute so that 5 m£ media contain 300 to 500 cells.
Add 5 mJi media and cells to T-25 flasks.
Incubate 12 hr to 18 hr to allow attachment using normal media.
Replace 5 m£ of media and sample.
Incubate 6 days to 7 days total.
Fix with 10% formaldehyde/0.5% sodium chloride/4% methanol for
30 min.
Stain with crystal violet (0.04% for 15 min).
Count clonal colonies of remaining cells macroscopically using
Fisher Count-All Model 600.
Score with respect to experimental vs. controls as percent
survival.
37
-------
SECTION 8
ANALYTICAL AND BIOASSAY RESULTS
INTRODUCTION
Results of chemical analyses and bioassay of the wastewater
streams sampled at each of the eight pilot plant sites are
presented in the following subsections. All analytical and bio-
assay data acquired from each pilot plant site are presented
together in a separate subsection for each site.
As discussed previously, individual unit processes were often
operated in series during "candidate mode" studies when MRC
conducted its sampling/analysis program. In general, MRC
collected samples of the secondary effluent and samples after
each unit operation in each candidate treatment system. For
example, if the following unit processes were operated in series;
SECONDARY i FLOCCULATION/ MULTIMEDIA
EFFLUENT '''SEDIMENTATION * FILTRATION "
PILOT PLANT OPERATIONS
then samples of secondary effluent, flocculation/sedimentation
effluent, and multimedia filter effluent were sampled and subse-
quently analyzed. Thus, the example sampling/analysis program
would assess the performance of two tertiary process systems:
flocculation/sedimentation, and multimedia filtration preceded by
flocculation/sedimentation.
In this same manner, several tertiary process systems of the
tertiary pilot plant were characterized at each textile mill
location, simply by conducting the sampling/analysis program
between unit processes in series. Tertiary process systems
evaluated in the Phase II program fell into eight categories,
as shown in Figure 1 (repeated here for reader convenience).
Resulting chemical and bioassay data are classified in tables of
the following subsections based on the tertiary process system
type operated at each pilot plant location. Table 5 indicates
which types of tertiary process systems were employed at each
location. At the end of each subsection, chemical analysis/bio-
assay results are presented in five tables: results of organic
38
-------
TERTIARY PILOT PLANT OPERATIONS
TYPE 1 :
TYPE 2:
TYPE 3:
TYPE 4:
TYPES:
TYPE 6:
TYPE 7:
TYPES:
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFaUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
SECONDARY
EFFLUENT
— — SEDIMENTATION
— — COAGULANT — FLOCCULATION/
ADDITION SEDIMENTATION
— — MULTIMEDIA
FILTRATION
— *• COAGULANT -MULTIMEDIA
ADDITION FILTRATION
— *- COAGULANT — FLOCCULATION/ —MULTIMEDIA
ADDITION SEDIMENTATION FILTRATION
— — MULTIMEDIA — GRANULAR
FILTRATION ACTIVATED CARBON
— — MULTIMEDIA — — OZONATION
FILTRATION
• — LUAuULAIN 1 ~- rLUCLULAI \\Jnl ^ /VIULI IfVltL/l A ^ uKANULAK
ADDITION SEDIMENTATION FILTRATION ACTIVATED CARBON
— — TERTIARY PILOT PLANT OPERATIONS
Figure 1. Tertiary treatment systems.
TABLE 5. TERTIARY TREATMENT SYSTEMS USED
AT SPECIFIC PILOT PLANT SITES
Type of tertiary
treatment system studied
Plant 1 2345678
A -a X X X
C X X X
W X X XX
S XXX
P XX XX
N XXX
V X X X X
T XXX
Blanks indicate treatment technology
not tested in "candidate" mode studies
at this location.
39
-------
toxic pollutant analyses, results of inorganic toxic pollutant
analyses, results of other pollutant analyses, bioassay results,
and effluent descriptions.
Tables indicating results of organic toxic pollutant analyses
present concentrations of only those organic compounds on the
toxic pollutant list (see the appendix) that were found above
analytical detection limits (see Table 6) in the wastewater
sample. In other words, all organic compounds found on the toxic
pollutant list were analyzed by the chemical analytical technique
formerly discussed (see Section 6), but only those observed in
the wastewater samples are listed in the organic toxic pollutant
tables.
The same tables present concentrations of pollutants found in the
textile plant intake water at the time of Phase II sampling,
concentrations of pollutants found in the secondary effluent
during the Phase I sampling/analysis program (4), and concentra-
tions of pollutants found in the secondary and tertiary process
system effluents during the Phase II sampling/analysis program.
In addition, some pollutant removal efficiencies of the tertiary
process systems were calculated. Since results of toxic pollut-
ant analyses only indicate general concentrations, the presented
removal efficiency data must be treated with extreme care. These
data are only useful to indicate general trends. Removal
efficiencies were calculated only in cases where the Phase II
secondary effluent or tertiary process series effluent exceeded
10 vg/H, since low level contamination of the samples for some
toxic pollutant species often occur in the analyses procedure.
The removal efficiencies presented were calculated as follows:
A — B
—^— x 100 = % removal
f\
where A = concentration of pollutant species present in the
Phase II secondary effluent.
B = concentration of pollutant species present in the
Phase II tertiary effluent.
When A or B was less than the detection limit, the detection
limit was used in the calculation.
Tables indicating results of inorganic toxic pollutant analyses
and other pollutant analyses are organized in much the same way as
tables presenting results of organic toxic pollutant analyses.
Tables of bioassay results present results of the bioassay proce-
dures described in Section 7 for secondary and tertiary effluents
only, since bioassays were not conducted on intake water in the
Phase II program. Since the specific bioassay parameter measured
40
-------
TABLE 6. MINIMUM DETERMINABLE CONCENTRATIONS
FOR ORGANIC TOXIC POLLUTANTS
Compound
Concen-
tration ,
yg/liter
Compound
Concen-
tration,
jjg/liter
Acids:
2-Chlorophenol 0.09
Phenol 0.07
2,4-Dichlorophenol 0.1
2-Nitrophenol 0.4
p-Chloro-m-cresol 0.1
2,4,6-Trichlorophenol 0.2
2,4-Dimethylphenol 0.1
2,4-Dinitrophenol 2.0
4,6-Dinitro-O-cresol 40.0
4-Nitrophenol 0.9
Pentachlorophenol 0.4
Volatiles:
Chloromethane 0.2
Dichlorodifluoromethane 0.2
Bromomethane 0.2
Vinyl chloride 0.4
Chloroethane 0.5
Methylene chloride 0.4
Trichlorofluoromethane 2.0
1,1-Dichloroethylene 2.0
1,1-Dichloroethane 3.0
Trana-1,2-dichloroethylene 2.0
Chloroform 5.0
1,2-Dichloroethane 2.0
1,1,1-Trichloroethane 2.0
Carbon tetrachloride 4.0
Bromodichloromethane 0.9
Bis(chloromethyl) ether 1.Q-.
1,2-Dichloropropane 0.7
2Vans-l,3-dichloropropene 0.4
Trichloroethylene 0.5
Dibromochloromethane 0.3
Cis-l,3-dichloropropene 0.5
1,1,2-Trichloroethane 0.7
Benzene 0.2
2-Chloroethyl vinyl ether 1.0
Bromoform 0.6
Tetrachloroethylene 0.9
1,1,2,2-Tetrachloroethane 0.6
Toluene 0.1
Chlorobenzene 0.2
Ethylbenzene 0.2
Direct Injectables:
Acrolein 200
Acrylonitrile -100
Base/Neutrals:
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachloroethane
1,2-Dichlorobenzene
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
1,2,4-Trichlorobenzene
Naphthalene
Bis(2-chloroethyl) ether
Hexachlorocyclopentadiene
Nitrobenzene
Bis(2-chloroethoxy) methane
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Isophorone
Fluorene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
2,4-Dinitrotoluene
N-nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene
Anthracene
Dimethyl phthalate
Diethyl phthalate
Fluoranthene
Pyrene
Di-n-butyl phthalate
Benzidine
Butyl benzyl phthalate
Chrysene
Bis(2-ethylhexyl) phthalate
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
N-Nitrosodimethylamine
N-nitrosodi-n-propylamine
4-Chlorophenyl phenyl ether
3,3'-Dichlorobenzidine
Di-n-octyl phthalate
Pesticides and PCB's
0.02
0.04
0.1
0.05
0.06
0.08
0.09
0.007
0.07
0.2
0.08
0.06
0.02
0.02
0.04
0.06
0.02
0.2
0.02
0.02
0.07
0.05
.1
.01
.01
.03
0.03
0.02
0.01
0.02
0.02
0.03
0.02
0.04
0.02
0.02
0.02
0.02
0.02
0.02
0.01
0.8
0.2
0.03
1.0
0.9
1.0
Based on the lowest quantifiable area obtained from the GC/MS.
41
-------
varied from test to test, a column indicating the measured para-
meter is included in the bioassay results tables. Explanation of
these parameters can be found in Section 7. Where ECso's or
LCso's were the measured parameters, 95% confidence intervals are
also stated.
A table of effluent descriptions is also included with each pilot
plant assessment. Results presented in these tables generated
concurrently by individuals conducting static acute toxicity
tests.
The chemical analysis/bioassay data discussions include overviews
of background material, sampling/analysis deviations from proto-
cols described in earlier discussions, and signficiant trends
specific to the results from each of the eight pilot plant
studiesi A more complete evaluation of the data is provided in
Section 9.
PLANT DATA
Plant A
Textile plant A generated wastewater from wool finishing opera-
tions. Existing treatment facilities included screens, equaliza-
tion, aeration, secondary clarification, and chlorination; sludge
dewatering techniques included dissolved air flotation and
vacuum filtration. Phase I screening studies (4) indicated that
plant A wastewater treated by the existing treatment system was
1 of the more toxic effluents of the 22 secondary effluents
actually evaluated in the program. Therefore, plant A was
included as a site for tertiary pilot plant studies and MRC
sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was decided that tertiary treatment
types 2, 5, and 8 held the best promise for improving secondary
effluent quality to meet suggested BATEA guidelines; they were
thus selected for candidate mode studies. Alum and lime were
used as coagulants in each of the treatment systems. A flow
diagram of the candidate mode configuration employed is shown in
Figure 10. Sampling of the candidate mode operation was conducted
by MRC, and results of subsequent chemical analyses and bioassay
tests 'are presented in Tables 7 through 11.
In evaluating the data, it is apparent that type 2 treatment
(flocculation/sedimentation) removed significant amounts of most
of the organic toxic pollutants found in the secondary effluent,
except for bis(2-ethylhexyl) phthalate. Subsequent multimedia
filtration (type 5) and granular activated carbon treatment
(type 8) generally removed additional amounts, but type 5
treatment appeared to add trace amounts of some organic pollutants
such as total phenol, benzo(a)pyrene, specific phenols, and
42
-------
INTAKE
(g) INTAKE WATER SAMPLE
TEXTILE PLANT A
SECONDARY TREATMENT
35 mg/l ALUM (AS Al+3)
100mg/ILIME(ASCa(OH)2r
0 SECONDARY EFFLUENT
SAMPLE
PILOT PLANT
UNIT OPERATIONS
FLOCCULATION/SEDIMENTATION
0 TYPE 2 EFFLUENT SAMPLE
I
MULTIMEDIA FILTRATION
,;—®
TYPE 5 EFFLUENT SAMPLE
GRANULAR
ACTIVATED CARBON
0 TYPE 8 EFFLUENT SAMPLE
Figure 10.
Candidate wastewater treatment
system studied at plant A.
dichlorobenzenes. A possible source of these contaminants
was leaching from the filter media used in type 5 treatment.
Contaminants may have been adsorbed onto the filter media during
a former pilot plant study, or they may have been present in the
virgin filter media.
Except for chromium, copper, cyanide, and zinc, inorganic toxic
pollutants were added to the secondary effluent by the tertiary
process series. Most of the chromium (72%) was removed by type 2
treatment (flocculation/sedimentation), with subsequent filtration
(type 5) and activated carbon treatment (type 8) doing little to
remove additional chromium. Cyanide was removed by type 2 and
type 8 treatment, and copper was removed to a slight degree (6%
to 11%) by all three types of tertiary treatment. As expected,
aluminum and calcium concentrations increased through tertiary
treatment because alum and lime were used as coagulants. Phos-
phorus was removed (more than 75%) by all three treatment systems.
This is expected since alum and lime coagulation are classical
methods of phosphorus removal.
In evaluating bioassay results, it is apparent that the secondary
effluent was as acutely toxic during Phase II sampling/analysis
43
-------
as it was during Phase I sampling/analysis. Slight improvement
in toxicity to freshwater algae was observed when type 2 treat-
ment (flocculation/sedimentation) was employed. Subsequent
filtration (type 5) and activated carbon treatment (type 8) did
little to improve toxicity to freshwater algae.
All three types of tertiary treatment were effective in removing
toxicity to Daphnia. Type 8 treatment (flocculation/sedimenta-
tion followed by filtration and activated carbon treatment)
improved the secondary effluent with regard to acute toxicity to
Daphnia to the point that no acute toxicity was observed. Type 2
and type 5 treatment systems added something to the wastewater
(possibly aluminum or calcium used in coagulation), which was
toxic to bluegills. However, subsequent treatment of the waste-
water by granular activated carbon improved the toxic effect to
the point where no toxicity was observed.
TABLE 7. PLANT A ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Secondary effluent
Pollutant
Bis ( 2-ethylhexyl) phthalate
Pyrene
Heptachlor
1 , 2-Dichlorobenzene
1,2,4-Trichlorobenzene
a-BHC
4,4'-DDT
Toluene
Ethylbenzene
Phenol
Benzo (a)pyrene
N-nitrosodiphenylamine
2 , 4-Dimethylphenol
Pentachlorophenol
1 , 4-Dichlorobenzene
Phenol (total)
Intake Phase I
5.4 6
1.2 -
1.6
1
46
8.4
0.05
12 65
Phase II
32
1.4
20
1,600
5.8
2.1
31
5
60
Tertiary effluent
Type 2
44 (-38)a
(100)
150 (91)
14 (55)
3
47 (22)
Type 5
14 (56)
5.4 (73)
94 (94)
1.9
12 (31)
3
0.8
0.4
0.9
10
55 (8)
Type 8
4.7 (85)
(100)
(100)
(100)
1.5
17 (72)
Minus percent removals indicate an increase in the concentration of the specific
pollutant.
Blanks indicate concentration below detection limit (see Table 6).
44
-------
TABLE 8. PLANT A INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/fc; percent removal in parentheses)
Secondary Effluent
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Intake
<10
72
0.2
7.5a
<4
<4
<4
<22
NA
<36
NA
<5
NA
56
Phase I
30
<5
NAC
<0.5
180
27
15
<1
<0.5
140
<5
<5
<5
6,400
Phase II
<10
60
<0.04
<2
110
20
10
<22
NA
<36
NA
<5
NA
6,400
Type 2
<10
62 (-3)
<0.04
<2
31 (72)
13a (35)
<4 (>60)
<22
NA
<36
NA
<5
NA
5,700 (11)
Tertiary effluent
Type 5
<10
103
1.2
97
34
110
10
79a
NA
<36
NA
<5
NA
5,900
(-72)
(-2,900)
(-4,800)
(69)
(-4,500)
(0)
(-260)
(8)
Type 8
24a
<1
5.4
5.2a
19a
47
<4
<22
NA
<36
NA
<5
NA
6,000
(-140)b
(>98)
(-130,000)
(-62)
(83)
(-140)
(>60)
(6)
Semiquantitative region; value not within 95% confidence limits.
Minus percent removals indicate an increase in the concentration of the specified pollutant.
'Not analyzed.
-------
TABLE 9. PLANT A OTHER POLLUTANTS DETECTED
(Concentration, yg/Jt; percent removal in parentheses
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Phosphorus
Sodium
Silicon
Strontium
Tin
Titanium
Vanadium
Intake
<12
<0.2
50
16,000
7.7b
175
3,000
49
490b
8,000
480
90
17
Secondary
effluent
230
20
270
37,000
16b
2,000
5,000
92
280
270,000
1,400
220
\2b
40
Tertiary effluent
Type
1,600
18
270
70,000
17b
2,800
4,900
100
<70
270,000
1,300
240
20b
2.0b
53
2
(-600) a
(10)
(0)
(-89)
(-6)
(-40)
(2)
(-9)
(>75)
(0)
(7)
(-9)
(-33)
(38)
(33)
Type
520
18
300
70,000
110
2,700
5,300
200
<70
280,000
1,300
260
17b
42
5
(-130)
(10)
(-11)
(-89)
(-590)
(-35)
(-6)
(-120)
(>75)
(-4)
(7)
(-18)
(-13)
(>69)
(-5)
Type
100
50
320
70,000
18b
1,700
5,800
120
<70
265,000
1,400
370
33
8
(57)
(-150)
(-19)
(-89)
(-13)
(15)
(-16)
(-30)
(>75)
(2)
(0)
(-68)
(>69)
(18)
Minus percent removals indicate an increase in the concentration of the specified pollutant.
Semiquantitative region; value not within 95% confidence limits.
-------
TABLE 10. PLANT A BIOASSAY RESULTS
Test species •
Freshwater algae -
S. capricornutum
Daphnia -
D. magna
Bluegill -
L. maorochiruB
Fathead minnow -
P. promelaa
S. typhimurium -
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
Secondary effluent
Parameters Phase I Phase II
ECso
ECso
ECso
LCgo
LCso
LCso
LCso
LCso
LCso
LCso
- 7 day.
- 12 day,
- 14 day,
- 24 hr.
- 48 hr.
- 24 hr.
- 48 hr,
- 72 hr.
- 96 hr,
- 96 hr,
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
NM3
NM
NMd
9
NM
NM
NM
NM
19
15 (4.2-52)b
18 (5.9-52)
22 (5.6-87)
>100
25 (17-32)
73 (64-85)
54 (36-88)
NM
Response to Ames test for (-) (-)r
mutagenicity
- (-) or (+)
73
Tertiary effluent
Type 2
(46-100)
>32<56
30
<100
56
71
53
42
38
NM
NM
(6.9-100)
(49-62)
(64-79)
(41-69)
(37-47)
(33-43)
38
36
30
41
57
74
44
40
35
NM
NM
Type 5
(12-100)
(12-100)
(13-63)
(31-50)
(50-63)
(61— >100)
(37-58)
(35-46)
(32-40)
Type 8
42
26
31
>100
>100
>100
>100
>100
>100
NM
NM
(26-68)
(11-61)
(16-61)
Not measured.
95% confidence interval.
°20% secondary effluent failed to support the growth of S. capricornutum.
ECso - 48 hr determined with Daphnia pulex.
Insufficient data to calculate LC00.
fThis sample was also concentrated to 1000X; an increase in revertants were observed using the concentrate and
TA98; however, no dose response was observed.
-------
TABLE 11. PLANT A EFFLUENT DESCRIPTIONS
Secondary effluentTertiary effluent
Parameter Phase I Phase II Type Z Type 5 Type T
Physical description Gray with considerable Dark purple with Light purple Light purple with Clear
amount of fine partic- particulate matter particulate
ulate; chlorinated matter
pH 6.2 6.6 6.1 6.6 6.2
Salinity, g/t NMa 0.05 0.02 0.05 0.05
Specific conductivity, NM 850 900 850 900
pmhos/cm3
aNot measured.
Plant C
Textile plant C generated wastewater from woven fabric finishing
operations. Existing treatment facilities included screens, pH
adjustment, two-stage aeration, and secondary clarification.
Sanitary wastewater was chlorinated prior to discharge into the
treatment plant influent. Phase I screening studies (4) indi-
cated that plant C wastewater treated by the existing treatment
facilities was 1 of the more toxic effluents of the 22 secondary
effluents actually evaluated in the program. Therefore, plant C
was included as a site for Phase II tertiary pilot plant studies
and MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was decided that tertiary treatment
types 2, 5, and 8 held the most promise of improving secondary
effluent quality to meet suggested BATEA guidelines, and they
were selected for candidate mode studies. Alum was used as a
coagulant in all three systems. A flow diagram of the employed
candidate mode configuration is shown in Figure 11. Sampling of
the candidate mode operation was conducted by MRC, and results of
subsequent chemical analyses and bioassay tests are presented in
Tables 12 through 16.
Low levels of toluene, total phenol, and other organic toxic
pollutants were removed by type 2 (flocculation/sedimentation)
treatment; however, levels of bis (2-ethylhexyl) phthalate and
1,2-dichlorobenzene increased. Bis(2-ethylhexyl) phthalate and
1,2-dichlorobenzene were subsequently removed by filtration (type 5),
while toluene and total phenol levels were further reduced. As
in plant A, the level of pentachlorophenol increased by type 5
treatment but was reduced by type 8 treatment (subsequent granular
activated carbon treatment). Type 8 treatment also removed
remaining levels of total phenol, but bis(2-ethylhexyl) phthalate
levels increased.
Except for copper, silver, and zinc, levels of inorganic toxic
pollutants increased or remained the same after all three types
of treatment. Most of the copper appearing in the secondary
effluent was removed by type 2 treatment, and type 8 treatment
48
-------
INTAKE
| (g) INTAKE WATER SAMPLE
TEXTILE PLANT C
SECONDARY TREATMENT
40 mg/l ALUM (AS AI+3I
0 SECONDARY EFFLUENT
SAMPLE
PILOT PLANT
UNIT OPERATIONS
FLOCCULATION/SEDIMENTATION
| 0 TYPE 2 EFFLUENT SAMPLE
MULTIMEDIA FILTRATION
I (g) TYPE 5 EFFLUENT SAMPLE
GRANULAR
ACTIVATED CARBON
$ TYPE 8 EFFLUENT SAMPLE
Figure 11. Candidate wastewater treatment
system studied at plant C.
removed zinc. As expected since alum was used as a coagulant,
aluminum concentrations increased through tertiary treatment.
In evaluating bioassay data, it is apparent that flocculation/
sedimentation with alum was detrimental to freshwater algae and
Daphnia. The wastewater became more toxic to these species after
type 2 treatment (flocculation/sedimentation) and never recovered
to the original toxicity levels after subsequent filtration
(type 5) and granular activated carbon treatment (type 8). No
toxicity was observed in any of the effluents when fathead
minnows or bluegills were used as the test species. Microbio-
logical bioassay work provided no indication of effluent improve-
ment or degradation by the treatment types.
49
-------
TABLE 12. PLANT C ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant Intake
Di-n-butyl phthalate 1.9
Bis(2-ethylhexyl) phthalate 6.6
2-Chlorophenol 0 . 2
Anthracene
Pentachlorophenol
Phenol 0.9
Toluene
Dibromochlorome thane
1 , 2-Dichlorobenzene
Ethylbenzene
Acenaphthene
1,2, 4-Tr ichlorobenzene
Methylene chloride0 35
Phenol (total)
Secondary^
Phase I
_a
3.0
4.4
0.3
0.5
10
88
effluent
Phase II
0.6
7.6
0.05
0.4
15
0.6
160
23
0
33
0
1
13
1
210
16
Tertiary effluent
Type 2 Type 5
.6 0.6
(-330)b 5.3 (30)
.1 0.03
12 (-79)
.0 (93) (>99)
(-260,000) 5.8
.3
(-31) 110 (31)
(30) 19 (17)
Type 8
0.4
11 (-45)
0.01
O99)
(100)
(>91)
Blanks indicate concentration below detection limit (see Table 6).
Minus percent removals indicate an increase in the concentration of the specified pollutant.
Methylene chloride may originate from analysis contamination.
TABLE 13. PLANT C INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Secondary effluent
Pollutant Intake Phase I Phase II
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
<10
<1
30
29
<4
65
<4
<22
NAC
<36
NA
54
NA
53
4
<5
6
31
20
13
120
0.7
140
<5
<5
<5
120
Minus percent removals indicate
Semiquantitative region; value
Not analyzed.
96
1.6
1.5
<2
5.5b
57
<4
27b
NA
<36
NA
80
NA
160
Type
120
<1
2.2
2.9b
17b
llb
<4
66b
NA
<36
NA
72
NA
190
Tertiary effluent
2
(-25) a 140
<1
1.2
2.7
(-210) 14b
(81) 25
<4
(-140) 64b
NA
<36
NA
(10) 77
NA
(-19) 230
an increase in the concentration
not within 95% confidence limits.
Type 5 Type
(-46) 120
<1
2.7
b 9.8b
(-150) 15b
(56) 35
<4
(-140) 64b
NA
<36
NA
(4) 91
NA
(-44) 83
8
(-25)
(-170)
(39)
(-140)
(14)
(48)
of the specified pollutant.
50
-------
TABLE 14. PLANT C OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Phosphorus
Silicon
Strontium
Tin
Titanium
Vanadium
Intake
<12
81
<1
3,300
29b
110
720
33
<10
120b
7,500
49
<15
<1
<2
Secondary
effluent
98
72
54
5,200
<6
230
3,700
17
<10
2,700
15,000
67
69b
2b
410
Tertiary effluent
Type 2
13,000
70
58
5,700
<6
930
3,700
24
20b
2,300
15,000
68
62b
14
560
(-13,000)a
(3)
(-7)
(-10)
(-300)
(0)
(-41)
(-100)
(15)
(0)
(-1)
(10)
(-600)
(-37)
Type 5
11,000 (-10,000)
71
57
5,600
<6
750
3,700
24
22b
2,000
15,000
71
66b
11
520
(1)
(-6)
(-8)
(-230)
(0)
(-41)
(-120)
(26)
(0)
(-6)
(4)
(-450)
(-27)
Type 8
9,200
81
29
5,600
<6
310
3,700
28
19b
1,900
14,000
74
56b
11
180
(-9,300)
(-13)
(46)
(-8)
(-35)
(0)
(-105)
(-90)
(30)
(7)
(-10)
(19)
(-450)
(-56)
Minus percent removals indicate an increase in the concentration of the specified pollutant.
Semiquantitative region; value not within 95% confidence limits.
-------
TABLE 15. PLANT C BIOASSAY RESULTS
Test species
Freshwater algae -
S. aapricornutum
Daphnia
D. magna
Bluegill -
L. machrochiruB
Fathead minnow -
P. p romelas
S, typhimurium -
Secondary effluent
ECso
ECso
ECso
LCso
LCso
LCso
LCso
LCso
LCso
LCso
LCso
LCso
LCso
Parameters
- 7 day, % effluent
- 12 day, % effluent
- 14 day, % effluent
- 24 hr, % effluent
- 48 hr, % effluent
- 24 hr, % effluent
- 48 hr, % effluent
- 72 hr, % effluent
- 96 hr, % effluent
- 24 hr, % effluent
- 48 hr, % effluent
- 72 hr, % effluent
- 96 hr, % effluent
Phase I Phase II
NMa
NM
~C
NM.
41d
NM
NM
NM
NM
NM
NM
NM
47
63 (47-85)b
56 (40-78)
49 (27-89)
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
Tertiary
Type 2
7.7 (2.3-25)
5.6 (2.3-13)
5.2 (1.3-20)
>100
79
>100
>100
>100
>100
>100
>100
>100
>100
Response to Ames test for (-) (-)e (-)
effluent
Type 5 Type 8
12 (1.2-100) 17 (0.3-100)
6.5
5.3
>100
85
>100
>100
>100
>100
>100
>100
>100
>100
NM
(2.5-17) 7.4
(2.2-13) 4.5
>100
89
>100
>100
>100
>100
>100
>100
>100
>100
(-)
(1.9-30)
(2.2-9.4)
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
E. coli -
strains W3110
and p3478
Chinese hamster
ovary cells
Response to pol A test for
mutagenicity-zone of
inhibition, nun
Response to CHO-K1 test
for acute cytotoxicity-
ECSO
>100
>100
NM
>100
Not measured.
95% confidence interval.
C20% secondary effluent was highly stimulatory to the growth of S. caprioornutum.
d
ECso - 48 hr determined using Daphnia pulex.
elncrease in number of revertants over background was observed; however, the results were not twofold, nor was
there a dose response.
fECSo not determinable; cytotoxicity procedure employing rabbit alveolar macrophage (RAM) used in Phase I.
-------
TABLE 16. PLANT C EFFLUENT DESCRIPTIONS
Secondary effluent Tertiary eTfluent
Parameter Phase I Phase II Type 2 Type 5 Type 8
Physical description Clear, blue-black with Orange-brown with Light orange- Light orange- Cloudy white
moderate amount of particulate matter with partic- brown with liquid
particulate; ulate matter particulate
unchlorinated matter
PH
Salinity, g/l
Specific conductivity.
umhos/cm3
10.2
NMa
NM
8.3
3
3,800
6.9
3
4,000
7.0
3
3,900
7.1
2.5
3,900
aNot measured.
Plant W
Textile plant W generated wastewater from wool scouring opera-
tions. Existing treatment facilities included a grit chamber,
oxidation ditch, secondary clarification, and chlorination, while
waste sludge was treated on sludge drying beds. Phase I screen-
ing studies (4) indicated that plant W wastewater treated by the
existing treatment facilities was 1 of the more toxic effluents
of the 22 secondary effluents actually evaluated in the program.
Therefore, plant W was included as a site for Phase II tertiary
pilot plant studies and MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was apparent that further clarifica-
tion of the secondary effluent was necessary before subsequent
tertiary process system studies could be made. Therefore, the
reactor/clarifier contained in the tertiary pilot plant trailer
was operated as an additional secondary clarifier (i.e., no
coagulant addition) before the tertiary processes were evaluated.
The MRC sampling/analysis program included sampling and analysis
of the secondary effluent before and after the additional
clarification. In tables of analytical/bioassay results which
follow, the waste stream after additional clarification is
referred to as type 1 treatment effluent; it is referred to as
secondary effluent as it is generated by the existing facilities.
After the screening studies, it was determined that tertiary
treatment types 3, 6, and 7 after additional clarification
(type 1) held the most promise of improving secondary effluent
quality to meet suggested BATEA guidelines and were thus selected
for candidate mode studies. Figure 12 is a flow diagram of the
candidate mode configuration used. Sampling of the candidate
mode operation was conducted by MRC, and results of subsequent
analysis and bioassay work are presented in Tables 17 through 21.
Bis(2-ethylhexyl) phthalate and total phenol were the only organic
toxic pollutants found in plant W secondary effluent at levels
greater than 10 yg/Ji. Type 1 treatment (additional clarification) ,
type 3 treatment (subsequent filtration), and type 6 treatment
53
-------
INTAKE
INTAKE WATER
SAMPLE
TEXTILE PLANT W
SECONDARY TREATMENT
PILOT PLANT
UNIT OPERATIONS
X> SECONDARY
\' Vy EFRUENT SAMPLE
ADDITIONAL
CLARIFICATION
(NO COAGULANT ADDITION)
I /OX TYPE1
| (& EFFLUENT SAMPLE
MULTIMEDIA
FILTRATION
TYPE 3
EFFLUENT SAMPLE
GRANULAR
ACTIVATED CARBON
OZONE CONTACT
EFFLUENT SAMPLE Q$)
TYPE?
EFRUENT SAMPLE
J
Figure 12.
Candidate wastewater treatment
system studied at plant W.
(subsequent activated carbon) removed some bis(2-ethylhexyl)
phthalate, but this pollutant was added by type 7 treatment
(ozonation following filtration and clarification). This
observed addition of organic toxic pollutants by type 7 treatment
can be attributed to leaching from the ozone contactor materials
of construction. Total phenol was slightly removed (19%) by
ozonation (type 7).
Antimony, cadmium, copper, nickel, silver, lead, and zinc were
removed by additional clarification (type 1) alone. These same
metals, except for lead, were added by type 7 treatment (ozona-
tion preceded by additional clarification and filtration); they
may have been added by decay of electrode plates in the ozone
generator. Cyanide was removed by activated carbon and ozonation
(types 6 and 7), while lead and zinc were removed by all four
treatment types.
Type 1 treatment (additional clarification) removed significant
amounts of aluminum, barium, cobalt, iron, silicon, titanium, and
vanadium. Subsequent tertiary treatments (types 3 and 6) removed
additional amounts of most of the metals, while ozonation (type 7)
added aluminum, boron, cobalt, manganese, and vanadium.
54
-------
In evaluating bioassay results, it is apparent that the secondary
effluent was toxic to all species used in static acute toxicity
tests. None of the treatment types significantly improved the
toxicity of the wastewater. Microbiological bioassay work
provided no indication of effluent improvement or degradation by
the treatment types.
TABLE 17. PLANT W ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Secondary effluent
Pollutant
Bis (2-ethylhexyl) phthalate
Anthracene
Benzo (a ) anthracene
Fluoranthene
Benzolalpyrene
Pyrene
Benzo (k) f luoranthene
Di-n-butyl phthalate
Toluene
Ethylbenzene
Isophorone
Hethylene chloride0
Phenol (total)
Intake Phase I
15 19
0.9 -b
0.1
0.7
0.7
0.5
0.4
1.7
6 232
Phase II
42
1.
1.
1.
1.
0.
0.
1.
16
5
5
1
2
8
8
4
Type 2
23
0.4
0.4
0.2
9.5
3.0
2.2
49
(45) 14
0
0
0
0
0
3
4
(-67) 17
Tertiary effluent
Type 3
(67)
.2
.2
.2
.3
.1
.1
.8
(-6)
Type 6 Type 7
26 (67) 106 (-1501*
0.1 • 0.4
0.1
0.1
1.1
3.1 1.2
1.3
1.8 61 (-15,000)
17 (-6) 13 (19)
aMinus percent removals indicate an increase in the concentration of the specified pollutant.
Blanks indicate concentration below detection limit (see Table 6).
Methylene chloride may originate from analysis contamination.
TABLE 18. PLANT W INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Secondary effluent
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Intake
<10
<1.0
<5
<2
<4
<4
<4
<20
NAb
<40
NA
6
NA
17
Phase I Phase II
<0
4
<0
13
3
2
20
57
0
60
<5
95
<5
90
Minus percent removals
Not analyzed.
.5 540
38
.1 <2
130
<80
320
200
3,500
.5 NA
2,000
NA
500
NA
1,500
Type 1
<200
39
<2
<40
<80
110
240
<400
NA
<700
NA
<100
NA
190
indicate an increase in
(>63)
(-3)
(>69)
(66)
(-20)
(>86)
(>65)
(>80)
(87)
Tertiary
Type 3
<200
83
<2
<40
<80
120
260
<400
NA
<700
NA
<100
NA
400
(>63)
(-120)
(>69)
(63)
(-30)
(>86)
(>65)
(>80)
(73)
the concentration of the
effluent
Type 6
<200
42
<2
<40
<80
<80
40
<400
NA
<700
NA
<100
NA
120
(>63)
(-10)
(>69)
(>75)
(80)
(>86)
(>65)
(>80)
(92)
Type 7
1,200
43
<4
250
<200
590
<4
<900
NA
5,000
NA
1,300
NA
460
(-120)3
(-13)
(-92)
(-84)
(>98)
(>74)
(-150)
(-160)
(69)
specified pollutant.
55
-------
TABLE 19. PLANT W OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Ul
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Silicon
Tin
Strontium
Titanium
Vanadium
Ammonia
nitrogen
Nitrate
nitrogen
Phosphate
phosphorus
Intake
22
110
16,000
5
1,100
1,700
30
<10
2,400
5,600
<20
95
<1
12
NAb
NA
NA
Secondary
effluent
8,400
290
490
31,000
170
5,000
7,000
20
<200
54,000
4,800
<300
170
200
2,700
3,300
5,300
200
Tertiary
Type
4,700
120
640
31,000
<40
3,400
6,600
70
<200
56,000
3,200
<300
160
110
120
3,000
7,100
210
1
(44)
(59)
(-33)a
(0)
(>76)
(32)
(6)
(-250)
(-4)
(33)
(6)
(45)
(96)
(9)
(-34)
(-5)
Type
3,100
110
600
33,000
60
2,400
6,600
40
<200
61,000
2,700
<300
160
60
110
2,600
6,500
100
3
(63)
(62)
(-22)
(6)
(65)
(52)
(6)
(-100)
(-17)
(44)
(6)
(70)
(96)
(21)
(-23)
(50)
effluent
Type
3,100
50
630
22,000
<40
1,900
4,900
20
<200
57,000
2,200
<300
120
80
<40
2,200
6,500
100
6
(63)
(83)
(-29)
(29)
(>76)
(62)
(30)
(0)
(-6)
(54)
(29)
(60)
(>99)
(33)
(-23)
(50)
Type
7,000
120
1,000
30,000
380
2,300
6,100
90
<400
56,000
2,600
<600
2
180
540
5,500
8,800
160
7
(17)
(59)
(-104)
(3)
(-124)
(54)
(13)
(-350)
(-4)
(46)
(99)
(10)
(80)
(-67)
(-66)
(20)
aMinus percent removals indicate an increase in the concentration of the specified pollutant.
D
Not analyzed.
-------
TABLE 20. PLANT W BIOASSAY RESULTS
Secondary
Test species
Freshwater algae -
5. capriaornutum
Daphnia -
D. magna
Blue gill -
L. macrochirus
Fathead minnow -
P. pivmelae
S. typhimuriwn -
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
E. coli -
strains W3110
and p3478
Chinese hamster
ovary cells
Parameter
ECso - 7 day, % effluent
ECso - 12 day, % effluent
ECso - 14 day, % effluent
LCso - 24 hr, % effluent
LCso - 48 hr, % effluent
LCso - 24 hr, % effluent
LCso - 48 hr, % effluent
LCso - 72 hr, % effluent
LCso - 96 hr, % effluent
LCso - 24 hr, % effluent
LCso - 48 hr, % effluent
LCso - 72 hr, % effluent
LCso - 96 hr, % effluent
Response to Ames test for
mutagenicity - (-) or (+)
Response to pol A test for
mutagenicity-increase in
zone of inhibition, mm
Response to CHO-Kl test
for acute cytotoxicity-
ECso
Phase I
NM3
NM
—
NM
6.3
NM
NM
NM
NM
NM
NM
NM
55
(-)
0
_f
1.8
2.4
4.0
>36<
56
Ml
71
65
60
75
63
61
61
(-)
0
>100
effluent
Phase II
(0.6-5.4)b
(0.5-12)
(2.1-7.6)
60
(33-97)
(63-81)
(58-71)
(53-66)
(70-80)
(52-76)
(51-75)
(51-75)
Tertiary effluent
6.
10
8.
57
48
>100
77
72
64
76
59
53
48
(-)
0
>100
Type 1
0 (0.9-4.0)
(4.2-24)
9 (2.6-30)
(33-99)
(34-66)
(67-85)
(65-81)
(57-71)
(68-89)
(50-77)
(45-62)
(39-55)
12
17
11
58
58
>100
68
61
60
Type 3
(3.6-41)
(1.5-100)
(3.4-37)
(34-100)
(34-100)
(61-75)
(54-67)
(53-66)
>77<100
73
69
68
(-)*
0
>iOO
(65-84)
(61-79)
(59-79)
!
Type 6
47
33
28
51
49
>100
75
68
66
76
68
65
61
<-)
0
>100
(23-95)
(16-68)
(13-61)
(36-72)
(35-70)
(69-80)
(61-75)
(59-73)
(68-86)
(61-75)
(58-72)
(54-67)
37
44
29
55
54
NM
MM
NM
NM
Type 7
(26-53)
(5.5-100)
(16-54)
(32-95)
(31-93)
>60<100
68
68
.65
(-)
0
->ioo
(54-84)
(54-84)
(51-80)
Not measured.
95% confidence limits.
°Growth of S. capricornutwn supported with 2% and 5% secondary effluent, but inhibited at 10% and 20% levels.
ECso - 48 hr determined using Daphnia pulex.
elncrease in number of revertants was observed with TA1538, with and without metabolic activation; however, a dose response was not
observed.
ECso not determinable; cytotoxicity procedure employing rabbit alveolar macrophage (RAM) used in Phase I.
-------
TABLE 21. PLANT W EFFLUENT DESCRIPTIONS
Parameter
Physical description
pH
Salinity, g/fc
Specific conductivity,
pmhos/cm2
Secondary effluent
Phase I
Cloudy orange with
a moderate amount
of particulate;
nonchlorinated
e.o
NM*
NM
Phase II Type 1
Cloudy brown Cloudy brown
liquid liquid
7.7 7.8
2 2
2,400 2,900
Tertiary effluent
type 3
Cloudy brown
liquid
7.8
2
2,800
Type 6
Pale yellow
liquid
7.9
2
2,400
Type 1
Cloudy pale
yellow liquid
7.S
2
2,900
Not measured.
Plant S
Textile plant S generated wastewater from knit fabric finishing
operations. Existing, operating treatment facilities included a
gravity separation tank, an equalization basin, an aeration basin,
a secondary clarifier, and chlorination. Phase I studies (4)
indicated that plant S wastewater treated by the existing treat-
ment facilities was toxic, but ranked eighth when compared to the
other 21 secondary effluents evaluated in the program. It was
recommended, though, that plant S be included as a site for
Phase II tertiary pilot plant studies and MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering, Science, Inc., it was decided that tertiary treat-
ment types 3, 4, and 6 held the best promise for improving
secondary effluent quality to meet BATEA guideline limitations
and were thus selected for candidate mode studies. Cationic
polymer was used as a precoagulant in the type 4 treatment. A
flow diagram of the employed candidate mode configuration is
shown in Figure 13. Sampling of the candidate mode operation was
conducted by MRC, and results of subsequent analyses and bioassay
studies are presented in Tables 22 through 26. In evaluating the
data, it is apparent that very few organic toxic pollutants
existed in the secondary effluent at levels greater than 10 yg/£.
Type 3 treatment (filtration without precoagulation) removed
methylene chloride and total phenol while adding bis(2-ethylhexyl)
phthalate. Type 4 treatment (filtration with precoagulation)
removed bis(2-ethylhexyl) phthalate and methylene chloride while
adding total phenol, specific phenols, and cresols. These
compounds may have been present in the cationic polymer used as a
filter aid or may have leached from the filter media used in
type 4 treatment. Type 6 treatment (filtration without pre-
coagulation followed by activated carbon) removed total phenol
while adding significant amounts of bis(2-ethylhexyl) phthalate,
trichlorofluoromethane, and methylene chloride.
-------
INTAKE
INTAKE WATER
SAMPLE
TEXTILE PLANT S
SECONDARY
TREATMENT
r
L
<7\ SECONDARY
3 mg/l 572C POLYMER Q? EFFLUENT
(AMERICANCYANAMID-CATIONIC) 1' SAMPLE
\^- — — ^--^
f^~^ ^^^^1
MULTIMEDIA MULTIMEDIA
FILTRATION FILTRATION
TYPE 4 _
EFRUENT 6c)
SAMPLE *~"
PILOT PLANT
UNIT OPERATIONS
i
L 6& EFRUENT
T SAMPLE
GRANULAR
ACTIVATED CARBON
i
TYPF d
£— lire o
OOEFFLUENT
^ SAMPLE
1
- 1
1
Figure 13.
Candidate wastewater treatment
system studied at plant S.
Except for copper and zinc, little change in the concentration of
inorganic toxic pollutants occured due to tertiary treatment.
Significant amounts of copper (more than 85%) and zinc (24%) were
removed by type 6 treatment (activated carbon preceded by
filtration), while zinc was added by treatment types 3 and 4.
Aluminum, vanadium, and ammonia were removed by all three treat-
ment systems. Iron was added by treatment types 3 and 4, which
employ steel filtration columns.
Static acute toxicity testing with freshwater algae was the only
bioassay test which indicated the effects of the three treatment
types. Toxicity levels remained about the same when type 3
treatment was used; however, the wastewater became more toxic
when type 4 treatment was used. All toxicity to freshwater algae
was removed by type 6 treatment.
59
-------
TABLE 22. PLANT S ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Secondary effluent
Pollutant Intake
Bis(2-ethylhexyl) phthalate 1.2
Acenaphthene
Di-n-butyl phthalate
Phenol 0.5
2 , 4 -Dime thy Iphenol
2 , 4-Dichlorophenol
p-Chloro-m-cresol
Chloroform 120
Toluene 3
Trichlorofluorome thane
1,2, 4-Trichlorobenzene
Naphthalene
Ethylbenzene
Tetrachloroethylene
Methylene chloride0 55
Phenol (total) 5
Phenol (total)0 -f
Phase I
41
21
920
260
110
0.4
29
29
Phase II Type 3
25 42 l-68)a
2.2 0.6
2.8 6
0.6 0.4
7
1.8 0.4
12 4.6 (62)
15 -d
11 9.0 (18)
Tertiary effluent
Type 4
16 (36)
0.6
0.2
0.4
0.2
0.3
1.4
7.9 (34)
21 (-40)
16 (-45)
Type 6
410 (-1,500)
1.6
69 (-3,500)
940 (-7,700)
_d
(>32)
Minus percent removals indicate an increase in the concentration of the specified pollutant.
Blanks indicate concentration below detection limit (see Table 6).
°Methylene chloride may originate from analysis contamination.
Sample bottle broken in shipment.
eSample taken day after all other samples were taken.
Sample not taken.
TABLE 23. PLANT S INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, ug/£; percent removal in parentheses)
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Secondary effluent
Intake
20
<10
<5
3b
<4
10b
<10
K
34D
0.5
61b
<10
<5
<50
42
Phase I
70
<10
<5
2
<4
60
<10
<22
<0.3
<36
<10
<5
<50
84
Phase II
610
<10
<5
5b
<4
26
<10
K
75b
1.7
83b
<10
<5
<50
41
620
<10
<5
5
<4
27
<10
81
0
81
<10
<5
<50
75
Tertiary effluent
Type 3
(-2)a
(0)
b
(-4)
t^
b (-8)
.4
b (2)
(-83)
600
11
<5
6
<4
24
<10
85
0
98
<10
<5
<50
55
Type 4
(2)
b (-10)
b
(8)
V,
b (-13)
.7
b (-18)
(-34)
Type
590
llb
<5
6b
<4
<4
< 10
H
79b
0.4
96b
<10
<5
<50
31
6
(3)
010)
(>85)
(-5)
(-16)
(24)
Minus percent removals indicate an increase in the concentration of the
specified pollutant.
Semiquantitative region; value not within 95% confidence limits.
60
-------
TABLE 24. PLANT S OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Silicon
Tin
Strontium
Titanium
Vanadium
Ammonia
nitrogen
Nitrate
nitrogen
Phosphate
phosphorus
Intake
110
12
<1
5,500
8b
240
860
7.7
<10
10,000
3,600
<15
21
2b
11
NAC
NA
NA
Secondary
effluent
690
8.3
1,100
5,900
10b
100
1,600
11
13
180,000
11,000
<15
22
4b
57
6,600
250
1,700
Type
450
6.2
1,100
6,200
7b
150
1,500
12
14
190,000
11,000
<15
22
4b
23
60
120
2,100
3
(35)
(0)
(-5)a
(-50)
(6)
(-9)
(-8)
(-6)
(0)
(0)
(60)
(99)
(52)
(-24)
Tertiary
Type
330
5.9
1,000
5,800
llb
190
1,500
11
13
180,000
11,000
<15
22
4b
23
5,600
210
4,500
effluent
4
(52)
(9)
(2)
(-10)
(-90)
(6)
(0)
(0)
(0)
(0)
(0)
(60)
(15)
(16)
(-170)
Type
310
5.7
1,100
5,200
6b
58
1,400
8
17
190,000
11,000
<15
22
4b
22
1,200
670
2,000
6
(55)
(0)
(12)
(42)
(13)
(27)
(-31)
(-6)
(0)
(0)
(61)
(82)
(-170)
(-18)
Minus percent removals indicate an increase in the concentration of the specified
pollutant.
3
Semiquantitative region; value not within 95% confidence limits.
-»
'Not analyzed.
-------
TABLE 25. PLANT S BIOASSAY RESULTS
CTi
Test species
Freshwater algae -
S. oapriaornutum
Daphnia -
D. magna
Fathead minnow -
P. ppomelas
Secondary effluent
Parameter
EC50
EC50
EC 50
LCso
LCso
LC90
LCso
LCso
LC,0
- 7 day, <
- 12 day,
- 14 day,
- 24 hr, I
- 48 hr, (
- 24 hr, <
- 48 hr, (
- 72 hr, (
- 96 hr, <
4 effluent
% effluent
% effluent
I effluent
I effluent
fc effluent
i effluent
& effluent
& effluent
Phase I
NMa
NM.
a
NM
NM
NM
>100
Phase II
79 (5-100)b
79 (6-100)
72 (7-100)
>100
>100
>100
>100
>100
>100
Tertiary effluent
Type 3
>100
40 (6-100)
>56<100
>100
>100
>100
>100
>100
>100
Type 4
73 (26-100)
62 (16-100)
49 (25-95)
>100
>100
>100
>100
>100
>100
Type 6
>100
56 (3-100)
>100
>100
>100
>100
>100
>100
>100
S. typhimurium —
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
E. aoli - strains
W3110 and p3478
Chinese hamster
ovary cells
Response to Ames test for
mutagenicity - (-) or (•»-)
Response to pol A test for
mutagenicity-increase in
zone of inhibition, mm
Response to CHO-K1 test
for acute cytotoxicity-
EC50
NM
>100
>100
>100
>100
Not measured.
95% confidence interval.
C20% secondary effluent was highly stimulatory to the growth of S. capriaornutum.
LCso not calculated since a heavy solids concentration abscured the analysis; sample did not appear to be
acutely toxic; Daphnia pulex used in determination.
-------
TABLE 26. PLANT S EFFLUENT DESCRIPTIONS
Secondary effluent
Parameter
Physical description
pH
Salinity, g/1
Specific conductivity,
pmhos/cma
Phase I
Clear, light champagne
with small amount of
particulate;
unchlorinated
7.7
NMa
NM
Phase II
Orange liquid
containing a
precipitate
7.2
1
1,100
Type 3
Orange liquid
containing a
precipitate
7.3
0
870
Tertiary effluent
Type 4
Light orange
liquid con-
taining a
precipitate
7.0
1
1,100
Type 6
Clear liquid
7.4
1
1,100
a
Not measured.
Plant P
Textile plant P generated wastewater from knit fabric finishing
operations. Existing treatment facilities included screens,
aeration, secondary clarification, and chlorination. Phase I
screening studies (4) indicated that plant P wastewater treated
by the existing facilities ranked ninth in terms of toxicity when
compared to the other 21 secondary effluents evaluated in the
program. Therefore, plant P was included as a site for Phase II
tertiary pilot plant studies and MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was decided that tertiary treatment
types 2, 3, 5, and 6 held the best promise of improving secondary
effluent quality to meet suggested BATEA guidelines; they were
thus selected for candidate mode studies. Cationic polymer was
used as a coagulant in treatment types 2 and 5. A flow diagram
of the candidate mode configuration used is shown in Figure 14.
Sampling of the candidate mode operation was conducted by MRC,
and results of subsequent analysis and bioassay work are
presented in Tables 27 through 31. Organic toxic pollutant
analysis provided few data on relative removal efficiencies
because few such pollutants were found in the secondary effluent.
Only total phenol existed at a level greater than 10 yg/£. This
was removed by type 6 treatment (activated carbon preceded by
filtration).
Significant (more than 38%) removals of antimony, chromium,
copper, and zinc were attained by all four treatment systems.
Arsenic was apparently added by type 6 treatment (activated carbon
preceded by filtration). Aluminum, iron, manganese, molybdenum,
titanium, and vanadium were also removed by all four treatment
systems.
Again, only freshwater algae toxicity studies indicated the
detrimental effects of the wastewaters to bioassay test species.
Only type 6 treatment improved the effluent quality in terms of
freshwater algae toxicity.
-------
INTAKE
ff\ INTAKE WATER
SAMPLE
TEXTILE PLANT P
SECONDARY
TREATMENT
f~
20 mg/l 572C POLYMER
(AMERICAN CYANIMID-CATIONICI 1
O^J
r^^
FLOCCULATION/
„-,, SEDIMENTATION
TYPE 2 -ex 1
EFFLUENT SAMPLE Q9 1
($?\ SECONDARY EFFLUENT
<> SAMPLE
^\^
^^
MULTIMEDIA
FILTRATION
|___/0v ^P"
£ 12> EFFLUENT SAMPLE
MULTIMEDIA PILOT PLANT GRANULAR
FILTRATION UNIT OPERATIONS ACTIVATED CARBON
TYPE 5 s-^
EFFLUENT SAMPLE Q9
L
\
1
/cx TYPE6
Q9 EFaUENT SAMPLE
.
Figure 14.
Candidate wastewater treatment
system studied at plant P.
TABLE 27. PLANT P ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Anthracene
Phenol
Chloroform
Trichloroethylene
Toluene
Benzene
N-nitroso-di-n-propylamine
Ethylbenzene
Methylene chloride
Phenol (total)
Secondary
effluent
Intake Phase I Phase II
2.0 72
0.9
4.1 6.9
1.4
1.5 22
19
280
20
11 32
10
2.1
1.3
0.8
0.7
0.4
0.4
72
Type 2
10
2.8
0.9
0.5
0.8
0.4
0.4
0.1
2.5
82 (-14)°
Tertiary
Type 3
3.9
1.6
0.8
0.5
1.8
2.7
1.0
4.1
68 (6)
effluent
Type 5 Type 6
3.3 3.9
2.5
1.0 1.4
0.5 0.1
2.6
2.6 3.6
0.5
4.7 7.3
130 (-81) 18 (75)
Blanks indicate concentration below detection limit (see Table 6).
Methylene chloride may originate from analysis contamination.
«
Minus percent removals indicate an increase in the concentration of the specified pollutant.
64
-------
96)
<4 (>89)
<4
<22 (>12)
<0.3
43a (35)
<8
<5
<50
160 (97)
Tertiary effluent
Type 3
48a (38)
<2
<0.2
<2
<4 (>96)
<4 (>89)
<4
<22 (>12)
0.3
58a (12)
<8
5
<50
150 (97)
Type 5
34a (56)
<2
<0.2
<2
<4 (>96)
<4 (>89)
<4
<22 (>12)
0.4
36a (83)
<8
<5
<50
160 (97)
Type 6
36a (53)
12 (-500)b
<0. 2
<2
<4 (>96)
<4 (>89)
<4
<22 (>12)
0.4
50a (24)
<8
<5
<50
<1 (100)
Semiquantitative region; value not within 95% confidence limits.
Minus percent removals indicate an increase in the concentration of the specified pollutant.
-------
TABLE 29. PLANT P OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
en Sodium
Silicon
Tin
Strontium
Titanium
Vanadium
Ammonia
nitrogen
Nitrate
nitrogen
Phosphate
phosphorus
Intake
670
11
150
3,600
<6
1,400
1,600
73
ioa
6,200
6,400
163
25
36
21
NA
NA
NA
Secondary
Phase I
140
<0.2
520
9,500
0.5
100
1,800
20
<0.6
>100,000
4,800
<10
NAC
<1
20
200
80
20d
effluent
Phase II
300
<0.2
950
8,300
<6
1,000
1,800
80
20a
130,000
2,400
<15
35
36
18
790
300
2,800
Tertiary
Type
20a
<0.2
880
7,500
<6
300
1,800
49
<10
120,000
2,300
22a
33
<1
14
700
280
2,900
2
(93)
(7)
(10)
(70)
(0)
(39)
(>50)
(8)
(4)
<-40)b
(6)
(>97)
(22)
(11)
(7)
(-4)
Type
30a
<0.2
860
7,500
<6
300
1,800
50
<10
120,000
2,300
<15
33
<1
15
360
130
2,700
3
(90)
(9)
(10)
(70)
(0)
(38)
(>50)
(8)
(4)
(6)
(>97)
(17)
(54)
(57)
(4)
effluent
Type
50a
<0.2
880
7,300
<6
600
1,800
43
<10
120,000
2,100
18a
35
<1
15
580
250
2,500
5
(83)
(7)
(10)
(40)
(0)
(46)
(>50)
(8)
(13)
(-20)
(0)
(>97)
(17)
(27)
(17)
(11)
Type
40a
<0.2
660
5,000
<6
20
1,500
<0.5
<10
110,000
2,600
<15
35
<1
14
830
300
2,400
6
(87)
(31)
(40)
(98)
(17)
(>99)
(>50)
(15)
(-8)
(0)
(>97)
(22)
(-5)
(0)
(14)
Semiquantitative region; value not within 95% confidence limits.
Minus percent removals indicate an increase in the concentration of the specified pollutant.
"Not analyzed.
o-Phosphate only.
-------
TABLE 30. PLANT P BIOASSAY RESULTS
-J
Secondary^ effluent •
Test species
Freshwater algae -
S. capriaornutum
Daphnia -
D. magna
Fatheat minnow -
P. promelas
S. typhiimurium -
strains TA98,
TA100, TA1535,
TA1537 and
TA1538
Chinese hamster
ovary cells
ECso
ECso
ECso
LCso
LCso
LCso
LCso
LCso
LCso
Parameter
- 7 day, % effluent
- 12 day, % effluent
- 14 day, % effluent
- 24 hr, % effluent
- 48 hr, % effluent
- 24 hr, % effluent
- 48 hr, % effluent
- 72 hr, % effluent
- 96 hr, % effluent
Phase I
NMa
NM
NM
MOO
NM
NM
NM
>100
Phase II
54 (30-100) b
54 (18-100)
53 (20-100)
>100
>100
e
e
e
Type 2
41 (14-100)
24 (13-42)
26 (15-43)
>100
>100
e
e
_
_e
Tertiary
Type 3
42 (29-62)
42 (14-100)
33 (10-100)
>100
>100
e
e
—
e
effluent
Type 5
64 (25-100)
>32<100
41 (28-59)
>100
>100
e
e
e
Type 6
83 (18-100)
>56<100
>56<100
MOO
MOO
e
e
e
Response to Ames test for (-) (-) (-) (-) (.-) (-)
mutagenicity (-) or (+)
Response to CHO-K1 test
>100
>100
>100
>100
MOO
MOO
Not measured.
95% confidence interval.
°20% secondary effluent stimulated the growth of S. oapriaornutum.
ECso - 48 hr determined with Daphnia piilex.
eLCso's not calculated because of data scatter; however, none of the samples appear to be toxic since there was no more
than a 20% kill in any of the tests with 100% effluent.
-------
TABLE 31. PLANT P EFFLUENT DESCRIPTIONS
Secondary effluent
Tertiary effluent
Phase II
Physical description NM Brown turbid liquid Brown turbid liquid. Brown turbid liquid, Brown turbid liquid Slightly cloudy pale
containing sus- suspended parti- suspended parti- suspended parti- yellow liquid
pended particulate culate .matter culate matter culate matter
matter present present present
pH NM
Salinity, g/l NM
Specific conductivity, NM
umhos/cma
6.6
0
600
6.9
0
520
6.8
0
500
6.8
0
490
6.9
0
480
Not measured.
Plant N
Textile plant N generated wastewater from wool finishing opera-
tions. Existing treatment facilities included screens, aeration,
and secondary clarification. Phase I screening studies (4),
indicated that plant N wastewater treated by the existing
facilities was 1 of the more toxic effluents of the 22 secondary
effluents evaluated in the program. Therefore, plant N was
included as a site for Phase II tertiary pilot plant studies and
MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was decided that tertiary treatment
types 3, 5, and 6 held the best promise for improving secondary
effluent quality to suggested BATEA guidelines, and they were
selected for candidate mode studies. Alum was used as a coagulant
and NaOH used for adjusting pH in treatment type 5. Figure 15 is
a flow diagram of the candidate mode configuration employed.
Sampling of the candidate mode operation was conducted by MRC,
and results of subsequent chemical analyses and bioassay studies
are presented in Tables 32 through 36. In evaluating organic
toxic pollutant data, it can be seen, as has been seen in data of
former plants, that only very few organic toxic pollutants
occurred in the secondary effluent. Those that did occur include
bis(2-ethylhexyl) phthalate, methylene chloride, and total phenol.
Type 3 treatment (filtration) removed bis(2-ethylhexyl) phthalate
and total phenol, while treatment 5 and 6 reduced levels of
bis(2-ethylhexyl) phthalate, methylene chloride, and total phenol.
Antimony, chromium, cobalt, iron, zinc, and sulfide were removed
by all three treatment types, while copper was added. As
expected, aluminum was added by type 5 treatment, where alum was
used as a coagulant, and removed by treatment types 3 and 6.
Phosphorus was removed by treatment types 5 and 6.
68
-------
Type 5 treatment (filtration preceded by flocculation/sedimenta-
tion) was effective in reducing toxicity to Daphnia. The terti-
ary technologies employed had little effect upon effluent
toxicity to other bioassay species.
WOL INTAKE
TYPES
EFFLUENT f
SAMPLE
ROCCULATION/
SEDIMENTATION
*
MULTIMEDIA
FILTRATION
Ov 1
ft
^4
1
MULTIMEDIA
FILTRATION jypj j
1 (52) EFFLUENT
f ** SAMPLE
GRANULAR
ACTIVATED CARBON
I _. TYPE 6
(50 EFFLUENT
I v SAMPLE
t ~
Figure 15.
Candidate wastewater treatment
system studied at plant N.
TABLE 32. PLANT N ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Secondary effluent
Intake Phase I Phase
II
Bis(2-ethylhexyl) phthalate 53 16.7 230
Anthracene
Diethyl phthalate
Oi-n-butyl phthalate
Kethylene chlorideb
Toluene
1 , 2-Dichlorobenzene
Dimethyl phthalate
Fluoranthene
Pyrene
Fluorene
2 i 4-Dichlorophenol
Phenanthrene
1 , 2-Dichloropropane
1,4-Dichlorobenzene
Tetrachloroethylene
Ethylbenzene
Phenol
2 , 4-Dimethylphenol
Phenol (total)
0.2 -tt 0
1.0 9.4 0
1.2 0
47 46
0.9 17 0
6.0 0
1
0
0
1.5
0
7S 0
11
8
14 68 31
.4
.8
.6
.4
.9
.4
.07
.1
.7
.9
Tertiary effluent
Type 3
29 (87)
0.4
1.1
47 (-J)c
0.6
0.08
0.1
0.5
1.0
17 (45)
Type 5 Type 6
31 (87) 78 (66)
0.4 0.4
0.3 1.2
0.6 1.8
28 (39) 27 (41)
0.4
0.5
0.05
0.09
0.05
0.5
25 (19) 11 (65)
'Blanks indicate concentration below detection limit (see Table 6).
Methylene chloride may originate from analysis contamination.
GMinus percent removals indicate an Increase in the concentration of a specified
pollutant.
69
-------
TABLE 33. PLANT N INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Intake
14a
5
0.6
<2
<4
160
<5
<22
<0.1
<36
<1
ioa
<50
22
Secondary
Phase I
<10
<5
NAb
<0.5
1,800
8
<4
<1
<0.5
30
<5
<5
<5
38,000
effluent
Phase II
18a
3
<0.04
<2
170
14a
<5
<22
<0.1
<36
<1
5.5a
<50
1,300
Tertiary effluent
Type 3
<10 (>44)
3
<0.04
<2
95 (44)
130 (-830)°
<5
<22
<0.1
<36
<1
<5
<50
590 (55)
Type 5
<10 (>44)
<1
o.ia
<2
34 (80)
86 (-510)
<5
<22
<0.1
<36
<1
<5
<50
440 (66)
Type 6
<10 (>44)
3
<0.04
<2
5.2a (97)
24 (-71)
<5
<22
<0.1
<36
<1
<5
<50
430 (67)
Semiquantitative region; value not within 95% confidence limits.
Not analyzed.
'Minus percent removals indicate an increase in the concentration of the
specified pollutant.
-------
TABLE 34. PLANT N OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Phosphorus
Silicon
Tin
Strontium
Titanium
Vanadium
Sulfide
Ammonia
nitrogen
Nitrate
nitrogen
COD
TSS
Color at
pH 7.6
Color at
sample pH
PH6
Intake
120
6.7
0.6
5,400
6.23
620
1,000
530
<10.
12,000
<70
4,000
<15
51
2.la
a
6.9
14
NAC
NA
11,000
6,000
47
48
6.46
Secondary
effluent
120
6.0
9.1
7,100
12a
720 '
1,100
210
<10.
180,000
2,500
3,800
<15
41
1.9a
a
8.5
12
1,700
5,200
128,000
75,000
39
36
7.97
Tertiary effluent
Type
36a
3.3
6.7
6,200
8.7a
290
990
190
<10
180,000
2,300
3,700
<15
40
1.2a
a
7.7a
<5
1,200
4,600
210,000
<1,000
38
43
6.95
3
(67)
(13)
(28)
(60)
(10)
(10)
.•
(0)
(8)
(3)
(2)
(>58)
(29)
(12)
(-64)
(>99)
(3)
(-19)
Type
390
2.7
6.4
6,200
8.6a
55
1,000
200
<10
200,000
1,200
3,400
<15
39
<1
A
8.5
<5
1,600
5,200
172,000
8,000
52
48
7.45
5
(-260)b
(13)
(28)
(92)
(9)
(5)
<-ll)b
(52)
(11)
(5)
(>58)
(6)
(0)
(-34)
(89)
(33)
(-33)
Type
2la
4.8
9.0
5,000
<6
110
860
160
<10
180,000
1,000
3,800
<15
40
<1
a
6.5
<5
1,300
3,100
44,000
12,000
51
51
746
6
(81)
(30)
(>50)
(85)
(22)
(24)
(0)
(60)
(0)
(2)
(>58)
(24)
(40)
(66)
(84)
(-31)
(-42)
(6.4)
Semiquantitative region
b
Minus percent
CNot analyzed.
d
ADMI units.
removals
; value not
indicate an
within 95%
increase in
confidence limits.
the concentration of the specified pollutant.
6pH units (- log [H+]).
71
-------
TABLE 35. PLANT N BIOASSAY RESULTS
-j
Test species
Freshwater algae -
5. capricornutum
Daphnia -
D. magnet
Fathead minnow -
P. promelas
Secondary effluent
Parameter
ECso
ECso
ECso
LCso
LCso
LCso
LCso
LCso
LCso
- 7 day,
- 12 day.
- 14 day,
- 24 hr.
- 48 hr.
- 24 hr.
- 48 hr,
- 72 hr.
- 96 hr.
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
Phase I
NMa
NM
NM-
NM
NM
NM
49
Phase II
20
28
23
>100
77
>100
91
81
81
(ll-36)b
(20-41)
(18-31)
(86->100)
(60-100)
(73->100)
(68-99)
(68-99)
Tertiary effluent
Type 3
23
38
30
>100
78
>100
>100
>100
>100
(13-41)
(27-53)
(16-56)
(67-92)
Type 5
44 (26-75)
35 (19-66)
29 (15-57)
>100
>100
>100
>100
>100
>100
Type 6
23
16
23
>100
77
>100
>100
>100
>100
(10-51)
(10-27)
(14-38)
(60-100)
S. typhimufium -
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
E. ooli -
strains W3110
and p3478
Chinese hamster
ovary cells
Response to Ames test for
mutagenicity - (-) or (+)
Response to ppl A test for.
mutagenicity-increase in
zone of inhibition, mm
Response to CHO-K1 test
for acute cytotoxicity-
ECso
>100
>100
>100
>100
Not measured.
95% confidence interval.
CA11 concentrations of secondary effluent (2%, 5%, 10%, and 10%) failed to support the growth of S. caprioornutum.
d!00% kill in all dilutions (4.7% - 100%), ECso determined with Daphnia pulete.
eECSo not determinable; cytotoxicity procedure employing rabbit alveolar macrophage (RAM) used in Phase I.
-------
TABLE 36. PLANT N EFFLUENT DESCRIPTION
Secondary effluent . Tertiary effluent ___
Parameter Phase I Phase II Type 3 Type 5 Type 6
Physical description Clear, light grey Turbid, brown liquid Turbid, brown liquid Cloudy, light brown Slightly turbid
liquid with with suspended with suspended liquid with liquid
moderate amount particles particles suspended particles
of particulate
matter; non-
chlorinated
pH
Salinity, g/l
Specific conductivity.
ymhos/cm2
3.7
NM
NH
6.6
0
600
6.7
0
650
6.9
0
650
6.S
0
850
Plant V
Textile plant V generated wastewater from woven fabric finishing
operations. Existing treatment facilities included bar screens,
aeration, secondary clarification, and chlorination. Phase I
screening studies (4) indicated that plant V wastewater treated
by the existing treatment facilities was 1 of the more toxic
effluents of the 22 secondary effluents evaluated in the program.
Therefore, plant V was included as a site for Phase II tertiary
pilot plant studies and MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was decided that tertiary treatment
types 3, 4, 6, and 7 held the best promise of meeting suggested
BATEA guidelines and were thus selected for candidate mode
studies. Ferric chloride was used as a precoagulant in type 4
treatment. A flow diagram of the employed candidate mode con-
figuration is shown in Figure 16. Sampling of the candidate
mode operation was conducted by MRC, and results of subsequent
analysis and bioassay work are presented in Tables 37 through
41. As shown in Table 37, bis(2-ethylhexyl) phthalate was added
to the secondary effluent by all four treatment systems, while
methylene chloride and total phenol were removed. Treatment
type 3 (filtration without precoagulation) also added some
di-n-butyl phthalate.
Treatment type 3 removed cyanide and small amounts of copper and
zinc while adding only lead, while type 4 treatment added seven
inorganic toxic pollutants to the secondary effluent. Type 6
treatment removed additional copper, cyanide, and zinc while
adding antimony, lead, nickel, and silver. Type 7 treatment
removed only cyanide while adding four other inorganic toxic
pollutants.
A significant amount of iron (6,000 yg/&) was added to the waste-
water by type 4 treatment, since ferric chloride was used as a
precoagulant. Aluminum, cobalt, and manganese were also added
by type 4 treatment, but they were not added by the other three
treatment systems. As expected, type 4 treatment removed
73
-------
INTAKE
INTAKE WATER
SAMPLE
TEXTILE PLANT V
I
SECONDARY TREATMENT
16 mg/l Fed
SECONDARY EFFLUENT SAMPLE
PI LOT PLANT
UNIT OPERATIONS
MULTIMEDIA
FILTRATION
MULTIMEDIA
FILTRATION
—®1YPE 4 EFFLUENT
SAMPLE
TYPE 3 EFFLUENT
SAMPLE
OZONE CONTACT
TYPE?
EFFLUENT «H
SAMPLE
GRANULAR
ACTIVATED CARBON
~® TYPE 6 EFFLUENT
SAMPLE
Figure 16.
Candidate wastewater treatment
system studied at plant V.
phosphorus, since iron coagulation used in type 4 treatment is a
classical phosphorus removal method.
By reviewing Table 40, it is apparent that type 4 treatment
(filtration with precoagulation) was detrimental to freshwater
algae, and Daphnia. All other treatment series (3, 6, and 7)
maintained the original toxic level of the secondary effluent.
74
-------
TABLE 37. PLANT V ORGANIC TOXIC POLLUTANTS DETECTED
01
Pollutant
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Anthracene
Butyl benzyl phthalate
Methylene chloride0
Toluene
Trichloroethylene
1 , 1-Dichloroe thane
Benzene
Ethylbenzene
Chloroform
Trans-i, 2-dichloroethylene
Phenol (total)
Intake
17
2
18
1
1
0
0
0
1,000
.0
.3
.5
.4
.05
.07
Secondary effluent
Phase I Phase II
9.5 9.5
-b 5.7
0.2
24
1>400 1.1
0.7
16 29
Type 3
16 (-68)a
12 (-110)
0.3
0.9
13 (46)
1.3
0.4
0.05
13 (55)
46
5
0
14
1
2
0
22
Tertiary
Type- 4
(-380)
.4
.1
(42)
.1
.1
.2
(24)
effluent
Type 6
17 (-79)
17 (29)
1.0
0.6
0.1
1.1
8 (72)
90
2
15
0
0
0
2
21
Type 7
(-850)
.7
(38)
.9
.9
.1
.1
(28)
aMinus percent removals indicate any increase in the concentration of the specified pollutant.
Blanks indicate concentration below detection limit (see Table 6).
°Methylene chloride may originate from analysis contamination.
-------
TABLE 38. PLANT V INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Secondary effluent
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Intake
<10
<1
<0.04
<2
<4
<4
<2
<22
<1.1
<36
<1
<5
<50
98
Phase I
4
<5
<0.1
<0.5
3
170
18
<1
<0.5
<10
<5
<5
<5
340
Phase II
<10
4
<0.04
<2
4.3a
85
23
<22
<1.1
<36
<1
<5
<50
240 .
Type 3
<10
4
<0.04
<2
<4
75 (12)
3 (87)
3ia (-41)
<1.1
<36
<1
<5
<50
190 (21)
Tertiary effluent
Type 4
24a (-140)b
<1
<0.04
<2
6.7a
100 (-18)
27 (-17)
37a (-68)
<1.1
73a (-103)
<1
12a (-140)
<50
330 (-38)
Type 6 Type 7
24a
5
<0.04
<2
<4
16a
<2
26a
<1.1
67S
2
15a
<50
69
(-140) 25a
4
<0.04
<2
6.3a
(81) 89
(>91) <2
(-18) <22
<1.1
(-86) 66a
<1
(-200) 16a
<50
(71) 240
(-150)
(-5)
(>91)
(-83)
(-220)
(0)
Semiquantitative region; value not within 95% confidence limits.
Minus percent removals indicate an increase in the concentration of the specified pollutant.
-------
-J
TABLE 39. PLANT V OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Phosphorus
Silicon
Tin
Strontium
Titanium
Vanadium
Ammonia
nitrogen
Nitrate
nitrogen
COD
TSS
Sulfide
Colord at
pH 7.6
Colord at
sample pH
PH6
Intake
380
23
3.1b
3,700
6.1b
2,200
. 1,400
150
<10
3,900
7.0
5,900
<15
30
20
10
NAC
NA
9,500
38,000
<3
47
46
7.3
Secondary
effluent
128
14
730
5,100
<6
210
2,200
77
<10
54,000
1,200
4,600
<15
31
1.4b
13
420
1,300
93,000
12,000
<3
180
180
7.7
Tertiary effluent
Type
70
13
740
4,500
<6
210
2,200
80
<10
54,000
1,100
4,800
<15
31
1.0
14
220
3,400
72,000
4,000
<3
180
182
7.6
3
(45)
(7)
(1)
(12)
(0)
, (0)
(-4)
(0)
(8)
(-4)
(0)
(-8)
(48)
(-160)
(23)
(67)
(0)
(-1)
Type
520
18
730
5,000
21b
6,200
2,200
190
<10
53,000
230a
4,800
<15
33
2.2b
21
560
2,000
36,000
20,000
<3
43
34
4.0
4
(-306)3
(-29)
(0)
(2)
(-250)
(-2,800)
(0)
(-150)
(2)
(81)
(-4)
(-6)
(-62)
(-33)
(-54)
(61)
(-67)
(76)
(81)
Type
100
21
730
4,400
<6
160
2,000
36
<10
51,000
1,100
4,800
<15
27
1.9b
22
210
2,000
22,000
6,000
<3
30
31
7.8
6
(22)
(-33)
(0)
(14)
(24)
(9)
(53)
(6)
(8)
(-4)
(13)
(-69)
(50)
(-54)
(76)
(50)
(83)
(83)
Type
130
13
740
4,800
7.6
250
2,200
73
<10
53,000
1,100
4,700
<15
31
2.1b
16
260
1,800
76,000
12,000
<3
130
140
7.4
7
(-2)
(7)
(-1)
(6)
(-19)
(0)
(5)
(2)
(8)
(-2)
^
(0)
(-23)
(38)
(-38)
(18)
(0)
(28)
(22)
5Minus percent removals indicate an increase in the concentration of the specified pollutant.
bSemiquantitative region; value not within 95% confidence limit.
cNot analyzed.
"ADMI units.
epH units (- log [H+]).
-------
TABLE 40. PLANT V BIOASSAY RESULTS
oo
Test species
Freshwater algae -
S. capricoTnutum
Daphnia -
D. magna
Fathead minnow -
P. promelas
Secondary effluent
ECSO -
ECso -
ECso -
LCso -
LCSO -
LCso —
LCso -
LCso -
LCso -
Parameter
7 day, % effluent
12 day, % effluent
14 day, % effluent
24 hr, % effluent
48 hf, % effluent
24 hr, % effluent
48 hr, % effluent
72 hr, % effluent
96 hr, % effluent
Phase I
NM3
NMC
NM.
9.4d
NM
NM
NM
36
Phase II
78 (59-100)b
94 (57-100)
>100
>100
>60<100
_e
~e
_e
_e
Tertiary effluent
Type 3
76 (60-96)
95 (52-100)
>100
>100
>100
_e
%
~e
%
Type 4
19 (14-27)
25 (13-47)
24 (12-48)
77 (60-100)
54 (44-66)
_e
~e
~e
e
Type 6
>100
>100
>100
>100
>100
_e
~e
^e
~e
Type 7
>100
>100
>100
>100
>100
_e
~e
~e
~e
S. typhimurium -
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
E. eoli -
strains W3110
and p3478
Chinese hamster
ovary cells
Response to Ames test for
ntutagenicity- (-) or (+)
Response to pol A test for 0
mutagenicity-increase in
zone of inhibition, mm
Response to CHO-Kl test
for acute cytotoxicity-
EC50, % effluent
>100
>100
>100
>100
>100
Not measured.
95% confidence limits.
C20% secondary effluent was highly stimulatory for the growth of 5. aappicornutum..
d.
ECso determined with Daphnia pulex.
eLC50 not calculated since mortality data did not follow a normal dose - response relationship; secondary effluent
(Phase II), Type 3 tertiary effluent, Type 7 tertiary effluent, and Type 8 tertiary effluent do not appear to be
acutely toxic to the fathead minnow.
fEC50 not determinable; cytotoxicity procedure employing rabbit alveolar macrophage (RAM) used in Phase I.
-------
TABLE 41. PLANT V EFFLUENT DESCRIPTIONS
Secondary effluent
Parameter
Physical description
PH
Salinity, g/i
Specific conductivity.
umhos/cma
Phase I
NMa
NM
NM
NM
Phase II
Turbid dark
brown
liquid
6.5
0
210
Type 3
Turbid dark
brown
liquid
6.3
0
220
Tertiary effluent
Type 4
Turbid , tan
liquid
with sus-
pended
particles
3.5
0
300
Type 6
Slightly turbid
liquid
6.6
0
210
Type 7
Turbid brown
liquid.
particles
present
6.5
0
220
Not measured.
Plant T
Textile plant T generated wastewater from woven fabric finishing
operations. Existing treatment facilities included aerated
equalization, and an aeration basin. Phase I screening studies
(4") indicated that plant T wastewater treated by the existing
treatment facilities was 1 of the more toxic effluents of the
22 secondary effluents evaluated in the program. Therefore,
plant T was included as a site for Phase II tertiary pilot plant
studies.and MRC sampling/analysis.
After tertiary process screening studies were conducted by
Engineering Science, Inc., it was decided that tertiary treatment
types 2, 3, 5, and 6 held the best promise for meeting suggested
BATEA guidelines; they were thus selected for candidate mode
studies. Alum was used as a coagulant and NaOH was used for
adjusting pH in treatment types 2 and 5. A flow diagram of the
employed candidate mode configuration is shown in Figure 17.
Sampling of the candidate mode operation, with the exception of
type 2 effluent, was conducted by MRC, and results of subsequent
analyses and bioassay studies are presented in Tables 42 through
46. In evaluating the organic toxic pollutant data shown in
Table 42 it can be seen that only three pollutants exist in the
secondary effluent in concentrations greater than 10 yg/£.
Significant amounts of bis(2-ethylhexyl) phthalate and total
phenol were removed by type 5 treatment (flocculation/sedimenta-
tion followed by filtration). Total phenol was added by treat-
ment types 3 (filtration) and 6 (filtration followed by granular
activated carbon), but these treatment systems also removed some
bis(2-ethylhexyl) phthalate.
In evaluating the inorganic toxic pollutant data shown in
Table 43, it is apparent that treatment type 5 (flocculation/sedi-
mentation followed by filtration) provided the best removal of
inorganic toxic species. Type 5 treatment removed eight species;
type 3 treatment (filtration) removed four species; and type 6
79
-------
RIVER INTAKE ~15%
WELLINTAKE~85*
RIVER INTAKE SAMPLE
WELL INTAKE SAMPLE
TEXTILE PLANT T
SECONDARY
TREATMENT
m mg/l ALUM (AS Al+ 3I
pH ADJUSTED TO 6. 5 WITH NaOH '
vZ^
r^
aOCCULATION/
SEDIMENTATION
1
1
MULTIMEDIA
FILTRATION
/0\ SECONDARY
v* EFFLUENT SAMPLE
-^_
^^
MULTIMEDIA
FILTRATION
1 /^^
di ^^y
T
GRANULAR
ACTIVATED CARBON
TYPES
EFaUENT (X)
SAMPLE ^
I1
\
— ®
PILOT PLANT
UNIT OPERATIONS
TYPE 3
EFFLUENT
SAMPLE
TYPE 6
EFFLUENT
SAMPLE J
Figure 17.
Candidate wastewater treatment
system studied at plant T.
treatment (filtration followed by granular activated carbon)
removed six.
Aluminum and sodium were added by type 5 treatment, since alum
and NaOH were used in the coagulation step of type 5 treatment.
Type 5 treatment removed most of the phosphorus present in
plant T secondary effluent.
Daphnia and fathead minnow bioassays provided toxicity data
indicating that treatment types 5 (flocculation/sedimentation
followed by filtration) and 6 (filtration without coagulation
followed by activated carbon) improved the wastewater quality, as
shown in Table 45. Treatment type 3 (filtration without precoag-
ulation) slightly improved toxicity to Daphnia but had no effect
on toxicity to fathead minnows.
80
-------
TABLE 42. PLANT T ORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, ug/£; percent removal in parentheses)
00
Well River Secondary effluent
Pollutant Intake Intake Phase I
Benzene 7.1 6.2
a
Chlorobenzene
1 , 1-Dichloroethylene
p-Chloro-m-cresol
1 , 1-Dichloroethane
Ethylbenzene 0.3
Methylene chloride 24 18
Trichlorofluorome thane
Phenol 0.7
Bis(2-ethylhexyl) phthalate 4.8 6.1 23
Butyl benzyl phthalate 1.2 1.1
Di-n-butyl phthalate 0.4 0.04
Tetrachloroethylene 2 . 9
Toluene 1.2 0.6 33
Trichloroethylene
Phenol (total) 10 36 41
Phase II
5.7
4.1
4.2
0.5
20
0.4
24
5.2
4.4
1.0
0.3
26
Tertiary effluent
Type 3
6.9
4.8
0.6
0.2
19 (5)
0.8
1.1
19 (21)
2.5
7.0
0.8
0.8
0.4
160 (-520)°
Type 5
6.8
0.1
1.8
1.1
0.3
18 (10)
0.3
5.2 (78)
1.3
1.7
1.4
1.0
14 (46)
Type 6
9.8
1.4
0.5
19
0.9
14
1.7
0.6
0.1
120
(5)
(42)
(-360)
Blanks indicate concentration below detection limit (see Table 6).
Methylene chloride may originate from analysis contamination.
Minus percent removals indicate an increase in the concentration of the specified pollutant.
-------
TABLE 43. PLANT T INORGANIC TOXIC POLLUTANTS DETECTED
(Concentration, yg/Jl; percent removal in parentheses)
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Well
intake
<10
<1
<0.04
<2
<4
780
<2
<22
<1
55a
<1
19a
<50
99
River
intake
18a
<1
<0.04
<2
<4
8a
<2
<22
<1
60S
<1
27
<50
370
Secondary effluent
Phase I
<0.5
<5
NAC
<0.5
<0.2
60
<4
<1
<0.5
4
<5
<5
<5
80
Phase II
54
3
<0.04
2a
97
110
11
22a
<1
93a
2
23a
<50
150
Type
58
3
<0.04
<2
95
100
20
26a
<1
a
iooa
2
32
<50
97
Tertiary effluent
3
(-7)b
(2)
(9)
(82)
(-18)
(-8)
(-39)
(35)
Type 5
49a (9)
1
0)
<1
a
59 (37)
2
19a (17)
<50
52 (65)
Type
39a
3
<0.04
<2
84
87
<2
29a
<1
a
90
<1
28a
<50
110
6
(28)
(13)
(21)
(>82)
(-32)
(3)
(-22)
(27)
Semiquantitative region; value not within 95% confidence limits.
Minus percent removals indicate an increase in the concentration of the specified pollutant.
Not analyzed.
-------
TABLE 44. PLANT T OTHER POLLUTANTS DETECTED
(Concentration, yg/£; percent removal in parentheses)
CO
Pollutant
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Phosphorus
Silicon
Tin
Strontium
Titanium
Vanadium
Ammonia
nitrogen
Nitrate
nitrogen
COD
TSS
Sulfide
Colord at
pH 7.6
Color at
sample pH
pH
Well
intake
50a
5.5
<1
13,000
<6
61
4,300
300
<10
20,000
140
6,700
<15
85
1.9a
33
NAC
NA
22,000
<1,000
<3
9
9
7.6
River
intake
100
6.0
<1
4,700
<6
210
1,500
16
<10
7,700
<70
2,100
<15
33
3.2a
18
NA
NA
95,000
<1,000
<3
32
26
6.9
Secondary
effluent
160
7.7
270
12,000
<6
520
3,000
690
<10
180,000
14,000
6,400
<15
72
4.0a
32
16,000
1,200
630,000
20,000
21
177
174
8.0
Tertiary 'affluent
Type
180
7.1
260
11,000
<6
520
3,000
710
10a
170,000
13,000
6,300
<15
70
4.8a
35
18,000
1,200
160,000
14,000
20
164
164
7.6
3
<-13)b
(4)
(8)
(0)
(0)
(-3)
(6)
(7)
(2)
(3)
(-9)
(-13)
(0)
(75)
(30)
(5)
(7)
(6)
Type
3,600
0.6a
270
7,600
<6
340
2,700
430
<10
370,000
1,900
3,300
<15
50
4.0a
56
16,000
1,200
140,000
28,000
9
99
120
7.9
5
(-2,200)
(0)
(37)
(35)
(10)
(38)
(-106)
(86)
(48)
(31)
(-75)
(0)
(0)
(78)
(-40)
(57)
(44)
(31)
Type 6
130
5.3
250
11,000
<6
590
3,300
610
<10
170,000
14,000
6,400
<15
70
5.0a
32
19,000
1,100
340,000
12,000
13
106
115
7.5
(19)
(7)
(8)
(-13)
(-10)
(12)
(6)
(0)
(0)
(3)
(0)
(-19)
(8)
(46)
(67)
(38)
(40)
(34)
aSemiquantitative region; value not within 95% confidence limits.
bMinus percent removals indicate an increase in the concentration of the specified pollutant.
cNot analyzed.
ADMI units.
epH units (- log [H+]).
-------
TABLE 45. PLANT T BIOASSAY RESULTS
oo
Test species
Freshwater algae -
S. capficornutum
Daphnia -
D. magna
Fathead minnow -
P. ppomelas
Secondary effluent
Parameter
ECso
EC so
ECso
LCso
LCso
LCso
LCso
LCso
LCso
- 7 day.
- 12 day,
- 14 day.
- 24 hr,
- 48 hr.
- 24 hr.
- 48 hr.
- 72 hr,
- 96 hr.
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
% effluent
Phase I
NMa
NMb
NM
>iood
NM
NM
NM
47
Phase II
MOO
>100
>100
54
16
22
18
18
17
(47-63)°
(14-19)
(15-32)
(15-22)
(15-22)
(15-19)
Tertiary effluent
Type 3
>100
>100
>100
77
23
18
17
17
17
(66-100)
(23-36)
(15-22)
(15-19)
(15-19)
(15-19)
Type 5
>100
>100
>100
100
80
68
56
56
56
(69-93)
(46-100)
(46-68)
(46-68)
(46-68)
Type 6
MOO
>100
MOO
MOO
MOO
_e
S. typhimurium -
strains TA98,
TA100, TA1535,
TA1537, and
TA1538
E. coli -
strains W3110
and p3478
Chinese hamster
ovary cells
Response to Ames test for (-)
mutagenicity - (-) or (+)
Response to pol A test for
mutagenicity-increase in
zone of inhibition, mm
Respone to CHO-K1 test
for acute cytotoxicity
ECso
MOO
MOO
MOO
MOO
aNot measured.
20% secondary effluent was extremely stimulatory to the growth of S. eapvicornutum.
C95% confidence limits.
ECso determined with Daphnia pulex.
eLCso not calculated since mortality data did not follow a normal dose-response relationship; effluent
did not appear to be acutely toxic.
fECso not determinable; cytotoxicity procedure employing rabbit alveolar macrophage (RAM) used in Phase I.
-------
TABLE 46. PLANT T EFFLUENT DESCRIPTIONS
oo
Parameter
Physical description
PH
Salinity, g/i.
Specific conductivity,
nmhos/cm2
Secondary
Phase I
Clear, blue green
with a moderate
amount of
particulate,
nonchlorinated
7.4
NMa
NM
effluent
Phase II
Turbid, green -
brown
liquid
7.1
0
750
Tertiary effluent
Type 3
Turbid, dark
green
liquid
3.5
0
700
Type 5
Turbid, light
green
liquid
7.2
0
1,500
Type 6
Turbid yellow-
brown liquid
7.2
0
700
Not measured.
-------
SECTION 9
DATA INTERPRETATION
INTRODUCTION
The primary objective of the Phase II textile plant wastewater
study was to assess the capabilities of tertiary treatment to
remove toxic pollutants and toxicity (as measured by bioassay
tests), and to rank the treatment technologies based on this
assessment. However, it would be a misuse of the data to accom-
plish these objectives by a purely quantitative analyses for a
number of reasons.
Data collected under the Phase II program are difficult to
normalize such that a direct comparison of tertiary treatment
system performance can be made.
Concentrations of toxic pollutants and results of bioassay tests
varied widely in the secondary effluents and tertiary effluents
from a single system type. This was due in part to the semiquanti-
tative nature of the data, but primarily to the fact that treat-
ment studies were conducted at eight different textile mills,
each of which discharges a unique wastewater.
Since no more than four tertiary technologies were investigated
at a single textile mill, and operating parameters of a single
system varied from plant to plant, a reliable basis for compari-
son of tertiary treatment systems does not lie in the toxic
pollutant or bioassay data.
The data does serve, however, to identify preliminary positive
and negative results which might be expected in applying various
technologies to further treat secondary effluents from textile
mills. In most cases, additional research would be required to
adequately confirm the preliminary results. In the following
discussion, these preliminary results are identified, and sup-
ported to the extent possible with data from the Phase II program.
86
-------
TOXIC ORGANIC REMOVAL CAPABILITIES
Very few toxic organic compounds, other than total phenol, were
found in secondary effluents in concentrations greater than
10 yg/&. Bis(2-ethylhexyl) phthalate, methylene chloride, and
di-n-butyl phthalate did appear in a few cases, however, the
appearance of these compounds could have originated from contami-
nations by the materials of which the pilot plant was constructed,
or by sample analysis techniques. Only data from Plants A and C
(see Tables 7 and 12) provide insite into the ability of the ter-
tiary systems to remove other specific toxic organic pollutants.
Toluene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene were
found in concentrations greater than 10 yg/& in the secondary
effluent of Plant A. Tertiary system types 2, 5, and 8 were
operated at Plant A, and all were effective in reducing the levels
of these three compounds. Toluene was found in the secondary
effluent of Plant C, and treatment types 2, 5, and 8 again were
effective in reducing its concentration. Type 2 treatment of
Plant C secondary effluent did appear, however, to add
1,2-dichlorobenzene, although subsequent filtration (type 5 treat-
ment) and activated carbon (type 8 treatment) appeared to remove
it.
Total phenol was found in many of the secondary effluents in con-
centrations greater than 10 yg/Jl. In both cases in which it was
used (Plants A and C), type 8 treatment reduced levels of total
phenol. Treatment type 2, used at Plants A, C, and P, treatment
type 6, used at Plants W, S, P, N, V, and T, and treatment type
7, used at Plants W and V, appear to be somewhat successful at
reducing levels of total phenol. Inconclusive results were
obtained when treatment type 3 operated at Plants W, S, P, N, V,
and T, treatment type 4, operated at Plants S and V, and treat-
ment type 5, operated at Plants A, C, P, N, and T, were used.
TOXIC METAL REMOVAL CAPABILITIES
Results of toxic metals analysis provided much more insite into
the performance of the tertiary systems. Based on the results,
treatment types 3, 5, and 6 appear to be the best of the 8 sys-
tems at removing toxic metals. Based on data .generated at Plants
W, S, P, N, and T, treatment type 3 removed antimony in 3 of the
5 cases. In the two remaining cases, the antimony concentration
remained about the same. Cadmium was also removed by type 3
treatment in the sole case in which the cadmium concentration in
the secondary effluent was greater than 10 yg/£, and type 3 treat-
ment was used (Plant W). Based on data generated at Plants P, N,
and T, chromium was removed by type 3 treatment in 2 of the 3
cases. In the third case, its concentration essentially remained
the same. At Plants W and P, type 3 was effective in removing
copper from secondary effluent, however the copper concentration
increased at Plant N. At Plants S, V, and T, the copper concen-
tration remained about the same. Lead was removed by type 3
87
-------
treatment at Plant W, however, it was added at Plant V. Lead
concentrations remained about the same before and after type 3
treatment at Plants S, P, and T. Nickel was removed at Plant T,
while concentrations of nickel remained essentially unchanged at
Plants S, P, and T. In 5 of 6 cases, zinc was removed by type 3
treatment based on results from Plants W, S, P, N, V, and T.
Zinc was added to the secondary effluent at Plant S. In the sole
cases in which the metal concentration was greater than 10 yg/&
in the secondary effluent, and type 3 treatment was used, arsenic
was added based on results at Plant W, and silver was added based
on results from Plant T.
As mentioned treatment type 5 also appeared to be effective in
removing toxic metals. In 2 of 4 cases, antimony concentrations
were reduced by type 5 treatment based upon results from Plants
C, P, N, and T. At Plant C, antimony was added, and at Plant T,
the antimony concentration remained about the same. Chromium
was removed by type 5 treatment in 4 of 5 cases based upon
results from Plants A, C, P, N, and T. At Plant c, however, the
chromium concentration increased. In 3 of 5 cases, copper was
also reduced by type 5 treatment, again based upon results from
Plants A, C, P, N, and T. Copper concentrations increased at
Plants A and N. Nickel was removed by type 5 treatment in two
cases based on results from Plants P and T. Zinc was removed in
3 of 5 cases based upon results from Plants A, C, P, N, and T.
At Plant C, zinc appeared to be added, while at Plant A, the zinc
concentration remained essentially unchanged. Based upon results
from a single plant, Plant A, arsenic, beryllium, and cadmium
were added to the secondary effluent by type 5 treatment. Lead
appears to be added by type 5 treatment based upon results from
Plants A, C, P, and T. In two cases, the lead concentration
increased, while at the remaining two plants, Plants P and T,
secondary and tertiary concentrations were too close to the
detection limit of 22 yg/£ to draw conclusions from. Type 5
treatment appears to have little effect upon the silver concen-
tration based upon results generated at Plants C and T.
Treatment type 6 also appears to be effective at removing toxic
metals. In 4 of 6 cases, antimony was removed by type 6 treat-
ment based on results from Plants W, S, P, N, V, and T. At Plant
V, however, antimony appears to be added, and at Plant S, anti-
mony appeared to be uneffected by type 6 treatment. Cadmium
appears to be removed by type 6 treatment based upon results from
Plant S. Chromium was effectively removed by type 6 treatment at
Plants P and N. At Plant T, however, chromium was only slightly
removed. In 5 of 6 cases, copper was removed by type 6 treatment
based upon results from Plants W, S, P, N, V, and T. At Plant N,
the copper concentration increased. Zinc was removed in all
cases in which the zinc concentration in the secondary effluent
was greater than 10 yg/£, and type 6 treatment was used based
upon results from Plants W, S, N, V, and T. Treatment type 6
does not appear to be effective in removing arsenic and silver.
88
-------
At Plant P, the arsenic concentration increased, while at Plants
W and S, arsenic concentrations remained about the same. At
Plant W, silver was removed by type 6 treatment, while at Plants
V and T, silver concentrations increased as a result of type 6
treatment. Mixed results were obtained when type 6 treatment was
used to remove lead and nickel. Lead was removed by type 6 treat-
ment at Plant W, however, it was added at Plant T. The lead con-
centration appeared to remain essentially the same at Plants S,
P, and V. Nickel was removed at Plants W and P, but added at
Plant V. At Plants S and T, the nickel concentration before and
after type 6 treatment remained about the same.
Treatment types 4 and 7 appeared to be especially ineffective, or
detrimental in the removal of toxic metals from secondary efflu-
ents. Based on data from Plants S and V, type 4 treatment had
essentially no effect upon levels of arsenic, copper, and nickel.
At Plant V, antimony, lead, silver, and zinc were added by type
4 treatment. Perhaps, filtration used in type 4 treatment was
ineffective in capturing suspended solids formed in the precoagu-
lation step prior to direct filtration. These solids may have
contained toxic metals.
Type 7 treatment was used at Plants W and V. Concentrations of
antimony, copper, nickel, silver, and zinc increased as a result
of the ozonation step used in type 7 treatment both at Plants W
and V. In addition, cadmium concentrations increased at Plant W,
and chromium increased at Plant V.
TOTAL CYANIDE REMOVAL CAPABILITIES
Treatment types 6 and 7 appear to be the best system of the eight
at removing total cyanide whereas treatment type 3 appeared to be
the worst. Cyanide was effectively removed by type 6 treatment
based on results from Plants W, V, and T where greater than 80%
removal efficiencies were observed in all three cases. Cyanide
was also effectively removed by type 7 treatment based on results
from Plants W and V where greater than 90% removal efficiencies
were observed.
On the other hand, cyanide appears to be added by type 3 treat-
ment based on results obtained at Plants W and T.
TOXICITY REMOVAL CAPABILITIES
Toxicity, was measured by bioassay tests, appears to be best re-
moved by treatment types 3 and 6, whereas treatment types 2 and
4 appear to be detrimental to water quality in terms of acute
toxicity. In four cases in which acute toxicity to algae was
detected in the secondary effluent (Plants W, S, P, and N), type
3 treatment improved water quality in terms of acute toxicity to
algae in two cases. At Plant S, acute toxicity to algae remained
about the same, and at Plant P, type 3 treatment appeared to be
89
-------
detrimental to water quality. In four cases where acute toxicity
to Daphnia was detected (Plants W, N, V, and T), type 3 treatment
improved water quality in terms of acute toxicity to Daphnia in
two cases. In the remaining cases, acute toxicity to Daphnia
remained unchanged. In three cases in which acute toxicity to
fathead minnows was detected in the secondary effluent (Plants W,
N, and T), water quality in terms of acute toxicity improved in
two cases as a result of type 3 treatment, and remained the same
in the third case. In the sole case where acute toxicity to blue-
gills was detected in the secondary effluent (Plant W), no change
in acute toxicity was observed as a result of type 3 treatment.
Type 6 treatment also appeared to improve water quality in terms
of acute toxicity to various species. In the four cases in which
acute toxicity to algae was detected in the secondary effluent,
toxicity to algae was removed in three of the cases as a result
of type 6 treatment, and in the fourth case, the acute toxicity
to algae remained the same. In the cases in which acute toxicity
to Daphnia was detected in secondary effluents, type 6 treatment
removed the toxicity in two cases, and slightly added toxicity
in one case. In the three cases in which acute toxicity to fat-
head minnows was detected in secondary effluent, type 6 treatment
removed the toxicity in two of the cases. Toxicity to fathead
minnows remained the same in the third case. In the sole case
in which acute toxicity to bluegills was detected in the secon-
dary effluent, the toxicity was slightly removed by type 6
treatment.
As mentioned, treatment types 2 and 4 appeared to be detrimental
to improving water quality in terms of acute toxicity removal.
In two of three cases, toxicity to algae worsened as a result of
type 2 treatment based on results from Plants A, C, and P. At
Plant A, however acute toxicity to algae only slightly improved.
At Plant C, no acute toxicity to Daphnia was detected in the
secondary effluent, but acute toxicity was detected following
type 2 treatment. Toxicity to algae did improve at Plant A as
a result of type 2 treatment, however toxicity to bluegills
worsened. Based on data from Plants S and V, type 4 treatment
added toxicity to algae in both cases, and toxicity to Daphnia
in one case.
Toxicity increases as a result of treatment types 2 and 4 may
have been caused by insufficient removal of residual inorganic
coagulant or filter aid used in these treatment systems. For
example, the data appear to indicate that tertiary effluents with
higher levels of residual aluminum (aluminum present in effluent
after discharge from a tertiary treatment system in which alum
was used as a coagulant) are more toxic than effluents with
lower levels of residual aluminum. Plant A tertiary effluents
resulting from type 2, type 5, and type 8 treatment which employ
alum and lime coagulation improved in terms of Daphnia and algal
90
-------
toxicity, when compared to Plant A secondary effluent. Residual
aluminum levels were 1,600 yg/&, 520 yg/£, and 100 yg/& in
effluents from type 2 treatment, type 5 treatment, and type 8
treatment, respectively. High levels of residual calcium
(70,000 yg/H in all three tertiary effluents, compared to
37,000 yg/& in the secondary effluent) apparently were not high
enough to make Plant A tertiary effluents more toxic than Plant A
secondary effluent. Similarly, Plant N secondary effluent sub-
jected to type 5 treatment, which employed alum coagulation,
improved improved wastewater quality in terms of algal, Daphnia,
and fathead minnow acute toxicity. Residual aluminum levels in
the tertiary effluent were low (110 yg/& aluminum in Plant N
secondary effluent and 390 yg/& aluminum in Plant N type 5
effluent).
Conversely, effluents resulting from tertiary treatment of Plant
C effluent remained as toxic as, or more toxic than, Plant C
secondary effluent with respect to algae, Daphnia, and fathead
minnows. High levels of residual aluminum were found in type 2,
type 5, and type 8 effluents: 13,000 yg/£, 11,000 yg/£, and
9,200 yg/£, respectively. Only 98 yg/£ of aluminum was found in
Plant C secondary effluent. When a more moderate concentration
of aluminum was found in the tertiary effluent (3,600 yg/£ alumi-
num in Plant T effluent treated by the type 5 system), toxicity
to algae remained the same as in the secondary effluent, while
toxicity to Daphnia and fathead minnows improved.
High levels of residual iron or increased chloride levels result-
ing from ferric chloride coagulation used in type 4 treatment
of Plant V effluent may have had a detrimental effect on water
quality in terms of algal toxicity. Type 4 effluent was more
toxic to algae than Plant V secondary effluent. The residual
iron level in the type 4 effluent was 6,200 yg/£, compared to
210 yg/£ in Plant V secondary effluent.
The use of cationic polymers may also be detrimental to water
quality improvement in terms of acute todicity, especially to
algae. In two cases in which polymers were used, toxicity to
algae worsened. At Plant S, cationic polymer was used as a
filter aid in type 4 treatment, and toxicity to algae worsened
significantly. At Plant P, cationic polymer was used as a
coagulant in type 2 treatment, and toxicity to algae worsened
significantly. After flocculation/sedimentation (type 2 treat-
ment) at Plant P, the wastewater was treated with carbon (type 5
treatment). As a result, acute toxicity to algae improved with
respect to that observed with the type 2 effluent, however, the
acute toxicity of the type 5 effluent was still worse than that
observed with the secondary effluent.
91
-------
OTHER OBSERVATIONS
In analyzing bioassay data generated in the Phase II program,
several other observations can be made. Generally, freshwater
algae toxicity testing was the most sensitive of the bioassays
employed in the Phase II study. Toxicity to algae (EC50 - 14
days less than 100%) was detected in 74% of the samples tested;
toxicity to Daphnia (LC50 - 48 hr less than 100%) was detected in
54% of the samples tested; toxicity to bluegills (LC50 - 96 hr
less than 100%) was detected in 44% of the samples tested; and
toxicity to fathead minnows (LC50 - 96 hr, less than 100%)
detected in 33% of the samples tested. No toxicity was detected
when any of the microbiological bioassay techniques were used.
Overall, the secondary effluents at the eight textile plant
locations subjected to MRC sampling/analysis/bioassay during both
Phase I and Phase II have improved in terms of toxicity, since
Phase I testing. An improvement was observed at five plants,
while degradation of secondary effluent quality in terms of
toxicity was observed at one plant.
OVERVIEW
In summary, a number of trends concerning toxic pollutant levels,
toxicity levels, and tertiary treatment type have been identified
by analyzing the Phase II data. These trends are described below,
1. Multimedia filtration without precoagulation followed by
granular activated carbon (type 6 treatment) was the best
system employed in terms of removing both toxicity and toxic
pollutants. Other tertiary systems rank as follows:
Removal
of toxic
organic
compounds
Removal
of toxic
metals
Removal
of
cyanide
Best removal ability
Intermediate removal
ability
Type 3, Type 6,
Type 5, Type 7
Type 6
Removal
of acute
toxicity
Type 3,
Type 6
Composite
Type 6
Type 1,
Type 2,
Type 8
Type 1,
Type 2,
Type 4,
Type 5,
Type 8
Type 1,
Type 5,
Type 7,
Type 8
Type 1,
Type 2,
Type 3,
Type 5,
Type 7,
Type 8
Least removal ability
Type 4,
Type 7
Type 3
Type 2,
Type 4
Type 4
Inadequate data with which to base conclusions.
92
-------
2. Systems employing alum or iron coagulation, in which resi
dual concentrations of alum or iron were high (greater than
9,000 yg/Jl Al or greater than 6,000 yg/£ Fe) , generally
increased the toxicity of the wastewater.
3. Coagulation with cationic polymers appeared to be detri-
mental to freshwater algae.
4. Freshwater algae toxicity testing was the most sensitive
of the bioassays employed in the Phase II study.
5. Overall, the secondary effluents at the eight textile
plant locations subjected to MRC sampling/analysis/bio-
assay during both Phase I and Phase II have improved in
terms of toxicity, since Phase I testing.
93
-------
SECTION 10
RESULTS OF SPECTRA ANALYSIS OF PHASE I SAMPLES
TOTAL ORGANIC CONCENTRATION
Another portion of the Phase I chemical characterization study
involved determining the total organic concentration (4).
Following the procedure specified by EPA, 10 H of each secondary
effluent sample were filtered through 0.45-ym filter paper (12).
A portion of this sample was then extracted three times with
methylene chloride. The extracts were then dried at 105°C and
weighed to determine the total amount of methylene chloride-
extractable, nonvolatile organics. Results of this analysis are
shown in Table 47 (12) .
TABLE 47. CONCENTRATION OF METHYLENE CHLORIDE-EXTRACTABLE
ORGANICS IN FILTERED SECONDARY EFFLUENTS
Plant
Organic
concentration,
g/m3
Plant
Organic
concentration,
g/m3
A
B
C
E
F
G
K
L
63.7
3.18
28.2
3.60
16.0
27.2
2.73
18.3
N
S
T
U
V
W
X
9.24
5.40
17.8
14.6
_a
15.0
13.5
Analysis not performed.
(12) Hamersma, J. W., S. L. Reynolds, and R. F. Maddalone. IERL-
RTP Procedures Manual: Level 1 Environmental Assessment.
EPA-600/2-76-106a (PB 257 850), U.S. Environmental Protec-
tion Agency, Research Triangle Park, North Carolina,
June 1976. 147 pp.
94
-------
PHASE I PRIORITY POLLUTANTS
For the purposes of data comparison, Table 48 shows the organic
priority pollutants found in the 23 secondary effluents in Phase
I of the study (4).
OTHER ORGANIC COMPOUNDS IDENTIFIED
Results of re-examining the GC/MS spectra of the Phase I secon-
dary effluent samples are shown in Tables 49 through 71. Each
table shows the results from 1 of the 23 samples, and each is
divided to show which compounds were detected in each of the
three priority pollutant fractions: volatile, base/neutral, and
acid fraction organics.
Methylene chloride was found in all volatile samples, but its
presence is principally due to laboratory contamination. Some of
the data stored on magnetic tape were lost due to a power surge,
and some data were not retrievable due to GC/MS scanning
malfunctions.
95
-------
TABLE 48. PHASE I PRIORITY POLLUTANTS IN SECONDARY EFFLUENTS
Plant
Compound identified ana concentration observed, ug/t
Volatiles
Base/neutrals
Acids
L
N
Toluene 8.4
Trichlorofluoromethane 2.6
Toluene 2.6
Ethylbenzene
Toluene 1.7
Toluene 5.5
Trichlorofluoromethane 1,7
rran8-l,3-dichloropropene 3.9
Cis-1,3-dichloropropene 5.6
Toluene 0.8
Ethylbenzene 2.7
Toluene 0.8
Toluene 12
Trichlorofluoromethane 2,100
Toluene 8
Ethylbenzene 51
Chloroform 58
Trichloroethylene 4.6
Toluene 24
Ethylbenzene 0.7
Benzene 0.5
Toluene 0.4
1,2-Dichlorobenzene 1 NPPO
1,.4-Dichlorobenzene 0.05
Bis(2-ethylhexyl) phthalate 6
1,2,4-Trichlorobenzene 46
N-nitroso-di-n-propylamine 2 NPPO
Bis(2-ethylhexyl) phthalate 3
Pyrene 0.3
1,2-Dichlorobenzene 0.3 NPPO
1,2,4-Trichlorobenzene 10
Acenaphthene 0.5
Bis(2-ethylhexyl) phthalate 3
Anthracene 4.4
Diethyl phthalate 1 NPPO
Bis(2-ethylhexyl) phthalate 5
1,2-Dichlorobenzene 0.2 NPPO
1,4-Dichlorobenzene 0.2
Dimethyl phthalate 1
Diethyl phthalate 0.5
Bis(2-ethylhexyl) phthalate 18
Pyrene 0.1
1,2,4-Trichlorobenzene 6.3
Bis(2-ethylhexyl) phthalate 23
2,4-Dimethylphenol 9
Acenaphthene 2 Phenol 2
Hexachlorobenzene 0.8
Diethyl phthalate 11
Bis(2-ethylhexyl) phthalate 10
Bis(2-ethylhexyl) phthalate 230 NPPO
Bis(2-ethylhexyl) phthalate 35 NPPO
Di-n-butyl phthalate 3.6
Pyrene 0.1
Naphthalene 0.5 NPPO
Bis(2-ethylhexyl) phthalate 8
Bis(2-ethylhexyl) phthalate 2 NPPO
1,2,4-Trichlorobenzene 1.8 NPPO
Di-n-butyl phthalate 58
3No priority pollutants observed.
(continued)
-------
TABLE 48 (continued).
Plant
Compound identified and concentration observed, ug/t
Volatiles
Base/neutrals
Acids
Toluene 17
Ethylbenzene 75
P Chloroform 6.9
Toluene 22
Ethylbenzene 280
R Toluene 17
Ethylbenzene 29
S Toluene 21
Ethylbenzene 110
1,1,2,2-Tetrachloroethylene 0.4
T Toluene 33
1,1,2,2-Tetrachloroethylene 3
U Chloroform 18
Bromodichloromethane 1.5
Trans-1,3-dichloropropene 0.9
Toluene 13
V Toluene 1,400
W Toluene 1.7
X Toluene 40
Trichlorofluoromethane 35
1,1,2,2-Tetrachloroethylene 41
Y Chloroform 5
Trichlorofluoromethane 10
Toluene 110
Ethylbenzene 3,020
Chlorobenzene 3.5
Trichlorofluoromethane 89
1,2-Dichlorobenzene 6
1,4-Dichlorobenzene 1.5
Diethyl phthalate 9.4
Bis(2-ethylhexyl) phthalate 16.7
Bis(2-ethylhexyl) phthalate 72
N-nitroso-di-n-propylamine 19
Diethyl phthalate 2
Bis(2-ethylhexyl) phthalate 12
Bis(2-ethylhexyl) phthalate 41
Naphthalene 255
1,2 ,4-Trichlorobenzene 916
Bis(2-ethylhexyl) phthalate 23
Bis(2-ethylhexyl) phthalate 140
Naphthalene 22
Bis(2-ethylhexyl) phthalate 9
Bis(2-ethylhexyl) phthalate 19
Hexachlorobenzene 0.5
Diethyl phthalate 3
Bis(2-ethylhexyl) phthalate 2
1,2-Dichlorobenzene 0.6
Naphthalene 0.6
Diethyl phthalate 3
Di-n-butyl phthalate 7
Hexachlorobenzene 0.3
Bis(2-ethylhexyl) phthalate 25
Bis(2-ethylhexyl) phthalate 2
2,4-Dimethylphenol 8
NPPO
Chloro cresol 32
Pentachlorophenol 56
NPPO
NPPO
NPPO
NPPO
NPPO
NPPO
NPPO
No priority pollutants observed.
-------
TABLE 49. PLANT A: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Bromochloromethane Minor
Dichlorobenzene Minor
1 unknown (possibly an alkyl Minor
alcohol)
Base/neutrals
Dichlorobenzene 0.1
Trichlorobenzene 4.2
Aliphatics (Cis on up, paraffinic) 52.0
Aliphatics (Cis on up, olefinic) 43.6
Di-Cs alkyl phthalate 0.1
Acids
Ce-aliphatic acid 0.1
Trichlorobenzene 0.1
Cg-aliphatic acid 0.1
C-io-aliphatic acid 0.1
Ci2-aliphatic acid 0.2
Cm-aliphatic acid 0.4
Aliphatics (olefins Ci2 and up) 95.3
Cie-aliphatic acid 1.2
C-i a-aliphatic acid 1.5
C2o-aliphatic acid 1.0
Methylene chloride presence due to laboratory
contamination.
98
-------
TABLE 50. PLANT B: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride Major
Bromodichloromethane Minor
Base/neutrals
Aliphatics (Cie-C3a) 44.1
Diethyl phthalate 0.9
Dipropyl phthalate 1.8
Dibutyl phthalate 1.0
Di-C8 alkyl phthalate 1.0
Triphenylphosphine 7.7
Triphenylphosphine oxide 9.6
Triphenylphosphine sulfide 2.1
Cis-hydroxy amide 0.6
Cis-hydroxy amide 6.0
Ci7-hydroxy amide 13.7
Unknown ester, CaiHauOa 0.4
Unknown ester, CaiH3«Oa 0.6
Unknown ester, not a methyl ester 4.5
KG 17 or Cie)
Unknown ester, possibly methyl 0.8
dehydroabietate
Compound, either dihydroxyaceto- 2.0
phenone or acetylhydroquinone
Co-alky 1 phenols 1.2
Anthracene/phenanthrene 0 . 7
Methyl-anthracenes/-phenanthrenes 0 . 4
Dimethyl-anthracenes/-phenanthrenes 0 . 3
Fluoranthene 0 . 1
Pyrene 0 . 4
Methyl-f luoranthenes/-pyrenes 0 . 1
Acids
Cio-aliphatic
Ci i-aliphatic
Ci2-aliphatic
Ce-aliphatic acid
Cis-aliphatic
Ce-aliphatic acid
Cio-aliphatic acid
Ci B-aliphatic
Cia-aliphatic acid
-aliphatic
-aliphatic acid
-aliphatic acid
-aliphatic acid
Ci7-aliphatic acid
Cia-aliphatic acid
(lauric acid)
Methylene chloride presence due to laboratory
contamination.
In general, Cio-Cie aliphatics are weak
based on area for 43 ion). Among Cs-Cie
aliphatic acids, Cla-Ciu are moderate and
Cis and CIB are strong (total acids i93%
based on 73 and 60 ions).
99
-------
TABLE 51. PLANT C: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Bromodichloromethane Minor
Toluene Minor
Base/neutrals
Data not retrievable from
magnetic tape
Acids
Alcoholic ether, unknown
Butoxy ethanol
Phenol
Diethylene glycol ether
Cresols
Dime thy Iphenols
Benzoic acid
C-i o-aliphatic acid
Ci2-aliphatic acid
Ci i*-aliphatic acid
Ci e-aliphatic acid
Ci e-aliphatic acid
7.3
5.3
0.8
4.0
0.3
0.6
1.7
1.8
5.6
12.2
24.8
35.6
Methylene chloride presence due to laboratory
contamination.
100
-------
TABLE 52. PLANT D: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Data not retrievable from
magnetic tape
Base/neutrals
Aliphatics (Cie^on up, primarily 92.2
paraffinic)
Unknown ester, ^Cie, not a methyl 2.3
ester
Diethyl phthalate 0.6
Dibutyl phthalate 2.9
Di-C8 alkyl phthalate 1.2
Benzanthrene 0.8
Acids
Butoxy ethanol 2. 0
Diethylene glycol ether 3.0
Unknown aliphatic ether/alcohol 2.0
Benzoic acid 7.5
Cis-aliphatic 2.0
Undeterminated phthalate 5.5
Ci<»*Ci7-aliphatic acids 78.0
(& C-ie-above)
101
-------
TABLE 53. PLANT E: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
percent
Compounds
Volatiles
Carbon dioxide a Minor
Methylene chloride Major
Toluene Minor
Xylenes Minor
Ethylbenzenes Minor
Base/neutrals
Dichlorobenzenes 0.2
Naphthalene 0.1
Methyl-naphthalenes <0.1
Biphenyl <0.1
Phthalic acid/or anhydride 0.7
Unknown ester 11.4
Dichlorodimethoxybenzene 0.3
Unknown, possibly dichloro- 0.1
trimethoxybenzene
Diethyl phthalate 0.4
C-is-hydroxy amide 2.9
Ci7-hydroxy amide 7.1
Dibutyl phthalate 0.5
Di-Ce-alkyl phthalate 5.4
Triphenylphosphine 3.1
Triphenylphosphine oxide 1.8
Triphenylphosphine sulfide 0.5
Aliphatics (CiS-»on up, paraffinic 40.3
character)
Aliphatics (Cis-*on up, olefinic 25.2
character)
Acids
Butoxy ethanol 1.1
Phenol 1.5
Cresols 0.5
Dimethylphenols 1.9
Ce-aliphatic acid 0.6
Cio-aliphatic acid 0.7
Tetrachlorophenol 0.4
Pentachlorophenol 3.9
Di-(Cs-alkyl) phthalate 9.5
da & above aliphatic acids 16.2
Cie & above aliphatics 63.7
Methylene chloride presence due to laboratory
contamination.
102
-------
TABLE 54. PLANT F: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Only peak
Base/neutrals
Alkyl oxygenates (e.g., ethers), 0.8
dominant 59 ion
Alkyl oxygenates (e.g., ethers), 0.7
dominant 45 ion
Unknown (2) with dominant 6.7
42 & 45 ions
Alkyl oxygenates (e.g., ethers), 14.3
dominant 59 ion
Aliphatics, Cis & above 68.9
Trichlorobenzenes 0.5
Ce-alkylphenols 1.2
Diethyl phthalate 0.1
Dibutyl phthalate 0.2
Di-C8 alkyl phthalate 4.8
Triphenyl phosphine 0.2
Triphenylphosphine oxide 0.8
Triphenylphosphine sulfide 0.8
Acids
Phenol 0.5
Methyl benzoate 0.1
Benzoic acid 21.7
Toluic acid 14.5
Ciz-methyl ester 1.8
Ci3-methyl ester 0.4
de-methyl ester (palmitate) 0.8
Ci7-methyl ester 0.2
C-iB-methyl ester (stearate) 2.3
Biphenyl 0.7
Cio & above aliphatic acids 10.5
Cis & above aliphatics 46.5
Methylene chloride presence due to laboratory
contamination.
103
-------
TABLE 55. PLANT G: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride*
Toluene
C3-alkyl benzene
Base/neutrals
Aliphatics (Cie & up)
character
Aliphatics (Cie & up)
character
Dibutyl phthalate
Di-Ce alkyl phthalate
Triphenylphosphine
Triphenylphosphine oxide
Triphenylphosphine sulfide
Acids
Butoxyethanol
Ca-alkyl benzene
Co-aliphatic acid
Ce-aliphatic acid
Naphthalene
Cio-aliphatic acid
Ci2-aliphatic acid
Caprolactam
Biphenyl
Cm-aliphatic acid
Cis-aliphatic acid
Ci e-aliphatic acid
Cie & above aliphatics
paraffinic
olefinic
Major
Minor
Minor
54.5
45.3
0.1
0.1
<0.1
4.6
0.1
0.4
0.2
1.1
0.5
5.6
6.4
3.2
2.3
2.6
2.6
70.4
Methylene chloride presence due to laboratory
contamination.
104
-------
TABLE 56. PLANT H: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Carbon dioxide Minor
Methylene chloride Major
Acetone Minor
Trichlorof luoromethane Minor
Unknown (possibly an alkyl Minor
alcohol)
Methyl pentanol Minor
Hexane
Toluene
Base/neutrals
Unknown (45 ion), similar to 2.9
ethoxy ethyl acetate
Aliphatics, Cis-*on up (paraffinic 54.1
character)
Aliphatics, Cis-»on up (olefinic 39.5
character)
Di-t-butylphenol 0.1
Unknown, ester, Cis or Ci6 1.6
Diethyl phthalate 0.2
Dibutyl phthalate 0.2
Di-Cs alkyl phthalate 1.3
Ester, C2iH3402 0.05
Ester, C2iH3(40a 0.05
Acids
Weak alcoholic ethers Very weak
Ci2 & above aliphatics Very weak
Methylene chloride presence due to laboratory
contamination.
105
-------
TABLE 57. PLANT J: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Toluene Minor
Ethylbenzene Major
Base/neutrals
Oxindole 0.1
Toluidine/or methyl aniline 0.2
Cs-alkylphenol 0.3
Cg-alkylphenols 1.3
Unknown ester, dominant 71 ion 1.4
Unknown esters (3), dominant 2.0
57 ion (possibly long-chain 2.9
alkyl esters of acids < C5) 4.8
Aliphatics, C2o & above 56.9
(paraffinic character)
Aliphatics, Czo & above (olefinic 27.1
character)
Acids
Cs & above aliphatics Very weak
Methylene chloride presence due to laboratory
contamination.
106
-------
TABLE 58. PLANT K: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride Major
Bromochloromethane Minor
Chloroform Minor
Trichloroethylene Minor
Base/neutrals
Diiodochloromethane 1.1
Aliphatics (Ci5-on up, paraffinic 57.4
character)
Aliphatics (Cis*on up, olefinic 26.4
character)
Unknown ester, ds or CIB 5.5
Diethyl phthalate 0.9
Anthracene/phenanthrene 0.5
Dipropyl phthalate 0.2
Methyl-anthracenes/-phenanthrenes 0.2
Dibutyl phthalate 0.6
Cis-hydroxy amide 0.7
Dimethyl-anthracenes/-phenanthrenes 0.1
Fluoranthene 0.05
Pyrene 0.05
Ester, Ca-iHauOa 0.3
Dioctyl adipate 0.1
Ci7-hydroxy amide 1.4
Triphenylphosphine 1.1
Ester, C2iH3«02 0.6
Triphenylphosphine oxide 1.2
Triphenylphosphine sulfide 0.8
Di-Ce alkyl-phthalate 0.8
Acids
Diethylene glycol ether 15.5
Unknown (alcoholic ether/or 1.3
di-ether)
Aliphatic (C9-olefin) 0.6
Benzoic acid 1.1
Cie-aliphatic acid 0.2
Cia-aliphatic acid 1.7
Trichlorophenol 0.1
C-i^-aliphatic acid 3.8
de-aliphatic acid 25.9
da-aliphatic acid 28.7
Pentachlorophenol 0.3
Di-Ce-alkyl-adipate 20.8
Methylene chloride presence due to laboratory
contamination.
107
-------
TABLE 59. PLANT L: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride'
Major
Base/neutrals
Data not retrievable from
magnetic tape
Acids
Dimethylformamide
Dime thy lace tamide
Unknown
Cresols
Alcoholic ether
Ciz-aliphatic acid
Unknown-possibly ethyl hydrogen
phthalate
Ci ^-aliphatic acid
C-t e-aliphatic acid
Ci B-aliphatic acid
23.1
24.0
1.8
1.0
11.2
4.1
5.0
3.5
11.1
15.2
Methylene chloride presence due to laboratory
contamination.
108
-------
TABLE 60. PLANT M: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride
Base/neutrals
Data not retrievable from
magnetic tapes
Acids
Unknown
Phenol
Diethylene glycol ether
Nonlinear Ca-aliphatic acid
Cresols
Ce-aliphatic acid
Cg-olefin or cyclic alkane
Benzoic acid
Dimethylphenols
Unknown alcoholic ether
Cio-aliphatic acid
Cis-aliphatic
Ci2-aliphatic acid
Trichlorophenol
Cie-aliphatic
Ciu-aliphatic acid
Cie-aliphatic acid
Cie-aliphatic acid
C20-aliphatic acid
Only peak
1.3
4.9
5.9
1.4
0.1
1.4
1.0
2.0
0.1
6.1
3.6
1.4
8.4
0.1
1.5
9.6
22.8
28.4
28.4
Methylene chloride presence due to laboratory
contamination.
109
-------
TABLE 61. PLANT N: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds ; percent
Volatiles
Methylene chloride Major
Bromochloromethane Minor
Unknown (possibly an alkyl Minor
alcohol)
Cz-alkyl benzene Minor
Dichlorobenzene Minor
Base/neutrals
Dichlorobenzenes 0.4
Dichlorodimethoxybenzenes <0.1
Dichloroaniline 2.6
Cio-Ci<* alkyl benzenes 11.9
Cs-alkyl phenol 0.4
Cg-alkyl phenols 3.8
Di-Cs alkyl phthalate 0.1
Aliphatics, Cis-»on up, primarily 80.8
paraffinic
Acids
Data not retrievable from
magnetic tapes
Methylene chloride presence due to laboratory
chloride.
110
-------
TABLE 62. PLANT P: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride3 Minor
Chloroform Minor
Toluene Minor
Ca-alkyl benzene Major
Base/neutrals
Benzaldehyde 0.4
Benzoyl alcohol 47.7
Aliphatics, Ci*»-Ca<» 16.6
Unknown ester (^15 or Ci6) 3.2
Unknown (192/190/188 isotope) 0.3
Diethyl phthalate 0.4
Anthracene/phenanthrene 0.1
Methyl-anthracenes/-phenanthrenes 0.1
Dimethyl-anthracenes/-phenanthrenes 0.1
Fluoranthene 0.05
Pyrene 0.05
Dibutyl phthalate 0.6
Ester CaiHa^Oa (MW 318) 2.2
Ester C2iH3«»Oa (MW 318) 0.6
Dioctyl adipate 14.3
Unknown (94 ion) 1.7
Di-C0 alkyl-phthalate 7.7
Unknown (70 ion)-possibly an ester 0.3
Long-chain alkyl esters (Caz and 3.6
greater)
Acids
Ca-alkylbenzenes (ethyl benzene/ 0.8
xylenes)
do-aliphatic 2.2
C-i i-aliphatic 5.0
Benzoyl alcohol 63.8
Benzoic acid 0.4
da-aliphatic acid 1.0
Ethyl hydrogen phthalate 1.0
Ci«,-aliphatic acid 0.9
Cia-hydroxy amide 1.1
Cie-aliphatic acid 1.9
C-is-hydroxy amide 7.8
CiB-aliphatic acid 2.7
Ct7-hydroxy amide 11.4
Methylene chloride presence due to laboratory
contamination.
Ill
-------
TABLE 63. PLANT R: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Only peak
Base/neutrals
Data not retrievable from
magnetic tapes
Acids
Data not retrievable from
magnetic tapes
Methylene chloride presence due to laboratory
contamination.
112
-------
TABLE 64. PLANT S: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Acetone Minor
Bromochloromethane Minor
Toluene Minor
C2-alkyl benzene Minor
Base/neutrals
C3-alkyl benzenes 2.2
Cu-alkyl benzenes 2.5
Cs-alkyl benzenes 1.5
Aliphatics, Ca & above 54.5
(paraffinic character)
Aliphatics, Cs & above (olefinic 32.8
character)
Butyl benzoate 1.7
Trichlorobenzenes 1.0
Dimethyl aniline 1.5
Anisidine 0.8
Naphthalene 0.6
Methyl-naphthalenes 0.3
Biphenyl 0.5
Di-Ce alkyl-phthalate 0.1
Acids
Dimethyl acetamide 0.6
Benzoic acid 3.2
Ci2~aliphatic acid 2.0
Cut-aliphatic acid 3.5
Cg & above aliphatics 78.6
Cie-aliphatic acid 5.8
Ci8-aliphatic acid 6.3
Methylene chloride .presence due to laboratory
contamination.
113
-------
TABLE 65. .PLANT T: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Acetone Minor
Bromochloromethane Minor
Tetrachloroethylene Minor
Base/neutrals
Aliphatics (Cia on up, mixed 58.9
species)
Alkyl oxygenates (e.g., ethers), 16.7
dominant 59 ion
Alkyl oxygenates (e.g., ethers), 13.4
dominant 45 ion
Unknown, isotopic mass 195, <0.1
containing Cl, N, S
CB-alkylphenol 5.5
Cg-alkylphenols 5.2
Di-Ce alkyl phthalate 0.3
Acids
Data not retrievable from
magnetic tapes
Methylene chloride presence due to laboratory
contamination.
114
-------
TABLE 66. PLANT U: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride
Bromodichloromethane
Chloroform
Toluene
up, paraffinic
Base/neutrals
Chloroaniline
Aliphatics (C-
character)
Aliphatics (Ci2~on up, olefinic
character)
C6 and C7 alkyl-phthalates
Di-C8 alkyl-phthalate
Triphenylphosphine oxide
Triphenylphosphine sulfide
Acids
Butoxy ethanol
Phenol
Ce-alkene
o-Methoxyphenol
Benzoic acid
d o-aliphatic acid
Benzothiazole
Ci2-aliphatic acid
da-aliphatic acid
Ci 6-aliphatic acid
Cie-aliphatic acid
Di-Ce alkyl-phthalate
Major
Minor
Minor
Minor
0
62
0
0
<0
3
5
36.2
<0.1
4 . 5
0.3
4.6
0.2
3.7
0.4
4.0
2.2
4.4
23.7
35.8
16.2
Methylene chloride presence due to laboratory
contamination.
115
-------
TABLE 67. PLANT V: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Toluene Minor
Base/neutrals
Aliphatics, Cie & above (primarily 98.8
paraffinic)
Methylthiobenzthiozole 0.2
Dibutyl phthalate 0.5
Di-C8 alkyl phthalate 0.2
Triphenylphosphine oxide 0.2
Triphenylphosphine sulfide 0.1
Acids
Data not retrievable from
magnetic tapes
Methylene chloride presence due to laboratory
contamination.
TABLE 68. PLANT W: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Only peak
Base/neutrals
Phenol 0.1
Benzaldehyde 0.1
3 Unknowns, dominant 100 ion 1.8
C7-»C9 alkylphenols 13.1
Dipropyl phthalate 0.5
Dibutyl phthalate 0.2
Di-Cs alkyl phthalate 0.9
Unknown ester, dominant 71 ion 1.4
Aliphatics, C-|5 & above 81.9
Acids
Data not retrievable from
magnetic tapes
Methylene chloride presence due to laboratory
contamination.
116
-------
TABLE 69. PLANT X: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Compounds
Estimated
percent
Volatiles
Methylene chloride
Acetone
Bromochloromethane
Trichloroethylene
Tetrachloroethylene
Unknown (possibly an alkyl
alcohol)
Ca-alkyl benzene
Base/neutrals
Data not retrievable from
magnetic tapes
Acids
Tetrachloroethylene
Butoxy ethanol
Gamma butyrolacetone
Diethylene glycol ether
N-methyl-2-pyrrolidine
Benzoic acid
Trichlorobenzene
Naphthalene
Cio-aliphatic
Methyl naphthalenes
Isobutyl benzoate
Caprolactam
Biphenyl
Vanillin
Phenylphenol
Cm-»Ci7-aliphatic acids
Cie~Cie-aliphatics
Di-(Ce-alkyl)-adipate
Major
Minor
Minor
Minor
Minor
Weak
Weak
0.05
0.7
1.8
2.8
1.9
2.4
0.4
0.05
0,
0,
1.0
0.8
1.7
0.4
2.0
10.9
50.1
22.5
,3
,2
Methylene chloride presence due to laboratory
contamination.
117
-------
TABLE 70. PLANT Y: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Acetone Minor
Trichloroethylene Minor
Base/neutrals
Dichlorobenzenes (2 isomers) 0.5
Toluidine 0.4
Ct*-alkylphenol 0.2
Chlorotoluidine 0.4
Dichloroaniline 0.4
Di-t-butylphenol 0.5
Aliphatics, ds-on up (paraffinic 63.0
character)
Aliphatics, C-i5-*on up (olefinic 28.1
character)
Unknown ester, Cis or Cte 3.6
Azobenzene 0.4
Phenanthrene/anthracene 0.2
Diethyl phthalate 0.4
Dibutyl phthalate 0.2
Di-Ca alkyl-phthalate 1.3
Benzanthrone 0.4
Acids
Phenol 1.2
2-Ethyl hexanoic acid 0.7
Benzoic acid 69.5
Nitrocresol or nitroanisole 7.8
Cia-*Ci8 aliphatic acids 20.8
Methylene chloride presence due to laboratory
contamination.
118
-------
TABLE 71.' PLANT Z: OTHER GC/MS ORGANIC
COMPOUNDS IN SECONDARY EFFLUENT
Estimated
Compounds percent
Volatiles
Methylene chloride Major
Trichlorofluoromethane Minor
Hexane Minor
Toluene Minor
C2~alkyl benzene Minor
Base/neutrals
Data not retrievable from magnetic
tapes
Acids
Data not retrievable from magnetic
tapes
Methylene chloride presence due to laboratory
contamination.
119
-------
REFERENCES
1. Gallup, J. D. Development Document for Effluent Limitations
Guidelines and New Source Performance Standards for the
Textile Mills Point Source Category. EPA-440/l-74-022a
(PB 238 832), U.S. Environmental Protection Agency, Washing-
ton, D.C., June 1974. 246 pp.
2. Draft Final Report: Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority Pollutants.
U.S. Environmental Protection Agency, Cincinnati, Ohio,
April 1977. 145 pp.
3. Duke, K. M., M. E. Davis, and A. J. Dennis. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment Biolog-
ical Tests for Pilot Studies. EPA-600/7-77-043 (PB 268 484),
U.S. Environmental Protection Agency, Research Triangle Park,
North Carolina, April 1977. 114 pp.
4. Rawlings, G. D. Source Assessment: Textile Plant Waste-
water Toxics Study, Phase I. EPA-600/2-78-004h, U.S. Envi-
ronmental Protection Agency, Research Triangle Park, North
Carolina, March 1978. 153 pp.
5. Eight Peak Index of Mass Spectra, Vol. Ill, Second Edition,
Table 3 (Part 1). Mass Spectrometry Data Centre, AWRE,
Aldermaston, Reading, United Kingdom, 1974. 1933 pp.
6. Standard Methods for the Examination of Water and Wastewater,
Fourteenth Edition. American Public Health Association,
Washington, D.C., 1976. 874 pp.
7. Manual of Methods for Chemical Analysis of Water and Wastes.
EPA-625/6-76-003a (PB 259 973), U.S. Environmental Protection
Agency, Cincinnati, Ohio, 1976. 317 pp.
8. McCann, J., E. Choi, E. Yamasaki, and B. N. Ames. Detection
of Carcinogens as Mutagens in the Salmonella/Microsome Test:
Assay of 300 Chemicals. Proceedings of the National Academy
of Science, 72:5135-5139, 1975.
9. Ames, B. N., J. McCann, and E. Yamasaki. Methods for Detect-
ing Carcinogens and Mutagens with the SaZmoweZZa/Mammalian-
Microsome Mutagenicity Test. Mutation Research, 31:347-364,
1975.
121
-------
10. Slater, E. E., M. D. Anderson, and H. S. Rosenkranz. Rapid
Detection of Mutagens and Carcinogens. Cancer Research,
31:970-973, 1971.
11. Wininger, M. T., F. A. Kulik, and W. D. Ross. In Vitro
Clonal Cytotoxicity Assay Using Chinese Hamster Ovary Cells
(CHO-K1) for Testing Environmental Chemicals. In Vitro,
14(4) :381, 1978.
12. Hamersma, J. W., S. L. Reynolds, and R. F. Maddalone. IERL-
RTF Procedures manual: Level 1 Environmental Assessment.
EPA-600/2-76-160a (PB 257 850) , U.S. Environmental Protec-
tion Agency, Research Triangle Park, North Carolina,
June 1976. 147 pp.
13. Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
122
-------
APPENDIX
TOXIC POLLUTANT ANALYSIS FRACTIONS
TABLE A-l. VOLATILE AND DIRECT INJECTABLE COMPOUNDS
Compound
Compound
Chloromethane
Dichlorodifluoromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Trichlorofluoromethane
1,1-Dichloroethylene
1,1-Dichloroethane
27r>ans-l,2-dichloroe thane
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
Bis(chloromethyl) ether
1,2-Dichloropropane
Trans-1,3-dichloropropene
Trichloroethylene
Dibromochloromethane
Cis-l,3-dichloropropene
1,1,2-Trichloroethane
Benzene
2-Chloroethyl vinyl ether
Bromoform
1,1,2,2-Tetrachloroethylene
1,1,2,2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Acrolein
Acrylonitrile
123
-------
TABLE A-2. BASE NEUTRAL EXTRACTABLE COMPOUNDS
Compound
Compound
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachloroethane
1,2-Dichlorobenzene
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
1,2,4-Trichlorobenzene
Naphthalene
Bis(2-chloroethyl) ether
Hexachlorocyclopentadiene
Nitrobenzene
Bis(2-chloroethoxy) methane
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Isophorone
Fluorene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
2,4-Dinitrotoluene
N-nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene
Anthracene
Diethyl phthalate
Dimethyl phthalate
Fluoranthene
Pyrene
Di-n-butyl phthalate
Benzidine
Butyl benzyl phthalate
Chrysene
Bis(2-ethylhexyl) phthalate
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
N-nitrosodimethylamine
N-nitroso-di-n-propylamine
4-Chlorophenyl phenyl ether
3,3"-Dichlorobenzidine
2,3,7,8-Tetrachlorodibenzo-
p-dioxina
Bis(chloromethyl) ether
This compound was specifically listed in the consent decree.
Because of TCDD's extreme toxicity, EPA recommends that labora-
tories not acquire analytical standards for this compound.
TABLE A-3.
ACID EXTRACTABLE
COMPOUNDS
2-Chlorophenol
Phenol
2,4-Dichlorophenol
2-Nitrophenol
p-Chloro-m-cresol
2,4,6-Trichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
4-Nitrophenol
Pentachlorophenol
124
-------
TABLE A-4. PESTICIDES AND PCB's
Compound
3-Endosulfan
a-BHC
Y-BHC
0-BHC
Aldrin
Heptachlor
Heptachlor epoxide
a-Endosulfan
Dieldrin
4,4'-DDE
4,4'-ODD
4,4'-DDT
Endrin
Endosulfan sulfate
6-BHC
Chlordane
Toxaphene
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
TABLE A-5. METALS AND OTHER COMPOUNDS
Metals,
total Others
Antimony Asbestos
Arsenic Cyanide
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
125
-------
GLOSSARY
acute toxicity: Toxic effects to an organism due to a short-
term exposure.
Ames test: Microbial mutagenicity bioassay developed by
Dr. Bruce N. Ames.
cytotoxicity: Toxicity to mammalian cells.
ECso: Effective concentration at which 50% of the test organisms
reach the desired effect. The "effect," for example, can be
growth inhibition or stimulation.
in vitroi Describing a biological reaction which can be per-
formed outside the living organism, such as in a test tube.
LCgo: Lethal concentration fifty - calculated concentration of
substance which is expected to cause death in 50% of the
test organism population, as determined from their exposure
to the substance.
secondary effluent: Textile wastewater treated by areated
lagoons and clarified.
steady state: A condition of operation of a technology in which
operating parameters are constant with respect to time.
tertiary effluent: Textile wastewater treated by technologies
following aeration and clarification.
toxic pollutants: The 129 specific chemical species identified
by EPA as a result of the consent decree.
toxicity: detrimental effects to the life of the test species
such as fathead minnows, Daphnia, aglae, and cell cultures
or an increase in the number of bacteria colonies in the
Ames test (since the Ames test is a back-mutation test) as
a result of exposure to the effluent sample.
126
-------
CONVERSION FACTORS AND METRIC PREFIXES (13)
To convert from
Grams/meter (g/m3)
Kilogram (kg)
Meter3 (m3)
Meter3 (m3)
CONVERSION FACTORS
to
Milligrams/liter
Pound-mass (avoirdupois)
Gallon (U.S. liquid)
Liter
Multiply by
1.0
2.205
2.642 x 102
1.0 x 103
METRIC PREFIXES
Prefix Symbol Multiplication factor
Example
Kilo k
Milli m
Micro y
103
io-3
5-kg = 5 x 103 grams
5 mg = 5 x 10~3 gram
5 yg = 5 x 10~3 gram
(13) Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76 , IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
127
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-79-019J
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Source Assessment: Textile Plant Wastewater
Toxics Study, Phase n
5. REPORT DATE
December 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J. R. Klieve and G. D. Rawlings
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-884
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM-071
11. CONTRACT/GRANT NO.
68-02-1874, Task 33
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 8/77-5/79
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL-RTP project officer is Max Samfield, Mail Drop 62, 919/
541-2547. The Phase I report was EPA-600/2-78-004h.
16. ABSTRACT
report gives results of Si study concerned with BATEA for the textile
manufacturing industry. The level of removal of specific toxic pollutants and toxicity
(measured by results of bioassays) attained by selected tertiary systems treating
secondary effluents from textile plants was examined. Tertiary treatment systems
(unit processes arranged in various ways) were ranked according to their apparent
capabilities for removing specific toxic pollutants and toxicity. Unit processes used
included flocculation/sedimentation, multimedia filtration with and without precoag-
ulation, granular activated carbon adsorption, and ozonation. The assessment of the
treatment systems was based on specific toxic pollutant analysis data and on bioas-
say data gathered at eight textile plant locations where the treatment systems were
tested. Samples from secondary and tertiary effluent streams were analyzed for spe-
cific toxic pollutants. Based on apparent specific toxic pollutant removal and toxicity
removal, multimedia filtration-activated carbon was the best system. Tertiary
treatment systems whose effluents contained a high level of residual coagulant
appeared to be more detrimental to water quality, based on bioassays , than systems
not using coagulants.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Pollution
Assessments
Textile Industry
Waste Water
Toxicity
Bioassay
Pollution Control
Stationary Sources
13B
14B
HE
06T
06A
18. DISTRIBUTION STATEMENT
Re lease, to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
141
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
128
------- |