United States Industrial Environmental Research EPA-600/2-80-043
Environmental Protection Laboratory February 1980
Agency Research Triangle Park NC 27711
Research and Development
Treatment Technology for
Pesticide Manufacturing
Effluents: Atrazine, Maneb,
MSMA, and Oryzalin
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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. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-80-043
February 1980
Treatment Technology for
Pesticide Manufacturing
Effluents: Atrazine, Maneb,
MSMA, and Oryzalin
by
L.W. Little, R.A. Zweidinger,
E.C. Monnig, and W.J. Firth
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2612
Program Element No. 1BB610
EPA Project Officer: David K. Oestreich
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
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ABSTRACT
Laboratory and pilot studies were conducted of treatability of waste-
waters generated from manufacture of the pesticide maneb, oryzalin, atra-
zine, and MSMA. Wastewaters were characterized for pesticide content,
routine wastewater parameters, and toxicity to fish, algae, and activated
sludge organisms. Biological treatability was evaluated in terms of ability
of pilot activated sludge systems (1) to successfully operate on a mixture
of municipal wastewater and pesticide wastewater and (2) to remove the
pesticide and other toxic materials. Ability of activated carbon to treat
the wastewaters was determined in adsorption isotherm tests and in granular
activated carbon column tests.
Results of studies showed that atrazine, oryzalin and maneb wastes
could be treated successfully with activated carbon, though treatment in
this fashion had high cost potential. Oryzalin waste disrupted biological
treatment. Atrazine and MSMA waste did not disrupt biological treatment but
pesticide concentration was not reduced by biological treatment. Maneb
concentrations were reduced by biological treatment but additional work is
needed to determine the fate of breakdown products from the biological
treatment of maneb wastewaters.
This report was submitted in fulfillment of Contract No. 68-02-2612,
Tasks 7 and 8, by the Research Triangle Institute under the sponsorship
of the United States Environmental Protection Agency. The project was
conducted from March 11, 1977 to September 30, 1978.
ill
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CONTENTS
Page
Abstract iii
Contents iv
Figures ix
Tables xiv
Conversion Factors xx
List of Abbreviations xxi
Section 1 - Introduction 1
Section 2 - Conclusions and Recommendations A
Task 1 - Carbon Treatment 4
Task 2 - Biological Treatment 6
Section 3 - Experimental Design, Materials, and Methods .... 8
Introduction 8
Sampling and Collection 9
Analytical Procedures 10
Routine Wastewater Characterization 10
Pesticide Analyses 12
Treatability Tests 13
Activated Carbon Tests 13
Activated Sludge Tests 14
Ecological Assessment Tests 15
Test of Effects of Pesticide Wastewaters on Domestic
Sewage and Activated Sludge Organisms 16
Section 4 - Atrazine Wastewater Treatability Studies 18
General Background Information .... 18
Pesticide 18
Structure 18
Chemical Category 18
iv
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CONTENTS (Cont'd)
Page
Properties 18
Intended Use 19
Mode of Action 19
Manufacturing Information 19
Health and Ecological Effects 20
Manufacturing Process 22
Current Waste Disposal Practice 23
Characterization of Wastewater from Atrazine Manufacture . 24
Activated Carbon Treatability Studies 29
Adsorption Isotherm Studies 29
GAC Column Studies 34
Biological Treatability Studies 37
Section 5 - Oryzalin Wastewater Treatability Studies 46
General Background Information 46
Pesticide 46
Structure 46
Chemical Category 46
Properties 46
Intended Use 47
Mode of Action 47
Manufacturing Information . . . 47
Manufacturing Process 47
Health and Ecological Effects 49
Characterization of Wastewaters from Oryzalin
Production 50
Activated Carbon Studies 53
Adsorption Isotherm Studies 53
Granular Activated Carbon Treatment of Oryzalin
Wastewater 53
Biological Treatability Studies of Oryzalin
Manufacturing Wastewater 64
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CONTENTS (Cont'd)
Page
Effect of Aeration on Oryzalin Wastewater 69
Effect of Ultraviolet Irradiation on Effluent from
Oryzalin- Manufacture 71
Section 6 - MSMA Wastewater Treatability Studies 73
General Background Information . 73
Pesticide 73
Structure 73
Chemical Category 73
Properties 73
Intended Use 73
Mode of Action 73
Manufacturing Information 74
Health and Ecological Effects 74
Manufacturing Process 75
Current Waste Disposal Practice 76
Characterization of MSMA Wastewater 76
Activated Carbon Treatability Studies 78
Biological Treatability Studies 81
Section 7 - Maneb Wastewater Treatability Studies 87
General Background Information 87
Pesticide 87
Structure 87
Chemical Category 87
Properties 87
Intended Use 89
Mode of Action 89
Manufacturing Information 89
Manufacturing Process . 89
Health and Ecological Effects: Maneb 91
Health and Ecological Effects: ETU 91
Potential Biodegradation Products 92
Current Waste Disposal Practice 92
vi
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CONTENTS (Cont'd)
Page
Characterization of Maneb Wastewaters 93
Activated Carbon Treatability Studies 97
Adsorption Isotherm Studies 97
GAC Column Studies 102
Effect of GAC Column Treatment on Toxicity to Fish and
Algae 110
Biological Treability Studies 112
Effect of Biological Treatment on Pesticide Removal 112
Section 8 - Literature Review and Discussion 121
General Characteristics of Pesticide Manufacturing
Wastewaters 121
Activated Carbon Treatment of Pesticides, Pesticide-
Contaminated Water, and Pesticide Manufacturing
Wastewater 126
Other Physical and Chemical Treatment Methods . 136
Biological Treatability 138
Biodegradability of Pesticides 138
Treatment of Pesticide Manufacturing Wastewaters . . 142
Section 9 - References and General Bibliography 149
APPENDIX A: Analytical Procedures for Routine Wastewater
Characterization 167
APPENDIX B: Analytical Procedure for Arsenic 169
APPENDIX C: Analytical Procedure for Determination of
Atrazine 171
APPENDIX D: Analytical Procedures for Determination of
Oryzalin 173
APPENDIX E: Analytical Procedure for Determination of MSMA . . 174
APPENDIX F: Analytical Procedures for Maneb and its
Breakdown Products 182
APPENDIX G: Procedure for Conducting Activated Carbon
Treatability Tests 187
vii
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CONTENTS (Cont'd)
APPENDIX H: Procedures for Conducting Activated Sludge
Treatability Tests 189
APPENDIX I: Procedures for Algal Assay Tests 191
APPENDIX J: Procedure for Fish Bioassay Tests 193
APPENDIX K: Fish and Algal Bioassay Data—Atrazine
Wastewater Studies 195
APPENDIX L: Fish and Algal Bioassay Data--0ryzalin
Wastewater Studies 204
APPENDIX M: Fish and Algal Bioassay Data—MSMA Wastewater
Studies 214
APPENDIX N: Fish and Algal Bioassay Data—Maneb Wastewater
Studies 223
APPENDIX 0: Tests of Effects of Pesticide Wastewaters on
Domestic Sewage Organisms: Spot Tests 246
APPENDIX P: Oxygen Uptake Studies With Pesticide
Wastewaters 249
viii
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FIGURES
Number Page
1 Schematic diagram of treatment of atrazine manufacturing
wastewater 25
2 Adsorption isotherm of atrazine manufacturing
wastewater 33
3 Carbon column treatment of atrazine wastewater -
2nd trial 35
A GAC column treatment of atrazine wastewater -
3rd trial 38
5 Influent and effluent COD of control activated sludge
units 40
6 Influent and effluent COD of activated sludge units
fed 8.3% atrazine 41
7 Influent and effluent COD of activated sludge units
fed 16.7% atrazine 42
8 Possible synthesis of oryzalin from chlorobenzene .... 48
9 Adsorption isotherm of oryzalin production wastewater . . 56
10 Absorbance of effluent from GAC column treating
oryzalin production wastewater, pH 6; breakthrough
of color at progressively larger cumulative bed
volumes is indicated 61
11 Absorbance of effluent from GAC column treating
oryzalin production wastewater, pH 9; breakthrough
of color at progressively larger cumulative bed
volumes is indicated 62
12 GAC column treatment of oryzalin manufacturing
wastewater, pH 9 and pH 6 63
13 Influent and effluent COD for activated sludge units
fed 1% oryzalin 66
ix
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FIGURES (Cont'd)
Number Page
14 Influent and effluent COD for control activated
sludge units fed primary settled wastewater
alone 67
15 Production and waste schematic for MSMA 76
16 Carbon column treatment of MSMA 80
17 Influent and effluent COD for activated sludge units
fed primary settled wastewater with 10% MSMA 86
18 Influent and effluent COD for control activated
sludge units fed primary settled wastewater
alone 86
19 Liquid adsorption isotherms for Plant B
manufacturing wastewaters 100
20 Thin-layer chromatogram of Plant B wastewater
and filtrates of carbon isotherm determination.
(a) 10 jJl untreated wastewater; (b) 50 \il treated
with 0.04 g carbon/100 ml wastewater; (c) 50 |Jl
wastewater treated with 0.08 g carbon/100 ml.
Absorbance sensitivity is twice that of a and b 103
21 Thin-layer chromatogram of carbon isotherm
filtrates. (a) 10 min iodine exposure; (b)
30 min iodine exposure. Plant B wastewater 104
22 Thin-layer scans of ETU in Plant B wastewater
and carbon treated filtrate: (a) 10 pi untreated
wastewater; (b) 50 pi wastewater treated with
2.0 g carbon/100 ml; (c) 50 \il wastewater treated
with 0.16 g carbon/100 ml; (d) 4.15 Mg ETU
standard 105
23 Thin-layer chromatogram of untreated and
GAC treated wastewater from Plant B 108
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FIGURES (Cont'd)
Number Page
24 Thin-layer chromatogram of ETU and extracts of carbon
column effluent in the treatment of maneb wastewater.
(a) 50 pi Fraction III (23-33 column volumes), (b) 50
pi of Fraction IV (34-44 column volumes). (c) 50 pi
Fraction V (45-55 column volumes), (d) 50 pi Fraction
VI (56-66 column volumes). (e) 10 pi wastewater
filtrate, untreated, (f) 0.41 pg ETU 109
25 Effectiveness of GAC column treatment for ETU
removal from Plant B wastewater Ill
26 Influent and effluent COD for activated sludge units;
(a) control units; (b) units fed Plant A wastewater;
(c) units fed Plant B wastewater 118
E-l Ion chromatogram of standard anion mixture 177
E-2 Ion chromatogram of MSMA wastewater 178
E-3 Ion chromatogram of MSMA wastewater diluted
with sewage 179
E-4 Ion chromatogram of MSMA wastewater in sewage -
after chloride removal 180
E-5 Ion chromatogram of effluent from activated
sludge treatment of MSMA wastewater 181
F-l Thin-layer chromatogram of the extract of
commercial formulated maneb and ETU 186
F-2 Thin-layer chromatogram of the extracts of
Plant A (right) and Plant B (left) wastewaters 186
H-l Diagram of activated sludge pilot units 190
K-l Algal assay of atrazine wastewater (as received) 196
K-2 96 hr LC^ determination: atrazine manufacturing
wastewater (as received) 197
K-3 96 hr LCL determination: atrazine manufacturing
wastewater, filtered, Whatman 2V filter 198
K-4 Algal assay of influent and effluent to activated
sludge units fed with atrazine wastewater (16.7%)
(Data shown in Table 11-4) 199
xi
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FIGURES (Cont'd)
Number Page
L-l 96 hr jLCeQ determination: oryzalin manufacturing
wastewater 206
L-2 Algal assay of oryzalin wastewater 207
L-3 96 hr LC._ determination: GAC treated oryzalin
wastewater 210
L-4 96 hr LC determination: untreated domestic
wastewater with 1% oryzalin manufacturing
wastewater 211
L-5 96 hr LCLn determination: effluent from activated
sludge unit I fed domestic wastewater with 1%
oryzalin manufacturing wastewater 212
L-6 96 hr LC,-0 determination: effluent from activated
sludge unit II fed domestic wastewater with 1%
oryzalin manufacturing wastewater 212
M-l Algal assay (rangefinding) of MSMA wastewater
(Data shown in Table 13-1) 220
M-2 Algal assay (narrow range) of MSMA wastewater
(Data shown in Table 13-2) 221
M-3 Algal assay of GAC column-treated MSMA wastewater
(Data shown in Table 13-5) 222
N-l 96 hr LCc0 determination: maneb manufacturing
wastewater, Plant A, unfiltered. (Data shown in
Table 14-4) 226
N-2 96 hr LC determination: maneb manufacturing
wastewater, Plant A, filtered (What 2V). (Data
shown in Table 14-4) 226
N-3 Algal assay of Plant A wastewaters. (Data shown
in Table 14-6) 228
N-4 Algal assay of Plant B wastewater. (Data shown
in Table 14-8) 230
N-5 Algal assay of Plant B wastewater. (Data shown
in Table 14-9) 232
xii
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FIGURES (Cont'd)
Number Page
N-6 Algal assay of Plant A wastewater, GAC treated,
(Data shown in Table 14-11) 235
N-7 Algal assay of Plant B wastewater, GAC treated,
(Data shown in Table 14-12) 237
N-8 Algal assay of Plant B wastewater, GAC treated,
(Data shown in Table 14-13) 239
N-9 Algal assay of influent and effluent of activated
sludge units fed with Plant A maneb manufacturing
wastewater (10%). (Data shown in Table 14-15) 242
N-10 Algal assay of influent and effluent of activated
sludge units fed with Plant B maneb. (Data shown
in Table 14-10) 244
0-1 Spot tests showing toxicity of oryzalin wastewater
and washwater to domestic sewage flora 248
P-l Oxygen uptake studies with MSMA wastewater 251
P-2 Oxygen uptake studies of atrazine wastewater 252
i»
P-3 Oxygen uptake study of oryzalin wastewater 253
P-4 Oxygen uptake study with maneb wastewater -
Plant A 254
P-5 Oxygen uptake study with maneb wastewater -
Plant B 255
xiii
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TABLES
Number Page
1 Characterization of Atrazine Wastewater 27
2 Atrazine Content of Liquid and Solids Portions of
Atrazine Manufacturing Wastewater 27
3 Toxicity to Fish of Solid and Liquid Phase of
Atrazine Manufacturing Wastewater 28
4 Liquid Adsorption Isotherm Data for Atrazine
Wastewater , . . . 30
5 GAC Column Studies, Atrazine Wastewater (Column
15.2 cm x 2.2 cm i.d.) 36
6 GAC Column Test: Atrazine Wastewater (Column
15.0 cm x 2.2 cm i.d.) 36
7 Effect of Activated Sludge Treatment of Atrazine
Wastewater (Run I) 39
8 Effect of Activated Sludge Treatment of Atrazine
Wastewater (Run II) 39
9 Performance and Operating Characteristics of Bench
Scale Activated Sludge Units, Atrazine Wastewater
Series 43
10 Analysis of Contribution of COD of Atrazine
Manufacturing Wastewater to COD of Influents and
Effluents of Activated Sludge Units 44
11 Characterization of Oryzalin Wastewaters 51
12 Liquid Adsorption Isotherm Data for Oryzalin
Wastewater--Screening Studies . 54
13 Liquid Adsorption Isotherm Data for Oryzalin
Wastewater !>5
xiv
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TABLES (Cont'd)
Number
14 Liquid Adsorption Isotherm Data for Oryzalin
Washwater—Screening Studies 57
15 Liquid Adsorption Isotherm Data for Oryzalin
Washwater 58
16 Effect of GAC Treatment on Oryzalin Wastewater
at pH 6 and pH 9 60
17 Effect of GAC Treatment on Oryzalin Wastewater 60
18 Performance Characteristics of Bench Scale
Activated Sludge Units - Oryzalin Wastewater
Series 65
19 Operating Characteristics of Bench Scale
Activated Sludge Units - Oryzalin Wastewater
Series 68
20 Screening Tests: Effect of Ammonia Stripping on
Toxicity of Oryzalin Wastewater to Fish 70
21 Effect of Ultraviolet Irradiation on Oryzalin
Wastewater ' 72
22 Characterization of MSMA Wastewater 77
23 Effectiveness of GAC Treatment for Removal of MSMA
from Manufacturing Wastewater 79
24 Determination of Effectiveness of Activated Sludge
Treatment of MSMA Wastewater 82
25 Operating Characteristics of Bench Scale Activated
Sludge Units - MSMA Wastewater Series 84
26 Performance Characteristics of Bench Scale
Activated Sludge Units, MSMA Wastewater Series 85
27 Characterization of Maneb Wastewaters 94
28 Study of Variation in Maneb Manufacturing
Wastewaters 95
29 Liquid Adsorption Isotherms for Two Maneb
Manufacturing Wastewaters 98
xv
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TABLES (Cont'd)
Number
30 Liquid Adsorption Isotherm for Plant B
Manufacturing Wastewater 99
31 Adsorption Isotherm Studies of Ability of Activated
Carbon to Remove ETU from Plant A Wastewaters 101
32 Effect of GAC Column Treatment on Plant A
Wastewater 106
33 Effectiveness of GAC Treatment of Plant B
Wastewater-Run I (1.2 m column) 106
34 Effectiveness of GAC Treatment of Plant B
Wastewater-Run II (15 cm column) 107
35 Effectiveness of Filtration and GAC Treatment
Reducing COD of Plant B Wastewater 107
36 Maneb and ETU Concentrations in Influents and
Effluents from Activated Sludge Units 113
37 Performance Characteristics of Bench-Scale
Activated Sludge Units, Maneb Wastewater Series -
Ability of Units to Remove COD 115
38 Performance Characteristics of Bench-Scale Activated
Sludge Units, Maneb Wastewater Series—Suspended
Solids Levels in Effluents 116
39 Operating Characteristics of Bench-Scale
Activated Sludge Units (Maneb Wastewater Series) .... 117
40 Generalized Scheme of Production and Wastes Generation—
Halogenated Organic Pesticides (from Hackman
1978) 123
41 Generalized Scheme of Production and Wastes
Generation—Phosphorus-Containing Pesticides (from
Hackman, 1978) 124
42 Generalized Scheme of Production and Wastes
Generations--0rganonitrogen Pesticides (from
Hackman, 1978) 125
xvi
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TABLES (Cont'd)
Number Page
43 Feasibility of Soil Disposal for 45 Pesticides
(from Sanborn et aj.. , 1977) 140
B-l Calibration and Instrumental Data for Atomic
Absorption Determination of Arsenic 170
K-l Effect of Atrazine Wastewater (as received) on
Algal Growth 200
K-2 Screening Tests on Toxicity to Fish of Untreated
and GAG Treated Atrazine Wastewater 201
K-3 Effect of Activated Sludge Treatment on Toxicity
of Atrazine Wastewater to Fish 202
K-4 Algal Assay of Influent and Effluent to Activated
Sludge Units fed with Atrazine Manufacturing
Wastewater (16.7%) 203
L-l Toxicity of Oryzalin and Oryzalin Wastewaters to
Fish—Screening Test 205
L-2 Toxicity to Fish of Oryzalin Manufacturing
wastewater 206
L-3 Effect of Oryzalin Washwater on Algal Growth,
Expressed as Percentage of Algal Growth in
Control 208
L-4 Effects of Oryzalin Wastewater after Carbon
Treatment on Algal Growth Expressed as Percentage
of Algal Growth in Control 209
L-5 Fish Bioassay of GAC Treated Oryzalin Wastewater .... 210
L-6 Algal Assay of Influent and Effluent to Activated
Sludge Units Fed with Oryzalin Manufacturing
Wastewater (1%) 213
M-l Effects of MSMA Wastewater on Algal Growth (Range-
finding) , Expressed as Percentage of Algal Growth
in Control 215
xvii
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TABLES (Cont'd)
Number Page
M-2 Effect of MSMA Wastewater on Algal Growth (Narrow
Range), Expressed as Percentage of Algal Growth in
Control 216
M-3 Toxicity of MSMA Wastewater to Fish—Screening Tests . . 217
M-4 Effect of Aeration on Toxicity to Fish of MSMA
Wastewater—Screening Tests ... 217
M-5 Effect of MSMA Wastewater after Carbon Treatment on
Algal Growth, Expressed as Percentage of Algal
Growth in Control 218
M-6 Algal Assay of Influent and Effluent of Activated
Sludge Units Fed with MSMA Manufacturing
Wastewater (10%) 219
N-l Screening Tests of Toxicity to Fish of
Commercial Maneb Preparation 224
N-2 Screening Tests for Toxicity of Maneb
Wastewaters to Fish 224
N-3 Screening Tests of Toxicity of Plant B
Wastewaters to Fish 225
N-4 Determination of LC Q for Fish of Maneb
Manufacturing Wastewater (Plant A) 227
N-5 Determination of LC for Fish of Maneb
Manufacturing Wastewater (Plant B) 227
N-6 Effects of Filtered Plant A Wastewater on Algal
Growth (Rangefinding) Expressed as Percentage
of Algal Growth in Control 229
N-7 Effect of Filtered Plant B Wastewater Sample 1
on Algal Growth (Rangefinding) Expressed as
Percentage of Algal Growth in Control 231
N-8 Effect on Filtered Plant B Wastewater Sample 2
on Algal Growth (Rangefinding) Expressed as
Percentage of Algal Growth in Control 231
xviii
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TABLES (Cont'd)
Number Page
N-9 Effects of Filtered Plant B Wastewater Sample 2
on Algal Growth (Narrow Range) Expressed as
Percentage of Algal Growth in Control 233
N-10 Effect of Activated Carbon Treatment on Toxicity
of Maneb Wastewaters to Fish 234
N-ll Effect of Plant B Wastewater after Carbon
Treatment on Algal Growth Expressed as Percentage
of Algal Growth in Control 236
N-12 Effects of Plant B Wastewater after Carbon
Treatment on Algal Growth (Rangefinding) Expressed
as Percentage of Algal Growth in Control 238
N-13 Effect of Plant B Wastewater after Carbon Treatment
on Algal Growth Expressed as Percentage of
Algal Growth in Control 240
N-14 Effect of Activated Sludge Treatment on Toxicity
of Maneb Wastewaters to Fish 241
N-15 Algal Assay of Influent and Effluent of Activated
Sludge Units Fed with Plant A Maneb Manufacturing
Wastewater (10%) 243
N-16 Algal Assay of Influent and Effluent of Activated
Sludge Units Fed with Plant B Maneb Manufacturing
(10%) 245
0-1 Effects of Pesticide Wastewater in Spot Tests 247
xix
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CONVERSION FACTORS
To Convert from to Multiply by
Foot (ft2) Meter2 0.0929
Gallons per day (gpd) Liter per day 3.79
Gallons per minute per Liter per minute per 40.796
**l *\ A.
22 2
foot (gpm/ft ) meter
Pound/1000 gallon Gram per liter 0.115
(lb/1000 gal)
Million gallons per day Liter per day 3.79 x 10
(mgd)
xx
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LIST OF ABBREVIATIONS
AS
BOD
CA
COD
DO
DSMA
ETD
ETM
ETU
GAC
GC/ECD
GC/MS
i.d.
LC50
^O
LDL
MAA
MM
MLSS
MSMA
ODFS
ppb
ppm
Activated sludge.
Biochemical oxygen demand.
Cacodylic acid.
Chemical oxygen demand.
Dissolved oxygen.
Disodium methanearsonate.
Ethylene dithiocarbamate disulfide.
Ethylene thiuram monosulfide.
Ethylene thiourea.
Granular activated carbon.
Gas chromatography/electron capture detection.
Gas chromatography/mass spectrometry.
Gallons per day.
% Inhibition of growth of treated algae, compared to control
at 14 days.
Inside diameter.
Lethal concentration 50% kill.
Lethal dose 50% kill.
Lowest published lethal dose.
Methanearsonic acid.
Micro-molar.
Mixed liquor suspended solids.
Monosodium methanearsonate.
Optical density full scale.
Parts per billion (by weight).
Parts per million (by weight).
xxi
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LIST OF ABBREVIATIONS (Cont'd)
SS - Suspended solids.
TDS - Total dissolved solids.
TKN - Total Kjeldahl nitrogen.
TLC - Thin layer chromatography.
TOC - Total organic carbon.
TP - Total phosphorus.
TS - Total solids.
UV-VIS - Ultraviolet-visible.
v/v - Volume per volume.
X/M - Weight of pesticide adsorbed per weight of carbon.
xxii
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SECTION 1
INTRODUCTION
In March 1977, Research Triangle Institute (RTI) was requested by the
Industrial Environmental Research Laboratory, Research Triangle Park (IERL-
RTP) of the U. S. Environmental Protection Agency (EPA) to conduct laboratory
and pilot studies of the treatability of pesticides manufacturing wastewaters.
Specifically, the project was addressed to two tasks:
(1) Characterization of pretreatment technology needs.
(2) Development of dynamic carbon sorption data.
The objective of the first task was to develop performance data and
design data for biological treatment of actual pesticides manufacturing
wastewaters to assist EPA in setting realistic standards for effluents from
pesticides manufacture. The manufacturing wastewaters were characterized
for their pesticide content and for routine wastewater parameters, including
toxicity to fish, algae, and activated sludge. They were then subjected to
bench-scale continuous activated sludge (AS) treatment. Biological treat-
ability of wastewaters was evaluated in terms of the ability of AS systems
to (1) successfully operate on a mixture of municipal wastewaters and pesti-
cide wastewaters and (2) remove the pesticide and other toxic materials in
the wastewaters.
The objective of the second task was to develop dynamic carbon sorption
data for actual pesticide manufacturing wastewaters. Ability of activated
carbon to treat the wastewaters was determined in adsorption isotherm tests
and in granular activated carbon (GAC) column tests. Performance was measured
by (1) analysis of pesticide and related compounds before and after treatment
and (2) bioscreening of the influent and effluent.
-------
Pesticide analyses were conducted using procedures appropriate for the
specific pesticides. These procedures included gas chromatography/mass
spectrometry (GC/MS), fluorescence, scanning densitometry, thin layer
chromatography, ion chromatography, ultraviolet and visible spectrophoto-
metry, and gas chromatography/electron capture (GC/EC).
Additional objectives in both tasks included compilation of relevant
data on the chemistry, health and ecological effects, environmental fate,
biological treatability, and physical-chemical treatability of pesticides,
particularly those investigated in this project.
In all these studies, requests were made for samples typical of the
effluent from a single manufacturing process, i.e., from production of a
single pesticide. This sampling approach was chosen to increase the
interpretability of data, to aid in isolation of factors which could
contribute to problems in treating combined plant effluent, and to facili-
tate general application of the findings to all plants producing the
particular pesticide. The studies were in no way intended to be site-
specific, i.e., directed toward characterization and treatment of the
combined plant effluent, generally representing wastewaters from a variety
of pesticide and non-pesticide manufacturing processes, from a single manu-
facturer.
Wastewaters for the study were selected after consultation with the
project officer and representatives of the National Agricultural Chemicals
Association. Factors influencing selection were (1) potential for con-
tinued use of pesticide, i_.£., those pesticides highly likely to be banned
were not considered; (2) production of a significant liquid waste stream;
(3) large annual production and widespread use; (4) chemical class, i_.e.,
representatives of several types of chemical structures were selected; (5)
availability of the wastewater, i-e., interest of the manufacturers in
cooperating with the study.
Pesticide wastewaters were obtained from the manufacture of atrazine,
oryzalin, maneb, and MSMA. Atrazine, a herbicide, is ranked Number 1 in
terms of production in the triazine category as well as among herbicides in
3
general. The estimated 1974 production was 49.4 x 10 metric tons (Archer
-------
et al., 1978). MSMA is ranked Number 1 in the organoarsenical and organo-
3
metallic category with an estimated 1974 production of 15.9 x 10 metric
tons (Archer et al., 1978). The Number 1 thiocarbamate pesticide is maneb,
3
a fungicide, with 1974 estimated production of 5.4 x 10 metric tons (Archer
et al., 1978). Manzate is a combination of manganese and zinc forms of
maneb/zineb. Oryzalin is a typical member of an important class of herbi-
cides, the nitrated aromatics.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
TASK I - CARBON TREATMENT
1. Wastewater from manufacture of oryzalin can be treated by granular
activated carbon. However, because of the high concentration of
oryzalin and closely related compounds there is a large carbon
requirement. In addition, the high concentration of ammonia (and
possibly other non-colored components) is not sufficiently reduced
to eliminate toxicity to fish. The ammonia also stimulates algal
growth. Comparative studies with unformulated oryzalin suggest
that the ammonia content, rather than the oryzalin content, is
primarily responsible for fish toxicity. Ammonia could be re-
moved by other processes, for example, air stripping at high pH.
In practice, ammonia could be removed before or after carbon
treatment for removal of the oryzalin and other colored compounds;
or if sufficiently diluted with other wastewaters, could be
biologically nitrified.
2. Currently recommended procedures for determining MSMA are based
on arsenic measurement and do not distinguish between MSMA and
its degradation products. Determination of MSMA itself can be
performed by ion chromatography. MSMA is not appreciably removed
from MSMA manufacturing wastewater by activated carbon treatment.
The wastewater also contains substantial amounts of oxygen-
demanding materials (including methanol) which are not signifi-
cantly removed by activated carbon treatment.
3. Wastewaters from manufacture of atrazine and maneb contain large
amounts of particulate pesticide. The liquid portion, therefore,
is essentially a saturated solution. Economical carbon treatment
-------
of these wastewaters, especially the atrazine wastewater, will
require pretreatment for removal of these solids. Otherwise, the
column will become clogged and the solid will also serve to
saturate liquid passing through the column.
(A) Atrazine particulates are approximately 5-500 (Jm in diameter.
After pretreatment by filtration, atrazine wastewaters are
readily treated by activated carbon.
(5) In maneb manufacturing wastewaters the actual concentration of
maneb is low, since the majority quickly degrades to the more
stable compounds ethylene thiuram monosulfide (ETM) and ethylene
thiourea (ETU). ETU has been implicated in causing adverse
health effects in several species of animals. Maneb, ETM, ETU,
and other maneb intermediates can be effectively removed by GAC
treatment. An important finding was that breakthrough of ETU
occurs well in advance of breakthrough of the other compounds.
Therefore, in practice, monitoring of GAC performance should be
directed toward ETU. Relatively quick and simple thin layer
chromatography techniques could be adapted for routine ETU deter-
minations .
(6) On the basis of its performance in adsorption isotherm studies,
Calgon Filtrasorb 400 was employed for all pesticides in GAC
column tests. Since virgin carbon was used, it cannot be assumed
that this carbon would be best in long-term performance. Losses
caused in regeneration may vary from carbon to carbon.
(7) While wastewaters from manufacture of atrazine, maneb, and
oryzalin are all treatable by GAC, the large carbon requirements
indicate that the cost of such treatment may be unattractive.
Therefore, other methods of treatment should be investigated. In
the meantime, it is reassuring to find that this widely used and
accepted treatment method is effective.
-------
TASK 2 - BIOLOGICAL TREATMENT
(1) Wastewater from oryzalin manufacture could not be treated biologi-
cally in 1:10 or 1:100 dilution in municipal sewage. The activated
sludge units progressively lost sludge solids, and the color of
the wastewater was not significantly reduced. It was noted,
however, that some COD reductions were achieved. Additional
testing indicated this to be due to simple aeration. Evidently
some organic constituent of the wastewater is removed by air
stripping. This component should be identified and the feasi-
bility of treating (or pretreating before biological or GAC
treatment) the oryzalin wastewater by this method should be
investigated in further studies.
(2) In 1:10 dilution with municipal sewage, wastewater from atrazine
manufacture did not interfere with operation of AS units under the
conditions tested. On the other hand, atrazine was not signifi-
cantly removed in the process. Part of the problem appeared to be
due to transport of the fine atrazine particulates through the
system, resulting in saturated liquid phases (~33 mg/1). GAC
treatment was more effective in treating this wastewater.
(3) Activated sludge treatment of MSMA wastewater failed to satis-
factorily remove either the pesticide or the arsenic from the
wastewater. Some arsenic also tended to accumulate in the sludge,
possibly portending failure of the AS system during longer runs
(as would be encountered in actual practice). The methanol compo-
nent is readily removed in AS treatment. It is suggested that
other treatment processes, possibly coagulation/precipitation, be
investigated for removal of arsenic prior to biological treatment.
(4) Effluents from AS units treating maneb wastewaters (1:10 in
municipal sewage) contained substantial amounts of ETU, as well as
oxygen-demanding materials. Therefore, under the conditions
tested, biological treatment did not appear to be suitable for
treating these wastewaters, whereas GAC treatment readily removed
-------
ETU and other maneb decomposition products. Because of the
presence of ETU in biological effluents at some concentrations of
maneb wastewater, further studies should be conducted of effluents
from maneb production diluted in various proportions with municipal
wastewater in order to determine acceptable levels of maneb
wastewater in municipal sewage.
-------
SECTION 3
EXPERIMENTAL DESIGN, MATERIALS, AND METHODS
INTRODUCTION
As noted in Section 1, objectives of the tasks were to evaluate biolog-
ical treatment and granular activated carbon treatment of selected actual
pesticides manufacturing wastewaters. Biological treatability was evaluated
in terms of bench scale activated sludge systems to (1) successfully operate
on a mixture of municipal wastewaters and pesticide wastewaters and (2)
remove the pesticide and other toxic materials in the wastewaters. Perfor-
mance of granular activated carbon column treatment was evaluated by (1)
analysis of pesticide and related compounds before and after treatment and
(2) bioscreening of the influent and effluent of the columns.
Peltier and Tebo (1978) have pointed out that present EPA regulatory
programs directed to the control of toxic wastewaters emphasize specific
limits on individual chemicals, and they note that this approach has numer-
ous shortcomings:
(1) there is little or no information on toxicity of thousands of
chemicals in common use
(2) in many cases analytical methodology is unavailable or prohibi-
tively expensive
(3) toxicity may be due to chemicals other than those for which the
investigator has analyzed
(4) especially in wastewater discharges, the toxicity may be a func-
tion of the mixture of the chemicals.
Bioassays alone, however, may fail to identify causes of toxicity or
suggest approaches to its control (Duke et al., 1977). Miller et al.
(1978) reiterate these concerns stating that:
8
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"The continued acceptance of chemical analysis of specific constituents
... as the primary reference standard for the legislation of ecologi-
cal response criteria is both unwise and misleading. Only concurrent
evaluations of both chemical analyses and bioassays results will provide
the scientific base necessary to establish realistic water quality
criteria."
For these reasons EPA-IERL has developed an integrated physical, chemi-
cal and biological approach, designated "Level 1 testing," for assessment of
industrial effluents (Hamersma et al., 1976; Duke et al., 1977). An abbre-
viated version of this approach was utilized in assessing the treated and
untreated pesticides manufacturing wastewaters investigated in these tasks.
The tests, summarized below and detailed in the appendices, included the
following:
(1) Routine wastewater characterization
(2) Analysis for specific pesticides
(3) Bioassays with freshwater fish and algae.
In conjunction with biological treatability studies, tests were also per-
formed to evaluate toxicity of the wastewaters to domestic sewage and
activated sludge microorganisms.
SAMPLING AND COLLECTION
In each case the manufacturer was asked to supply a 4-5 gallon grab
sample of wastewater to be used in preliminary and screening studies. The
atrazine wastewater was shipped by the manufacturer in a plastic carboy. In
the other cases, RTI supplied the manufacturers with specially cleaned 1-
gallon glass jugs with Teflon-lined caps, and requested that the samples be
chilled after collection, then shipped in a special insulated container to
RTI. Screening samples are designated Sample 1 in text below.
Large samples (30-60 gal) of wastewater were obtained by RTI personnel
on site. The type of sample (grab or composite) was determined by the
nature of the manufacturing process (batch or continuous). These samples
were collected in 55-gallon drums lined with Teflon bags, or in 5-gallon
-------
glass jars with Teflon or aluminum foil lined caps. The samples were trans-
ported to RTI by RTI personnel and were kept chilled in transit. The samples
were stored until analysis and testing in iced containers or under refrig-
eration. Large samples are designated Sample 2 in text below.
ANALYTICAL PROCEDURES
Routine Wastewater Characterization
Unless otherwise noted, wastewater analyses were conducted according to
Standard Methods for the Examination of Water and Wastewater, 14th edition
(APHA, AWWA, WPCF, 1976). The specific procedures used are shown in Appen-
dix A. Routine analyses were conducted for pH, chloride, acidity, alkalin-
ity, nitrogen forms, phosphorus, chemical oxygen demand (COD), and residues.
While the pH of natural waters is generally in the range of 4-9, indus-
trial wastewaters, including those from pesticide manufacture, may be
strongly acidic or basic. Extreme pH values may have diverse deleterious
effects on both biotic and abiotic components of receiving streams or waste-
water treatment plants. Such effects may include killing or inhibition of
biological treatment system biota, toxicity to fish and other organisms, and
corrosion.
High chloride levels are often associated with industrial wastewaters.
Undesirable effects of high chloride concentration include toxicity to fish
and other biota, interference with biological treatment systems, increased
corrosion rate, and interference with certain physical-chemical wastewater
treatment processes. The interference of chloride in analytical procedures
for other wastewater parameters, for example the COD analysis, necessitates
its early determination in wastewater samples.
Acidity, a measure of the capacity of a wastewater to neutralize a
strong base, indicates the amount of base required to neutralize the waste-
water to some desired pH. Acids in water affect corrosiveness, may inter-
fere with biological processes, and influence solubility of other compo-
nents. Alkalinity is the corresponding measure of the capacity of a waste-
water to neutralize a strong acid.
Nitrogen may occur in industrial wastewaters in a multitude of forms.
Ammonia is a common raw material in organic syntheses. In wastewaters it
10
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may (1) either stimulate or depress algal growth, depending on its con-
centration, (2) be toxic to fish and other fauna, (3) exert an oxygen demand
due to its potential for being nitrified.
Nitrate and nitrite, the oxidized forms of nitrogen, serve as plant
nutrients. They are typically found in effluents from biological nitrifi-
cation systems. Numerous compounds may be responsible for the organic
nitrogen content of wastewaters. Such compounds are frequently encountered
in effluents from manufacture of synthetic organic pesticides. A gross
measure of the combined organic and ammonia-nitrogen content of wastewaters
is given by the total Kjeldahl nitrogen analysis.
Phosphorus generally occurs in wastewaters in the form of organic or
inorganic phosphates. It is required for growth of all organisms, and since
it is frequently the limiting factor in productivity of freshwaters, its
presence in effluents may contribute to undesirable stimulation of algal
growth.
In reference to nitrogen and phosphorus, it should be noted that the
organisms responsible for biological wastewater treatment, like all organisms,
require these nutrients. Some industrial wastewaters are deficient in
nitrogen and phosphorus in proportion to the amount of organic carbon present,
and in such cases successful biological treatment may require addition of N
and P.
The COD determination is a measure of the amount of oxygen which would
be required to chemically oxidize organic matter. It is, therefore, in-
directly an estimate of the organic content of a sample. With wastes
containing toxic substances, this test or a total organic carbon determi-
nation is especially useful in determining the organic load since the
biochemical oxygen demand (BOD) test may be subject to inhibition.
Residue determinations indicate the amount of dissolved or suspended
solids in a wastewater. They are useful in determining the utility of
various solids separation procedures, such as settling or filtration, in
treating the wastewater, as well as estimating the amount of sludges which
will be produced. High dissolved solids levels may be indicative of the
presence of salts, such as chlorides, which may have adverse effects. A
11
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high dissolved solids level in itself will affect the osmotic pressure of
the solution and thus affect biological activity.
Wastewaters from manufacture of organoarsenical pesticides, such as
MSMA, contain arsenic. Arsenic may be acutely toxic to organisms or it may
produce chronic toxic effects as it accumulates over time. Arsenic deter-
minations were conducted by an atomic absorption procedure, as described in
Appendix B.
Pesticide Analyses
As noted above, major criteria for effectiveness of the wastewater
treatment processes were (1) ability to reduce or eliminate toxicity and (2)
ability to reduce or eliminate the pesticide component. In accordance with
the second criterion, it was necessary to find or to develop procedures for
determining concentration of the specific pesticides in a wastewater matrix
containing a multitude of organic compounds, including such closely related
compounds as raw materials and breakdown products. This proved to be a
major challenge in conducting the project since in several cases adequate
methods were not available.
Atrazine—
Atrazine was analyzed by gas chromatography by a procedure adapted from
Richard et al. (1975). The procedure is detailed in Appendix C.
Oryzalin—
Oryzalin in pure solutions can be measured by ultraviolet-visible (uv-
vis) spectroscopy. The wastewaters from oryzalin manufacture, however,
contained other colored components. Presence of these components was
confirmed by uv-vis spectroscopy and by thin-layer chromatography. Oryzalin
in wastewaters was determined by gas chromatography/electron capture detection
(GC/ECD) by the method of Sieck et al. (1976). The procedures are described
in Appendix D.
MSMA - Monosodium Methanearsonic Acid
None of the currently available analytical methods were adequate for
determining MSMA in a mixture containing other arsenic compounds. Since the
raw manufacturing wastewater and the effluents from the pilot activated
sludge units contained arsenic in several forms, it was necessary to develop
-------
a method for specific determination of MSMA. Preliminary experiments with
a new technique, ion chromatography (Small, et al., 1975), indicated that
methyl arsonic acid and arsonic acid could be distinguished and quantitated
by selection of appropriate columns. MSMA in the raw manufacturing waste-
waters and the effluents from activated carbon treatment was readily deter-
mined. In combination with domestic wastewater, as in the influents and
effluents of the activated sludge units, chloride interfered with the MSMA
analysis. It was necessary to develop a preparative procedure to remove
chloride prior to ion chromatographic analysis. The detailed procedures for
analysis of MSMA in wastewater are given in Appendix E. Insofar as is
known, they represent the first methods for specifically determining MSMA in
the presence of related arsenic compounds.
Maneb and its Breakdown Products—
Maneb occurs in wastewaters in combination with its breakdown products,
ethylene dithiocarbamate disulfide (ETD) or monosulfide (ETM) and ethylene
thiourea (ETU). Maneb was determined by a procedure adapted from McLeod and
McCully (1969) involving its reduction to carbon disulfide, which is then
measured by GC/ECD. Breakdown products were determined by thin layer
chromatography (Czegledi-Janko, 1967) followed by scanning spectrodensito-
metry. Details are given in Appendix F.
TREATABILITY TESTS
Activated Carbon Tests
As indicated in Section 7 (below), there is a considerable body of data
indicating the ability of activated carbon to adsorb pesticides and other
organic materials from solution. However, most of the extant data deal with
sorption of pesticides from (1) dilute solutions prepared from analytical
grade compounds, (2) potable water sources, or (3) agricultural runoff.
Relatively little information has been published on performance of activated
carbon for treatment of actual pesticide manufacturing wastewaters. For
protection of proprietary information on pesticide processes, the published
data generally do not disclose characterization of the wastewater components
and in only a few instances have both biological and chemical assessment
been attempted. Sontheimer (1976) and others have stressed the need for
13
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realistic laboratory tests for evaluating activated carbon, noting that
tests should be conducted on samples representing the concentration ranges
and mixtures of chemicals present in the wastewater to be treated. In this
task, actual pesticide wastewaters were employed, and the treated and un-
treated wastewaters were subjected to both biological and chemical assess-
ment.
For preliminary assessment of ability of various carbons to remove
pesticide from the wastewaters, liquid adsorption isotherm tests were
conducted using a procedure adapted from Metcalf and Eddy, Inc. (1972)
(Appendix 7). Based on its performance in liquid isotherm tests, Calgon
Filtrasorb 400 was selected for large-scale tests with granular activated
carbon (GAC) columns (Appendix 7). Influent and effluents were analyzed for
COD and pesticide content. Toxicity tests with fish and algae were conducted
on the untreated (influent) and treated (effluent, first fraction) wastewater.
Activated Sludge Tests
Biological treatment is often the most cost-effective method of removing
organic matter from municipal and industrial wastewaters. Such treatment
relies on the ability of mixed cultures of microorganisms to remove organic
pollutants by sorption, degradation to innocuous end products or incorpora-
tion into new growth. Since biological treatment systems rely on living
organisms, it is necessary (1) that the organics to be removed be biodegrad-
able and (2) that the wastewaters do not contain toxic materials in concen-
trations which inhibit biological activity. Fortunately, due to the variety
and adaptability of microorganisms, it is often possible to adapt or acclimate
biological treatment systems to tolerate and to treat toxic and/or refractory
materials.
One of the most commonly employed biological treatment systems utilizes
the activated sludge process. In this process high concentrations of
microorganisms (activated sludge) are maintained in suspension (mixed
liquor) with oxygen and mixing supplied by forced aeration. With appro-
priate control of oxygen levels, pH, quantity and quality of feed (wastewater)
and exposure period (detention or retention time), activated sludge organisms
are capable of rapid removal of organics and their accompanying oxygen
demand.
14
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In practice the activated sludge process generally operates on a
continuous feed basis. Fortuitously, it is possible to simulate the process
on a greatly reduced scale so that biological treatability of wastewaters
can be evaluated in the laboratory. For the studies conducted in this
project, the miniature complete mix continuous activated sludge unit designed
by Swisher (1970) was employed. To simulate effect of discharge of pesticide
manufacturing wastewaters to publicly owned treatment works, the units were
fed a mixture of the pesticide wastewater and domestic sewage. Treatability
of a wastewater mixture was evaluated in terms of (1) its effect on operation
of the units and (2) the ability of the units to remove the pesticide and to
produce an effluent in which toxicity was reduced or eliminated. Details of
the system are given in Appendix H.
ECOLOGICAL ASSESSMENT TESTS
The reasons for including ecological tests in assessment of industrial
wastewater treatability were outlined above. Due to time, space, and
financial constraints, it was not possible to conduct complete ecological
assessment testing on the wastewaters. Two tests, the static fish bioassay
and the algal assay procedure bottle test, were chosen on the basis of their
established value in predicting effects of toxicants on freshwater biota.
These level 1 tests (Duke et al., 1977) are also included in Standard
Methods for the Examination of Water and Wastewater (APHA et al., 1976).
The fish assay is the oldest standard method for assessing toxicity of
wastewaters. The relatively new algal assay procedure employs the green
alga Selenastrum capricornutum and may be used to detect stimulatory,
inhibitory, or toxic effects. Miller et al. (1978) reviewed studies of 23
textile wastewaters using 7 of the tests and concluded that the algal assay
test was the most sensitive and had the additional advantage in that it not
only identified toxic wastes but also those that were stimulatory. In
regard to pesticide wastewaters, it is noteworthy that green algae are often
very sensitive to herbicides, especially those herbicides which act by
inhibiting photosynthesis, and consequently green algae are frequently
employed in bioassays of herbicide residues (Greaves e_t al. , 1976).
The algal assay procedure is described in detail in Appendix I; the
fish bioassay procedure, in Appendix J.
15
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TEST OF EFFECTS OF PESTICIDE WASTEWATERS ON DOMESTIC SEWAGE AND ACTIVATED
SLUDGE ORGANISMS
Biological treatment systems rely on activity of the diverse community
of bacteria, fungi, protozoa, and other organisms which are able to utilize
for food and energy the organic constituents of the wastewater. In municipal
wastewater treatment systems domestic sewage influent is both a source of
organisms and of readily available organic compounds. In the biological
treatment units many additional species of adventitious organisms develop.
Industrial wastewaters, however, often contain constituents which are inhibi-
tory or toxic to organisms, especially if the biological treatment system
has not been acclimated to these constituents.
Potential adverse effects of industrial wastewaters on biological
treatment systems can often be predicted in relatively simple and inexpen-
sive tests in which the organisms are exposed to a mixture of domestic
sewage and the industrial wastewaters.
One such test is a modification of the agar diffusion method used in
assaying sensitivity of bacteria to antibiotics (Brock and Brock, 1973).
Basically, a petri plate containing an agar medium is prepared and evenly
inoculated with the test organism. Then, a filter paper disc containing a
measured amount of the test substance is placed on the surface of the agar.
During incubation (generally 24-48 hr) the test substance diffuses some
distance into the agar, and if the test organism is sensitive to the sub-
stance, no growth occurs in the area adjacent to the disc. After incubation,
inhibitory effects are readily apparent as clear zones of no growth adjacent
to the disc, surrounded by heavy growth in areas where the test substance is
absent or present in a lower concentration.
For these tests, petri plates were prepared from nutrient agar (Difco)
containing 1.5% agar. The surface of each plate was evenly spread with 0.5
ml of raw domestic sewage. The plate was allowed to stand for an hour to
permit the sewage to soak into the agar. Then, a sterile filter paper disc
was placed in the center of the plate and dosed with 0.1 ml of the pesticide
wastewater (or a dilution thereof). The plates were incubated at 25°C for
48 hr and observed for zones of inhibition around the disc.
16
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A test which can be used to detect toxicity of wastewater components to
activated sludge is the oxygen consumption rate test (Method 213B, APHA et
al., 1976). In the presence of suitable food sources and the absence of
toxic materials healthy activated sludge consumes oxygen at a steady rate
proportional to the amount of food present. In the presence of toxic
materials, this rate is decreased, and oxygen consumption may cease alto-
gether in cases of severe toxicity. By adding various percentages of an
industrial wastewater to the feed to activated sludge and measuring rate of
oxygen consumption under each condition, it is possible to estimate whether
or not the wastewater is toxic, and if so, at what dilution it can be
tolerated by the sludge. In full-scale treatment plants such testing is
used in detecting at an early stage potential problems in activated sludge
operation, problems which could possibly be controlled by eliminating en-
trance of a toxic stream into the system or by reducing the proportion of
that stream in the influent to a level tolerable by the system. In studies
conducted in this project, the oxygen consumption rate test was performed to
see how well the results correlated with those obtained in the more extensive
activated sludge treatability tests. Tests were conducted as described in
Method 213B (APHA et al., 1976), using activated sludge from a municipal
wastewater treatment plant (Hope Valley Plant, Durham, NC). The test
container was a BOD bottle, and oxygen consumption and temperature were
monitored with a polarographic oxygen sensitive membrane electrode equipped
with a self-stirring device (Yellow Springs Instrument Company).
17
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SECTION 4
ATRAZINE WASTEWATER TREATABILITY STUDIES
GENERAL BACKGROUND INFORMATION
Pesticide; Atrazine CAS No. 1912-24-9
TM TPM TM
Gesaprim ; Aatrex ; Atrasol ; G-30027
Structure
11 i
^r J
Cl
2-chloro-4-ethylamino-6-isopropylamino-l,3,5-triazine
Chemical Category
Triazine; other triazines include simazine, propazine, cyprozine, ter-
buthylazine, cyanazine, prometone, secbumetone, terburoetone, desmetryn,
ametryn, prometryn, metoprotryn, terbutryn, aziprotryn, dimethametryn,
dipropetryn.
Properties
Colorless crystals, m.p. 173-175 C; v.p. 3.0 x 10~ mm Hg at 20 C.
3
(Martin and Worthing, 1974). pKa (21 C) = 1.7; density of 1.187 g/cm
(Esser et a^., 1975). Soluble in 2% alcohol. Solubility in water at 20-25
C is 33 mg/1 (Esser e_t al., 1975), with the atrazine dissolving according to
a first order reaction, the solubility and rate constant increasing with
temperature (Calvet et al., 1975). The activation energy of solubilization
is approximately 4.1 - 4.8 kcal/mole, i.e., there is a 30% decrease in time
18
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required for 50% solubilization when the temperature increases by 10 C
(Calvet et al. , 1975). Sol. in methanol, 18,000 mg/1; in chloroform,
52,000 mg/1 (Martin and Worthing, 197A). Stable in neutral, slightly
acidic, or basic media, but hydrolyzed to the herbicidally inactive hydroxy
derivative by alkali or mineral acids at higher temperatures; non-corrosive
(Martin and Worthing, 1974). Undergoes photodecomposition with ultraviolet
light in aqueous solution to form the 2-hydroxy analogs (Esser et al.,
1975); acetone may serve as a photosensitizer (Burkhard and Guth, 1976).
Intended Use
Herbicide. Registered in 1958 as a herbicide. Used as selective pre-
and post-emergence herbicide on numerous crops, including corn, sorghum,
sugar cane, and nursery conifers (Martin and Worthing, 1974). Recommended
for use in fish ponds for selective control of farm pond weeds, especially
submerged aquatics (Johnson, 1965).
Mode of Action
Taken up by roots or foliage; inhibits growth of most plant organs; at
subtoxic levels may increase chlorophyll content, and resistant crops may be
a darker green; inhibits photosynthesis within photosystem II at the stage
where water is photolysed; inhibits respiration; causes pollen cell abnor-
malities in pollen cells of grain sorghum, but has no effect on yield
(Brian, 1976). Little if any effect on structure of chloroplast of the
green alga Chlorella ellipsoidea, but causes degradation of chloroplasts of
barnyard grass; does not affect mitochondria at up to 20 ppm; causes chromo-
somal aberrations in several plants (Linck, 1976). Inhibits photosynthetic
CO,, fixation but does not affect dark fixation of CO- in corn, cotton, and
soybeans (Frans e_t al., 1972).
Manufacturing Information
3
Amount Produced Annually: 49.9 x 10 metric tons in 1974
(Archer et al., 1978)
Manufacturers Locations
Ciba-Geigy St. Gabriel, LA
Missouri Chemical Company St. Joseph, MO
Vertac, Inc. Vicksburg, MS
19
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According to a recent farm periodical, "Big Farmer" (Anon. 1977), other
companies either make or formulate atrazine products since atrazine products
are listed as being available from Monsanto, Dow, Stauffer, Drexel, and
Shell companies.
Atrazine has the largest use volume of any pesticide in the United
States.
Health and Ecological Effects
Toxicity--
Oral, LD ., rat, 2000 mg/kg (Weber, 1977); 3080 rag/kg (Martin and
Worthing, 1974).
Mouse, 1750 mg/kg (Martin and Worthing, 1974).
Acute dermal LD-., rabbit, 7500 mg/kg (Martin and Worthing, 1974).
Not tumorigenic to the mouse at 10-22 mg/kg/day (Hayes, 1975).
LD , fish, 12.6 mg/1 (Weber, 1977).
Toxic to the carp Cyprinus corpio L. at 35 mg/1 and to the trout
Salmo irideus at 5-30 mg/1 (Ludemann and Kayser, 1965)
Toxic at levels as low as 3 ppm to fry of the fish Coregonus fera
(Gunkel and Kausch, 1976).
Toxic to daphnia at approximately 20 mg/1 (< 50% killed)
(Ludemann and Kayser, 1965).
With Daphnia magna and Moina rectirostris, at 1 ppm over 30-45
days increases duration of embryonic and postembryonic develop-
ment, as well as decreases number of broods and number of offspring
per brood. (Shcherban, 1973).
Limiting value for tubifex worm, 300 mg/1 (Ludemann and Kayser,
1965).
Atrazine at nontoxic levels acts synergistically with certain
insecticides, such as carbofuran, DDT, parathion, and diazinon, to
significantly enhance their toxicity to the fruit fly (Lichten-
stein et a_l., 1973).
20
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Fate in Soils—
Half-life in soil, 26-78 weeks (Weber, 1977); may be adsorbed by
components such as montmorillonite (Calvet and Terce, 1975).
Effect on nitrification in the soil is unresolved, as both stimulatory
and inhibitory effects have been noted (Greaves et al., 1976).
Atrazine treatment of soils does not affect subsequent crops of
sensitive species if residuals are <0.13 mg/1 (Fusi and Franci,
1972).
-3
Atrazine at 10 concentration produced no evidence of mutagenic
influence on the haploid flowering plant Pelargonium (Pohlheim
et al., 1977).
Monitoring of several major U. S. rivers and tributaries indicated
that atrazine is detectable year round, at values generally less
than 1 ppb; no nitrosoatrazine was found in the samples (Newby
and Tweedy, 1976).
Mutagenic Potential—
Atrazine alone produces no mutagenic effects in the usual short-term
tests for mutagenicity. For example, there is no effect on Tradescantia
hair cells and no evidence of cytogenetic activity on root tips of Hprdeum,
-3
Vicia, and Sorghum vulgare (Miiller et al., 1972). At 10 M concentration,
it produces no evidence of mutagenicity in the haploid flowering plant
Pelargonium (Polheim et al., 1977). However, it does induce genetic
alterations in maize germ cells (Plewa and Gentile, 1976) and extracts from
atrazine-treated maize do show mutagenic activity (Gentile and Plewa,
1976). Extracts from maize kernels treated with 5 and 20 ppm increased
mitotic gene conversion in the yeast Saccharomyces cerevisiae by (respec-
tively) 2.5 and 4 times over controls, whereas a 100 mg/1 solution of atra-
zine alone had no effect; even greater activity was found in leaf extracts
(18-30 times over controls) leading to speculation as to the food chain
effect (Gentile and Plewa, 1976).
21
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Manufacturing Process
Atrazine may be prepared by reaction of cyanuric chloride with one
equivalent of ethylamine followed by one equivalent of isopropyl amine in
the presence of an acid-binding agent (Sittig, 1977). The charts shown
below represent idealized schemes. They do not necessarily represent indi-
vidual plants, which vary somewhat in production processes.
(1) General production and waste scheme for atrazine (Sittig,
1977).
ADDITIVES
Oft SOL VENTS
VENT
N*OH
22
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(2) General chemistry of atrazine production (Sittig, 1977).
' I
3HCN 4 3CI2
H
. \
*~ \
C.-C^
^Nx
N
II
^C-CI
N
CCI4 C2HrNM'c^ ^C-CI
Cyinuric ehlorkU
CI CI
I
(CH3ljCHNH2
II j
..C-CI C2H6NH-C>W ^,C-NHCH(CH3I2 4 BHCI
i ^ ^>
-------
They summarize a recommended detoxification scheme for triazine wastewater
as follows:
(1) adjust pH to 1 or to 14
(2) pass through a hot water heater
(3) discharge to a holding pond
(4) monitor herbicide concentration to determine when effluent
may be discharged.
An alternate treatment scheme, using granular activated carbon, is
employed by at least one manufacturer. The treatment includes sand filtra-
tion, passage through Calgon Filtrasorb carbon and neutralization, as shown
in Figure 1.
Lawless e_t al. (1972) described the disposal of wastes at Ciba-Geigy,
St. Gabriel, LA. Liquid effluents from the cyanuric chloride unit were
subjected to pH adjustment and filtration prior to deep well disposal (6000
ft deep), and the remainder of the liquid wastes were discharged to a
river, contributing 500 Ib of BOD/day at the 100 million pound per year
production rate. Lawless et al. noted that the wastes contained large
amounts of NaCl.
CHARACTERIZATION OF WASTEWATER FROM ATRAZINE MANUFACTURE
At the plant of the manufacturer sampled, the wastewater stream of
interest was easily segregated. The manufacturer shipped the first small
sample to RTI. The large sample was collected and composited by RTI
personnel at the plant site.
The atrazine product occurs as fine solids, some of which escape into
the waste stream. The final unit process is continuous and is in operation
year-round. The wastewater flow from atrazine manufacture averages 144,000
gpd (range of 100,000-200,000 gpd). The atrazine concentration shows
substantial fluctuation, depending on plant operating conditions. This is
largely due to variations in the amount of fine solids escaping. The
company currently filters the wastewater through sand filters, then through
two GAC columns (Calgon Filtrasorb) in series, before discharge to a munici-
pal treatment plant. The company states that removal of pesticide averages
>99%, but notes that escape of solids at times results in higher effluent
24
-------
Co«t*>ln*ttd *ut»-
••(•r:
Niter Hoth*r Llquorj
filter Withvetcr;
Coitodnut Spllli
(••rblcldal)
Uncontaaliuted Waetevateri
Condeneate, Cooling Tover
Rlovdovn; Sanitary Hater;
Surface Water (Non-htrblcl-
Contaal-
pant
»aaln
Metering Huhoto
S««er to SUII
Send filter Seckveeh
(future Line)
Actlreted Carbon Abeorptlon Sjritea
Figure 1. Schematic diagram of treatment of atrazine
manufacturing wastewater.
-------
concentrations. (In further studies the possibility of more efficient
solids capture by coagulation and flocculation processes should be investi-
gated).
As shown in Table 1, the samples obtained by RTI were nearly neutral in
pH. In addition to the pesticide content, other parameters of interest
include the high chloride and Kjeldahl nitrogen content, the high soluble
COD and dissolved solids, and the highly variable settleable solids.
The wastewater samples from the atrazine manufacturer sampled contained
a variable amount of suspended solids. These samples of wastewater repre-
sented the influent into the carbon treatment system at the plant. To
determine the contribution of these solids to the pesticide content of the
wastewater, atrazine was determined in the total wastewater and in the
solids and liquid portions after centrifugation for five minutes (Inter-
national Clinical Centrifuge, Model CL, speed setting No. 3). Results are
shown in Table 2. These results indicate that the majority of the atrazine
is in the solids portion and that treatment to effectively remove these
solids would reduce the load of pesticide to be removed in activated carbon
or biological treatment. They also indicate that all of the solids were not
removed by centrifugation since the atrazine concentration exceeds the
solubility in water (33 mg/1).
An examination of the solids with the aid of a microscope indicated
them to be long slender crystalline rods, 5-50 (Jm long. The rods occurred
singly, rather than in clumps.
Fish toxicity screening tests were conducted with the wastewater. These
indicated the I-C50 to be > 10 ml/1 (1%). Further screening tests were
conducted on the liquid phase and the solid phase after centrifugation. The
solid phase was reconstituted to the original wastewater volume in glass-
distilled deionized water. Results are shown in Table 3.
These results indicated that the solid phase equilibrated with the
liquid phase and that the resulting solution was equally as toxic as the
total wastewater. They also provided evidence that LC for the wastewater
was between 10 and 100 ml/1 (1 and 10%).
26
-------
Table 1. CHARACTERIZATION OF ATRAZINE WASTEWATER
Parameter
PH
Cl", mg/1
Alkalinity, mg/1 as CaCO_
TKN, mg/1
NH^-N, mg/1
N02-N+N03-N, mg/1
TP, mg/1
COD, mg/1
Sol. COD, mg/1
Suspended solids, mg/1
Total solids, mg/1
Total dissolved solids,
mg/1
Settleable solids, ml/1
Atrazine, sol., mg/1
Sample 1
7.0
7,100
375
137
81
4,466
17,500
62
87
Sample 2
7.8
10,200
465
630
49
2.0
0.3
2,100
1,800
390
10,050
9,660
1.0
37.4
Table 2. ATRAZINE CONTENT OF LIQUID AND SOLIDS PORTIONS
OF ATRAZINE MANUFACTURING WASTEWATER
Sample
Replicate 1 -
Replicate 2 -
Liquid portion
Solids portion
Liquid portion
Solids portion
Atrazine, mg/1
94.1
1850.0
70.0
1880.0
27
-------
Table 3. TOXICITY TO FISH OF SOLID AND LIQUID
PHASES OF ATRAZINE MANUFACTURING WASTEWATERS
Wastewater Concen- No. Fish Surviving
Sample tration Replicate at 96 hr (Initial=3)
ml/1 Z, v/v
Control 001 3
002 3
Liquid Phase 10 1 1 2
2 3
100 10 1 0
2 0
Solid Phase 10 1 1 2
2 3
100 10 1 0
2 0
28
-------
Full scale fish toxicity tests (Appendix K) showed the 96 hr LC,-n to
be 18 ml/1 (1.8%) for both filtered and unfiltered wastewater. This was
surprising, in that (1) it was expected that dilutions of the unfiltered
wastewater would be more toxic since they would contain sufficient solids to
produce a saturated solution and (2) it was expected that the LC^ for the
filtered wastewater would be more than 1.8% since this concentration would
provide M).6 mg/1 of atrazine, much lower than the reported LC to fish (3-
35 mg/1). It is possible that components other than atrazine were partially
responsible for the observed toxicity.
From a technology control standpoint, a raw wastewater with an LC50 of
18 ml/1 (1.8%, v/v) would be expected to be toxic in 96 hr to approximately
50% of the fish in a receiving body even if diluted MaO times. With an
application factor of 0.1, 600 volumes of receiving water would be necessary
per volume of raw wastewater.
The effect of filtered atrazine wastewater on algal growth was deter-
mined. Preliminary studies with the initial "grab" sample provided by the
company showed that no growth occurred at wastewater concentrations of 1 and
10% (v/v) and that growth occurred at 0.1 and 0.01% after a ten-day lag
period. Full-scale studies were conducted with the composited wastewater
samples (Appendix K). Wastewater concentrations greater than 0.01%
inhibited growth during the first 10 days of incubation, while at 0.01% the
total growth achieved during incubation was less than half that of the
control. At a wastewater concentration of 0.01%, the I , was 60%. While
this is not considered a drastic reduction in growth, it is noteworthy that
concentrations of the wastewater as low as 0.01% consistently reduced algal
growth. This is not surprising since green algae often respond to the
herbicides effective against higher plants.
ACTIVATED CARBON TREATABILITY STUDIES
Adsorption Isotherm Studies
Adsorption isotherm studies were conducted with a variety of carbons
(Table 4, Figure 2). The most effective carbon overall proved to be Calgon
Filtrasorb 400, although the difference was not great. Adjustment of pH,
from pH 7 to pH 6, did not improve the removal of atrazine. The value of
29
-------
Table A. LIQUID ADSORPTION ISOTHERM DATA FOR ATRAZINE
WASTEWATER
M
Wt. of Carbon
Carbon g/100 ml of solution
1. Union Carbide, LCI 0
pulverized GAC 0.08
0.16
2.00
2.50
2. Nuchar S-A 0
0.04
0 0.08
0.16
2.0
3. Calgon Flltrasorb 0
400, pH 7.0 0.04
0.08
0.16
2.0
4. Calgon Flltrasorb 0
400, pH 7.0 0.04
0.06
0.16
2.0
C
Residual Pesticide,
tng/1
42.2
42.0
42.2
6.7
4.6
39.6
31.6
31.6
8.0
12.1
34.4
22.6
6.7
0.4
0.0
31.6
23.1
14.8
1.5
0.0
X
Pesticide Adsorbed,
mg/1
0
0.2
0
35.5
37.5
0
8.0
8.0
32.6
27.6
-
11.8
27.7
34.0
34.4
-
8.5
16.8
30.1
31.6
X/M
Pesticide Adsorbed,
g/g X/M at C.
0
•vO
0
0.0018 <0.01
0.0015
0
0.02 0.02
0.01
0.02
0.001
-
0.03
0.04
0.02
0.002
0.04
-
0.02
0.02
0.02
0.001
(continued)
0.02
-------
Table 4. (continued)
Carbon
5. Calgon Filtrasorb
400, pH 6.0
6. RX WV-G
0
mt
7. RX WV-L
8. Nuchar WV-C,
pulverized
M
Wt. of Carbon
g/100 ml of solution
0
0.04
0.08
0.16
2.0
0
0.04
0.08
0.16
2.0
0
0.04
0.08
0.16
2.0
0
0.04
0.08
0.16
2.0
C
Residual Pesticide,
mg/1
39.4
23.2
10.8
1.5
0.0
31.6
22.8
17.2
2.6
0.0
31.6
22.8
-
2.1
0.0
29.7
24.5
18.7
12.9
0.2
X
Pesticide Adsorbed,
mg/1
_
16.2
28.6
37.9
39.4
-
8.8
14.2
29.0
31.6
-
8.8
-
29.5
31.6
-
5.2
11.0
16.8
29.5
X/M
Pesticide Adsorbed,
g/g X/M at C.
-
0.04
0.04
0.02
0.002
0.04
-
0.02
0.02
0.02
0.002
0.02
-
0.02
-
0.02
0.002
0.02
-
0.01
0.01
0.01
0.002
0.02
(continued)
-------
Table 4. (continued)
Carbon
9. Union Carbide LCL
10. Kuchar WV-L,
pulverized
u>
N>
11. Union Carbide tCK
M
Wt. of Carbon
g/100 ml of solution
0
0.04
0.08
0.16
2.0
0
0.04
0.08
0.16
2.0
0
0.04
0.08
0.16
2.0
C
Residual Pesticide,
mg/1
29.7
29.5
.
28.3
0.3
29.7
26.6
25. 1
14.0
0.2
29.7
28.3
27.0
21.5
0.4
X
Pesticide Adsorbed,
mg/1
^
0.2
-
1.4
29.4
-
3.1
3.1
15.7
29.5
-
1.4
2.7
8.2
29.3
X/M
Pe&ticlde Adsorbed,
g/g X/M at C.
-
0.005
"
0.009 <0.01
0.002
-
0.008
0.004
0.010 <0.01
0.02
-
0.004
0.003
0.005
0.002
<0.01
-------
o.r
0.01-
O Union Carbide, LCL
4 Nuchar S-A
A Calgon Filtrasorb
400, pH 7.0
A Calgon Filtrasorb
400, pH 6.0
A
A
A •
o
o
o. ooi 4 i 1
0.1 1.0 10
C , Pesticide Remaining, mg/1
Figure 2. Adsorption isotherm of atrazine manufacturing
wastewater.
33
-------
X/M at C_ is used as the measure of adsorptive capacity of carbons. Gen-
erally, carbon systems are considered economically feasible if this value is
>0.10, questionable if between 0.05-0.10, and not feasible at values <0.05.
The best value achieved in the adsorption test reported here was 0.04,
therefore the utility of carbon could be considered to be marginal at best
for this application.
Figure 2 shows a plot of some of the values obtained. The slight slope
of the curves for each carbon tested indicates that there is comparable
adsorption of the atrazine over a range of concentrations. This is borne
out by the data in Table 4 (column X/M). Because activated carbon did
remove atrazine to nondetectable levels, since carbon treatment is presently
used at the plant tested, and because no better alternative treatments have
been found, studies were continued with GAC columns.
GAC Column Studies
Column studies were initially conducted in a long column, but it soon
became apparent that a very large volume of wastewater would be required to
achieve breakthrough. The test was repeated in a smaller column which was
2.2 cm (i.d.) and contained 26.6 g of carbon. Bed volume was 57.9 ml, and
2
the flow rate was 10 ml/min (0.64 gpm/ft ). In this column breakthrough to
the ppm level occurred after 67.2 bed volumes (Table 5, Figure 3). Before
breakthrough the atrazine was removed to ppb levels and the COD was reduced
by approximately 65%. Simple filtration of the wastewater before carbon
treatment also achieved some COD reduction (Table 5). It should be noted
that the remaining COD is still 2-3 times that of raw domestic sewage and
may require additional treatment for removal. Assuming that breakthrough
occurs at 67 bed-volumes, carbon requirements for the wastewater will be
6.85 g/L (67 lb/1000 gal).
In studies conducted by Calgon Corporation on 20 wastewaters from
industrial organic chemicals production, carbon requirements for TOC removal
ranged from 0.4-1496 lb/1000 gal, with the majority falling between 10-200
lb/1000 gal (Hager, 1974). Hager noted that "carbon exhaustion rates are
clearly in excess of those associated with domestic sewage treatment" and
that treatment costs for industrial wastewaters fall in the $/1000 gal
treated, compared to 10-30C/1000 gal of domestic sewage.
34
-------
oc
c
c w
•H C
N V
re u
t-i B
w O
< O
20 '
10
20 40 60 80 100 120 140 160 180 200 220 240
Number of Bed Volumes Throughput
Figure 3. Carbon column treatment of atrazine wactewater - 2nd trial.
-------
Table 5. GAC COLUMN STUDIES, ATRAZINE WASTEWATER
(Column 15.2 cm x 2.2 cm i.d.)
Cumulative
Fraction No. Bed Volumes
1
2
3
4
5
6
7
8
9
10
Column feed
(filtered wastewater)
Raw vastevater
16.6
34.0
50.6
67.2
128.3
144.8
162.3
181.6
198.2
214.7
-
-
Atrazine Concentration
< 25 ppb
< 25 ppb
92.6 ppb
1.37 ppm
NA*
NA
NA
NA
NA
16 . 8 ppni
37.7 ppm
NA
COD
mg/1
640
1840
2110
*KA • not analyzed.
Table 6. GAC COLUMN TEST: ATRAZINE WASTEWATER
(Column 15.0 cm x 2.2 cm i.d.)
Fraction
I
II
III
IV
V
VI
VII
VIII
Cumulative
Bed Volumes
12.5
23.5
27.6
30.5
33.4
36.2
47.2
56.4 36
Concentration of Atrazine in
Column Effluent (ppb)
< 25
< 25
< 25
< 25
< 25
< 25
160
868
-------
A third column run was conducted in a column 1 1/16 in (i.d.) with a 6
inch depth of activated carbon (39.0 g). One bed-volume equaled 87.2 ml and
2
the flow rate was 12.4 ml/min (0.52 gpm/ft ). One bed-volume was discarded
before collection of the eluate. Results are shown in Table 6 and Figure 4.
Detectible levels of atrazine occurred in the effluent between 36 and 47 bed
voluines, but were still less than 1 ppm after passage of 56 bed volumes.
These results are in general agreement with those of the second run.
In conjunction with these GAC tests, it was noted that in addition to
the pesticide present in the wastewater there was a large concentration of
surfactants which appeared to be unaffected by GAC treatment. This was
indicated by the presence of similar amounts of methanol-insoluble residue
in the freeze-dried aliquots of the untreated wastewater and the first
fraction collected from the column.
Due to a shortage of liquid for testing, only screening tests of the
toxicity to fish of treated and untreated atrazine wastewaters were con-
ducted. While these tests do not have validity of full-scale tests, the GAC
treatment appeared to reduce the toxicity (Appendix K).
BIOLOGICAL TREATABILITY STUDIES
Atrazine manufacturing wastewaters were diluted to 8.3% and 16.7% (v/v)
with municipal sewage and fed to bench-scale activated sludge units. In the
initial phases of the run the wastewater was subjected to primary settling
prior to AS treatment. Results, shown in Table 7, indicate that the atrazine
was not removed and that the concentration in the effluent ran close to the
solubility. In a second run, the unsettled wastewater was fed directly to
the units (Table 8). While the influent level in the more concentrated feed
was higher, as expected, effluent values still were near solubility levels,
probably reflecting removal of excess atrazine onto the sludges. Performance
and operating characteristics of the control and test units are shown in
Tables 8 and 9 and in Figures 5-7. An analysis of the COD data (Table 10)
indicates that the effluent COD from the test units is essentially equal to
that contributed by the atrazine wastewater. This possibly indicates that
the COD in the atrazine wastewater resists biological oxidation but at this
concentration has no deleterious effect on the oxidation of the domestic
wastewater components.
37
-------
00
0)
00
(0
u
(U
u
M
01
a
id
to
U 01
C 01
0) <4-l
iH G
-------
Table 7. EFFECT OF ACTIVATED SLUDGE TREATMENT
OF ATRAZINE WASTEWATER (RUM I)
Atrazlne (ag/1)
16. 7Z Atrazine Wastevater
Influent 37+6 (n«3)
Effluent, Unit 1 42
" Unit 2 41
8.3Z Atrazine Wastevater
Influent 28
Effluent, Unit 1 25
Unit 2 31
Table 8. EFFECT OF ACTIVATED SLUDGE TREATMENT
OF ATRAZINE WASTEWATER (RUN II)
Sample Atrazine (mg/1)
16.72 Atrazine Vastevater
Influent 60
Effluent, Unit 1 34
" Unit 2 45
6.3Z Atrazine Wasteuater
Influent 37-1-2
Effluent, Unit 1 30
" Unit 2 31
Control
Influent
Effluent, Unit 1
Unit 2
ND - < 5 mg/1
39
-------
320
280
240
S 200
en
160
120
80
40
-© Influent
- Effluent-Unit 1
•- -• Effluent-Unit 2.
_©
2468
DAY
10 12 14
Figure 5. Influent and effluent COD of control
activated sludge units.
40
-------
300
260
220
180
M 140
o
o
100
80
40
®——© Influent
• • Effluent-Unit 1
» EffluenMJnit 2,
i t
0 2 4 6 B 10 12 14
DAY
Figure 6. Influent and effluent COD of activated
sludge units fed 8.3% atrazine.
41
-------
400
360
320
280
240
200
160
120
80
40
•e Influent
- Effluent-Unit 1
•- -* EffluenMJnit 2
6 8
DAY
10 12 14
Figure 7.
Influent and effluent COD of activated
sludge units fed 16.7% atrazine.
42
-------
Table 9. PERFORMANCE AND OPERATING CHARACTERISTICS OF BENCH SCALE
ACTIVATED SLUDGE UNITS, ATRAZINE WASTEWATER SERIES
Parameter
COD Influent, mg/1
COD Effluent, mg/1
COD Effluent, mg/1
COD Influent, mg/1
COD Effluent, mg/1
COD Effluent, mg/1
•COD Influent, mg/1
COD Effluent, mg/1
Aerator pH
DO, mg/1
MLSS, ml/ 10 ml
Day
1-5
3
5
6-10
7
10
11-14
14
3
14
3
14
1
14
Control
I
144
36
48
176
26
28
166
36
6.80
6.50
5.5
6.1
0.5
0.35
II av. Z removal
144
72 62
56 64
176
54 77
64 74
166
88 63
6.58
6.50
5.9
5.2
0.3
0.23
8.
I
272
144
192
288
218
220
264
148
6.45
6.60
6.0
6.7
0.5
0.4
3Z Atrazlne
II av. Z removal
272
132 49
200 28
288
158 35
184 30
264
156 42
6.40
6.55
5.5
6.6
0.5
0.37
16.71 Atrazlne
I
400
172
312
380
294
290
352
272
6.70
6.77
6.2
6.7
0.5
0.5
II av. Z removal
400
152 60
320 21
380
274 25
220 33
352
272 23
6.65
6.65
6.0
5.4
0.6
0.22
-------
Table 10. ANALYSIS OF CONTRIBUTION OF COD OF ATRAZINE MANUFACTURING
WASTEWATER TO COD OF INFLUENTS AND EFFLUENTS OF ACTIVATED SLUDGE UNITS
Unit Day
Influents
8.32 atrazine waste 1-5
6-10
11-14
16.7% atrazine waste 1-5
6-10
11-14
Effluents*
8.3% atrazine waste 3
5
7
10
14
16.7% atrazine waste 3
5
7
10
14
COD, nig /I* in excess of
of control units
122
112
98
ave.
256
204
186
ave.
83
144
148
156
90
ave.
106
264
244
209
210
ave.
that
111
215
122
207
In each case, COD values from the two units are averaged.
44
-------
Toxicity tests were conducted on untreated and treated domestic and
atrazine wastewaters from the first run (Appendix K). In full-scale tests
with domestic wastewater there were no deaths at concentrations up to 180
ml/1. As indicated previously, LC5Q of the untreated full-strength wastewater
was 18 ml/1. Influents to the test units contained the wastewater at 8.3%
and 16.7% (v/v); stated in terms of dilution, this is equivalent to 1/12 or
1/6 of the original concentration. Therefore the LC-- would be expected to
be (18 x 12) or 216 ml/1 and (18 x 6) or 108 ml/1, respectively. Because of
limited availability of effluent, fish toxicity tests were conducted only at
concentrations up to 100 ml/1. No significant lethality of either influent
or effluents was noted, with the possible exception of one test with a 100
ml/1 concentration of effluent from one of the units treating the higher
concentration. Since the influents were subjected to primary settling
before biological treatment, and were exposed to biological solids during
treatment, it is conceivable that the atrazine was sorbed to other material
in such a manner that it was no longer available to the fish. Any insoluble
atrazine entering the AS unit would be likely to be retained in the sludge.
Examination of Tables 7 and 8 indicates that regardless of the amount of
atrazine wastewater in the feed, the concentration of atrazine in effluents
from the test units varied around the solubility level for atrazine (25-45
mg/1).
Algal assays of influents and effluents from the units receiving the
higher concentration of wastewater indicated little or no difference in
toxicity of the two. This might be anticipated since biological treatment
did not affect soluble atrazine concentration. At concentrations greater
than 0.1% (v/v) no algal growth was noted (Appendix K).
Spot tests indicated no inhibition of sewage flora by atrazine waste-
water, even at full strength (Appendix 0).
In summary, while atrazine wastewater did not seriously interfere with
biological treatment, on the other hand, AS treatment failed to remove
atrazine.
45
-------
SECTION 5
ORYZALIN WASTEWATER TREATABILITY STUDIES
GENERAL BACKGROUND INFORMATION
Pesticide; Oryzalin CAS No. 19044-88-3
® ®
Ryzelan , Surflan
Structure
4 4
3,5-dinitro-N ,N -dipropylsulfanilamide
Chemical Category
Dinitroaniline, sulfonamide; others of this class include trifluralin,
benefin, ethal-fluralin, nitralin, isopropalin, dinitramine, fluchloralin,
profluralin, butralin, and penoxalin. Dinitroaniline compounds are also
commonly used as dye intermediates.
Properties
M. W. 346.36. Yellow-orange crystalline solid, M.P. 141-142°C. Sol. in
H20: 2.5 mg/1 (25°C). Sol. in polar organic solvents: acetone, methanol,
ethanol, acetonitrile. Slightly sol. in benzene and xylene. Insol. in
hexane. Vapor pressure < 1 x 10 mm Hg at 30°C. No appreciable odor. Not
46
-------
corrosive. Highly soluble in alkaline solutions. May contain colored
impurities. Subject to decomposition by ultraviolet irradiation (Dekker and
Johnson, 1976).
Intended Use
Herbicide; recommended for weed control in soybeans.
Pre-emergence weedkiller in orchards and vineyards.
"Selective pre-emergence herbicide for control of annual grasses and certain
broadleaf weeds in soybeans and other selected crops" (Dekker and Johnson,
1976). Generally formulated as a 75% wettable powder.
Mode of Action
Oryzalin acts on mitochondria to uncouple succinate oxidation at the ADP-
limited second stage-4 (IV2); half-maximal increases in IV_ oxidation were
obtained with 55 |JM oryzalin and maximum stimulations at 80 pM with soybean
mitochondria. It evidently acts at a site on the energy-transfer system
closer to the formation of H_0 than does dinitrophenol or trifluralin
(Kirkwood, 1976).
At the whole plant level it inhibits root growth and shoot growth and
development (Probst et al. , 1975).
Manufacturing Information - Introduced in early 1970's
Amount Produced Annually: Unknown
Manufacturer Location
Sodyeco Division of Martin-Marietta Corp. Charlotte, NC
(for Blanco)
Manufacturing Process
Oryzalin manufacture is operated as a batch process year-round. The
manufacturing process shown here is generalized and is not necessarily
identical to that at the plant sampled. According to Sittig (1977), a
mixture of (3,5-dinitro-4[di(n-propyl) amino] benzenesulfonyl chloride and
an excess of concentrated NH.OH is heated to reflux temperature for several
hours and then filtered. The filtrate is concentrated to dryness i.n vacuo
and then recrystallized from an acetone-petroleum ether mixture. Synthesis
reactions beginning with chlorobenzene may be as depicted in Figure 8
(Dekker and Johnson, 1976).
47
-------
Cl
Cl
SO2CI
KNO,
POCI3
S03K
N-(CH2CH2CH3)2
S03K
SO2NH2
Figure 8. Possible synthesis of oryzalin from
chlorobenzene.
48
-------
Three major wastestreams are generated in oryzalin production. The
major wastewater (I) consists of two aqueous streams containing some
filterable solids. This wastewater is highly colored and is presently
thermally oxidized. Since this is a very costly process, there is incentive
to examine alternative methods of disposal. The second stream (II) is a
washwater containing oryzalin at very low levels (low ppb range). This
stream is currently discharged to the plant's extended aeration system.
The third waste (III) is a tar-like residue containing 10-20% oryzalin; the
solids in this stream are incinerated at >^ 1600°F. Streams I and II were
examined during the course of this project.
Subsequent to the completion of this project the manufacturer modified
the manufacturing process and eliminated the wash step; therefore this
wastestream is no longer generated.
Health and Ecological Effects
Toxicity--
Rat, oral, LD5Q: > 10 g/kg (Fairchild, 1977)
Gerbil, oral LD5Q: > 10 g/kg
Cat, adult, oral LD0: > 1 g/kg (Elanco information)
Chicken, adult, oral LD0: > 1 g/kg "
Dog, adult, oral LD0 : > 1 g/kg "
Fish, bluegill sunfish, TL_0, 96 hr: 2.88 mg/1
rainbow trout, TL , 96 hr: 3.26 mg/1;
"No effect level1': 1 mg/1
Of the dinitroaniline herbicides, nitralin and oryzalin are least
toxic to fish, while trifluralin is much more toxic with LC_ 's ranging
from 0.06-0.56 mg/1 (Probst et al.. , 1975).
Mutagenic Potential--
While no information is available on mutagenicity of oryzalin, the
related compound trifluralin does not induce point mutations in three
microbial systems which have been tested, and there are no reports of
oncogenic effects of dinitroaniline herbicides (National Research Council,
1977).
49
-------
Bioaccumulation and Other Effects—
Probst et al. (1975) state that neither oryzalin nor its metabolites
accumulate in the edible portion of tolerant crops and that with the excep-
tion of aquatic systems oryzalin is "a pesticide of maximum safety to the
environment." Since dinitroanilines are not used for aquatic weed control,
entry into aquatic systems would occur only by accident, by runoff from
agricultural areas, and by discharge of manufacturing wastewaters, and even
then, according to Helling (1976), photodecomposition and sorption to sedi-
ments would tend to minimize adverse effects.
CHARACTERIZATION OF WASTEWATERS FROM ORYZALIN PRODUCTION
As indicated above, two wastestreams are generated in oryzalin manu-
facture (Table 11). The wastewater was heavily colored, corresponding to an
absorbance of 420 units. Analysis indicated this to be due not to oryzalin
but to a closely related compound. Color was measured by ultraviolet-
visible spectroscopy. Measurements of color could not be directly related
to concentration of oryzalin itself, as spectra for pure oryzalin and for
the wastewater were substantially different. The absorbance maximum of pure
oryzalin is 350 nm, as compared to 420-430 nm for the untreated wastewater.
The pH was alkaline and the levels of chloride, alkalinity, nitrogen com-
pounds, dissolved solids, and COD were extremely high. The nitrogen occurred
primarily as ammonia, and the wastewater had a distinctive ammoniacal smell.
The washwater contained large amounts of organic solvent (toluene),
which interfered with certain analyses. This stream was a lighter yellow
version of the wastewater and except for the COD, was a more dilute version
of that stream.
Note the wide variation in the samples obtained from the manufacturer.
The second sample was taken at a time when the plant was not operating
efficiently due to problems caused by cold weather. Discussions with plant
personnel indicate that wide fluctuations in wastewater characteristics can
occur.
50
-------
Table 11. CHARACTERIZATION OF ORYZALIN WASTEWATERS
Washvater
Process Wastewater
Parameter
PH
Cl", mg/1
Alkalinity, mg/1 as CaCO
TKN, mg/1
NH^-N, mg/1
NO .— N*HIO , — N , mg / 1
TP, mg/1
COD, mg/1
Sol. COD, mg/1
Suspended solids, mg/1
Total solids, mg/1
Total dissolved solids,
mg/1
Settleable solids, mSL/1
Oryzalin, mg/1
Sample 1
9.2
730
0.21
97. 3; 131*
37; 66; 75
-
0.2
130,500
-
1.5
-
184
0
_
Sample 2
2.2
1,700
985
420
30
-
5.8
260,000
-
-
-
30,220
**
N.D.
Sample 1
8.8
27,000
960
25,900
23,800
-
299
36,500
79,200
2,450
-
-
8
N.D.**
Sample 2
9.2
45,000
20,750
28,700
28,000
870
12.5
79,000
73,000
368
73,000
72,540
12
N.D. **
Interferences made analysis difficult; values shown represent those obtained in
replicate analyses.
**
< 2 ppb
-------
Reported 96 hr LC,.n values for fish for commercial oryzalin are 2.88-
3.26 mg/1. However, unformulated oryzalin obtained directly from the manu-
facturer failed to kill fish in screening tests (3 fish/jar) at concen-
trations up to 5 mg/1 (Appendix L). Screening tests with the initial
actual wastestreams indicated these streams, especially the wastewater, to
be highly toxic.
The second (large) sample of oryzalin production wastewater was sub-
jected to toxicity testing with fish and algae. As noted above, oryzalin
itself was not detectable in the wastewater; however, the fish toxicity
tests showed the wastewater to be highly toxic, with an LC of 0.3 ml/1
(Appendix L).
It is probable that the ammonia content of the wastewater is respon-
sible for the major portion of the toxicity. The ammonia-N contents of the
two samples were, respectively, 23,800 and 28,000 mg/1. The toxicity of
ammonia is highly dependent on pH, temperature, hardness, and other factors,
but concentrations of -v 2.5 mg NH3/1 (2.0 mg NH/-N/1) at neutral pH are
generally considered harmful and 96 hr LC values of 3.24 mg/1 have been
reported (McKee and Wolf, 1963). The ammonia-N content of the oryzalin
wastewater at the £C50 concentration of 0.3 ml/1 would be 8.A mg/1. Further
indication that ammonia contributed to toxicity was given in screening tests
of the wastewater with and without air stripping at high pH (see below,
"Effect of Aeration on Oryzalin Wastewater").
Algal assays showed that the wastewater severely inhibited growth at
concentrations of 1 and 10%, had some inhibitory effect at 0.01 and 0.1%,
and was stimulatory at 0.001% (Appendix L). The washwater was considerably
less toxic (Appendix L). Ammonia may be toxic to algae, the toxic concen-
tration being highly dependent on algal species and on environmental factors,
or it may serve as a nitrogen source. Concentrations of ~ 300-400 mg/1 (as
NH--N) have been shown to inhibit growth of diatoms to 50% of the control
growth (McKee and Wolf, 1963). The expected NH.-N concentrations in the
test media, along with their effect on algal growth, may be summarized
below:
52
-------
Dilution NH3~N, mg/1 Effect
10% 2800 No growth
1% 280 No growth
0.1% 28 Moderate growth
0.01% 2.8 Moderate growth
0.001% 0.28 Growth stimulation
The values are in general agreement with those reported by others.
ACTIVATED CARBON STUDIES
Adsorption Isotherm Studies
Oryzalin wastewater was subjected to adsorption isotherm studies with
a variety of carbons and with two resins. Initial studies (Table 12) with 2
g carbon per 100 ml of wastewater indicated that a considerable amount of
color was removed but that there was such a large amount initially that the
amount remaining was still highly colored. Performance of the resins was
poor compared to most of the carbons. Further studies were conducted with
those carbons performing best (Table 13 and Figure 9). These studies indi-
cated that the color was readily absorbed onto carbon (note the very large
X/M values), but that carbon requirements would be very large.
Liquid adsorption studies were also conducted on the washwater (Tables
14 and 15). Although the color was much less intense, a smaller amount was
absorbed per unit weight of carbon, possibly due to the presence of compet-
ing organic materials in this wastestream.
Granular Activated Carbon Treatment of Oryzalin Wastewater
Treatability of oryzalin wastewater by GAC was evaluated in column
studies with Calgon Filtrasorb 400 carbon. Raw wastewater was filtered
through filter paper (Whatman 2V, medium porosity or Millipore prefilter)
prior to column treatment.
2
In initial studies a column with a cross-sectional area of 0.0144 ft
was packed to a height of 4 ft with 692.3 g of carbon which had been dried
at least 2 hours at 150°C. This carbon was slurried in hot water to expel
most of the air, then added to the column in small increments, keeping a
thin layer of supernatant liquid present at all times. The bed volume was
53
-------
Table 12. LIQUID ADSORPTION ISOTHERM DATA FOR ORYZALIN WASTEWATER--SCREENING STUDIES
M
We. of Carbon,
Carbon (or Resin) g/100 ml of solution
1.
2.
3.
4.
5.
S,,
7.
8.
9.
10.
11.
12.
None (control)
Nuchar SA
Nuchar WV-L
RX-WV-L
RX-WV-C
Nuchar WV-G
Calgon Filtrasorb 400
Calgon Filtrasorb 400
Union Carbide LCK
Union Carbide LCL
Dowex 1-X8, 50-100 mesh,
chloride form, ion-
exchange resin
Amberlide XAD-2
0
2
2
2
2
2
2
2
2
2
2
2
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
*
c
Residual Pesticide,
mg/1
60
32
40
39
34
36
33
34
49
52
48
53
,800
.800
.900
.100
.000
,800
,700
,100
.300
.200
.600
,100
X
Pesticide Adsorbed,
mg/1
0
28
19
21
26
24
27
26
11
8
12
7
,000
.900
,700
,800
,000
,100
,700
,300
,600
,200
,700
X/M
Pesticide Adsorbed,
Per Unit Weight of
Carbon
8/g
_
1.
1.
1.
1.
1.
1.
1.
0.
0.
0.
0.
4
0
1
3
2
4
4
6
4
6
4
TLC indicated that the principal chronophores were not oryzalin but two more polar compounds.
-------
Table 13. LIQUID ADSORPTION ISOTHERM DATA FOR ORYZALIN WASTEWATER
Carbon
Control
1. Calgon Filtrasorb
400
2. Calgon Filtrasorb
VI
3. Nuchar SA
4. RX-WV-G
M
Wt. of Carbon,
g/100 ml of Solution
0
0.04
0.08
0.16
2.0
0.04
0.08
0.16
2.0
0.04
0.08
0.16
2.0
0.04
0.08
0.16
2.0
C
Residual Pesticide,
mg/1
60,300
52,400
54,700
52,800
37,000
52,800
52,400
51.300
35,200
52,800
52,400
51,600
37,800
53,900
54,600
53,500
35,900
X
Pesticide Adsorbed,
ng/1
0
7,800
5,600
7,500
23,300
7,500
7,900
9,000
25,100
7,500
7,900
8,700
22,300
6,400
5,700
6,800
24,400
X/M
Pesticide Adsorbed,
Per Unit Weight
g/g X/M at C.
0
19.8
7.0
4.7
1.2
18.8
9.9
5.6
1.2
•U750
18.8
9.9
5.4
1.1
^2100
16.0
7.1
4.2
1.2
M.650
-------
J.UU _
r 10 .
c'
c
.e
K
U
E
bi
0)
4-J
3
0
tn
i i.o-
w
0.1
O Calgon Filtrasorb AOO
• Nuchar SA
4 RX-WV-G
a
9
A
9
*
$
^»rf
1 10 100
C-, Pesticide Analog Remaining in Solution, g/1
Figure 9. Adsorption isotherm of oryzalin production wastewater.
56
-------
Table 14. LIQUID ADSORPTION ISOTHF.RM DATA FOR ORYZALIN WASHWATER---SCREENING STUDIES
Carbon (or Resin)
1. None (control)
2. RX-WV-L
3. RX-WV-G
4. Nuchar SA
5. Nuchar WV-C
6. Nuchar W-L
7. Calgon Flltruorb 400
8. Calgon Flltrasorb 400
9. Union Carbide LCK
10. Union Carbide LCI
M
Wt. of Carbon,
g/100 nl of Solution
0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
C
Residual Pesticide,
•R/l
21.2
10.1
11.7
12.8
,.i
8.4
2.3
1.6
5.3
5.6
X
Pesticide Adsorbed
n.K/1
0
11.1
9.5
8.4
17.4
12.8
18.8
19.6
15.9
15.6
X/M
Pesticide Adsorbed
Per Unit Weight
R/X
-
0.0006
0.0005
0.0004
0.0009
0.0006
0.0009
0.001
0.0008
0.0008
-------
Table 15. LIQUID ADSORPTION ISOTHERM DATA FOR ORYZALIN WASHWATER
M
Wt. of Carbon,
Carbon 8/100 ml of Solution
Control 0
1. Muchar W-G 0.04
0.08
0.16
2.0
00
2. Calgon Tlltrasorb 0.04
400
0.08
0.16
2.0
3. Calgon Mltrasorb 0.04
400
0.08
0.16
2.0
C
Residual Pesticide.
sie/1
0.142
0.092
0.085
0.033
0.002
0.098
0.070
0.019
0.000
0.091
0.074
0.031
0.0
X
Pesticide Adsorbed
—
0.05
0.057
0.109
0.140
0.044
0.072
0.123
0.142
0.050
0.068
0.111
0.142
X/N
Pesticide Adsorbed
Per Unit Weight
«/*
1.25 x 10"*
7.12 x 10"5
6.81 x 10"5
7.0 x 10"6
1.1 x 10"*
9.0 x 10"5
7.7 x 10"5
7.1 x 10~6
1.25 x 10"4
8.5 x 10"5
6.9 x 10"5
7.1 x 10"6
-------
1600 ml. Filtered wastewater was pumped through the column at 36 ml/min
2
(0.65 gpm/ft ). Two runs were conducted, one at the pH of the filtered
wastewater and the other after adjustment to pH 6. Breakthrough was indi-
cated by appearance of color in the column effluent. Spectra of each frac-
tion were obtained with a Perkin-Elmer 402 visible spectrophotometer.
Results are shown in Table 16 and in Figures 10-12. CAC treatment was
capable of completely removing color of the wastewater and in reducing the
COD by > 95%. At the pHs tested, adjustment of pH of the column feed had
little or no effect on GAC treatment. The results indicate that GAC column
treatment is completely capable of high levels of treatment of this waste-
stream insofar as color and COD are concerned. Unfortunately, as antici-
pated from results of the isotherm tests, the carbon requirements are
exceedingly high, with breakthrough of color and COD occurring somewhere
between 1.5 and 2.0 bed volumes.
As noted previously, color was due largely to non-oryzalin components.
Note the shift of wavelength maxima which occurred with breakthrough (Figure
11). This shift is indicative of a multicomponent mixture, which was veri-
fied by thin-layer chromatography. On TLC analysis more than five compo-
nents, varying in color from pale yellow to rose, were observed. Assuming
that the color in the oryzalin wastewater will reach breakthrough in ~ 5 bed
volumes, indicated carbon requirements are 86.5-89.3 g/1 (720 lb/1000 gal).
This requirement is large in comparison with usual industrial requirements
of 50-400 lb/1000 gal.
More oryzalin wastewater was carbon treated in a second trial. The
column was 2.5 cm (i,d.) and was packed to a depth of 120 cm with carbon
(286 g). The bed volume was 618 ml and the flow rate was 10.0 ml/min (0.48
o
gpm/ft ). A void volume of 600 ml of liquid was discarded before fractions
of the eluate were collected. Spectra of each fraction were obtained as
above. Results are shown in Table 17. Results (COD, color removed) were
comparable to those obtained in the first trial.
Algal assays of the treated wastewater indicated that the inhibitory
effects at 1 and 10% (v/v) concentrations still persisted, whereas at lower
concentrations there was little difference from control growth (Appendix L).
59
-------
Table 16. EFFECT OF GAC TREATMENT ON ORYZALIN WASTEWATER AT pH 6 AND pH 9
Sample
pH 9
pH 6
Fraction
Untreated, unfiltered
Column influent
Effluent I
Effluent II
Effluent III
Effluent IV
Column influent
Effluent I
Effluent II
Effluent III
Effluent IV
Cumulative
Bed Volumes
0
0
1.77
2.67
4.64
7.01
0
1.56
2.18
4.55
6. '90
Absorbance
Units
-
632
0
1.45
22.4
45.3
545
0
0.20
0.65
42.9
Color
Remaining, %
-
-
0
0.23
3.49
7.1
-
0
0.04
0.12
7.87
COD, mg/1
57,020
53,600
2,160
27,200
65,740
2,320
44,000
Table 17. EFFECT OF GAC TREATMENT ON ORYZALIN WASTEWATER
Fraction
Untreated, unfiltered
Column feed
Effluent I
Effluent II
Effluent III
Effluent IV
Effluent V
Effluent VI
Cumulative
Bed Volumes
0
0
1.55
2.09
2.49
3.32
4.87
5.48
Absorbance
Units
0
420
0
0
0
0
0.725
3.50
Wavelength
of maximum,
nm
-
426
-
-
-
-
405
405
COD,
mg/1
(avg. of 2)
78,250
72,500
2,800
-
-
-
-
-
- - not analyzed
60
-------
03
*J
•H
c
ED
0)
O
c
o
w
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
300
First GAC effluent
Breakthrough 1
Breakthrough 2
Breakthrough 3 dil. 1:30
dil. 1:500
350
450
Wavelength, nm
550
650
Figure 10. Absorbance of effluent from GAC column treating oryzalin production wastewater,
pit 6; breakthrough of color at progressively larger cumulative bed volumes is
indicated.
-------
05
9)
U
3
.0
U
o
ON W
ro jo
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
First GAG Effluent
Breakthrough 1 dil. 1:5
Breakthrough 2 dil. 1:30
Breakthrough 3 dil. 1:30
Untreated dil- 1:500
300
350
450
Wavelength, nm
550
650
Figure 11.
Absorbance of effluent from GAG column treating oryzalin production wastewater, pH 9.
Breakthrough of color at progressively larger cumulative bed volumes is indicated.
-------
-r-4
c
01
u
c
Ui
o
w
10
0
23456 7 8 9 10 11 12
Cumulative Bed Volumes of Wastewater
Figure 12. GAG column treatment of oryzalin manufacturing wastewater, pH 9 and pH 6.
-------
Since all the color had been removed from the wastewater by the GAC treat-
ment, it is probable that the toxic component was not oryzalin or its ana-
logs, but some other component, possibly ammonia.
Fish assays of the GAC treatment wastewater (Appendix L) indicated that
toxicity of oryzalin wastewater was not substantially reduced by carbon
treatment. Complete mortality was noted at concentrations of 1.0 ml/1 and
greater. It was hypothesized that ammonia still present in the carbon
column effluent contributed to the toxicity of GAC treated effluent. To
test this hypothesis a second bioassay was conducted with carbon column
effluent subjected to ammonia stripping, as reported below.
BIOLOGICAL TREATABILITY STUDIES OF ORYZALIN MANUFACTURING WASTEWATER
Bacterial spot tests with both oryzalin wastewater and washwater
streams indicated that the undiluted streams were markedly inhibitory to
sewage flora (Appendix 0). Oxygen uptake studies (Appendix P) also indi-
cated that at a 10% (v/v) concentration, the wastewater severely inhibited
respiration by unacclimated activated sludge (AS), whereas a 1% concentra-
tion (v/v) caused much less inhibition.
Nevertheless, biological treatability studies were attempted at both 1
and 10% (v/v) feed concentrations. In both cases, the AS units failed to
operate. At the higher concentration, the test units rapidly lost all of the
sludge to the effluent. When it became apparent that a 10% concentration
would not be tolerated, another series of tests was set up at 1%. The units
failed to operate satisfactorily, again exhibiting loss of sludge from the
reactor. In terms of COD removal performance characteristics of the control
and test units are shown in Table 18 and in Figures 13 and 14. Operational
characteristics are shown in Table 19. Despite operational difficulties it
was noted that substantial reductions in COD were occurring (Table 18).
Since there could be little or no biological activity responsible for these
removals, additional tests (described below) were conducted to determine if
aeration alone could be responsible, for example, by volatizing or oxidizing
the pesticide or other organic components.
It is noteworthy (Table 19) that while the pH of the mixed liquor in
the control units (those receiving only domestic sewage feed) dropped below
64
-------
Table 18. PERI-GIIIIANCE CHARACTERISTICS OF BENCH SCALE ACTIVATED SLUDGE
UNITS - ORY/.ALIN WASTEWATER SERIES
0>
Control
Date*
1-6
2
4
7-1*
7
9
11
14
15-17
16
Effluent
Influent COD mg/1
•g/1 1
265
35
32
120
28
1ft
238
106
183
32
COD
It
31
32
24
79
35
40
44
X Removal
Average
88
88
78
62
•
*
79
Oryzalln Wastevater
Effluent COD
Influent COD tug /I X Removal
ng/1 I II Average
1,660
800 410 64
940 440 30
504 464 29
1,090
425 480 63
Oryzalln Waatevater
Effluent COD
Influent COD ag/1
•8/1 I II
7,800
1,880
1,720
-------
-» Influent COD
-• Effluent COD • Unit 1
1,600
1.400
1.200
1,000
> 800
I
i
' 600
400
200
• _. Eff|uent COD • Unit 2
Pesticide added •
Day?.
w.E
M
4 6 8 10 12 14 16
DAY
Figure 13. Influent and effluent COD for
activated sludge units fed 1% oryzalin.
18
66
-------
Influent COD
-• Effluent COD • Unit 1
. Effluent COD - Unit 2 ~ -g | $
500
=
-§ 400
o
o
300
200
i
100
*^B ^S ^^
Silt
= * =-
l=-o
*i jf*^^ E
^B «r v
f R««
S •« i' 2 B
«i||s-
ID ^j ^r ^^
^3 09 ^™ A} cs
, /ft / »-^*^
- y^^
0 -B
C 0)
0 X
i'g
gg
^^ g
a
.r •-
B O
= 5
09
*• 0)
5"s
1«
**
^^ *— V
f. M • . .-^__> •^>]/',*~-* — : ? — f— • .
2 4 6 8 10 12
DAY
14 16 18
Figure 14. Influent and effluent COD for control activated
sludge units fed primary settled wastewater alone.
67
-------
Table 19. OPERATING CHARACTERISTICS OF BENCH SCALE ACTIVATED SLUDGE
UNITS - ORYZALIN WASTEWATER SERIES
00
Parameter
DO, mg/1
PH
MLSS, ml/10 ml
Day
1
9
15
1
8
16
1
9
15
17
Control
I
5.7
7.2
7.1
7.4
5.6
6.8
0.4
0.4
0.1
0.15
II
5.8
7.3
7.1
5.9
5.7
6.1
0.5
0.2
0.15
0.05
Oryzalin, 1%
I II
7.2 7.4
6.7 6.6
8.0 8.1
8.2 8.1
0.2 0.0
0.1 0.0
0.1 0.0
Oryzalin, 10%
I LI
7.4 6.8
8.5 8.5
0.2 0.4
-------
neutral, that of the test units remained above pH 8. Such a drop in pH is
generally associated with nitrification and its failure to occur in the test
units may be indicative of interference of the wastewater with nitrifica-
tion. Further studies would be necessary in order to confirm or disprove
this conjecture.
Fish bioassay studies indicated that the LC,-Q of the untreated waste-
water containing 1.0% oryzalin wastewater was 60 ml/1 (Appendix L). This
was in agreement with the LC,-0 value of 0.3 ml/1 of the undiluted waste-
water, since it can be calculated that the LCL. of the 1% dilution would be
30 ml/1. After AS treatment, the wastewater was not toxic at levels up to
180 ml/1 (Appendix L), indicating that some mechanism occurring in the units
removed the toxicity.
Effect of Aeration on Oryzalin Wastewater
Although presence of oryzalin wastewater, even as low as 1%, caused
failure of bench scale activated sludge units, it was noted that some COD
removals were being obtained, evidently by a nonbiological process. Conse-
quently, the effect of simple aeration on COD levels in oryzalin-supplemented
primary domestic sewage was determined. Two different samples of primary
sewage were used and oryzalin wastewater was added to a final concentration
of 1%. The solutions were aerated for 8 hr with compressed air (humidified
by bubbling through water). Before and after aeration, aliquots were
removed for COD analysis. In one sample, the COD was reduced from 952 mg/1
to 476 mg/1; in the other, from 913 mg/1 to 436 mg/1. These results indicate
that some oxygen-demanding components of the oryzalin wastewater, responsible
for 50-52% of the COD, can be removed by air-stripping (or oxidation).
Further aeration tests were conducted at high pH with untreated,
filtered, and GAC treated wastewater to determine if conditions favorable
for air-stripping of NH_ would moderate toxicity of the wastewater to fish.
Although the amount of sample was only sufficient for screening tests,
survival of fish at a wastewater concentration of 1.0 ml/1 was consistently
greater when the wastewater had been pretreated by aeration at high pH
(Table 20). Note that at the 1 ml/1 (0.1%) concentration survival of fish
in carbon column effluents was markedly improved by air stripping.
69
-------
Table 20- SCREENING TESTS: EFFECT OF AMMONIA STRIPPING
ON TOXICITY OF ORYZALIN WASTEWATER TO FISH.
Sample
Wastewater
Concentration,
ml /I
No. fish surviving at indicated
tine (Initial - 3)
24 hr 96 hr
Control 3 2
Untreated 0.1 3 3
0.32 3 3
1.0 0 0
Filtered. Whatman 2V 0.1 3 3
0.32 3 2
1.0 0 0
GAC. 1st harvest 0.1 2 1
not stripped 0.32 3 3
1.0 0 0
stripped 0.1 3 3
0.32 3 3
1.0 3 3
GAC. Breakthrough (Fra"lon) 0.1 3 3
not stripped 0.32 3 3
1.0 0 0
stripped 0.1 3 3
0.32 3 3
1.0 3 2
Conditions for stripping: pH was raised to 1 11.2 with NaOH solution;
solution was aerated for 2 hr; pH was readjusted to 6.5.
70
-------
Overall, the results of the AS and air stripping tests indicated that
simple aeration for 6-8 hr removed much of the COD and greatly moderated
the toxicity to fish of the oryzalin wastewater and that short-term air
stripping at high pH also moderated the toxicity. No significant changes
in color of the solutions were noted. These results indicate that aeration
processes should be further investigated for eliminating toxicity and
reducing oxygen demand of wastewaters from oryzalin manufacture. Pre-
aeration might possibly improve performance of AS treatment by removing
toxic materials, reducing excess oxygen demand, or levering NH~ levels. By
removal of some of the organic material, it might also improve GAC treat-
ment.
EFFECT OF ULTRAVIOLET IRRADIATION ON EFFLUENT FROM ORYZALIN MANUFACTURE
Since oryzalin is reportedly degraded by ultraviolet (UV) irradiation,
an experiment was conducted at high levels of irradiation to determine if
significant color removal could be obtained. A 200 ml aliquot of oryzalin
effluent was irradiated with UV light for a period of 2 hrs. The UV light
source was a Hanovia High-Pressure Quartz Mercury Vapor Lamp with the fol-
lowing specifications: lamp watts, 450; arc inches, 4.5; lamp volts, 135;
lamp amps, 3.6. The lamp was enclosed in a water-cooled quartz casing which
was inserted into a glass tube containing the sample. Sample thickness in
the direct path of the light was ^ 4.5 mm. A small area at the base of the
tube received only indirect UV light. A Teflon stirring bar placed in the
sample facilitated mixing. Temperature of the sample ranged from 26-28 C.
Aliquots (10 ml) were removed at 15 min intervals during the first hour and
at the end of the second hour. Due to the high levels of color, these were
diluted to 0.25% solutions before spectrophotometric analysis at 300 nm
(Bausch and Lomb Spectronic 20). The results are shown in Table 21. Since
no color removal was obtained under these conditions (2 hr. at 450 watts) it
was concluded that large scale ultraviolet irradiation in commercial units,
which generally provide much shorter exposure times, would not be practical
for removing color (and, thus, presumably some of the organic components)
from this wastewater. It should be remembered, however, that the toxicity
of this wastewater is not directly correlated with its color and/or oryzalin
content.
71
-------
Table 21. EFFECT OF ULTRAVIOLET IRRADIATION ON ORYZALIN WASTEWATER
Irradiation
Sample No. Exposure (min) % Transmittance
10 13
2 15 13
3 30 13
4 45 15
5 60 15
6 120 13
72
-------
SECTION 6
MSMA WASTEWATER TREATABILITY STUDIES
GENERAL BACKGROUND INFORMATION
Pesticide: MSMA CAS No. 2163-80-6
. TM-.._ D TM _., , TM _ R _., . R ,, , ., _ ,R
Ansar 170; Bueno ; Phyban ; Daconate ; Silvisar ; Weed-E-Rad
Structure
0—Na
Monosodium methanearsonate; sodium acid methanearsonate; methanearsonic
acid monosodium salt.
Chemical Category
Organoarsenical; others in this class include methanearsonic acid (MAA),
disodium methanearsonate (DSMA), and cacodylic acid (CA).
Properties
M. W. 161.96; highly water soluble; solid, often marketed as a clear,
odorless solution at several concentrations such as 51% MSMA.
Intended Use
Herbicide for post-emergence control of weeds in cotton and turf.
Controls over 80 species of common weeds (Woolson, 1976).
Mode of Action
MSMA kills sensitive plants following foliar uptake and translocation. It
kills relatively slowly, apparently by inhibition of enzymes and thus
73
-------
inhibition of growth (Woolson, 1976). Atrazine has been shown to facili-
tate uptake of arsenic and since atrazine has a residual action of several
months in soil, these residues may enhance action of MSMA (Woolson, 1976).
Manufacturing Information - Introduced 1956
3
Estimated amount produced annually: 15.9 x 10 metric tons in 1974
(Archer et al., 1978).
Manufacturer Location
Diamond Shamrock Corp. Pasadena, TX
Crystal Chemical Co. Houston, TX
Vineland Chemical Co. Vineland, NJ
Health And Ecological Effects
Toxicity:—
Rat, oral, LD 50: 700 mg/kg (Fairchild, 1977)
900 mg/kg (Martin and Worthing, 1974)
Mammalian, LD 50: 50 mg/kg (Fairchild, 1977).
Bluegill sunfish (Lepomis macrichirus), LC,-0, 48 hr: > 1000
mg/1, but presence of surfactants causes increase in
toxicity (Martin and Worthing, 1974).
Fathead minnow (Pimephales promelas), I-CcQ. 96 hr, >510 mg/1
[Southwest Research Institute (SRI), 1979].
Sheepshead minnow (Cyprinodon varigatus), LCcn» 96 hr, >510 mg/1 (SRI,
1979).
Grass shrimp (Palaemonetes pugis), LC5Q, 96 hr, 510 mg/1 (SRI, 1979).
Worker bees, newly emerged (Apis mellifera L.), 100 ppm
(wt basis) is extremely toxic (Woolson, 1976).
Mutagenic Potential—
Does not cause point mutations in Salmonella typhimurium strains, T 4
bacteriophage, E. coli B host, or E. coli KB. (Anderson et al., 1972).
Negative response in the following in vivo and in vitro mutagenesis
tests: Ames test, with and without microsomes; Escherichia coli WP 2, with
and without microsomes; Saccharomyces cerevisiae mitotic recombination,
74
-------
with and without microsomes; E. coli, relative toxicity; Bacillus subtilus,
relative toxicity; and UDS DNA repair, with and without microsomes (Simmon
et aK, 1977).
Movement from treated weeds or soil to water is "likely to be minimal
because of fixation phenomena to plants, soils, and sediments" (Woolson,
1976).
Fate In Soil--
Certain soil microorganisms are able to metabolize MSMA via carbon
arsenic bond cleavage (Kaufman and Kearney, 1976). Arsenic is capable of
alkylation and subsequent dealkylation, so the process may be cyclic in
nature, the form of arsenic being governed by oxygen tension (Kearney and
Kaufman, 1975). According to Woolson (1976), the organic portion of MAA
can be metabolized in soil, and the arsenical portion may be reduced to
form a volatile compound which can escape to the air. Degradation of the
methyl carbon appears to require presence of other organic material (co-metab-
olism). Dimethylarsine has been found in the air over MSMA treated soils,
under both aerobic and anerobic conditions, with 0.8-12.5% of the MSMA
being degraded over a 160 day period.
Woolson (1976) also notes that the herbicidal effects are ultimately
eliminated by formation of insoluble salts, adsorption on soil colloids, or
ion exchange reactions of soils. These processes are dependent on soil
type, clays, such as kaolinite, being the most effective.
Manufacturing Process
The manufacturing process described here is generalized and it cannot
be assumed that this exact procedure is utilized at the plant site sampled.
The reactions are as follows (Sittig, 1977):
As0 + 6 NaOH ->• 2 NaAs0 + 3 H0
+ CH3C1 — ^CH3AsO(ONa)2 + NaCl
DSMA
OH
2 CH AsO(ONa)2 + H2S04— ^ 2 CH^s-ONa + N
MSMA
75
-------
DSMA is also a pesticide, but since it is not as soluble as MSMA and must
be applied at higher rates than MSMA, its use is not as great (Sittig,
1977).
The production and waste schematic are shown in Figure 15 (from
Sittig, 1977).
Current Waste Disposal Practice
Diamond Shamrock, Greens Bayou, TX, treats its wastewaters by clarifica-
tion, equalization, filtration, carbon filtration and aeration.
CHARACTERIZATION OF MSMA WASTEWATER
The wastewater from MSMA manufacture consists of evaporater distil-
late. Wastewater samples obtained appeared very clear, resembling tap
water. According to the manufacturer, the wastestream is of a highly
variable composition.
> VENT
•M>MSMA
Figure 15. Production and waste schematic for MSMA.
76
-------
Two samples of MSMA manufacturing wastewater were obtained from the
manufacturer at a 3 month interval. The two samples varied considerably in
solids, COD, and nitrogen content (Table 22). Analysis of the samples indi-
cated that much of the organic content was due to methanol, which was present
at concentrations of 3330 and 1600 mg/1. Arsenic content was 22.3 mg/1 in
the second sample. As described in the materials and methods section, it was
necessary to devise a method for measuring the MSMA molecule alone, rather
than as arsenic.
Methanol is a relatively common constituent of wastewaters from syn-
thetic chemicals production. It is readily utilized by many microorganisms
as a source of carbon and energy and is not considered difficult to treat in
biological treatment systems. The arsenic levels in the wastewater, as would
be expected, are higher than most industrial wastewaters.
Table 22. CHARACTERIZATION OF MSMA WASTEWATER
Parameter Sample 1
pH 5.0
Cl", mg/1 350
Acidity to pH 8.3,
mg/1 as CaCO_
TKK, mg/1 1.3
Nh^-N, mg/1 0.8
TP, mg/1 1.2
COD, mg/1 9,900
Suspended solids, mg/1
Total Solids, mg/1
Total Dissolved solids,
mg/1
Settleable Solids,
mg/1
MSMA, mg/1
Arsenic, mg/1
Methanol, mg/1 , 3,300
Sample 2
4.7
11
18.5
14.0
11.2
<2
3.0
4,100
8
60
52
<0.01
5.3
22.3
1,600
77
-------
Toxicity tests were conducted on the untreated wastewater (Appendix 13).
Algae failed to grow in media containing 10% (v/v) MSMA wastewater but at
levels of ~ 3% or less growth was approximately that of the control. This
implies that little or no effect on algal growth would be anticipated if the
wastewater were diluted by 30-fold.
A screening test of toxicity of the wastewater to fathead minnows was
conducted at test concentrations of 100, 180, and 320 ml/1 (10, 18, and 32%).
After 16 hr all fish in the two higher concentrations were dead. Dissolved
oxygen had dropped to 1.5 mg/1, possibly due to bacterial degradation of the
large amount of methanol present in the waste. To test this hypothesis and
to eliminate the confounding of MSMA toxicity with the stress of low oxygen
concentration, a second screening test was conducted at 180and 320 ml/1
concentrations. In each case one set of jars was aerated with compressed air
and the other set was not aerated. The results gave some indication that
aeration reduced toxicity at the 180 ml/1 concentration. Due to insufficient
quantities of the MSMA wastewater, this test could not be repeated with a
large scale assay.
Examining the reported toxicity to fish of two of the MSMA wastewater
components, methanol and arsenic, indicates that levels of As showing toxic
effects in < 6 days are > 1 mg/1 and that fish in general are very tolerant
to methanol, some being able to tolerate as much as 8100 mg/1 for 24 hours or
more (McKee and Wolf, 1963).
ACTIVATED CARBON TREATABILITY STUDIES
Because of time constraints, MSMA was subjected to GAC column treatment
directly, without preliminary isotherm studies. An activated carbon column
2.7 (i.d.) and 15 cm long was prepared with Calgon Filtrasorb 400. Due to
the clarity of the wastewater, it was not prefiltered. It was pumped through
2
the column at a flow rate of 750 ml/hr (0.535 gpm/ft ). One bed volume (87.2
ml) was discarded before collecting fractions. Results are shown in Table 23
and in Figure 16. Note that at <12 column volumes the COD level was approach-
ing that of the feed and the MSMA level was greater than 1 mg/1 (as As).
Thus, carbon treatment appears to be not very promising for treating this
78
-------
Table 23. EFFECTIVENESS OF GAG TREATMENT FOR REMOVAL OF MSMA FROM
MANUFACTURING WASTEWATER
Sample
Effluent
Effluent
Effluent
Effluent
Effluent
Effluent
Effluent
Cumulative
No. of Column Volumes
, fraction
, fraction
, fraction
, fraction
, fraction
, fraction
, fraction
I
II
III
IV
V
VI
VII
11.
22.
35.
47.
58.
76.
88.
5
6
3
9
9
8
2
Column feed (raw wastewater)
- * not
analyzed
MSMA
mg/1
1
3
3
3
3
3
4
5
in
as As
.8
.3
.7
.8
.8
.8
.0
.3
COD
mg/1
(avg. of 2 values)
2,115
-
-
-
-
_
-
2,510
-------
6
tn
W
rH
M
-O-
-O-
00
o
c
o
rt
c
OJ
o
c
o
u
10
I
20
Figure 16.
I
I
I
30 40 50 60
Number of Bed Volumes Throughput
Carbon column treatment of MSMA.
70
80
-------
wastewater unless no less costly alternative is available. Since the un-
treated wastewater has a total arsenic concentration of 22 mg/1, the MSMA
(arsenic equivalence) represents only about 25% of the total arsenic. Thus,
the MSMA may not be the most important component to consider. In any further
treatability studies, both MSMA and arsenic analyses should be performed on
all samples. The raw wastewater also contains a large amount of methanol (^
1,600-3,000 mg/1), which would give a theoretical oxygen demand of 2400-4500
mg/1. Examination of the COD data indicate that at a throughput of greater
than 11 bedvolumes little or none of the oxygen-demanding organic content
was removed during GAC treatment. This was to be expected since methanol
absorbs very poorly on activated carbon (Hager, 1974; Shumaker, 1977).
To get a better estimate of the actual carbon requirement, further
studies should be conducted to determine at just what point breakthrough of
MSMA and/or COD occurs. In determining overall costs, it should also be
noted that this wastewater, unlike most wastewaters, does not require prelimi-
nary treatment to remove suspended solids.
Tests with algae (Appendix M) indicated that the inhibitory effects of
the GAC-treated wastewater were essentially the same as for the untreated
wastewater, with no growth occuring at a 10% (v/v) wastewater concentration.
BIOLOGICAL TREATABILITY STUDIES
Four activated sludge pilot units were set up with domestic sewage
feed. Of these, two were controls and two received sewage supplemented with
the MSMA wastewater (10% vol/vol). After a 10-day period of acclimation
samples of influent and effluent from each unit were taken and analyzed for
MSMA. Direct analysis by ion chromatography was not possible for these
samples for two reasons: (1) the 10-fold dilution placed the final concen-
tration at or below the limit of detection and (2) the sewage contained such
high anion concentrations that simple concentration steps were not effective.
As described in the methods section, pretreatment of the activated sludge
wastewater samples by chloride removal made it possible to measure the MSMA.
No interferences were noted in the MSMA wastewater alone.
Results of the analyses of the influents and effluents of the activated
sludge units are given in Table 24. Concentration of MSMA in the effluent
81
-------
Table 24. DETERMINATION OF EFFECTIVENESS OF ACTIVATED SLUDGE TREATMENT OF MSMA WASTEWATER
Sample
MSMA
mg/1 as As
of Influent Value
I. Influents and Effluents
10% MSMA Wastewater - Influent
- Effluent, Unit 1
- Effluent, Unit 2
Domestic Sewage Control - Effluent, Unit 1
Effluent, Unit 2
II. Sludges
MSMA Wastewater, Unit 1
Unit 2
0.27
0.29
0.29
Not detectable (<0.03)
Not detectable (<0.03)
0.53
0.53
109
109
-------
of the test units was comparable to that in the influent, giving evidence
that activated sludge treatment was ineffective for its removal. As shown
by the analytical results, the influent concentration was also considerably
lower than would be expected in a 10% dilution of the wastewater (2.2 mg/1
expected, 0.27 mg/1 actually detected). This anomaly may result from either
losses in the analytical workup, or, more likely, from removal of some of
the soluble MSMA by sorption in the primary settling of the sewage/MSMA
wastewater mixture. While such removal by sorption may occur, it must be
noted that settling per se has not been considered a reliable method for
removing asenic, since longterm experience of the manufacturer indicates no
reduction of arsenic across the primary settling portion of the plant's
wastewater treatment system.
Performance and operating characteristics of the units are shown in
Tables 25 and 26 and in Figures 17 and 18. Despite the higher influent COD
to the test units, the units performed about as well as the controls in
terms of COD removal. Dissolved oxygen (DO) levels remained well above
requirements, and pH in the test units was similar to that of the controls.
Variability of effluent COD and SS values was to some extent due to opera-
tional problems with feed to the units.
Although COD reduction in the test units was reasonably good, ineffec-
tiveness of AS for removal of MSMA and arsenic precludes recommending acti-
vated sludge alone as a satisfactory control technology. Removal of these
components prior to activated sludge treatment would be desirable.
Only a relatively small amount of effluent was available for toxicity
testing with fathead minnows since the raw wastewater was not very toxic.
Replicate screening tests (6 fish total) were conducted on undiluted efflu-
ents from the test units and no deaths occurred in 96 hours.
83
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Table 25. OPERATING CHARACTERISTICS OF BENCH SCALE ACTIVATED
SLUDGE UNITS - MSMA WASTEWATER SERIES
UNITS
Parameters
DO, mg/1
pH
MLSS, ml/10 ml
Day
1
9
15
1
8
16
1
9
15
17
Control
I
5.7
7.2
7.1
7.4
5.6
6.8
0.4
0.4
0.1
0.05
II
5.8
7.3
7.1
5.9
5.7
6.1
0.5
0.2
0.15
0.05
10% MSMA
I
6.9
5.8
5.3
5.9
6.7
6.0
0.45
0.5
0.5
0.5
Wastewater
II
7.4
6.2
6.5
7.3
6.6
6.3
0.25
0.25
0.25
0.25
-------
Table 26. PERFORMANCE CHARACTERISTICS OF BENCH SCALE ACTIVATED SLUDGE UNITS,
MSMA WASTEWATER SERIES
Control
Units fed
Units 10% MSMA wastewater
Effluent Ave %
Parameter
COD, mg/1
Effluent
Suspended
Solids rag/1
Day Influent
1-6 265
2
4
7-14 120
7
9
11
14
15-17 183
16
2
4
7
11
I
35
32
28
14
238
106
32
24
4
72
195
II removal Influent
330
31 87
32 87
440
24 78
79 61
35 +
40 40
210
44 79
-
6
6
5*
Effluent
I
86
36
63
18
166
60
40
17
10
3
77
II
106
80
75
50
110
106
60
52
40
22
39
Ave %
removal
71
82
84
92
67
81
76
Sludge was lost into the effluent. The effluent was allowed to settle,
SS was determined on the supernatant, and the sludge was returned to the
unit.
85
-------
00
1.500
Influent COD
1,000
500
100
Figure 17.
• • Effluent COD • Unit 1
»• • Effluent COD • Unit 2
Pesticide added Day 1.
500
£ 400
a
o
w
300
200
1
100
fc:::^__^=4=^___z=z^
2 46 B 10 12 14 16
DAY
*
« ® Influent COD .2
• • Effluent COD - Unit 1 "g g jj-
_____ Effluent COD - Unit 2 £ -g | 1
"§ JJ ell
"" I •••
=5.2°
Ifgl
^
-------
SECTION 7
MANEB WASTEWATER TREATABILITY STUDIES
GENERAL BACKGROUND INFORMATION
Pesticide: Maneb
CAS No.: 000301031
TM T"M I? R T?
MEB; MnEBD, Manzate ; Dithane M-22; Maneba ; Manebgan ; Manesan ;
TJ R R
Sopranebe , Trimangol ; Vancide , Tersan LSR
Structure
Maneb is the general name for a class of formulations based on manganese
ethylenebisdithiocarbamate. The different formulations vary considerably
and may be toxicologically distinct from one another. Approximate formula
(actually a polymer)
[S-SC-NH-CH -CH -NH-CS-S] Mn
^ ^ «* y
Manganous ethylene-l,2-bis-dithiocarbamate; [ethylenebis(dithiocarbamato)]
manganese
Chemical Category
Ethylenebisdithiocarbamate (EBDC)--Others in this class include ferbam,
zineb, nabam, thiram, and ziram. Ethylene bisdithiocarbamates are also
widely used as slimicides in the paper industry and are used in rubber
processing.
Properties
MW 265.3--Decomposes before melting. Yellow crystalline solid. Stable to
storage in dry air but decomposes in the presence of moisture to give carbon
disulfide (CS2) and ethylene thiourea (ETU). Maneb is insoluble in organic
solvents. The apparent aqueous solubility of maneb determined in this study
87
-------
was 40 mg/1. Apparent maneb concentration is defined in terms of CS_
generated by the sample under the conditions of maneb analysis (Appendix 6).
The compounds determined included maneb and other compounds generating CS-
(e.g., ethylene thiuram disulfide or monosulfide). The solubility was
determined on aqueous filtrates which had been equilibrated with excess
maneb at room temperature. pH and ionic strength will of course influence
the value determined.
Hydrolysis reactions of maneb are complex and may occur under acid,
alkaline, or neutral conditions, according to Shih and Dal Porto (1975):
4 H2SO,
^^^-^^^
S acid
• i
CH-KnCSv
1 S-~
CH,NHCSX
* n
S 4 2 H?0 ,
^ ^""2
2 2
•thylane
dlamlne
k ru uu.
* 2CS2 -
carbon
dlaulflde
* «nS04
•anganeie
•ulfate
.
weak acid
•net-
\
CHjNH
neutral or
alkaline
^C-S * H2S * CS2 H
hydrogen I
•ulflde I
•thylenethlourea |
carbon
dlaulflde
Kn(OH)2
•anganece
hydroxide
\
•thylenethlurac:
•onoaulfide
polyverlzatlo
further
hydrolyala
polyethylene thiurar
•onoaulfide
C-S
•thylene
thlourea
Shih and Dal Porto (1975) also note that, in addition to the above
reactions, under neutral or alkaline conditions formation of ethylene
diisothiocyanate and ethylene diamine may occur. CS_ evolution accompanies
both alkaline hydrolysis and hydrolysis under strong acid conditions. Under
some conditions chemical hydrolysis may produce ETU, as indicated in the
diagram above. Chemical oxidation may likewise product ethylene-thiuram
88
-------
monosulfide which hydrolyses to ETU. For these reasons, these authors
recommend disposal of commercial maneb preparations by burial or incinera-
tion, rather than by chemical treatment. However, for the more dilute
pesticide manufacturing wastewaters, one cannot rule out the possible useful-
ness of hydrolysis under controlled conditions.
ETU is water-soluble [2 g/100 ml at 30°C (Merck Index, 1976)] and
stable to sunlight, but presence of added photosensitizers (such as acetone
or riboflavin) causes rapid photolysis; agricultural field waters taken from
locations of dithiocarbamate application catalyzed ETU photodecomposition
(Crosby, 1976).
Intended Use
Maneb is a fungicide for control of foliar fungal blights. It is
recommended for prevention of early and late blight on tomatoes and potatoes,
and can be combined with other fungicides for persistent fungal strains.
EBDC fungicides are used in control of over 400 fungus diseases for protec-
tion of over 70 crops.
Mode of Action
Unknown.
Manufacturing Information - Introduced 1950
3
Estimated Amount Produced Annually: 5.4 x 10 metric tons in 1974
(Archer et al., 1978)
Manufacturers Locations
DuPont La Porte, TX
Rohm & Haas Philadelphia, PA
Manufacturing Process
The processes described here are generalized and are not necessarily
identical to those in operation at the plants sampled. According to the
National Research Council (NRC, 1977) dithiocarbamates can be synthesized by
reacting a suitable amine, such as dimethylamine or ethylenediamine, with
CS under alkaline conditions to yield the alkaline salt of the alkyl
dithiocarbamic acid. These water-soluble salts can then be reacted with
89
-------
aqueous solutions of salts of zinc, manganese, and iron to form precipitates
of the corresponding highly insoluble metallosalts. Alternatively, the
metallosalts can be produced by reacting metal oxides with the appropriate
amine and CS?.
Sittig (1977) describes the reaction chemistry as follows:
S
CH2NH2
2CS
2NaOH
CH2NHCSNa
CH0NHCSNa
2 II
S
Nabam
2H20
CH.NHCSNa + MnSO,
2 A
CH2NHCSNa
n
[MnSCNHCHNHCS]
Na2S°4
Maneb
Nabam
Alternatively, maneb can be produced by reacting ethylenediamine with
sodium hydroxide solutions and CS2 to form the disodium ethylenebisdithio-
carbamate, which is then reacted with manganous chloride to form the fungi-
cide (Sittig, 1977). The major raw waste load from the maneb manufacturing
process is the wastewater remaining after the precipitate is removed.
As summarized by Sittig (1977), air, liquid, and solid waste problems
may occur. The liquid waste stream contains about 9 Ib. of salts for each
13 Ib. of maneb produced, these salts being primarily sodium sulfate with
some manganese sulfate.
90
-------
Health and Ecological Effects: Maneb
Mammalian Toxicity--
Toxicity rated as low:
Rat, oral LD5(): 6750 rag/kg (Fairchild, 1977)
Rat, inhalation, LC : 3000 mg/kg (Fairchild, 1977)
Recommended allowable daily intake, human: 0.005 mg/kg/day (NRC, 1977)
14
In animal metabolism studies with C-maneb, about 55% was excreted as
the metabolites ethylenediamine, ethylene-bis-thiuram monosulfide (ETM) and
ETU, these metabolites associated mainly with the feces; no evidence for
accumulation in tissues was found (NRC, 1977).
Aquatic Toxicity--
Aquatic toxicity rating, TLm, 96 hr.: 10-1 ppm (Fairchild, 1977).
Toxicity to fish, 96 hr TLm: 0.1-1.0 mg/1 (Kemp et aJL. , 1973).
Mutagenic Potential--
In. vitro mutagenesis tests:
Ames test, only weakly mutagenic; E. cojli B Y Vr-B strain, induced
5-fold increases in streptomycin resistant mutants (Warren et al., 1976).
Health and Ecological Effects: ETU
NRC (1977) notes that "the occurrence of ethylenethiourea (ETU) as a
major decomposition product (of maneb)...presents a potential hazard since
it is goitrogenic in laboratory animals and may produce thyroid carcinoma."
Rat, oral, 10 mg/kg/day: teratogenic (Khera, 1973)
Weakly mutagenic to mammals (NRC, 1977); mutagenic to Salmonella
typhimurium his G46 (Shirasu et al., 1977).
Produces hepatomas in mice (NRC, 1977)
In summarizing their review of ETU the National Research Council has recom-
mended "that very strict criteria be applied when limits for ETU in drinking
water are established" (NRC, 1977). Weisburger (1977) recommends that "in
view of the carcinogenicity of ethylenethiourea in two animal species, human
exposure should be avoided." It should be stressed, however, that the
validity of animal studies with ETU has been questioned and that additional
91
-------
animal studies with EDBC's are in progress (Gower and Gordon, 1979). For a
recent review of the health effects of ETU see Gregory, 1978.
Potential Biodegradation Products
Packer (1975) indicates that biodegradation of maneb probably proceeds
by first, a scission of MnS to form ethylene thiuram monosulfide polymer,
CH,
N=
CH2 - N- C
followed by loss of CS to form ETU:
Current Waste Disposal Practice
Plant A
Treatment of raw wastewater with sodium hydroxide to
remove manganese; precipitation of the insoluble Mn(OH)_.
Treatment of remaining wastewater by chemical oxidation, pH
adjustment, and activated sludge. Wastes from the other
products are treated in the same activated sludge unit, so
efficiency of the maneb waste treatment alone cannot be
calculated. The plant achieves an average of >99% BOD reduc-
tion and 70% COD reduction, representing excellent perfor-
mance by activated sludge.
92
-------
This system was adopted by Plant A after tests with
chemical oxidation, pH adjustment, temperature treatments,
iron salt precipitation, and carbon adsorption indicated
that chemical oxidation was the method of choice for re-
ducing fish toxicity.
Plant B Pretreatment with skimming, neutralization, before discharge
to a publicly owned treatment plant. (Communication,
Environmental Sciences & Engineering)
CHARACTERIZATION OF MANEB WASTEWATERS
Wastewaters from each manufacturer of maneb were collected on-site,
transported to RTI packed in ice, and analyzed for maneb and other compo-
nents as described previously. Results of the analyses are shown in Table
27. Both wastewaters had the appearance of orange juice in respect to
color and turbidity. Dissolved, suspended and settleable solids contents
were extremely high for both plants as would be expected based on the
manufacturing process. The Plant B sample had considerably higher levels
of dissolved solids, inorganic nitrogen, and total pesticide. For each
plant soluble pesticide levels were similar (40-46 mg/1) and approximated
the aqueous solubility, ^ 40 mg/1.
At Plant A, nine five-gallon grab samples of wastewater were collected
over a 2-week time period. Analysis of the wastewaters from each date gave
an indication of the great variability of the strength of this flow (Table
28), with the total "maneb" pesticide concentration ranging from less than
1.5 to nearly 1240 mg/1 (including particulates). The majority of the
values ranged from 100-400 mg/1. These stated concentrations of maneb
included particulate maneb present in the sample as received. Before
conducting the studies described below, each of the daily samples was mixed
thoroughly and equal aliquots from each daily sample were composited. All
full scale tests described below were run on this composited sample. The
magnitude of the variation indicates that the wastewater may be difficult
to treat biologically unless the effect of slugs can be moderated by load
equalization prior to biological treatment or by treatment in a unit with
long detention time, where the daily influent would represent only a small
93
-------
Table 27. CHARACTERIZATION OF MANEB WASTEMATERS
VO
Parameter
PH
Cl~, mg/1
Alkalinity, mg/1 as
CaC03
TO, mg/1
NH^-N, mg/1
N02-N+N03-N, mg/1
TP, mg/1
COD, mg/1
Sol. COD, mg/1
Suspended solids, mg/1
Total solids, mg/1
Total dissolved solids ,
mg/1
Settleable solids, ral/1
Plant A
Sample 1 Sample 2
6.8 6.9
640 770
55.0 45.0
880 740
560 640
4.0
0.3
8,800 4,140
1,990
24,800
22,800
74
Plant
Sample 1
990
152
6,100
930
0.01
2,400
1,980
1.0
B
Sample 2
7.8
840
120
3,660
3,580
60
0.1
2,000
1,600
102,000
100,400
9.5
-------
TABLE 28. STUDY OT VARIATION IN MANEB MANUFACTURING
WASTEWATER
Date
5/30
5/31
6/1
6/2
6/7
6/8
6/9
6/13
6/13
Concentration of
Maneb and Related Compounds
(ppm)
1240
400
110
360
130
1.40
140
130
120
95
-------
portion of the total volume. Such variation should have less effect on
performance of physical-chemical treatment systems. However, in GAC column
systems the daily variation may complicate reliable prediction of carbon
requirements and breakthrough time. Frequent monitoring of the effluent
would be necessary.
Plant B wastewater samples represented a mixture of wastes from the
straight line filter and from the scrubber. The straight line filter is
the largest source of effluent from the maneb production process. The
scrubber contributes the next largest flow. In actual practice these waste
streams enter the sewer with much additional wastewater from vacuum jets,
tote-bin washout, and wastewater from production of other pesticides. This
combined wastewater is then subjected to settling prior to discharge to the
main plant sewer. The Plant B wastewater sample from the scrubber and
filter was collected at a point prior to any mixture with other waste
streams, and thus represents a waste stream with maximum maneb content.
Toxicity tests were conducted on fathead minnows with both wastewaters
and with commercial maneb. Screening tests with commercial maneb indicated
the 96 hr LC to be between 0.1-1.0 mg/1 (Bioassay data are presented in
Appendix N). Screening tests with Plant A wastewater showed the 96 hr LC
for fish to be between 0.1 and 1% for both filtered and unfiltered samples.
The 96 hr LC5 of unfiltered Plant B wastewaters was between 0.01 and 0.1%
(v/v), while filtered wastewater was less toxic with a 96 hr LC „ between
0.1 and 1%. A definitive fish bioassay with unfiltered Plant B wastewater
gave a 96 hr LC5Q between 0.056 and 0.1% (v/v).
Full scale fish bioassay of unfiltered Plant A wastewaters (Sample 2)
showed a 96 hr LC of approximately 1.8 ml/1 or 0.18%. Filtered Plant A
wastewater was much less toxic with a 96 hr 1C > 32 ml/1 or 3.2%. Several
factors could account for the higher toxicity of unfiltered Plant A waste-
water. Solid material probably redissolves to the point of saturation
subsequent to dilution and thus is made more available to fish. It was also
noted that fish tended to "mouth" pieces of solid material, thus increasing
exposure to possibly toxic material.
Full scale fish bioassay of Plant B wastewater (Sample 2) resulted in
(r.
96
the same pattern as Plant A wastewater. The 96 hr LC of unfiltered Plant
-------
B wastewater was approximately 0.18 ml/1 (0.018%) while filtered wastewater
showed a 96 hr LC,.. of approximately 3.2 ml/1.
Unfiltered Plant B wastewater was consistently more toxic than unfil-
tered Plant A wastewater. Zinc was reported by plant personnel to be pres-
ent in the Plant B wastewater due to plant production of both Mn and Zn
forms of the fungicide. In soft water 96 hr LC values for zinc for fish
are in the vicinity of 2-4 mg/1 (McKee and Wolf, 1963). If present, zinc
could be partially responsible for the greater toxicity of Plant B waste-
waters as compared to Plant A wastewater.
In screening tests with algae wastewaters from both Plant A and Plant B
were inhibitory to algal growth at concentrations of 0.1% and above. Since
these wastewaters were filter-sterilized prior to addition to algal assays,
the soluble fractions of each waste appear equally toxic to algal growth.
Further tests with Plant B wastewater, using a narrow range of test concen-
trations, indicated that the 14-day EC5Q was 0.06-0.1%.
In bacterial spot tests all undiluted maneb manufacturing wastewaters
produced marked zones of inhibition (Appendix 0). This indicates that the
undiluted wastewater would be apt to interfere with activity of the organ-
isms present in sewage and possibly interfere with biological treatment sys-
tems .
ACTIVATED CARBON TREATABILITY STUDIES
Maneb manufacturing wastewaters were subjected to activated carbon
treatment in liquid adsorption isotherm and GAC column studies. Since, as
noted previously, aqueous preparations of maneb have a strong tendency to
undergo decomposition to the breakdown products ethylene dithiocarbamate
monosulfide (ETM), ethylene dithiocarbamate disulfide (ETD), and ethylene
thiourea (ETU), even in the dark in cold storage (Czegledi-Janko, 1967), and
since ETU is considered a more hazardous compound than is maneb (NRC,
1977), concentrations of these breakdown products, as well as maneb, were
determined.
Adsorption Isotherm Studies
Activated carbon isotherm studies with the wastewaters (Tables 29 and
30, Figure 19) indicated that maneb could be removed to low levels by
97
-------
Table 29. LIQUID ADSORPTION ISOTHERMS FOR TWO MANEB MANUFACTURING
WASTEWATERS
Carbon: Calgon Filtrasorb 400
x~
M C Pesticide Pesticide Adsorbed
Wt. of Carbon, Residual Pesticide, Adsorbed Per Unit Weight
g/100 ml of Solution mg/1 mg/1 g/g
Plant A*
0 1.2
0.04 0.43 o.77 0.0019
0.08 0.25 o.95 0.0012
0.16 0.19 i.o; 0.0006
2.0 0.05 1.13 0.00006
Plant B
0
0.04
0.08
0.16
2.0
19.1
5.9
3.8
0.74
0.30
-
13.2
15.3
18.36
18.8
0.033
0.019
0.011
0.009
Initial concentration of the maneb in the sample tested was very low
98
-------
VO
Table 30. LIQUID ADSORPTION ISOTHERM FOR PLANT B MANUFACTURING
WASTEWATER
wt.
g/100
Carbon:
M
of Carbon,
ml of Solution
0
0.04
0.08
0.16
2.0
Calgon Filtrasorb
C
Residual Pesticide,
mg/1
30.10
1.14
0.48
0.25
*
not detectable
400
X
Pesticide
Adsorbed, tng/1
—
28.96
29.62
29.85
^30.10
X/M X/M
Pesticide Adsorbed at
Per Unit Weight, g/g C»
—
.0724
.0370
.0186 12. 'j
*< 0.15 ng/1
-------
O Run 1 - at C0 = 12.5
M
Run 2 - £ at C0 = 1.8
M
10.0.
X
M
1.0.
0.1
0.1
Figure 19.
1.0 10
C-, Pesticide Remaining, rag/1
Liquid adsorption isotherms for Plant B
manufacturing wastevaters.
100
100
-------
Table 31. ADSORPTION ISOTHERM STUDIES OF ABILITY OF ACTIVATED CARBON
TO REMOVE ETU FROM PLANT A WASTEWATERS
Sample Carbon
Plant A
Wastewater None
Filtrasorb 400
Nuchar WV-L
Nuchar SA
Nuchar WV-G
UC-LCL
Amount of Carbon
g/100 ml
0
0.08
0.16
2.0
0.16
2.0
0.16
2.0
0.16
2.0
0.16
ETU in solution
in filtrate,
mg/1
31 + 7
29
23
<6
38
<13
34
<14
47
<14
25
101
-------
activated carbon. The results of isotherm studies with ETU indicated possible
removal of ETU by carbon treatment. This option was pursued further with
GAC column studies. Filtrates from the carbon isotherm studies with Plant B
wastewater were subjected to thin layer chromatography (Czegledi-Jankd,
1967) for maneb breakdown products. Figure 20 shows the chromatograms
obtained by scanning densitometry. In this figure the area where ETU would
appear is deleted since ETU concentrations were so high that the detection
system was saturated. The 10 minute exposure to*iodine vapor was insuffi-
cient to develop full color in the center of the ETU spot ("concentration
reversal"); however this exposure gave best visualization of the other
breakdown products. The same plate was exposed to iodine vapor for an
additional 30 min and rephotographed and rescanned (Figures 21 and 22).
Even at this much longer exposure there was still some concentration rever-
sal at the higher ETU concentrations which indicated insufficient exposure
to and complexing with the iodine vapor. It was possible under these condi-
tions to estimate the amount of ETU originally present in this wastewater
sample at 300 to 600 mg/JL Treatment with 2.0 g of activated carbon/100 ml
of filtered wastewater removed 90 to 95% of the ETU.
GAC Column Studies
Plant B wastewater was subjected to GAC treatment. A column 2.5 cm in
diameter was filled to a depth of 1.2 m with 360 g of carbon (Calgon Filtra-
sorb AGO). The filtered wastewater was pumped onto the column to give a flow
2
rate of 12.5 ml/min (0.607 gpm/ft ). Approximately one bed volume (650 ml)
was discarded before fraction collection was initiated. The data are given
in Table 33. No maneb or maneb decomposition products were detected in any
fractions.
Since no breakthrough of maneb was observed the procedure was repeated
with a smaller column. A 2.7 cm i.d. column was filled to 15 cm with 58.8
g of activated carbon. Filtered maneb wastewater was pumped through the
2
column at 12.5 ml/min (0.529 gpm/ft ). One bed volume (85 ml) was discarded
before collecting effluent fractions. The data are given in Tables 34 and
35. Simple filtration removed suspended solids and a substantial portion of
the COD (^79%), indicating that efficient settling or filtration processes
102
-------
x2
Figure 20. Thin-layer chromatogram of Plant B wastewater
and filtrates of carbon isotherm determination
(a) 10 yl untreated wastewater; (b) 50 pi
treated with 0.04 g carbon/100 ml wastewater;
(c) 50 pi wastewater treated with 0.08 g
carbon/100 ml. Absorbance sensitivity is twice
that of a and b.
103
-------
A
(B
!
?5£
§ & S1
'1,1
03
H. <
§ CL M
£ 3 O
i;
£ n> o
rt X B
Si S
. in o
C (TO
M i-t
-" fD Q)
I
! •
(I.
to
O
i '•
: b
i '-
; i
a
re
a
r !•
/
n
h
(5
P3
K
I
Blank
50 ul, 2.0 g C
50 ul,0.16 g C
50 ul,0.08 g C
50 ul.0.04 g C
10 ul, untreated
50 ul, untreated
4.15 ug ETU
<•
-------
0.4 ODFS
0.4 ODFS
0.4 ODFS
1.0 ODFS
Figure 22. Thin-layer scans of ETU in Plant B
wastewater and carbon treated filtrate:
(a) 10 ul untreated wastewater; (b) 50
pi wastewater treated with 2.0 g carbon/
100 ml; (c) 50 ul wastewater treated with
0.16 g carbon/100 ml; (d) 4.15 ug ETU
standard.
105
-------
Table 32. EFFECT OF GAC COLUMN TREATMENT OF PLANT A WASTEWATER
Fraction
No.
I
II
III
IV
V
VI
VII
VIII
Table 33.
Column Effluent
Fraction No.
I
II
III
IV
V
VI
VII
VIII
IX
X
XI
Cumulative
No. of
Bed Volumes
11.0
22.0
33.0
44.0
55.0
66.0
77.0
88.0
EFFECTIVENESS OF
WASTEWATER-RUN
Cumulative
No. of
Bed Volumes
1.62
3.24
4.86
6.47
12.46
14.08
15.70
17.32
18.93
20.55
21.80
Maneb
mg/1
< 0.15
< 0.15
< 0.15
< 0.15
< 0.15
< 0.15
< 0.15
< 0.15
GAC TREATMENT OF PLANT
I (1.2 m column)
Maneb
Concentration,
mg/1
<0.15
<0.15
<0.15
<0.15
<0.15
<0.15
<0.15
<0.15
<0.15
<0.15
<0.15
ETU
mg/1
< 1.0
< 1.0
< 1.0
1.1
4.4
4.2
-
-
B
Maneb
Decomposition
Products
Present?
No
-
No
-
No
-
No
No
-
No
-
106
-------
Table 34. EFFECTIVENESS OF GAG TREATMENT OF PLANT B WASTEWATER-
RUN II (15 cm column)
Column Effluent
Fraction No.
I
II
III
IV
V
VI
VII
Cumulative Maneb
No. of Concentration,
Bed Volumes mg/1
17.9 <0.1
29.4 <0.1
40.8 <0.1
52.8 <0.1
64.2 <0.1
75.7 <0.1
87.2 <0.1
Table 35. EFFECTIVENESS OF FILTRATION AND GAC TREATMENT
REDUCING COD OF PLANT B WASTEWATER
Sample
COD, mg/1
Replicate I Replicate II
Unfiltered wastewater
Filtered, Whatman 2V (column feed)
GAC Treated. 1st Effluent fraction
*
7,500
1,600
100
1,600
100
(Calgon Filtrasorb 400)
Due to the presence of fine solids in the Plant B wastewater, obtaining
reproducible COD values was difficult. This value represents a "best
estimate" of the COD concentration.
107
-------
"
;
H
n
;
1
g
I
s! (n
Co H
CO
rt n
ro y
co o
rt g
fD Co
t~\ r~t
o
l-h OQ
O Co
s g
T) O
M Mi
Co
0 C
rt a
rt
t^ ^""1
• fD
Co
' t
(B
PL
ETU, 1.66 yg
Fraction VII, 50 AJ!
Fraction V, 50 /jl
Fraction III, 50 AJ!
Fraction I, 50 AJ!
Untreated, 10 AJ!
-------
C3
O
J L
I I I L
CM
Figure 24. Thin-layer chromatograms of ETU and extracts of carbon
column effluent in the treatment of Maneb wastewater.
(a) 50 yfc Fraction III (23-33 column volumes). (b) 50 y£
Fraction IV (34-44 column volumes). (c) 50 yA Fraction V
(45-55 column volumes), (d) 50 \ii Fraction VI (56-66
column volumes). (e) 10 y£ wastewater filtrate, untreated,
(f) 0.41 yg ETU. 109
-------
in themselves would effect an impressive degree of treatment. GAC treatment
reduced COD to 100 mg/1, equivalent to removal of 94% of the COD in the
column feed and >98% of the COD in the unfiltered wastewater.
All of the fractions were analyzed for maneb by the headspace method
(Appendix F) and none was detected in any fraction (<0.15 ppm) (Table 34).
This was despite the appearance of particulate at the top of the carbon
column from the start of fraction IV. Analysis for breakdown products by
tic was performed on the odd numbered fractions. The results are shown in
Figures 23 and 24 and plotted in Figure 25. Fractions I and III are free of
any detectable breakdown products. Fraction V shows the presence of ETU at
20-40 ppm. By fraction VII the ETU concentration was approximately 20% (^
60-120 ppm) of the original untreated wastewater. Breakthrough for ETU
occurred between 40.8 and 64.2 bed volumes (Figure 25), Another breakdown
product (ETM) was observed in fraction VII (Figure 22). It is unclear
whether the larger volume prior to ETM breakthrough is attributable to the
lower concentration of this component in the wastewater or to less sensitiv-
ity of the analysis of ETM.
Based on results of carbon treatment of Plant B wastewater Plant A
wastewater was subjected to short GAC column treatment, using a 2.7 cm i.d.
column filled to 15 cm with 48.8 g of carbon. Filtered wastewater was
2
pumped through the column at 12.5 ml/roin (0.529 gpm/ft ). One bed volume
(85 ml) was discarded before collecting fractions. The data are shown in
Table 32. Carbon required to reduce ETU to < 1.0 mg/1 would be 107 lbs/1000
gallons.
Effect of GAC Column Treatment on Toxicity to Fish and Algae
Tests with untreated Plant A wastewater indicated the 96 hr LC Q to be
1.8 ml/1, while simple filtration reduced the toxicity to an ICCQ of > 32
ml/1. Due to volume constraints it was not possible to run toxicity tests
at dosages of GAC treated wastewater higher than 32 ml/1 so it is not
possible to determine if GAC treatment significantly affected toxicity;
however, the LC5Q, as expected, was > 32 ml/1. Untreated Plant B wastewater
had an LC of ~ 0.14-0.17 ml/1, which was increased to -v 3.2 ml/1 by
simple filtration and to > 3.2 ml/1 by GAC treatment.
110
-------
100 •
90 .
BO .
70 .
60 ,
50
tc
E
£
40
30
20 '
10 '
0
10
o
0)
V.
20 30 40 50 60
Number Bed Volumes
70
•'i—
80
02
o
0)
u.
CQ
g
w
90
Figure 25. Effectiveness of GAG column treatnent for ETU
removal from Plant B wastewater.
Ill
-------
In algal assay studies GAC treated wastewater from either plant inhib-
ited growth at concentrations of 0.1% and concentrations less than 0.1%
generally had little effect on growth. Since wastewater treated by simple
filtration gave similar results, GAC treatment cannot be credited with
significant removal of toxicity. The component(s) of the wastewater respon-
sible for the algal toxicity, as well as the residual fish toxicity, is
unknown.
It should be further noted that carbon treatment failed to eliminate
toxicity to sewage flora (Appendix 0), so that the maneb and its breakdown
products were evidently not the components responsible for the toxicity.
BIOLOGICAL TREATABILITY STUDIES
Effect of Biological Treatment on Pesticide Removal
Maneb manufacturing wastewaters were diluted to 10% (v/v) with munici-
pal sewage and fed to bench-scale activated sludge units. The wastewater
mixtures were subjected to primary settling prior to AS treatment. Results
taken after two weeks of operation are shown in Table 36. These results
indicate that there was some reduction in the already low maneb concentra-
tion, but that there were appreciable concentrations of ETU in the effluents
Because of the oncogenic potential of ETU further investigations should be
conducted to determine if these concentrations have an adverse health or
ecological effect when biologically treated wastewaters are released to the
environment. It should be noted that further treatment with GAC would
eliminate the ETU.
Determinations of "maneb" (maneb and related compounds) were also made
on the sludge from each set of units after termination of the experiment.
Because of the nature of the sludge, which contained components which
interfered with the analysis, these determinations cannot be considered to
be very accurate. Results showed the "maneb" concentration to be 213 + 70
mg/1 in the control units, 895 + 41 mg/1 in those units with Plant A waste-
water, and 940 + 50 mg/1 in the units with Plant B wastewater. The concen-
trations in the test units were over 4X that in the control units and in
all cases were many times greater than in the effluents.
112
-------
Table 36. MANEB AND ETU CONCENTRATIONS IN INFLUENTS AND
EFFLUENTS FROM ACTIVATED SLUDGE UNITS
Type
Control
(Municipal
Sewage)
Maneb,
Wastewater A
(10%, in
municipal
sewage)
Maneb ,
Wastewater B
(10% in
municipal
sewage)
Sample 1
Maneb and ETU
Stream related cpds.
Influent
Effluent, Unit 1
Effluent, Unit 2
Influent
Effluent, Unit 1
Effluent, Unit 2
Influent
Effluent, Unit 1
Effluent, Unit 2
mg/1 mg/1
ND
ND ND
ND
2.1
0.67 60
0.49 26
1.9
0.67 120
1.16 143
Sample
Maneb and
related cpds.
mg/1
ND
ND
ND
1.25
0.61
0.52
2.27
1.63
2.20
2
ETU
mg/1
ND
ND
52
34
22
103
86
76
ND » not detectable (<0.1 mg/1)
-------
Performance and operating characteristics of the units are shown in
Tables 37-39 and in Figure 26. COD removals in the units showed some
variation, but as is obvious from Table 37, performance of the units fed
maneb wastewaters was consistently less than that of the control units, and
the units fed Plant B wastewater consistently showed the poorest performance.
Suspended solids levels in the effluents from the test units were generally
greater than in the effluents from the control units, averaging about twice
as high (Table 38). However, these levels are still in the range of values
typical of effluents from well-operated biological treatment systems.
Examination of the operational data (Table 39) reveals difficulty in
maintaining mixed liquor suspended solids (MLSS) levels in several units.
Because of operational difficulties with the units it is not possible to
determine if addition of pesticide wastewater was the primary cause of this
loss. If so, it would portend a gradual loss of the activated sludge (and
of the treatment efficiency) of the units.
The pH of mixed liquor in the aerators of the control units was consis-
tently slightly lower than neutral (5.1-6.7), as would be expected if some
degree of nitrification were taking place. The pH in the test units was
consistently above neutral (7.6-7.9) and possibly indicates that nitrifi-
cation was not occurring.
Further evidence of effects on nitrification is provided by the follow-
ing data:
Influent NH , Effluent NH ,
AS Unit mg/1 as N mg/1 as N
Control 17 < 1
Test - Plant A 84 63
Test - Plant B 300 440
Thiourea compounds are well-known inhibitors of nitrification (see review in
Thiman, 1963).
Algal assay tests were conducted on composited influents and effluents
of the units receiving Plant A and Plant B wastewaters (Appendix 14). No
growth occurred in the presence of 10% concentrations of Plant A influents
114
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Table 37. PERFORMANCE CHARACTERISTICS OF BENCH-SCALE ACTIVATED SLUDGE UNITS,
MANEB WASTEWATER SERIES - ABILITY OF UNITS TO REMOVE COD
Day
IS*
17
22**
25
28
30
32
35
36
COD,
Influent
_
100
-
110
150
90
150
140
80
C
ag.fl
Unit
-
16
47
32
34
35
36
32
32
ontrol Units
Effluent
I Unit II
25
20
78
17
-
35
28
60
60
COO removal,
I (average
of two units)
-
82
-
78
73
61
80
67
42
Units
COD.
Influent
-
325
-
368
400
300
320
260
240
fed Plant A Waatevater (101)
ng/t
Effluent
Unit I Unit II
110
180
204
164
140
150
162
130
170
87
210
244
172
150
160
160
146
150
COD renoval.
Z (average
of two units)
-
42
-
55
64
48
50
39
3J
Unit fed Plant
CODj_
Influent
-
140
-
340
310
235
225
-
242
Bg/t
B Wastewater (10*)
Effluent
Unit I Unit II
99
-
210
216
180
200
214
160
HO
140
190
275
224
190
260
230
230
190
COD renoval.
X (average
of two units)
-
Kone
-
35
40
0
32
-
21
'Pesticide vastevater was added to teat Units on day 14.
••Sone difficulty with »lr fed to units was experienced on day 22.
-------
Table 38. PERFORMANCE CHARACTERISTICS OF BENCH-SCALE ACTIVATED SLUDGE UNITS,
MANEB WASTEWATER SERIES—SUSPENDED SOLIDS LEVELS IN EFFLUENTS
Parameter
Effluent Suspended
Solids, tng/1
tarf
I—I
&•
Ave- Value, mg/1
Day
21
23
25
30
32
35
36
Control
I
30
30
20
30
30
15
3
22
Units
II
30
30
-
30
30
6
A
Units Fed Plant A
Wastewater (10%)
I 11
70
70
50
30
50
30
45
Range, me/1 3-30
80
80
60
40
50
21
26
50
21-80
Units Fed Plant B
Wastewater (10%)
I II
30
30
60
60
60
25
25
44
25-60
50
50
40
30
60
50
40
-------
Table 39. OPERATING CHARACTERISTICS OF BENCH SCALE ACTIVATED
SLUDGE UNITS (MANEB WASTEWATER SERIES)
Parameter
MLSS
(centrif uged,
ml/10 ml)
Aerator pH
Aerator Dissolved
02(mg/£)
Dav*
1
2
6
7
8
9
10
13
14
17
21
22
24
27
30
32
35
36
25
28
30
36
25
28
30
32
35
36
Units Fed Plant A Units Fed Plant B
Control Units Wastewater, 102 Wastewater. 107.
I II I II I II
0.35
0.30
0.25
0.30
0.28
0.20
0.23
0.25
0.25
0.30
0.21
0.25
0.28
0.25
0.23
0.25
0.25
0.25
6.7
5.2
5.4
6.7
6.9
7.7
7.9
8.1
6.B
6.9
0.21
0.19
0.22
0.20
0.20
0.18
0.20
0.18
0.20
0.18
0.22
0.21
0.30
0.21
0.30
0.30
6.6
5.1
5.4
6.4
6.6
7.7
7.9
8.0
7.0
7.1
0.31
0.28
0.20
0.20
0.20
0.18
0.20
0.20
0.20
0.20
0.20
0.17
0.15
0.15
0.11
0.11
0.15
0.15
7.8
7.2
7.7
7.6
7.8
7.8
8.9
7.8
7.4
7.5
0.27
0.20
0.17
0.19
0.13
0.12
0.12
0.12
0.12
0.12
0.10
0.11
0.10
0.10
0.10
0.10
0.10
7.7
7.8
7.7
7.7
7.7
8.0
8.8
7.8
7.7
7.9
0.32
0.30
0.32
0.30
0.30
0.30
0.30
0.30
0.30
0.30
0,25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
7.8
7.7
7.8
7.7
7.7
7.9
8.7
8.4
7.1
7.1
0.36
0.30
0.32
0.30
0.30
0.30
0.30
0.28
0.20
0.17
0.19
0.12
0.12
0.10
0.10
0.10
0.10
0.12
7.9
7.7
7.9
7.7
8.1
8.1
8.9
8.3
7.8
7.7
Pesticide wasteuater addition to test units was begun on day 14.
117
-------
it it tl ii »• »
41
Figure 26.
Influent and effluent COD for activated
sludge units; (a) control units; (b)
units fed Plant A wastewater; (c) units
fed Plant B wastewater.
118
-------
and effluents. At the late logarithmic and stationary phases, growth at the
1% wastewater concentration was greatly reduced, generally representing
about <10% of that in the controls. At the 0.1% concentration, growth
occurred in both influent and effluent, but was only about half that of the
control.
Both influent and effluent from units fed Plant B wastewater totally
inhibited growth at a 1:10 dilution (10%). In the stationary phase, growth
was similar in both 1.0 and 0.1% influent concentrations, findings which
must be considered suspect as one would expect to see more inhibition at the
1% level. As was the case with Plant A, Plant B effluents greatly reduced
growth at a 1% concentration. At 0.1%, growth was nearly equal to that of
the control. The influent was somewhat more inhibitory. Results of the
algal assay tests may be summarized in terms of I.., as follows:
10% 1.0% 0.1% 0.01%
Untreated full strength Plant A wastewater 96 97 98 9
Influent, Plant A wastewater 100 95 65
(10% in domestic sewage)
Effluent, Plant A wastewater 100 93 36
(10% in domestic sewage)
Untreated, full strength Plant B wastewater 99 68(?) 98 4
Influent, Plant B wastewater 100 52 46
(10% in domestic sewage)
Effluent, Plant B wastewater 100 95 21
(10% in domestic sewage)
In both cases, the toxicity of the wastewater was reduced somewhat, but
not markedly, by AS treatment. The reduction certainly does not indicate
that AS treatment of maneb manufacturing wastewaters, even at 1:10 dilutions,
will be satisfactory for relieving toxicity to algae.
119
-------
Toxicity to fish of the influents and effluents of control and test
units was also determined (Appendix N, Table N-14). Influents and effluents
of control units fed domestic sewage were not toxic to fish at 10% and 18%
concentrations. The LC_0 values would thus be >18%. Due to volume con-
straints, high concentrations could not be tested. In sewage supplemented
with Plant A wastewater (10%, v/v), the fish assays gave anomalous results
(40% survival at 100 ml/1 and 70% survival at 180 ml/1), but in both cases
this influent was more toxic than the domestic sewage alone. The effluent
results were also anomalous and do not indicate whether or not toxicity was
relieved. Volume constraints prevented repeating the tests. Sewage supple-
mented with Plant B wastewater was extremely toxic, as would be expected
from the LC of the untreated wastewater (M).18 ml/1, compared to ^1 ml/1
for the Plant A wastewater). Activated sludge treatment greatly reduced the
toxicity of this wastewater. Whereas at a concentration of 10% the influent
killed all of the fish, 30-60% of the fish survived in effluent concentra-
tions of 18%.
In summary, activated sludge treatment of maneb manufacturing waste-
waters produced some reduction in COD and the system can operate at least
marginally on sewage containing 10% of this wastewater. However, effluents
from units treating these wastewaters contain very high levels of ETU
(Table 36). The significance of ETU in these effluents must be investigated
before AS can be recommended for treatment.
GAC treatment appears to offer several advantages as a choice for
removing maneb, ETU and COD from maneb manufacturing wastewaters. However,
GAC treatment systems should be monitored for ETU breakthrough, rather than
maneb breakthrough, since ETU (1) breaks through first and (2) is potentially
more serious from the standpoint of health impact.
The cost of the carbon treatment option dictates a search for alter-
native treatment methods. To this end, additional work will be undertaken
to investigate the possible biological treatment of maneb wastewaters at
concentrations other than those investigated in this study. Particular
attention will be given to the fate of ETU in biological treatment systems
and the impact of this wastewater on nitrification.
120
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SECTION 8
LITERATURE REVIEW AND DISCUSSION
GENERAL CHARACTERISTICS OF PESTICIDE MANUFACTURING WASTEWATERS
Pesticide manufacturing wastewaters are as diverse as the pesticides
themselves. The wastewaters vary greatly according to the nature of the
product — its chemical composition, its physical state (i^e. , oil, aqueous
solution, crystal, powder, etc.), and its purity. However, it is possible
to divide the myriad pesticides into five major classes and to make some
generalizations about production, wastes generation, and treatability.
Hackman (1978) has concisely summarized the EPA development documents
dealing with effluent limitations guidelines and come up with such a cate-
gorization. He notes that:
(1) "specific pesticide manufacturing operations are unique and
generally characteristic only of a given facility"
(2) "few, if any, pesticide plants manufacture one product or use only
one process", but "instead, almost all plants are multiproduct/-
process facilities" with a unique mix of products
(3) many plants produce materials which are used on-site as feed stock
for other products
(4) many plants produce materials other than pesticides.
He notes further that while there are over 500 commercially important
pesticides and over 34,000 formulated products, the major divisions of
pesticide products can be categorized as follows:
121
-------
(1) halogenated organic (example: DDT) - broad activity spectrum,
prolonged stability and residual activity.
(2) organophosphorus - highly toxic, usually hydrolyzed in alkaline
medium to yield materials of relatively less toxicity, usually
biodegradable.
(3) organonitrogen - very broad range of biological activity
(4) metallo-organic
(5) botanical and microbiological
(6) miscellaneous
Noted differences among the first three categories are as follows:
(1) Chlorinated hydrocarbons are much more persistent in the environ-
ment than the organophosphorus and organonitrogen compounds.
(2) the organophosphates and organonitrogen compounds are amenable to
chemical hydrolysis.
(3) certain chlorinated hydrocarbons are amenable to recovery, such as
by steam stripping.
Information on production and waste generation is summarized in Tables
40-42.
General sources of information on characteristics of pesticides manu-
facturing wastewaters include Archer et al. (1978), Kelso et al. (1978),
Nemerow (1971), Atkins (1972), Lawless et al. (1972), Ferguson (1975),
Parsons (1977), Becker and Wilson (1978), and Hackman (1978).
It was not possible within the scope of this project to prepare an
exhaustive review of all literature dealing with biological and physical
chemical treatability of pesticides and pesticide-contaminated environmental
media; impacts of pesticides on biota; and fate of pesticides in the environ-
ment. However, during the course of the project a great deal of information
in these areas was accumulated. In the following sections this information
is briefly reviewed and sources of further information, especially recent
reviews and other compilations, are referenced.
122
-------
Table 40. GENERALIZED SCHEME OF PRODUCTION AND WASTES GENERATION—
HALOGENATED ORGANIC PESTICIDES (from Hackman, 1978).
General Process Flow Diagram for Aldrin-Toxaphene Production
Facilities
CTCLOKMTADIEIII
t«tts
CATALVtT KtACTOK H,O
FOOMUKTIMG
O" rAHAGING
Wt**TKMt
MOOVfKT
rnoouct
mooucr
MCYCIC.
DUITt lit
Wastewaters generated in the production of this family of
pesticides are:
1. Vent gas scrubber water from caustic soda scrubber
2. Aqueous phase from the epoxidation step
3. Uastewater from the water wash and product purifi-
cation units
A. Periodic equipment cleaning wastewater
5. Wastes from cleanup of production areas
Tars, off-specification products and filter cake should
not generate wastewaters since they are usually incin-
erated.
Halogenated Organic Pesticides Plant
Waste Loads
Production (small plant), kkg/day 16.2
Production (large plant), kkg/day 85.7
Flow, 1/kkg
BOD, kg/kkg
COD, kg/kkg
TSS, kg/kkg
Phenol, kg/kkg
Total pesticide, kg/kkg
35.300
97.2
183
3.49
1.92
0.327
123
-------
Table 41. GENERALIZED SCHEME OF PRODUCTION OF WASTES GENERATION-
PHOSPHORUS-CONTAINING PESTICIDES (from Hackman, 1978).
General Process Flow Diagram for Phosphate and Phosphonate
Pesticide Production Facilities
MTIMhOHAO!
• •wrnuTi* »•
j—. mm* |__
•rmn o* *U»HVDI
•AimrlTIll
Organophosphorus Pesticide Plant
Waste Loads
Production (small plant), kkfi/day 6.57
Production (large plant), kkg/day 72.0
Flow, 1/kkg 43.900
BOD, kg/kkg 67.7
COD, kg/kkg 267
TSS, kg/kkg 11.7
NH4-N, kg/kkg 81.8
Total pesticide, kg/kkg 0.454
124
-------
Table 42. GENERALIZED SCHEME OF PRODUCTION OF WASTES GENEKATION-
ORGANONITROGEN PESTICIDES (from Hackman, 1978).
General Process Flow Diagram for Alkyl and Arylcarbamate
Production Facilities
tlOIMOIMm
Wastewaters associated with the production of these compounds are:
1. Brine process wastewater from
reactors
2. Wastewater from the caustic
soda scrubbers
3. Aqueous phase wasted following
the isocyanate reaction
4. Reactor cleanout washwater
3. Area washdowns
Organonitrogen Pesticide Plant
Waste Loads
Production (small plant), kkg/day 9.43
Production (large plant), kkg/day 116
Flow, 1/kkg 35.400
BOD, kg/kkg 45.5
COD, kg/kkg 1°3
TSS, kg/kkg 2-50
NH.-N, kg/kkg 60-2
Total pesticides, kg/kkg
2.82
125
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Activated Carbon Treatment of Pesticides, Pesticide-Contaminated Water
and Pesticide-Manufacturing Wastewater
Carbon treatment is often the most cost-effective means of removing
pesticides from water and wastewater. Use of activated carbon for this
purpose was recently exhaustively reviewed by Becker and Wilson (1978) in a
document also setting forth for major pesticides their production volumes;
uses; classes; manufacturing and disposal techniques; waste production;
toxicity and various treatment processes. In regard to activated carbon
treatment, the following are reviewed: (l)industrial wastewater treatment
installations using GAC treatment, (2) efficiency of carbon for adsorbing a
variety of pesticides; (3) carbon dosages required for treating 2,4-D com-
pounds, rotenone, toxaphene, "cube root", DDT, aldrin, and dieldrin; (4)
adsorption isotherm data on several pesticides; (5) typical GAC facility
flow diagram; and (6) six case studies including cost data.
Another review of AC treatment of pesticide wastewaters was that by
Atkins (1972), who reviewed and summarized much of the work on adsorption of
pesticides to AC and other sorbents and reprinted tables from much of the
literature extant in 1972 (Robeck et. al_., 1965; Faust and Suffet, 1966;
Sigworth, 1965; Aly and Faust, 1965; Cohen et al., 1960; Whitehouse, 1967).
Where applicable, work of these authors is summarized below.
Sharp and Lambden (1955) and Lambden and Sharp (I960) described the
wastewater treatment system at Fisons Pest Control Ltd., a British manufac-
turer of pesticides. The wastewater contains DNOC (dinitroorthocresol) ,
DNBP (dinitro secondary butyl phenol), MCPA (2-methyl 4-chlor phenoxy-acetic
acid), DDT, copper salts, sulphonated phenol and cresol, chlorinated cresol,
intermediate nitro compounds, cresol, phenol, solvents, surface active
agents, glycollic acid, amine salts, sodium sulfate, and sodium chloride,
and the BOD is about 2000-3000 mg/1. Pilot studies were described in the
earlier article (Sharp and Lambden, 1955); the full scale plant, in the
later article. The treatment plant incorporates three major processes:
(1) activated carbon pretreatment at neutral pH to remove toxic
organics
126
-------
(2) lime precipitation of toxic metals
(3) biological treatment.
Carbon regeneration is carried out on-site. The activated carbon
system can reduce phenols from 160 to 5 mg/1 and DNOC from 60 mg/1 to trace
levels. The authors stressed that the activated carbon pretreatment made
possible further treatment by trickling filters and that this system had
worked successfully at full-scale over a 5 1/2 year period. They stated
however, that "Treatment costs are high, providing an incentive to reduce
the load on the effluent plant by careful attention to the manufacturing
processes."
Mitkalev e_t al_. (1965) performed activated carbon studies on herbicide
manufacturing wastewater. The wastewater contained 2,4-D derivatives.
Activated carbon was stated to be an effective adsorbent, easily regenerated
with 5% alkali at 70-80°C or by superheated water vapor at 250-300°C.
Ismail and Wardowski (1974 a and b) investigated effectiveness of
activated carbon for removing the fungicide sodium o-phenylphenate (SOPP)
from actual and simulated citrus packinghouse effluents. Powdered activated
carbon (10 g/1) removed more than 99% of the phenolics from solutions and
wastewaters. In aqueous solutions containing 100 mg/1 of SOPP, 0.25% PAC
removed 99.6% of the pesticide. In actual effluents containing 311 mg/1
(as equiv. SOPP) 1% PAC removed 99.98% (1974 b). GAC column studies (1974
a) with large volumes of simulated effluents showed, as expected, decreasing
removal efficiency with increasing volume treated. The initial efficiency
was 81.5%.
Nemerow (1971) in his industrial wastes text notes the difficulties in
treating pesticide wastewaters in municipal biological plants because of
the toxicity of the constituents of the pesticide wastewater and the high
costs of treating with activated carbon (for 2,4-D wastewaters about $6/lb
of dichlorophenol removed, in 1959).
Minturn (1974) reviewed advanced wastewater technologies investigated
by the Oak Ridge National Laboratory, including experiments on herbicide
washwaters (water used in cleaning equipment used in manufacturing, storing,
127
-------
formulating, and spreading). Treflan and diphenamide were taken up "reason-
ably well" by PAC - Aqua Nuchar A, but paraquat was not as easily sorbed.
It was noted that the paraquat tests were run in 0.02 M NaCl solution and
that uptakes on PAC would have been higher at higher salt levels. It was
also noted that high levels of carbon were required to treat herbicide
washwaters with the levels of pesticides present (up to 1650 mg/1 of para-
quat; 318 mg/1 treflan, and 156 mg/1 diphenamid), thus making the cost
unattractive unless some use could be found for the pesticide-saturated
carbon. The potential for AC treatment of large volumes with low concen-
trations, as might be found in wastewaters from pesticide manufacturing, was
considered more atttractive.
Bernardin and Froelich (1975) conducted both laboratory and plant scale
tests to evaluate ability of GAC to adsorb organic toxicants. Their exten-
sive study addressed (1) laboratory tests of applicability of carbon in
removal of toxicants and (2) fish bioassay tests on influent and effluent
from five industrial plants employing AC treatment. The five plants manu-
factured, respectively, (1) specialty chemicals, producing a low pH - high
chloride wastewater, (2) specialty chemicals with a wastewater containing
high TDS and some floating oil, (3) soap and detergent with high pH waste-
water containing surfactants and organic amines, (A) phenolic resins, and
(5) plastics. Laboratory adsorption isotherm tests with Filtrasorb 300
(Calgon Corp.) indicated that final concentrations of less than 1 microgram
per liter could be obtained with a number of compounds. Fish bioassay tests
with bluegill fish, using actual wastewaters, indicated total removal or
significant reductions of toxicity after passage of the wastewater through
the AC system.
Wilder (1976), in a letter report of EPA Effluent Guidelines Division,
assembled field data on treatment of hazardous spills with AC columns, with
or without such pretreatment as pH adjustment, flocculation, and filtration.
One to three columns were employed at flow rates of 100-600 gpm and contact
times of 8-60 minutes. Pollutant removal was high (96.11-99.98%) and con-
sistent. The types of pesticide spilled and concentrations (as ppb) of the
influent to the carbon columns are as follows:
128
-------
toxaphene 36
dinitrobutylphenol 200
kepone 4000
PCBs 3.5
aldrin 60.5, 8.5
heptachlor 80, 6.1
dieldrin 64, 11
chlordane 1430, 13
Bunn (1975) in a letter report to EPA described treatment of several
Chemagro wastewaters with Nuchar C-190 AC, 20 g/250 ml. The wastewater con-
tained the pesticides sencor (a triazine type herbicide) and treflan (tri-
fluralin). Sencor removals of 99.8% (from 13-15 mg/1 to ~0.03 mg/1) were
achieved. Effect on trifluralin was not discussed. The wastewater appeared
to exert toxicity in BOD tests.
Schwartz (1967) investigated removal of 2,4-D and CIPC [isopropyl N-(3-
chlorophenyl)carbamate] from dilute aqueous solutions with PAC (Nuchar C-
140) and with the clay minerals illite, kaolinite, and montmorillonite. The
minerals were not effective even at concentrations of 800 mg/1, but adsorption
of CIPC with PAC was extensive. Initial CIPC concentrations of 5.0 mg/1
were reduced by 98% within 22 hr with 100 mg/1 of carbon, with approximately
90% of the adsorption occuring within the first 4 hr.
Information from EPA indicates that the following pesticide manufactu-
ring wastewaters are currently being treated with activated carbon:
ethalfluralin basagran
benfluralin N-propamide
dioxathion metham
carbofuran carbendazin
terrazole DEET
PCNB piperonyl butoxide
propachlor chlorothalonil
dodine
129
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Ability of GAC to reliably remove organics from potable water supplies
was reviewed by Hager and Flentje (1965). Primary interest was in costs of
removing odors from potable water.
Aly and Faust (1965) and Faust and Aly (1964) tested the effectiveness
of activated carbon and other technologies on removal of 2,4-D and deriva-
tives from natural waters. 2,4-D solutions were prepared using the sodium
salt and water; commercial formulations of 2,4-D isopropyl ester and 2,4-D
butyl ester were employed. Adsorption isotherm tests were conducted with
Aqua Nuchar A (West Virginia Pulp and Paper Company) having a specific sur-
o
face area of 550-650 m /g and a size of > 325 mesh. Compared to oxidation
(KMnO, and Cl_) and ion-exchange [Dowex 1 (Dow-Corning Corporation); Amber-
lite IR-120 and IR-50 (Rohm and Haas Company)], activated carbon was the
most effective method for removal of 2,4-D, 2,4-DCP, and the other deriva-
tives. Amounts of carbon required to reduce 3.0 mg/1 to 0.1 mg/1 were as
follows:
2,4-D, sodium salt 92 mg/1 carbon
isopropyl ester 49 mg/1 carbon
butyl ester 49 mg/1 carbon
isooctyl ester 53 mg/1 carbon
Evidently esters are sorbed more easily than the sodium salt. With
2,4-DCP an - value of 0.0166 was achieved.
' m
Cohen et al. (1960) conducted laboratory tests to determine if AC (Aqua
Nuchar A, Westvaco) would remove low concentrations of rotenone and toxa-
phene from raw water (spring water). Adsorption isotherm studies were
conducted and the treated solutions were subjected to fish bioassays.
Amounts of carbon required for toxaphene and rotenone were similar. AC
removed not only the poisons but also solvents and emulsifiers found in the
commercial preparations. It was far more effective than chlorination and
alum coagulation for removing these fish poisons. Curves were derived to
enable rapid determination of amounts of carbon required to reduce a given
poison concentration to a selected residual concentration.
130
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Robeck et al. (1965) investigated effectiveness of water treatment
processes in pesticide removal. The study was conducted in two 20-gpm pilot
water treatment plants which included in the treatment train the following
processes:
1) rapid mix with alum, activated silica, and activated carbon
2) flocculation
3) settling
4) filtration through sand or charcoal
5) optional 2-stage (series) activated carbon beds
In all pilot studies known quantities (~ 1-25 ppb) of pesticide were
added as an emulsion prior to the first process. Pesticides tested were
DDT, dieldrin, endrin, lindane, 2,4-5-T ester, and parathion.
Adsorption isotherm curves were obtained in jar tests with distilled
water and with river water. For these experiments a PAC (Aqua Nuchar A,
Westvaco) slurry was employed. Because of the background organic material
found in the river water, more carbon was required to reach the arbitrary
concentration of 0.1 ppb. Competition among pesticides for sorption was
also investigated. In river water with 10 fjg/l (each) concentrations of
lindane, dieldin, and parathion added, it appeared that dieldrin and lindane
reacted the same as in single pesticide applications. However, for some
unknown reason parathion removal appeared to be influenced by the presence
of other pesticides and to a degree not accounted for by the minute amount
of organic matter contributed by the other pesticides. Parathion was readily
removed by PAC; a 5 mg/1 carbon dose was capable of achieving > 99% removal
of parathion at an initial load of 10 ppb. GAC studies demonstrated that as
far as pesticides were concerned, they did not penetrate ahead of other
organics. Overall conclusions reached were as follows:
1) DDT was readily removed in conventional water treatment processes
(settling, coagulation, filtration); lindane and parathion were
not.
2) Lindane, parathion, 2,4-5-T, and dieldrin were removed in conven-
tional treatment followed by GAC filtration; 2-stage filtration
was generally required to achieve residual levels of < 0.1 ppb.
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Sigworth (1965) of West Virginia Pulp and Paper Company conducted
laboratory studies on removal of odor-causing pesticides from water. Effec-
tiveness of treatment was evaluated by determination of threshold odor
values and by chemical analysis. Powdered activated carbon was used, but
type was not disclosed. The author states the "removal of 90 percent or
more of the associated odors was readily accomplished with laboratory dos-
ages in the range of 2-20 ppm of carbon." Specific results are as follows:
Carbon dose Pesticide Concentration, tng/1
Pesticide mg/1 Initial Final
Parathion 10 10 2.6
BHC-37, gamma 5 25 0.08
Malathion (50%) 10 2 0.25
2,4-D (23.5%) 20 6 1.38
2,4-D (11.7%) 10 1 too low to detect
Chlordane (6%) 10 50 too low to detect
DDT (50%) 2 5 too low to detect
In connection with problems of insecticide contamination of livestock
drinking waters, Goodrich and Monke (1970) conducted laboratory studies to:
1) determine ability of GAC to remove low levels of dieldrin from
water,
2) determine size of the required GAC filter, and
3) evaluate radioactive tracer techniques for low level insecticide
detection.
Commercial grade activated carbon (Grade ACC derived from petroleum residue)
was employed in four size ranges, U. S. standard sieve (1) 6-8, (2) 8-10,
(3) 10-12, and (4). 12-14. GAC removed up to 99% of dieldrin from a solution
containing 65 ng/1. Size of carbon granules in the range tested had no
significance. The authors concluded that a GAC filter could protect against
the insecticide in a rural water source.
Eichelberger and Lichtenberg (1971) tested the efficiency of the
standard carbon adsorption method (CAM) for recovery of 11 organochlorine
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and 10 organophosphorus pesticides from water. A mixture of 21 pesticides,
each at 2 pg/1 concentration, in Cincinnati tapwater was applied at 130
ml/min to carbon cartridges containing Nuchar C-190. Pesticides were
lindane, heptachlor, aldrin, heptachlor epoxide, DDE (p,p'), DDT, endo-
sulphan, dieldrin, endrin, methoxychlor, chlordane, def, malathion, para-
thion, azodrin, trithion, bidrin, fenthion, methyl parathion, ethion, and
methyl trithion. After passage through the carbon, the water showed no
pesticide content above minimum detectable concentrations of 10 ng/1 of
organochlorine and 25 ng/1 of organophosphorus compounds. Therefore,
adsorption was very efficient.
The pesticide antimycin can be removed by AC according to Dawson and
Marking (1974). A solution containing 100 times the lethal concentration
was detoxified by passage through a 15 cm filter of AC (20 x 40 mesh carbon).
The sorptive capacity of the carbon was found to exceed 3 mg/g.
Cornelia and Belle (1975) determined adsorption isotherms with a variety
of carbons and a number of test compounds including aldrin, dieldrin, 3,4-
benzopyrene, lindane, and endosulfan. At a 20 mg/1 carbon dose, two PACs
were capable of removing > 99% of aldrin from a solution with initial concen-
tration of 100 M8/1- One carbon was able to accomplish similar removals
with lindane, dieldrin, and 3,4-benzopyrene. As noted in other studies,
application in several doses, rather than all at once, allowed considerable
reduction in amount of carbon required.
Sigworth and Smith (1972) reviewed potential of activated carbon to
remove trace metals from drinking water. Arsenic is listed as having a high
adsorption potential in the higher oxidation states, whereas Zn and Mn are
listed as having only slight potential.
Examining the possible use of adsorbents to protect crop roots, Coffey
(1967) investigated activated carbon adsorption of herbicides, including the
effect of carbon type, pH, and other factors. Eight pesticides were tested:
CIPA, trifluralin, 2,4-D, diphenamid, DCPA, DNBP, amiben, and paraquat.
Carbon types included Darco KB, Darco M, Hydro Darco B, and Darco G-60.
Darco G-60 had the greatest sorptive capacity. Trifluralin and CIPC were
most readily absorbed by carbon, while paraquat, a cationic herbicide, was
133
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not sorbed well. Under the conditions used, pH had little effect on carbon
sorption.
Ward and Getzen (1970) investigated influence of pH on adsorption onto
activated carbon of three carboxylic acid herbicides - 2,4-D, dicamba, and
amiben. Absorption data were obtained in laboratory studies using Pittsburgh
Chemical Company Type BL activated carbon. The herbicides were obtained as
crystals and prepared as aqueous solutions. In all cases, lowering the pH
below 7.0 markedly increased removals with maximum adsorption being obtained
near the point where pH = pKa. This behavior, the authors believe, might
help explain the tendency of these pesticides to accumulate in acidic, high
organic soils.
ICI (1974) has tabulated published data on activated charcoal in agri-
culture, giving some indication of other pesticides which might be treated
with AC. According to its summary the following pesticides should be sorbed
onto AC:
Alachlor
Aldrin
Amiben
Amitrol-T
Atrazine
Azak 10
Bandane 35
Bensulide
Bromacil
CIPC
Chlordane
Chloroxuron
DCPA
DDT
DMPA, bensulide
DMTT (mylone)
DDVP
Ingramfsic] (igran?)
Isocil
Karsil
Lindane
Linuron
Mecoprop 3
Methoprotryne
Metribuzin
Monuron
Neburon
Nitralin
Norea
Oryzalin
Paraquat
Parathion
Pebulate
Pichloram
134
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Dichlorbenil Planavin 1.5
Dieldrin Prometryne
Dimoben[sic] (dinoben?) Propazine
Diquat Sesone
Diuron Siduron
EPIC Silvex
Endrin Simazine
Eptam TCA
Ethyl-n-ethyl-n-cyclo- Terbacil
hexylthiol-carbamate Tricamba
Fenac Trifluralin
Fluometuron Vernolate
Heptachlor 2,4-D
IPC 2,4-5-T
In summary, activated carbon treatment is capable of reducing con-
centration of many pesticides to below detectable levels. Much of the
extant work, however, has been performed on laboratory-prepared solutions,
surface waters, and potable waters. Pesticide manufacturing wastewaters, on
the other hand, are quite complex and as shown in this project, may contain
other non-pesticidal components which may contribute a major portion of the
toxicity to aquatic organisms. Industry has stressed the need for realistic
performance criteria for AC treatment of organic chemical manufacturing
wastewaters (Lawson and Hovious, 1977), pointing out that laboratory studies
should be followed by on-site continuous adsorption studies because of such
factors as:
1. Plant-to-plant variations in adsorption performance.
2. Variability of production output and carbon performance with
time in a specific plant.
3. Dynamic adsorption/desorption interactions in continuous carbon
systems which are not predictable from isotherm tests.
4. Low predictability from batch isotherm tests of degree of
removal and economic feasibility of removal of organics by
continuous adsorption processes.
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Shumaker (1977) also pointed out that, in an actual case study with an
organic chemicals production plant, the AC unit treatment costs were higher
than predicted and that care had to be exercised in selecting wastestreams
to be put through the system. He noted that the AC system was ineffective
in treating benzene sulfonates or low-molecular weight organics such as
methanol, formaldehyde, and urea. He concluded that "while it has been
demonstrated that activated carbon can be effectively utilized in treatment
of complex chemical waste streams, it has also been demonstrated that
carbon treatment is not a panacea for all chemical waste problems." As
noted in this project, we found that removal of pesticide with GAC is not
equivalent to removal of COD or toxicity.
OTHER PHYSICAL AND CHEMICAL TREATMENT METHODS
Several other methods of pesticides removal from water and wastewater
are described in the literature.
Standard water treatment processes (chlorination, ozonation, uv-ozona-
tion, flocculation) may effectively remove many pesticides (Robeck et_ al.,
1965; Bauer, 1972); however, it is necessary to take care to insure that
chlorination or ozonation does not produce other toxic products (Robeck
et al., 1965).
Many organophosphorus and organonitrogen pesticides are susceptible to
destruction by acid or alkaline hydrolysis (Hackman, 1978; Shih and Dal
Porto, 1975; Ferguson, 1975). In many cases, rate of destruction is increased
by increasing temperature. As pointed out by Hackman (1978), hydrolysis can
be especially effective when used on segregated water streams since acid or
base additions, thermal requirements, and size of equipment are minimized
with these more concentrated flows. Hydrolysis is frequently useful in
dealing with small amounts of "leftover" pesticides or with waters from
washing pesticide application equipment. Care must be taken that toxic
products are not formed during heating or hydrolysis. If complex pesticide
manufacturing wastewaters are to be treated, even greater care must be taken
since other components (such as solvents) may also produce toxic or otherwise
dangerous products.
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Sorbents other than AC may be useful in treating pesticide wastewaters.
Kennedy (1973) described a process for treating chlorinated pesticide waste
effluents, employing XAD-4, a synthetic polymeric adsorbent with high poros-
ity, high surface area, and an inert, hydrophobic surface, capable of regen-
eration with an organic solvent (isopropanol) in such manner that the adsorbed
pesticides can be recovered in concentrate form. With an actual wastewater
from manufacture of a chlorinated pesticide, the leakage of unadsorbed
pesticides from XAD-4 columns was "significantly lower" than from an acti-
vated carbon column. An economic analysis indicated that a combination of
XAD-4 treatment with chemical regeneration would be more cost-effective than
GAC and external thermal regeneration ($0.83/1000 gal vs. $1.33/1000 gal,
assuming an influent with 200 ppm total chlorinated pesticides; pH 1.0;
150,000 gpd, run to 1 ppm leakage). Kunin (1976) reported more extensive
studies on application of XAD resin treatment to a variety of wastewaters,
including those from manufacture of chlorinated pesticides. According to
Kunin, the XAD-4 resin was "clearly superior to the conventional carbon
adsorbents."
Physical removal of certain pesticides from water can be accomplished
by reverse osmosis (Edwards and Schubert, 1974; Chian et al., 1975).
According to Edwards and Schubert, pesticides of low aqueous solubility
(i.e., DDT) are more easily removed than more soluble types (such as 2,4-D).
These authors noted that performance with mixtures of several solutes (as
would be found in pesticide manufacturing wastewaters) may be considerably
different from projections based on studies with individual components.
Chian et al. (1975) found that cellulose acetate and cross-linked polyethy-
lenimine membranes gave "excellent performance" in removing a variety of
pesticides, including chlorinated hydrocarbon and organophosphorus types.
More polar pesticides, such as atrazine, were not as readily removed, and it
appeared that mechanism of removal was due to both polarity of the solute
and adsorption of the pesticide onto the membrane materials. It was stated
that "higher concentration of pesticides in the feed" would have adverse
effects on performance, leading one to question applicability of reverse
osmosis procedures to pesticide manufacturing wastewaters.
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Sufficiently concentrated pesticide wastewaters may be treated by
incineration (Carnes and Oberacker, 1976; Hackman, 1978; Ferguson, 1975).
Temperature requirements vary with the specific pesticide. Potential prob-
lems include high fuel costs and generation of toxic gases (for example, CN
from incineration of organonitrogen pesticides).
BIOLOGICAL TREATABILITY
Biodegradability of Pesticides
Degradation of pesticides in soils and other environments has been
extensively and recently reviewed by Sanborn et al. (1977), Howard et al.
(1975), Blanck et al. (1978), Edwards (1973), Haque and Fried (1975),
Gillett et aj.. (1974), Kearney et al. (1969), Kearney and Kaufman (1975),
Khan (1977), Malakhov and Duttweiler (1978). The report by Sanborn et al_.
(1978) is particularly relevant to disposal of pesticide-containing wastes.
It reviews the published literature dealing with behavior in soil of 45
pesticides (including 17 herbicides, 20 insecticides, 6 fungicides, a furoi-
gant, and an acaricide). In each case, information, if available, is
included on (1) biological, chemical and physical degradation; (2) transport
in soil and water; (3) volatilization; (4) uptake by organisms; (5) persis-
tence, and (6) effects on nontarget organisms. The authors concluded that
of the 45 pesticides reviewed, 10 were suitable for soil disposal, 21 were
unsuitable, and in 14 cases available data were insufficient for conclusions,
Of particular relevance to our project, these authors note that "since most
of the available data deal with relatively small amounts of well-dispersed
pesticides and degradation is almost invariably inversely correlated with
concentration, bulk disposal of most pesticides will lead to long periods
of persistence of the parent compound and/or its degradation products."
Further, as we found in the course of our work, in actual pesticide waste-
waters there are not only pesticides but many other components whose effects
may be more serious than those of the pesticide or whose presence may
affect pesticide degradation. Sanborn et al. (1977) summarized their
review in a table, which is reproduced as Table 43. Feasibility of soil
disposal was based on whether or not the pesticides would degrade in the
soil environment. The authors also pointed out that incinerating pesticides
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would be a rapid efficient mode of disposing of many pesticides. In connec-
tion with our project, however, it must be recognized that the large quantity
of water in the effluent would vastly increase thermal requirements for
treatment.
In Table A3, several compounds studied in our project are included.
Atrazine was not recommended for soil disposal because there was no evidence
for degradation of the triazine ring under environmental conditions. The
finding of atrazine and metabolites in many surface waters also indicates
its persistence. We noted that while atrazine was readily (though not
cheaply) removed by GAC, it was not very susceptible to biological treatment.
Therefore we would agree with Sanborn et. al., that it would not be wise to
rely on biological activity for disposal of "an already pervasive contaminant
of uncertain biodegradability."
As we found, maneb did not persist long in the environment, but was
rapidly converted to other compounds and eventually to ETU. Therefore, we
reached the same conclusions as Sanborn e_t al. : "All methods of disposing
of the dithiocarbamate fungicides...must take into account the carcinogenic
metabolite ethylene thiourea."
Trifluralin is closely related to oryzalin which was investigated in
this project. Sanborn et al_. (1977) noted that while it is not very toxic
to mammals, it is highly toxic to aquatic organisms, highly persistent and
magnified in aquatic food chains. Oryzalin is less toxic to fish and is
also less persistent in the soil, persisting about 2-3 months compared to
5-6 months for trifluralin (Helling, 1976). Helling (1976) noted that
dinitroaniline herbicides degrade more rapidly under anaerobic than aerobic
conditions, produce numerous metabolites that tend to become associated
with soil organic matter as bound residue, and appear (on the basis of
limited evidence) to have no lasting effects on soil microorganisms. We
found that oryzalin itself was not a problem in the production wastewaters,
but that persistence of the colored metabolites and presence of other toxic
materials, expecially ammonia, were factors controlling treatability.
Sanborn et al. (1977) did not review literature dealing with organo-
arsenicals. However, other information on MSMA indicates that it is broken
139
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Table 43. FEASIBILITY OF SOIL DISPOSAL FOR 45 PESTICIDES [from Sanborn jit al., (1977)]
Herbicide
Atratlne*
BroMCll
CDAA
Chloramben
2,4-D
Dlcaaba
Dlquat
Dluroa
EPTC
Llnuron
Mooollnuron
Honuron
Nltralln
Paraquat
Plcloraa
2.4,5-T
Trlflurallab
Soil
disposal
no
7
7
yes
yes
7
no
no
yes
no
no
no
yes
no
no
7
yes
Insecticide
Aldrln
Chlordane
Chlordecone (Kcpone)
DDT
Dleldrln
Endoaulfan
End r In
Heptachlor
Methoxychlor
Mlrex
Toxaphene
Azlnphosuethyl
Diazinon
Diaulfoton
Malthlon
Methyl parathlon
Pa rath Ion
Phorate
Carbaryl
Metalkanate (Bun)
Soil
disposal
no
no
no
no
no
no
no
no
yes
no
no
7
7
7
yes
7
7
7
ye.
yea
Soil
Miscellaneous disposal
Cap tan yea
Dlcofol no
Dodln* 7
Maneb* 7
Methyl bronide no
Naba»b 7
Pentachlorophenol no
Zlnebb 7
Indicates compounds Inveutlgaied In this project.
Closely related to compounds Investigated In this project.
-------
down in soils, at least partially, by biological activity (von Endt et al.,
1968). As pointed out in Section 6, however, elemental arsenic is produced.
Fate of arsenic itself is the critical factor in final disposition of MSMA
wastewaters.
The processes of nitrification and denitrification are important in
the soil nitrogen cycle and may also be important in operation of advanced
biological wastewater treatment facilities.
Bartha et. al. (1967) determined the influence of 29 pesticides on
aerobic activities (CO- production and nitrification) of soil microorganisms.
Effects fell into 3 categories:
(1) Compound was stable and without significant effect (chlorinated
hydrocarbons)
(2) Compound persisted and depressed respiration and nitrification
(carbamates, cyclodienes, phenylureas, thiocarbamates)
(3) Compound displayed toxicity but was transformed by soil organisms
(amides, anilides, organophosphates, phenylcarbamates, triazines).
Analytical grade chemicals and sandy-loam soil were studied in labora-
tory scale studies. C00 production was measured volumetrically over a 30
day period and nitrification was indicated by increased nitrate over time
during incubation at 28°C for 18 days. Test levels were greatly in excess
of normal pesticide usage. The pesticides tested included atrazine and
carbaryl.
Atrazine was tested at 500 and 1000 ppm. At 500 ppm, it retarded
nitrification, but ability to do so decreased with time, indicating the
herbicide was transformed and detoxified or that a resistent nitrifying
population was developed. The atrazine molecule was degraded in soil.
Atrazine and simazine were very different in terms of effect on CC" pro-
duction, possibly due to ability of several organisms to produce CO from
ethyl amino side chains but not from the s-triazine itself. Atrazine also
more effectively inhibited nitrification and depressed soil respiration.
Carbaryl was tested at 150 and 1500 ppm. At 150 ppm, it retarded
nitrification but ability to do so decreased with time. Carbaryl has a
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half-life of 7 days in soil. At both test concentrations, carbaryl de-
pressed C0_ production and the effect persisted for some time. Added
glucose reduced the degree of inhibition of C0_ production by about 50-60
percent.
Bollag and Henniger (1976) investigated influence of pesticides on
denitrification and found that captan, maneb, nabam, and (to some degree)
2,4-D inhibited denitrification by soil microorganisms. Carbaryl, phenyl-
urea herbicides, and propham were less inhibitory. We noted that sludge
collected from AS units fed maneb wastewaters did not undergo the darkening
and gasification exhibited by the sludge in the control units.
Treatment of Pesticide Manufacturing Wastewaters
While most pesticide manufacturers have been reluctant to divulge
information about the effectiveness of their waste treatment procedures,
the published literature does contain some case studies.
In 1961 Monsanto completed a full-scale wastewater treatment plant at
Anniston, AL for the treatment of parathion wastewaters (Anon, 1961). The
plant was reported to successfully treat wastewaters containing paranitro-
phenol, organophosphorus compounds, sulfides, and other components and to
reduce BOD from 4000 mg/1 to 13 mg/1. Treatment steps included:
1) Limestone neutralization to raise pH from ~ 1 to 6.8,
2) Equalization, and
3) Acclimated activated sludge.
The sludge was fully acclimated to undiluted parathion wastewater. Aeration
3
capacity of 30 ft /lb BOD/day was supplied. A removal of 90-98% of the
phenolics was achieved.
Stutz (1966) reviewed the first 9 years of experimentation, pilot plant
testing, and wastes (liquid, solid) treatment at this plant. Initially the
wastewater was to be treated in conjunction with a municipal treatment
plant, but the increased production necessitated construction by Monsanto of
its own plant. The aerobic biological treatment system included 5-9 days
detention time with a mixed liquor suspended solids level of 15,000-18,000
mg/1. Typical treatment achieved was reported as follows:
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Parameter Raw Wastewater Plant Effluent
COD, mg/1 3,000 100
Total solids, mg/1 27,000 18,000
pH 2 > .0
Parathion, mg/1 ? <0.1
p-Nitrophenol, mg/1 ? <0.1
Further details of parathion treatment are given by Coley and Stutz
(1966). Although Monsanto has been successful in treating parathion waste-
waters with AS, other parathion manufacturers have not been able to dupli-
cate its success.
Lue-hing and Brady (1968) described Chemagro's biological treatment of
wastewaters from manufacture of organophosphorus pesticides, among them Co-
® ® ®
Ral (= coumaphos), Dasanit (= fensulfothion), Baytex (= fenthion), Di-
® ®
Syston (= methyl demeton), and Systox (= demeton). Raw wastewaters
contained residues from •*• 30 different formulations of organophosphorus
pesticides and were characterized by high BOD and COD, moderate SS, toxic-
ity, a heavy layer of scum, and high organic phosphate concentrations.
Certain wastewaters difficult to treat alone have been treated success-
fully when mixed with municipal sewage. This proved to be the case in
treatment of chlorophenolic herbicide wastewaters generated at Jacksonville,
AK (Evans, 1971; anon., 1973). The plant produces 2,4-D and 2,4,5-T. Prior
to the combined treatment, the plant wastewater had been treated only by
neutralization prior to discharge into a receiving stream. After neutral-
ization, the wastewater was still high in organic load and caused odors,
off-tastes in fish and fish kills.
Successful treatment was achieved as follows:
1) pretreatment by industry
a) skimming and sumps to remove light or heavy liquid phases
b) neutralization to pH 5.3-5.8 by passage through cruised
limestone
c) equalization
d) further pH adjustment to pH 7.2 with slaked lime slurry
1A3
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2) Combined industrial municipal treatment
a) biofiltration ("clarigester-filter")
b) aerated lagoon with 3 days detention time and 745 Ib/CL/hr
aeration
c) stabilization ponds
The following were noted:
1) domestic sewage bacterial flora readily degraded complex chloro-
phenols, glycolates, and acetates
2) high NaCl levels did not adversely affect biological activity
3) complaints of off-taste and odor in fish and in water ceased.
The entire treatment system removed 87-94% of the chlorophenols and
49-80% of the chlorophenoxy acids. The final effluent averaged 15 rag
BODe/1; 0.1 mg/1 of chlorophenols; and 1.1 mg/1 of chlorophenoxy acids.
Wastewater from other industries may also contain pesticides. Waste-
water from scouring rug wools mothproofed with dieldrin are difficult to
treat. Wilroy (1964) described a successful treatment system developed for
one large manufacturer. The wastewater from processing 50,000 Ib wool/day
would contain grease, 2400 Ib; SS, 4200 Ib; BOD5, 2250 Ib; and nonionic
detergents, in a volume of 60,000 gal. The associated dye wastewaters
would contribute 140,000 gpd containing grease, 310 Ib; SS, 290 Ib; BOD ,
790 Ib; dyes, 2000-3000 gal. In addition, 12000-15000 gpd of sanitary
wastes would be contributed. A treatment system was designed with the
following unit processes:
(1) fine screens on dyeing and scouring lines
(2) sedimentation, 6 hr detention, on wool scouring lines
(3) equilization and lagooning in 3.51 deep ponds, ^-80 days detention
time.
The treatment time was observed over the first year of operation. In the
lagoon active anaerobic decomposition occurred, achieving an overall BOD
reduction of 80-90% (effluent BOD averaging 130 mg/1) and a dieldrin
removal of about 99% (effluent concentration averaging 0.25 mg/1). The
receiving stream contained red-breasted bream for which the TL,-0 for dieldrin
is 8 ppb; however, sufficient dilution of the wastewater was provided to
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reduce the dieldrin to 0.5 ppb. In addition dieldrin was probably removed
onto suspended solids and thence into the sediments, since this phenomen is
known to occur with endrin, a related compound.
On the other hand, Garrison and Hill (1972) found that a total detention
time of 7 days in a series of three 4-ft deep anaerobic lagoons removed
only 10% or less of the dieldrin in wool scouring wastewaters from a carpet
mill. Influent and effluent from the system both averaged 0.4 mg/1 dieldrin.
High dieldrin levels, up to 124 mg/1, were found in caddis fly larve col-
lected in the river 4 miles below the outfall. The wastewater at this
plant contained dyes, salts, and surfactants, but evidently did not contain
domestic sewage, as did the plant described by Wilroy (1964). The dyes
were also different. The plant described by Wilroy contained certain red
and black dyes, while the plant described by Garrison and Hill contained
anthraquinone blue disperse dyes and the carriers associated with their
application. The blue dyes were not completely degraded during anaerobic
treatment.
Some investigators have performed laboratory studies of pesticide
degradation using organisms associated with biological treatment.
Halvorson et al. (1971) developed a method for testing biodegradability of
insecticides using resting cell preparations of bacteria from a sewage
lagoon. Rates of degradation of organophosphorus insecticides (malathion,
parathion, diazinon) were compared to those of chlorinated hydrocarbon
insecticides (heptachlor, dieldrin, DDT). Analytical grade preparations of
the insecticides were used. The experimental procedure was as follows:
1) concentrate and wash bacteria from sewage lagoon water
Q
2) suspend in phosphate buffer (final concentration about 4 x 10
cells/ml)
3) add standard insecticide solution
4) incubate
a) aerobic studies: incubate on a shaker
b) anaerobic: flush container with nitrogen, close completely,
keep stationary
145
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5) at intervals remove aliquots of suspension for insecticide analy-
sis.
The procedure for measuring biodegradation of chlorinated hydrocarbons was
similar.
The organophosphate insecticides were quickly degraded by the
bacteria. Presence or absence of oxygen appeared to have little effect
with the exception that the suspension exposed to diazinon appeared to
remain active longer in presence of oxygen. In order of increasing lability,
the insecticides were ranked malathion > parathion > diazinon. On the
other hand, chlorinated hydrocarbons were very resistant to biodegradation.
Presence or absence of oxygen had no effect. Under anaerobic conditions
DDT was quickly converted to DDD which was not further metabolized.
The authors felt that use of concentrated resting cell preparations
had several advantages over use of growing cultures, such as (1) completion
of test in hours rather than weeks or months, (2) ease of measuring degra-
dation rate in the relatively "clean" preparation, (3) ready detection of
acclimation or adaptation, and (4) feasibility of testing several insecti-
cides at once since their studies showed that rate of use of any one pesti-
cide was unaffected by presence of others.
Canter et al. (1969) used BOD and COD tests to evaluate effect of
commercial pesticide products on oxygen demand of wastewater using BOD and
COD tests. Toxicity of the preparations was assessed with BOD tests and
with Escherichia coli (as measured by streaking plates containing the
pesticide). Presence of commercial preparations of dieldrin and endrin
markedly increased BOD of domestic sewage: dieldrin, BOD increased by 130
mg/1 per mg/1 of pesticide; endrin, by 40 rag/1 per mg/1 pesticide. Pure
endrin alone exhibited no additive effect. Neither in concentrations up to
50 mg/1 had any toxic effect in BOD tests. COD was also increased by
addition of commercial preparations and the increase in COD was greater
than for BOD, possibly due to the greater susceptibility of the organic
solvents to biological than to chemical oxidation.
Toxicity to E. coli was low. E. coli grew for 24 hr in the presence
of commercial preparations of up to 500 mg/1. At 3000 mg/1 the E. coli
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could survive and grow in the presence of dieldrin but not endrin. In
growth studies 600 mg/1 of endrin was the highest concentration at which E.
coli could survive for 14 days. The importance of pesticide solubility was
stressed. Both dieldrin and endrin have low solubility in water and at
concentration > 5 mg/1 form colloidal sols which are physically unavailable
to bacteria and thus show no toxic effect at up to 600 mg/1.
Vaicum and Eminovici (1974) described the effects of trinitrophenol
and Y~nexachlorocyclohexane on the biochemical characteristics of activated
sludge. Object of the laboratory and field studies was to see if certain
biochemical measurements could be used to provide a means of early detection
of toxic wastes.
For the laboratory studies continuous AS units were used. Three syn-
thetic substrates with a COD of 400 mg/1 were prepared for feed. They
included (1) nutrient broth, glucose, aniline, dipotassium phosphate, ammo-
nium sulfate; (2) as above, but without aniline; and (3) sodium acetate,
urea, dipotassium phosphate. The units were allowed to operate at steady-
state for three months. Then test compounds were added. Respiration rate,
enzymatic activity (catalase and dehydrogenase), and protein content proved
to be sensitive indices of the sludge activity. There appeared to be
threshold concentrations of the test compounds which if exceeded led to
irreversible damage to the sludge.
As might be expected, pesticides have also been found in biological
wastewater systems not associated with the pesticide industry. Liu e_t al.
(1975) sampled anaerobically digested chemical sewage sludges for chlori-
nated hydrocarbon pesticides. The studies were conducted at 4 plants in
Ontario, where phosphorus removal is required. Iron sludge from a heavy
industry area had the highest pesticide concentration (103 |Jg/l); iron
sludge from a medium industry area, 63 H8/l> alum sludge from a light
industry area, 45 M8/lj an^ lime sludge from a residential area, 20 |Jg/l.
Lindane, dieldrin, aldrin, heptachlor and heptachlor epoxide, Y~chlordane,
d-chlordane, 0,P'-DDT, P,P'-DDT, P,P'-DDE, and P,P'-DDD were found in all
sludges; heptachlor, chlordane, DDT, and DDT accounted for over 85% of the
total. The presence of DDE and DDD indicated some transformation of DDT
147
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during treatment. Since DDT had been banned for some time, either the DDT
persisted for a long time or some DDT was still being discharged illegally.
There were no seasonal trends in type and quantity of pesticides. The
presence of pesticides in sludge may possibly be a consideration if sludges
are to be spread on land, although the total amounts applied at present
should pose no problem according to the authors.
Jensen et al. (1972) identified another metabolite of DDT in anaerobic
digested sewage sludge and lake sediment. In their work a liter of acti-
14
vated sludge was fed 100 mg P,P'-DDT fortified with C-DDT and containing
as contaminants ODD (4%) and DDE (3.1%). The sludge was incubated at 20°C
for 8 days in a nitrogen environment, and aliquots were removed for pesti-
cide analysis. DDT had a half life of 7 hours, and the original DDE disap-
peared in 48 hours. The DDT was transformed to DDD, DBF (P,P*-dichlorodi-
phenylbenzophenone), DDMU [(l-chloro-2,2-bis-(p-chlorophenyl)-ethylene) ],
and a newly identified product identified as DDCN [bis-(p-chlorophenyl)-
acetonitrile]. This new compound was also found in a lake sediment—the
first time it has been found in nature. After transformation to DDD and
DDCN, no further transformation of DDT occurred. DDCN is patented for use
against soil organisms.
In conclusion, there is a great deal of published information on bio-
degradation of some pesticides, especially in the soil environment. On the
other hand, there are many pesticides for which information is sparse or
nonexistent. Published case studies of biodegradability of actual pesticide
manufacturing wastewaters, which are multicomponent and which tend to vary
greatly in strength, are very limited in number and scope. Such studies,
accompanied by (1) precise and complete chemical characterization; (2)
assessment of effects on biological treatment organisms, including those
responsible for aerobic degradation, anaerobic degradation, nitrification,
and denitrification, and (3) assessment of impact on receiving stream
organisms, are sorely needed to develop control technology which is both
cost-effective and environmentally sound.
148
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SECTION 9
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Sources of general interest which are not cited in the text are indicated
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149
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Esser, H. 0., G. Dupuis, E. Ebert, C. Vogel, and G. J. Marco. S-Triazines,
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» 11 it
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161
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163
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164
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165
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166
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APPENDIX A
ANALYTICAL PROCEDURES FOR ROUTINE WASTEWATER CHARACTERIZATION
Routine wastewater analyses were conducted according to Standard
Methods for the Examination of Water and Wastewater, 14th Edition, (APHA,
AWWA, WPCF, 1976).
PH-
pH was determined electrometrically by Method 424.
Chloride--
Chloride was measured by the mercuric nitrate method (Method 408 B).
Acidity--
Acidity, as CaCO-, was determined by Method 402.
Alkalinity--
Alkalinity, as CaCO~, was determined by Method 403.
Nitrogen Forms--
Total Kjeldahl nitrogen was determined after digestion, according to
Method 421. Ammonia (NH -N) was determined by an acidimetric method as
described in Sections 418 A and 418 D. Nitrite and nitrate nitrogen (NO -
N, NO -N) were determined by the Devarda's alloy method (419 F).
Phosphorus--
Tota] phosphorus (TP) was determined by the ascorbic acid method (425
C and F).
COD--
Chemical oxygen demand (COD) was determined by Method 508.
167
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Residues—
Suspended solids (SS) were determined by Method 208 D. Total solids
(TS) were determined by Method 208 A. Total Dissolved solids (TDS) were
determined by Method 208 A. Settleable solids were determined by Method
208 F.
168
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APPENDIX B
ANALYTICAL PROCEDURE FOR ARSENIC
Analysis for arsenic was performed using a Perkin-Elmer Model 403
atomic absorption spectrophotometer equipped with an HGA-2000 graphite
furnace and a deuterium arc background corrector. The samples were diluted
9:1 sample: 1.75% HNO. solution containing 10,000 ppm nickel. Calibration
standards were prepared from stock 1000 ppm arsenic solution and diluted
like the samples with 1.75% HNO^ solution containing 10,000 ppm nickel.
Previous work in our laboratory has shown that an organo-arsenic compound
gives approximately 80% of the instrument response as an inorganic standard
for the same weight of arsenic, with some variation due to a concentration
effect. Calibration and instrumental data are shown in Table B-l.
169
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Table B-l. CALIBRATION AND INSTRUMENTAL DATA FOR ATOMIC
ABSORPTION DETERMINATION OF ARSENIC.
Element
As
Effective calibration range
Instrumental Data
0-150 ng/ml
source
wavelength
slit
sample volume
purge gas
gas interrupt
drying time temp.
temp.
charring time
temp.
atomizing time
temp.
electrodeless discharge lamp
195.4 nm
4
20 yl
N2
auto
20 sec.
100 °C
30 sec.
1200 °C
8 sec.
2500 °C
170
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APPENDIX C
ANALYTICAL PROCEDURE FOR DETERMINATION OF ATRAZINE
The procedure for analysis of atrazine was adapted from Richard e_t al.
(1975) and involved sorption of the atrazine on XAD-2 resin prior to separa-
tion, identification, and quantification.
Petroleum ether, acetonitrile, and ethyl ether of pesticide quality
were obtained from Burdick and Jackson. XAD-2 macro-reticular resin (Rohm
and Haas) was purified by sequential Soxhlet extraction with methanol and
acetonitrile. The resin was passed through a sieve and divided into three
portions: > 30 mesh, 30-60 mesh, and < 60 mesh. It was then stored under
methanol in glass-stoppered bottles.
Gas chromatography was performed with a Fisher-Victoreen Series 4406
/• o
gas chromatograph equipped with a Ni EC detector, the column (170 cm x
0.2 cm i.d.) was a 1.5% OV-17/1.95% QF-1 on Chromasorb W(HP) (80/100).
To perform the analysis, five columns were prepared using ^ 5 ml each
of 30/60 mesh XAD-2 resin. The methanol in which the XAD-2 was stored was
drained off, and each column was washed with 50 ml of ether, then equili-
brated with deionized water by running 100 ml of deionized water through
the column. The stopcock was closed when the deionized water was at the
top of the column.
An aliquot (5 ml) of sample was placed on the top of each column. The
sample was allowed to drain to the top of the column. Deionized water (5
ml) was placed on the column to wash the particulate sticking to the side
of the glass into the column; it was allowed to drain completely, then
diethyl ether (15 ml) was added to the resin. About 5 ml was allowed to
flow through the resin and collect in a separatory funnel (60 ml). Then
the stopcock was closed for 15-30 min after which the remaining 10 ml of
171
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ether was collected in the funnel. This elution procedure was repeated
with a second 15 ml portion of ether which was combined with the first.
The water layer was drained from the funnel and removal of the final traces
of water in the eluate was accomplished by adding petroleum ether (10-15
ml) and anhydrous Na?SO, . The resulting mixture was shaken ~ 30 sec and
the liquid extract was transferred quantiatively to a test tube. The
extract was concentrated to 1 ml by a blowdown under a gentle stream of N?.
Gas chromatography was performed with a Fisher-Victoreen Series 4400
/•q
gas chromatograph equipped with a Ni EC or tritium EC detector. The
column (170 cm x 0.2 cm i.d.) was a 1.5% OV-17/1.95% QF-1 on Chromasorb
W(HP) (80/100). Carrier gas was N at 20 ml/min and the sample injection
amount was 1 i.
172
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APPENDIX D
ANALYTICAL PROCEDURES FOR DETERMINATION OF ORYZALIN
Ultraviolet-visible spectra of the samples before and after various
treatments were measured on a Perkin Elmer Model 402 ultraviolet-visible
spectrophotometer. Dilutions were made as necessary to maintain absor-
bances less than 2.0 for the region of 330 to 600 nm. This permitted the
evaluation of the removal of colored components. The absorbance maximum
for oryzalin is at 378 nm; however, the wastewaters contain other colored
materials. The presence of other colored materials was further confirmed
in some cases by thin layer chromatography. Silica gel thin layers (Brink-
mann) were washed with methanol and activated at 110°C. After spotting the
samples, the plates were developed in hexane: acetone 55:45 (v/v). Scanning
densitometry may be used to quantitate oryzalin down to ^ 500 ppb in water;
however, this was not sensitive enough to detect oryzalin in wastewater
samples.
The method of Sieck et al. (1976) was used for oryzalin determination.
In this method the sample was cleaned by a liquid-liquid partition and
column chromatography on alumina using 95:5, benzene:ethylacetate, as the
eluent. The purified oryzalin was then derivatized with methyliodide to
give the N,N-dimethyl derivative. The quantitation was made by GC/ECD on a
column packed with 5% SE 30 on Supelcoport. Detection limits of ^ 2 ppb
were obtained with this method, but no oryzalin itself was detected in the
wastewaters although there were very high levels of closely related colored
compounds.
173
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APPENDIX E
ANALYTICAL PROCEDURE FOR DETERMINATION OF MSMA
Currently available analytical methodology for MSMA is deficient on
several counts for the analysis of this compound if other arsenic compounds
are present. A few methods based upon .the formation of volatile derivatives
and subsequent gas chromatographic analysis are available (Johnson et al. ,
1973; Lodmell, 1973; Salmi et al_., 1946; Talmi and Bostick, 1975; and Talmi
and Feldman, 1975). Problems exist with derivitization reactions which tend
to give artifacts and produce extremely toxic volatile products. With these
gas chromatographic methods special spectrophotometric detectors such as
microwave emission spectrometric detectors or flame spectrometric detectors
are utilized. These drawbacks led us to attempt liquid phase analysis. The
range of pK's of the various probable arsenic compounds (i.e., arsenic acid,
methylarsenic acid and dimethylarsenic acid) indicated separation by ion
exchange chromatography should be possible if a sensitive detection system
were available. The recently developed technique of ion chromatography
(Small et al.., 1975, Sawicki et al., 1978) was ideally suited to the problem.
The basic principle of this technique is the use of a low capacity, high
resolution analytical ion exchange column and a high capacity, low volume
suppressor column, of the opposite type from the analytical column, i_.e., a
cationic suppressor column with an anionic analytical column. A buffer is
then chosen which results in a nonionic species when neutralized by the
suppressor column; a microflow conductivity detector is used to detect
ionic species remaining. An example is HCO /CO used as eluent. The neutra-
lization of these ions results in H.CO which yields a very low conductivity
background.
-------
Initial experiments revealed that methylarsenic acid and arsenic acid
could be readily detected and were well separated from each other when using
a 500 mm anion exchange analytical column and a 250 mm cation suppressor
column. The eluent was 0.003 M NaHCCL/0.0024 M Na^O-. Under these condi-
tions nitrite and nitrate interfered. Since methylarsenic acid was the
species of interest here, the chromatographic conditions were optimized for
its resolution from nitrite at the expense of arsenic acid. A sample
chromatogram is shown in Figure E-l. Analysis of the untreated wastewater
samples produced the chromatogram in Figure E-2. Only small amounts of
fluoride or chloride were present in addition to the methylarsenic acid.
The manufacturing wastewater could be injected directly into the instrument
with no preparation other than filtering through a 5 pm membrane filter
(Millipore Corp.). The effluents from evaluation of activated carbon for
the removal of MSMA were analyzed in the same way.
Influents and effluents from the activated sludge units fed 10% MSMA
wastewater could not be injected directly since (1) the ten-fold dilution
placed the final MSMA concentration at or below the limit of detection and
(2) the domestic sewage contained such high anion concentrations that
simple concentration steps were not effective. With a 11.6 mg/1 MSMA
concentration (6.2 mg/1 As) in the filtered wastewater a 10-fold dilution
would give a 1.2 mg/1 final concentration, approaching the limit of detec-
tion (0.5 mg/1 MSMA). Freeze-drying the sample (100 ml) and redissolving
it in 10 ml was effective in concentrating the sample; however, the other
anions were also concentrated and the ion chromatogram which resulted is
shown in Figure E-3.
The principal interferent was chloride ion and the following steps
were added to the procedure for removal of excessive chloride. A cation
+
exchange resin (Bio-Rad AG 50W-X8, 100/200 mesh) was converted to the Ag
form with 1M AgNC> and washed with deionized water until no Ag could be
detected in the wash water. Columns were prepared in thistle tubes with a
tip drawn in the end and a glass wool plug was used to retain the resin.
The resin was protected from light by wrapping with opaque material. The
175
-------
columns were about 2 nun (id) and 6 cm long. Each freeze dried sample (100
ml initial volume) was taken up in 8 ml of deionized water and transferred
to the columns. The effluents were collected in 10 ml volumetric flasks
and diluted to the mark after the column cleanup. In most cases, a clear
chloride-free sample was obtained and precautionary filtration through a 5
\m membrane filter was all that was required to obtain ion chromatograms
such as those shown in Figures E-4 and E-5.
Colored samples were obtained from the sludge samples, apparently due
to the formation of a silver chloride suspension. This suspension could
effectively be removed by ultrafiltration. To eliminate this interference,
therefore, activated sludge samples from the test units were treated in the
same manner as the influent and effluent samples, with the following excep-
tions: (1) filtration through a Whatman No. 1 filter before removal of
chloride; (2) filtration through a filter of nominal porosity of 10,000
molecular weight (Diaflow UM-10 filter) prior to ion chromatography.
176
-------
Sample: 10 ppm F~_, Cl , NC>2 , Br ,
NO
PO,
and SO,
'3 • '^4 • " 2
20 ppm MSMA and 20 ppm
Injection volume: 100 \il
Eluent: 0.004 M NaHCO-j
Flovrate: 2.3 ml/min
Scale: 30 pMHO Full scale
Columns: 400mm anion exchange
separator column
250 mm cation exchange
suppressor column
Instrument: Dlonex System 14
Ion Chromatograph
(xlO)
(xl)
Time (min)
Figure E-l. Ion chromatogram of standard anion mixture,
177
-------
Sample: Filtered H3:iA
vasteuater
Injection volume: ll)0> ul
Eluent: 0.004 M NaHC03
Flowrate: 2.3 nl/min
Scale: 30 ViMHO Full scale
Columns: 400mm anion exchange
separator column
250 urn cation exchange
suppressor column
Instrument: Dionex System 14
Ion Chromatograph
MS MA
(xlO)
Figure E-2. Ion chromatogram of MSMA
wastewater.
178
-------
Sample: 10% MSMA vastewater In raw
• ew«pi-, concentrated 10-fold
by freeze-drying.
Injection volume: 100 pi
Eluent: 0.004 M NaHCOj
Flovrate: 2.3 ml/mln
Scale: 30 wMHO Full scale
Columns: 400c~ anlon exchange
separator colunn
230 mm cation exchange
•oppressor column
Instrument: Dionex Syiten 1A
Ion Chromatograph
(xlO)
(zl)
10
20
Time (min)
30
Figure E-3. Ion chromatograin of MSMA wastewater
diluted with sewage.
179
-------
00
o
MSMA
Sample: 10% MSMA wastewater In raw sewage
concentrated 10-fold and treated with Ag
form cation exchange resin.
Injection volume: 100 ul
Fluent: 0.004 M NaHCO-j
Flowrate: 2.3 ml/mln
Scale: 30 UMHO Full scale
Columns: 400mm anlon exchange
separator column
250 mm cation exchange
suppressor column
Instrument: Dlonex System 14
Ion Chromatograph
10
20
30
Time (min)
40
-^
60
Figure E-A. ion chromatogram of MSMA wastewater in sewage - after
chloride removal.
-------
Oo
I A MSHA
UJIA
10
20
±
30
Time (mln)
40
Sample: Effluent from Unit 3,
day 10, concentrated
10-fold and treated
to remove chloride.
Injection volume: 100 ul
Eluent: 0.004 M NaHCO..
Flovrate: 2.3 ml/mtn
Scale: 30 pMHO Full scale
Columns: 400mm anlon exchange
separator column
250 mm cation exchange
suppressor column
Instrument: Dlonex System 14
Ion Chromatograph
50
60
Figure E-5..
Ion chromatogram of effluent from activated
sludge treatment of MSMA wastewater.
-------
APPENDIX F
ANALYTICAL PROCEDURES FOR MANEB AND ITS BREAKDOWN PRODUCTS
Maneb—
The procedure for maneb determinations was adapted from McLeod and
McCully (1969) and involves reduction of maneb to carbon disulfide (CS«)
using stannous ion, followed by measurement of CS_ by GC/ECD. This method
does not provide information on speciation of the dithiocarbamate breakdown
products and is sensitive to the disulfide and monosulfide cyclic thio-
carbamates as well as the metal complex. The method is insensitive to
ethylthiourea, the end product of maneb oxidation.
The maneb reference standard (98% pure) was obtained from the Quality
Assurance Section, Environmental Toxicology Division of EPA, Research
Triangle Park, NC. The CS_ standard (certified ACS) was obtained from
Fisher Scientific Co. The stannous chloride reagent was prepared fresh
daily from the ACS grade chemical (Fisher Chemical Co.) by dissolving 1.5 g
in 100 ml of 6 M HC1. Standards were prepared by weighing out the appropri-
ate amount of maneb and placing it into a 50 ml narrow mouth amber bottle
along with 1 ml HO and 9 ml of the stannous chloride reagent. Bottles
were closed with septum caps. Samples were prepared in the same way, using
1 ml of the sample or a dilution. Samples and standards were then shaken
for at least 0.5 hr. at 65°C in a water bath. For analysis, an appropriate
amount of headspace was withdrawn with a gas-tight syringe (Pressure-Lok,
Series A-2, Precision Sampling Corporation) and analyzed by GC/ECD.
Gas chromatography was performed with a Fisher-Victoreen Series 4400
gas chromatograph equipped with a tritium scandide detector. The column
(170 x 0.2 cm) was Pyrex glass packed with 0.2% Carbowax 1500 on 60/80
Carbopack C, with an anhydrous sodium sulfate plug (2.5 cm long) preceding
the packing. The oven and injection port were at ambient temperature and
182
-------
the detector was at 300°C. Nitrogen gas was used as a carrier (at 15
ml/min) and as makeup gas (10 ml/min). Sample injection size was 0.025-0.5
ml.
A standard curve indicated a linear response over the range of 2-130
mg/1 of maneb.
Analysis of Maneb in Manufacturing Wastewaters—
Wastewaters, both filtered and unfiltered, were analyzed for maneb.
In actual Wastewaters there appeared to be a solubility limit of maneb and
its breakdown products which generate CS_ under conditions of acid hydrolysis.
One of the Wastewaters contained an appreciable amount of undissolved
solids and an extremely high concentration of maneb and related compounds
was detected, whereas the concentration in filtered samples was 40-46 mg/1
for all Wastewaters. It is presumed that the solids are undissolved dithio-
carbamates.
In order to gain some information on the possible role of dissolved
CS_ on the analytical results, a series of experiments was performed in
which the amount of CS_ generated was monitored for maneb and a maneb
wastewater as a function of the presence or absence of the acid hydrolysis
reagent and/or shaking at 65°C. Ninety |Jg of maneb was placed in each of
three 50 ml narrow-mouth amber bottles. To the first was added 1 ml of
H_0. The bottle was stoppered and allowed to remain at room temperature for
0.5 hr. To the second was added 10 ml of HO, and the bottle was stoppered
and shaken at 65°C for 0.5 hr. To the third was added one ml of HO and 9
ml of SnCl.-acid reagent; it was then stoppered and shaken at 65°C for 0.5
hr. One ml of unfiltered maneb wastewater was placed in each of four 50-ml
narrow-mouth amber bottles. The first bottle was allowed to stand at room
temperature for 0.5 hr, while the other three were shaken for 0.5 hr at
65°C. The latter three bottles contained respectively:
(1) 1 ml wastewater alone
(2) 1 ml wastewater + 9 ml H20
(3) 1 ml wastewater + 9 ml of SnCl -acid reagent.
Results were as follpws:
183
-------
Sample Normalized Peak Areas
Maneb Standards
90 ppm maneb, 1 ml HJ}, unheated 2.99
90 ppm maneb, 10 ml HO, heated 4.64
90 ppm maneb, 1 ml HO,
9 ml SnCl_-acid reagent, heated 18.50
Vastewater, unfiltered
1 ml wastewater, unheated 3.61
1 ml wastewater, heated 4.87
1 ml wastewater + 9 ml H.O, heated 4.52
1 ml wastewater + 9 ml SnCl2-acid
reagent, heated 6.70
Apparently, there is an equilibrium which is temperature dependent
established between the various breakdown products of maneb including CS_.
Only a small fraction of the CS generated is to be found in the head
space, while most remains dissolved. The solubility of CS in water is 2.2
mg/ml at 22°C and 1.4 mg/ml at 50°C (from CRC Handbook of Chemistry and
Physics, 53rd Edition).
It is not feasible to measure the residual CS2 in the sample before
acid hydrolysis, since in the presence of only H^O some hydrolysis does
occur, and the amount of CS_ present in the head space is affected by the
change in equilibrium created by heating the sample to 65°C.
Maneb Breakdown Products—
Maneb breakdown products were determined by the method of Czegledi-
Janko (1967). The procedure involves chloroform-ethanol extraction of the
dry maneb sample followed by thin layer chromatography of the extract. No
standards are commercially available for ethylene dithiocarbamate disulfide
(ETD) or monosulfide (ETM). The ETU standard was 97% pure and was obtained
from Aldrich Chemical Company.
184
-------
Solid samples were weighed to yield approximately 0.5 g of maneb;
unfiltered liquid samples were mixed and a 200 ml aliquot freeze-dried
before the extraction. The commercial maneb was extracted with 5 ml of 1:1
chloroform: ethanol mixture. The wastewater samples from plants A and B
were extracted with 20 and 50 ml chloroform:methanol (1:1) respectively.
The adjustment of volume was based upon the amount of residue. Aliquots of
10 to 25 pi of these extracts were spotted on Silica Gel G TLC plates
(Brinkman) and developed with chloroform: butanol-methanol-water (100:5:-
1:0.5). After evaporation of the solvents, the TLC plates were placed in a
chamber saturated with iodine vapor for about 10 min. The color developed
was preserved by covering with a glass plate. Photographs of these plates
are shown in Figures F-l and F-2 with an ethylene thiourea (ETU) standard.
Although no standards of ETD or ETM were available, comparison of our
plates with those published by Czegledi-Janko (1967) indicate spots having
the same R relative to ETU. Areas corresponding to ETU showed extensive
concentration reversal after the initial 10 min exposure to iodine. However,
this exposure gave the best visualization of the other breakdown products.
Chromatograms of the plates were obtained via scanning spectrodensitometer
(Schoeffel SD 3300, transmission mode, 680-nm wavelength, 2 mm slits).
185
-------
ETM?
ETD?
ETU
Origin
•8
Origin
H
P,
Figure F-l.
Thin-layer chromatogram of the
extract of commercial formulated
maneb and ETU.
Figure F-2.
Thin-layer chromatogram of the
extracts of Plant A (right) and
Plant B (left) wastewaters.
-------
APPENDIX G
PROCEDURE FOR CONDUCTING ACTIVATED CARBON TREATABILITY TESTS
Liquid Adsorption Isotherm Tests
Sources of Carbon--
The following types of carbon were used in preliminary liquid adsorp-
tion isotherm teats:
LCL Union Carbide
LCK Union Carbide
Nuchar SA Westvaco
Nuchar WV-L
Nuchar WV-G
Filtrasorb 400 Calgon Corporation
Hydrodarco ICI Americas, Inc.
Carbons which were not received in powder or pulverized form were crushed
and passed through a 325-mesh screen as recommended for isotherm testing
(Metcalf & Eddy, Inc., 1972).
Procedure--
The procedure for isotherm tests was modified from Hetcalf and Eddy,
Inc. (1972). Aliquots (100 ml) of the filtered (Whatman 2V) wastewater were
placed in flasks and dosed with the carbon to give a final carbon concen-
tration of 0, 400, 800, 1600, or 20,000 mg/1. They were placed on a shaker
and agitated for 2 hr at 22-24 C. Carbon was removed ty passage through a
glass-fiber filter and residual pesticide levels were measured.
GAC Column Tests
Calgon Filtrasorb 400 was chosen for large-scale tests. It was dried
(> 2 hr at 150 C) to constant weight before use. It was slurried in hot
187
-------
water to expel trapped air, then added to the column in small increments,
keeping a thin layer of supernatant liquid present at all times. Wastewater
was pumped (Masterflex) pump onto the top of the column at a rate giving a
2
flow of -v- 0.5 gpm/ft . This is recommended as a good starting rate in
pilot tests but is lower than is generally used in practice (Metcalf and
Eddy, 1972). Because of the limited amount of wastewater available, it was
chosen for these studies. Depending on sorptive capacity of the carbon for
the specific wastewater, a short (15.2 cm height x 2.2 cm i.d.) or long
(120 cm height x 2.5 cm i.d.) glass column was used. With the exception of
the MSMA wastewater, which was free of suspended solids, the wastewaters
were filtered (Whatman 2V, medium porosity) prior to GAC column treatment.
In each run, an initial void volume was collected and discarded before
collection of fractions for analysis.
188
-------
APPENDIX H
PROCEDURES FOR CONDUCTING ACTIVATED SLUDGE TREATABILITY TESTS
For biological treatability studies the miniature complete mix con-
tinuous activated sludge unit designed by Swisher (1970) was employed (Figure
H-l). This unit has an aerator capacity of 0.3 1 and a settler capacity of
0.075 1- The unit is completely made of glass, avoiding the possibility of
contamination by organics leaching from the container. Feed to the units
was supplied continuously through Teflon tubing by gravity feed or by peri-
staitic pumps to give a nominal retention time of 8 hr.
A battery of 6 units was run in each test. The units were started with
activated sludge from the Hope Valley Treatment Plant, Durham, NC, which
treats municipal wastewater. The units were then fed from a reservoir of
primary sewage from this plant. When a steady-state condition was reached,
as indicated by consistent effluent quality in terms of COD and by similar
mixed liquid suspended solids levels, the feed to the test units was spiked
with pesticide wastewater. Control units were fed only primary sewage.
In most cases the pesticide spiked wastewater feeds were prepared by
adding pesticide wastewater to the primary sewage to make a final mixture
of 10% pesticide wastewater/90% primary sewage. After thorough mixing, the
mixture was allowed to settle for ~ 120 min to simulate primary settling.
In some cases, depending on toxicity of the pesticide wastewater, higher or
lower concentrations were employed.
Routine determinations were made of dissolved oxygen, pH, mixed liquor
suspended solids, COD, and pesticide. Dissolved oxygen was determined with
an oxygen probe (Yellow Springs Instrument Co.).
189
-------
EFFLUENT
COLLECTION
AIR
Figure H-l. Diagram of activated sludge pilot unit.
190
-------
APPENDIX I
PROCEDURES FOR ALGAL ASSAY TESTS
Algal bioassays were conducted according to the freshwater algal assay
procedure: bottle test, according to the procedure described in the IERL-
RTP Procedure Manual: Level I Environmental Assessment Biological Tests for
Pilot Studies (Duke et al_. , 1977; APHA et aJL., 1976). The test alga was
Selenastrum capricornutum Printz, obtained from the National Eutrophication
Research Program, EPA, Corvallis, Ore. This test was designed to measure
algal response to changes in nutrient concentrations and to determine
toxicity or inhibition.
Wastewaters to be tested were filter sterilized through a sterile
prewashed membrane filter (Millipore Filter, 0.45 pm pore size). Serial
dilutions were then made in sterile algal media to give the appropriate
final concentration. Sufficient inoculum was added to produce an initial
3
cell concentration of 10 cells/ml.
In each set of experiments, algal growth in the presence of a series
of concentrations of the wastewater as added to the nutrient medium was
compared to that in the nutrient medium alone. Growth was determined by
direct counts (see below) of the algae during the 10-14 day incubation
period. Effect of the wastewater on algal growth was determined in terms
of the effect on the growth rate and of the effect on the cell yield.
Direct cell counts were performed (I) visually or (II) by an automated
procedure. Direct, visual counting with a hemacytometer and microscope was
the basic cell counting technique employed in the algal bioassay. Utilizing
a hand counter, the algae in 5 squares (4 corners and center) in a ruled
0.1 mm square divided into 25 squares were counted. This number was multi-
plied by 5 to give the total cells in the 0.1 mm square. Multiplying this
191
-------
3
number by 10 gave the total cells in a mm and further multiplication by
103 gave the number of cells per ml. The automated method of cell counting
followed the same preparation procedure as above, however, an automatic
cell counter was incorporated. A television camera (Fisher auxiliary
camera, 7-909-15) viewed the algal cells through the photographic tube of a
microscope, allowing for rapid cell counts following the pattern as described
in Method I.
The tests were conducted in water bath shakers at 24 + 2 C and approxi-
mately 110 oscillations per minute with constant white fluorescent lighting
at 4300 lux. Test containers were 250 ml Erlenmeyer Pyrex flasks containing
60 ml of test medium and covered with an inverted Pyrex beaker.
Initially, a series of 10-fold dilutions of pesticide wastewaters was
tested (generally 10 to 10 ) to determine the approximate toxic range.
Further tests were conducted at concentrations based on progressive bisection
of intervals on a logarithmic scale in order to more precisely define that
concentration producing 50% inhibition of growth (EC--.) •
An alternate method of expressing inhibitory or stimulatory effects
was that recommended by Miller et al. (1978), i. .e., as the percent growth
inhibition (I) or stimulation (S), as compared to growth in a control
culture without the test materials. These authors suggest that, in general
practice, the results be based on the growth at 14 days, i-e., as % I,, or
% S , at a given concentration of the effluent being tested.
Decreased growth, compared to the control, is evidence of an inhibitory
effect. The manner in which the test is conducted does not allow determina-
tion of whether this inhibition is temporary (algistatic) or permanent
(algicidal). Such a determination would require further testing by sub-
culturing into fresh medium free of the test material.
192
-------
APPENDIX J
PROCEDURE FOR FISH BIOASSAY TESTS
The fish bioassay procedure chosen was the standard 96-hour static
bioassay (APHA, et a^. , 1976; Duke et a].., 1977). The static method has
been criticized as being rather simplistic, and more complex alternate
methods have been suggested (Brown, 1973; Cairns, 1969; Eaton, 1973; Peltier,
1978; Scheier and Burton, 1973, Sprague, 1973; Stephen, 1973). However, the
relative simplicity and economy of the static method make it the method of
choice in initial screening. The test fish was the fathead minnow, Pimephales
promelas, selected from a list of recommended species prepared by D. I.
Mount of the National Water Quality Laboratory (as reported in Cairns,
1969). This species has been widely used in fish bioassay studies and is
adaptable to laboratory conditions. Test fish were obtained from Windmill
Fish Hatcheries, Kernersville, NC and Kurtz's "Fish Hatchery, Elverson, PA.
New shipments of fish were routinely exposed on arrival to the broad-spectrum
antibiotic tetracycline HC1 at a dose of about 13 mg per gallon of water for
24-48 hr. This treatment helps prevent introduction into the stock tank of
diseases from fishery stock or from fish damaged in shipment. On evidence
of disease in the stock tanks, the tetracycline treatment was repeated.
Fish were maintained in 30-gal glass aquaria equipped with devices for
aeration, recirculation, and filtration. The water was Durham tapwater
treated to remove chlorine and organic carbon by passage through an activated
carbon filter (Sears No. 42-3464). The tanks were kept in a room maintained
at 24 + 2 C, with a light cycle of 8-hr dark and 16-hr light.
Small-scale exploratory bioassays were conducted to determine the range
of concentrations to be tested in full-scale tests. For these screening
tests solutions were prepared as decimal dilutions of the wastewater (such
as 0.01, 0.1, 1.0 percent). A test volume of 3 liters and 3 fish per
container were used.
193
-------
Based on results of the screening assays, a full-scale test range was
chosen, with the concentrations falling between the highest concentration
at which all fish or most of the fish died. In these tests, the LC5Q was
determined by testing a series of concentrations based on progressive bi-
section of intervals of the logarithmic scale, such as 1.0, 1.8, 3.2, 5.6,
and 10.0 percent, multiplied or divided as necessary by any power of 10.
These values are evenly spaced when plotted on a logarithmic scale.
In each test series, control tests were conducted concurrently with
the experimental dilution water. In the large scale tests, results were
considered invalid if more than 10% mortality occurred among the control
fish. In the large scale tests, test containers were 5-gal wide-mouth
glass jars, 25 cm (d) x 47 cm (h), containing 15 liters of test solution.
To test each experimental concentration, 10 fish were used. Fish were not
fed for 48 hr prior to testing nor during the tests.
Use of 10 or more test fish per toxicant concentration has been the
"usual practice" for short-term static tests according to Standard Methods
(APHA et al., 1976). As noted in this document, "a number of factors
govern the precision of the results of a bioassay and the arbitrary setting
of the number of test organisms will not assure a certain precision for the
results." An example is cited of tests with sewage effluent indicating
that with 10 fish per toxicant concentration, the 95% confidence interval
was within + 20% of the means while when 20 fish were exposed it was within
+ 14% of the mean value.
LC50 values were estimated by interpolation after plotting the data on
semilogarithmic coordinate paper with concentrations on the logarithmic and
percentage dead on the arithmetic scale, as described in Section 801F.1
(APHA et al., 1976). This method of interpretation has been shown to give
values within the precision of the test.
194
-------
APPENDIX K
FISH AND ALGAL BIOASSAY DATA--ATRAZINE WASTEWATER STUDIES
195
-------
E
K
Wastewater (v/v)
Control
Wastewater, 0.1%
Wastewater, 0.032%
Wastewater, 0.01%
A 5 67 8 9 10 11 12 13 14 15 16 17 18
Time, days
Figure K-l. Algal assay of atrazine wastewater (as received).
196
-------
1
—
-
96 hr LC5Q - 18 ml/1 (1.8%)
100
10
1.0
0 10 20 30 40 50 60 70 80 90 100
Fish Surviving at 96 hr, %
Figure K-2. 96 hr LC^Q determination: atrazine manu-
facturing wastewater (as received).
197
-------
100
to
-
4J
f
t-
10
1.0.
96 hr
10 20 30
40
SO 60
70
Test Fish Surviving, %
18 ml/1 (1.8%)
so 90 100
Figure K-3. 96 hr LC5Q determination: atrazine manu-
facturing wastewater, filtered, Whatman 2V
filter.
198
-------
Control
0.12 dilution of Influent
0-1X dilution of effluent
6 7 B 9 10 11 12 13 14 15 16 17 18
Fieure K-4. Algal assay of influent and effluent to
8 activated sludge units fed with atrazine
wastewater (16.7%). (Data shown in Table
199
-------
Table K-l. EFFECT OF ATRAZINE WASTEWATER (AS RECEIVED) ON ALGAL
GROWTH.
Day
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Control
_
-
-
-
-
-
25
80
197
403
1058
1843
2350
3633
5717
6383
5483
5910
6325
7560
6850
6342
Growth, 10-*
cells/ml
Wastewater, %
0.1 0.032
—
-
-
-
-
-
-
30
43
100
-
470
750
1533
1783
2167
2350
2483
2467
2550
2750
2183
-
-
-
-
-
-
-
30
80
290
-
860
1260
1850
2050
2025
2075
2325
2700
2425
2675
3025
(v/v)
0.01
-
-
-
-
-
-
-
205
345
1107
-
1983
2133
1850
2267
1850
2267
2167
2400
2183
1983
2400
Growth
, % of
Wastevater, '
0.1 0.032
-
-
-
-
-
-
-
38
22
25
-
26
32
42
31
34
43
42
39
34
40
34
_
-
-
-
-
-
-
38
41
72
-
47
54
51
36
32
38
39
43
32
39
48
Control
I (v/v)
0.01
-
-
-
-
-
-
-
256
175
275
-
108
91
51
40
29
41
37
38
29
29
38
200
-------
Table K-2. SCREENING TESTS ON TOXICITY TO FISH OF UNTREATED AND
GAC TREATED ATRAZINE WASTEWATER
Sample
Wastewater
Concentration,
rol/1
No. fish surviving at 96 hr
(Initial = 3)
Dilution water
control
Filtered wastewater
(column feed)
GAC column effluent,
before breakthrough
GAC column effluent,
after breakthrough
of 1 ppm atrazine
10
18
56
100
10
18
56
100
10
18
56
100
7.0
7.1
7.5
7.8
7.2
7.1
7.1
7.1
7.1
7.2
8.5
8.7
3
2
0
0
3
2
3
2
3
3
2
2
201
-------
Table K-3. EFFECT OF ACTIVATED SLUDGE TREATMENT ON TOXICITY
OF ATRAZ1NE WASTEWATERS TO FISH
O
NJ
Sample Concentration, ml/1
Control, dilution water
Control, dilution water
Primary Sewage Influent
Primary Sewage Effluent,
Unit 1
-
-
180
100
180
% Fish Surviving at 96 hr
100
100
100
100
100
Primary Sewage + 8.3% Atrazine Wastewater:
Before Treatment (influent)
After Treatment (effluent)
Unit 1
Unit 2
Primary Sewage + 16.7% Atrazine
Before Treatment (influent)
After Treatment (effluent)
Unit 1
Unit 2
32
100
32
100
32
100
Wastewater:
32
100
32
100
32
100
100
100
100
90
90
90
100
100
80
90
90
70
-------
Table K-4. ALGAL ASSAY OF INFLUENT AND EFFLUENT TO ACTIVATED SLUDGE
UNITS FED WITH ATRAZINE MANUFACTURING WASTEWATER (16.17,)
Time (days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Growth. Percei
Influent cone. X(v/v)
10 1.0 0.1
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
-
-
-
-
-
—
•
-
-
-
- •
-
w»
-
-
40
24
15
24
32
34
52
t of Control
Effluent cone., 7. (v/v)
10 1.0 0.1
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
•
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
^
-
-
-
-
-
-
-
-
-
16
15
15
18
26
29
29
- = beneath detection limits.
203
-------
APPENDIX L
FISH AND ALAGAL BIOASSAY DATA—ORYZALIN WASTEWATER STUDIES
204
-------
Table L-l. TOXICITY OF ORYZALIN AND ORYZALIN WASTEWATERS
TO FISH — SCREENING TESTS
No. fish surviving at 96 hr
Test Sample (Initial = 3)
Oryzalin, unformulated, mg/1
0.005 3
0.05 3
0.5 3
5.0 3
Oryzalin wastewater (grab sample), % (v/v)
0.01 2
0.1 0
1.0 0
10.0 0
Oryzalin washwater (grab sample), % (v/v)
0.01 3
0.1 3
1.0 3
10.0 0
Dilution water control 3
205
-------
Table L-2. TOXICITY TO FISH OF ORYZALIN MANUFACTURING WASTEWATER
Sample
Concentration, ml/1
Fish Surviving at 96
hr, % (Initial = 10)
Control
Oryzalin wastewater
Oryzalin wastewater
Oryzalin wastewater
Orvzalin wastewater
0.0
0.1
0.13
0.56
1.0
100
80
90
:
:
10
E
. 1.0
c
c
_j
c
u
0.]
=»»
If
1
•—•
«.
•*«.
•**^
•t^.
-*.
•^«
•*-.
/
/
'96 hr LC5Q - 0.3 ml/1
40 70
lest Fish Surviving, %
*o
IOC
Figure L-l. 96 hr LC5Q determination: oryzalin manu-
facturing wastewater.
206
-------
Concentration of vastewater, % (v/v)
Figure L-2. Algal assay of oryzalin wastewater.
207
-------
ro
o
oo
Table L-3. EFFECT OF ORYZALIN WASHWATER ON ALGAL GROWTH,
EXPRESSED AS PERCENTAGE OF ALGAL GROWTH IN CONTROL
Growth, Percent of Control, in:
Time (days)
1
2
3
4
5
6
7
8
9
10
Oryzalin Washwater Cone.
10 1.0 0.1
127
45
73
71
59
67
64
72
63
58
161
102
95
83
90
87
75
90
87
87
150
74
110
95
97
79
88
96
99
98
, Percent (v/v)
0.01 0.001
150
97
103
88
89
98
83
93
104
93
133
83
91
84
121
87
67
102
97
88
-------
Table L-4. EFFECTS OF ORYZALIN WASTEWATER AFTER CARBON
TREATMENT ON ALGAL GROWTH EXPRESSED AS PERCENTAGE OF
ALGAL GROWTH IN CONTROL
Growth, Percent of Control, in:
Time
(days)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
10
—
-
-
-
-
-
-
0
25
8
0
0
0
2
1
3
6
2
0
Oryzalin Wastewater
1.0
—
-
-
-
-
-
-
200
13
0
0
3
54
1
1
2
2
2
0
Cone. ,
0.1
-
-
-
-
100
200
200
200
150
40
21
45
104
71
77
101
109
99
94
Percent (v/v)
0.01
-
-
-
-
0
-
0
200
113
104
49
56
70
61
65
80
36
53
40
0.001
-
-
-
-
0
100
100
200
128
50
28
64
82
83
68
108
82
77
66
209
-------
Table L-5. FISH BIOASSAY OF GAC TREATED ORYZALIN WASTEWATER
Sample
Concentration of Wastewater
ml/1 % (v/v)
% Fish Surviving at 96
hrs (Initial = 10)
Control
Oryzalin Wastewater, 1.0 0.1
GAC Treated
Oryzalin Wastewater, 1.8 0.18
GAC Treated
Oryz.ilin Uasteu-ater, 5.6 0.56
GAC Treated
100
0
C
100.0
o
c
l-
4-1
V
u
10.0
1.0
96 hr-LC5Q < 1.0 ml/I
20 JO 40 SO M 70 SO W 100
Test Fish Surviving, /;
Figure L-3- 96 hr LC5Q determination: GAC treated
oryzalin wastewater.
210
-------
1000
96 hr -
100
§
L;
10 -1
- 60 ml/1
—
10 20 30 40 $0 60 70
Test Fish Surviving, Z
10 90 100
Figure L-A.
96 hr-LC50 determination: untreated
domestic wastewater with 1% oryzalin
manufacturing wastewater.
211
-------
96 br-l
180
180
.
e
LOO .
10 .
OI020J040IOWTOK)
90
I
IOC
Test Fish Surviving, J
Figure L-5. 96 hr-LC5Q determination: effluent
from activated sludge unit 1 fed
domestic wastewater with 1% oryzalin
manufacturing wastewater.
96 hr - LC5Q > 180 ml/1
•s
g
180
100
10 _
(
i
OIOJD*>40M4010MfOIOC
T*>t n«h Surviving, X
Figure L-6. 96 hr-LC5Q determination: effluent
from activated sludge unit II fed
domestic wastewater with IX oryzalin
manufacturing wastewater.
212
-------
Table L-6. ALGAL ASSAY OF INFLUENT AND EFFLUENT TO ACTIVATED SLUDGE UNITS
FED WITH ORYZALIN MANFACTURING WASTEWATER (1%)
Growth, Percent of Control
Time
(days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Influent
10
-
—
-
-
—
—
-
50
-
25
9
6
6
7
12
29
concn. ,
1.0
-
—
—
-
—
—
-
200
140
138
85
78
86
84
95
112
% (v)
0.1
-
—
—
—
—
—
—
300
180
225
113
100
91
79
82
120
Effluent
10
-
—
—
—
~
~
—
-
-
50
5
3
4
4
15
26
Concn. , %
1.0
-
^
"•
~
^
™
™
250
220
325
100
62
80
83
89
114
(v/v)
0.1
-
"
^
^
"
~
™
300
80
162
108
47
68
74
84
85
213
-------
APPENDIX M
FISH AND ALGAL BIOASSAY DATA—MSMA WASTEWATER STUDIES
214
-------
Table M-l. EFFECTS OF MSMA WASTEWATER ON ALGAL GROWTH (RANGE-
FINDING), EXPRESSED AS PERCENTAGE OF ALGAL GROWTH
IN CONTROL
Time
(days)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Growth,
Percent
of Control, in:
MSMA Wastewater Concentration, Percent
10
_
-
-
-
55
0
0
4
3
2
5
1
1
1
1.0
_
-
-
-
44
400
124
94
64
49
40
64
134
46
0.1
-
-
-
50
22
137
76
54
73
89
87
106
108
90
0.01
-
-
-
-
11
156
60
62
51
92
85
78
113
86
(v/v)
0.001
-
-
-
50
0
100
94
56
43
102
80
12B
130
76
beneath detection limits
215
-------
Table M-2. EFFECT OF MSMA WASTEWATER ON ALGAL GROWTH (NARROW
RANGE), EXPRESSED AS PERCENTAGE OF ALGAL GROWTH IN
CONTROL
Growth, Percent of Control, in:
Time (days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
MSMA Wastewater Concentration, Percent (v/v)
10.0
—
-
-
-
-
—
—
0
0
0
1
0
0
0
0
0
0
0
3.2
-
-
-
-
-
-
-
314
475
134
226
172
99
107
95
47
95
98
1.0
-
-
-
-
-
-
-
200
155
119
179
133
70
67
66
78
62
68
216
-------
Table M-3. TOXICITY OF MSMA WASTEWATER TO FISH—SCREENING TESTS
Concentration
ml/1
0
100
180
320
of MSMA Wastewater
%
0
10
18
32
Fish Surviving at 96 hr.
(initial=3)
3
2
0
0
Table M-A. EFFECT OF AERATION ON TOXICITY TO FISH OF MSMA WASTEWATER—
SCREENING TESTS
MSMA Wastewater
Concentration No. Survivors at
ml/1
180
320
180
320
%
18
32
18
32
Aeration?
No
No
Yes
Yes
72 hr. (Initial=3)
0
0
2
0
217
-------
Table M-5. EFFECT OF MSMA WASTEWATER AFTER CARBON TREATMENT ON
ALGAL GROWTH, EXPRESSED AS PERCENTAGE OF ALGAL GROWTH
IN CONTROL
Growth, Percent of Control, in:
Time (days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
MSMA Wastewater Concentration, Percent (v/v)
10.0
_
-
-
-
-
_
—
—
0
1
0
0
0
0
0
0
0
0
3.2
_
-
-
-
-
-
-
242
83
31
85
57
97
106
133
140
104
84
0.1
-
-
-
-
-
-
-
86
424
39
66
72
49
53
48
57
55
56
218
-------
Table M-6. ALGAL ASSAY OF INFLUENT AND EFFLUENT OF ACTIVATED SLUDGE UNITS
FED WITH MSMA MANUFACTURING WASTEWATER (10%)
Growth, Percent of Control, in
Time
(days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Influent
10
-
—
—
_
-
-
-
250
360
588
206
116
179
205
150
168
cone. , % (v/v)
1.0
—
—
-
_
-
-
-
500
720
938
238
136
142
134
130
144
Effluent
10
-
-
-
—
-
-
-
750
128
125
438
210
182
155
140
175
cone. , % (v/v)
1.0
-
-
-
—
-
-
-
650
920
1025
282
124
120
95
95
95
- = beneath detection limits.
219
-------
10
7 .
:o6-!
io5H
10 •
10J
Concentration of Wastewater, Z (v/v)
• • 0 (control)
o— — —o 10
* » 1
•— — —» 0.1
• • 0.01
o- — —o 0.001
V . \ I
0 12 345 678 9 10 11 12 13
Tine, days
Figure M-l. Algal assay (rangefinding) of MSMA
wastewater. (Data shown in Table
M-l).
220
-------
c
LJ
Concentration of Uastevater, ~ (v/v)
10.0
3.2
1.0
0 (control)
10 •* 1 1 f 1
0 34 56 78 9 10 11 12 13
Figure M-2. Algal assay (narrow range) of MSMA
wastewater. (Data shown in Table
M-2).
221
-------
Concentration of MSMA Uastevater. % (v/v)
—o 0 (Control)
12 345 6 7 8 9 10 11 12 13 14
10
10
10
Time, days
Figure M-3.
Algal assay of GAC column-treated MSMA
wastewater. (Data shown in Table M-5).
222
-------
APPENDIX N
FISH AND ALGAL BIOASSAY DATA--MANEB WASTEWATER STUDIES
223
-------
Table N-l. SCREENING TESTS OF TOXICITY TO FISH OF COMMERCIAL
MANEB PREPARATION
Maneb, tng/1
(Calculated)
No. fish surviving at stated time
(Initial = 3)
Final pH
24 hr
48 hr
72 hr
96 hr
0
0.01
0.1
1.0
10.0
6.5
6.0
6.5
6.5
6.5
3
3
3
3
0
3
3
3
1
0
3
3
3
1
0
3
3
3
1
0
Table N-2. SCREENING TESTS FOR TOXICITY
OF MANEB WASTEWATERS TO FISH
% Wastewater (v/v)
0 (Control)
Raw Wastewater
0.01
0.1
1.0
10.0
Filtered Wastewater
0.01
0.1
1.0
10.0
No. Fish Surviving at 96 hr.
(Initial = 3)
Plant A
Wastewater
3
2
3
0
0
3
3
1
1
Plant B
Wastewater
2
3
0
0
0
3
2
1
1
224
-------
Table N-3. SCREENING TESTS OF TOXICITY OF PLANT B
WASTEWATER TO FISH
Sample
Control
it
Raw wastewater
Wastewater
Concentration
% (v/v)
0
0
0.01
0.01
0.018
0.018
0.032
0.056
0.056
0.056
0.1
0.1
10.0
10.0
£H
6.7
6.7
6.6
6.7
6.7
6.8
6.8
6.8
6.8
6. ,8
6.8
6.9
7.2
7.2
No. fish surviving at 96 hr
(Initial = 3)
3
3
3
2
3
3
3
2
3
3
0
0
0
0
225
-------
96 hr - LC5Q £ 1.0 ml/1
96 hr -
> 32 ml/1
100
1-1
H
B 1.0
s
o
u
n)
H
S3 C
O
s
n i
i
-
.
s
5
\
v-
^
•-I
H
a
. 10
c
o
•H
u
a
\->
u
s
CJ
C
O -
o
1 .ft.
t
- 0 10 20 M 40 M 60 70 tO 90 100 0 10 20 JO 40 JO 60 TO _«O 90 19
Test Fish Surviving, /, Test Fish Surving, %
Figure N-l.
96 hr LC5Q determination: maneb manu-
facturing wastewater, Plant A,
unfiltered. (Data showin in Table
14-4) .
Figure N-2.
96 hr LCcQ determination: maneb
manufacturing wastewater, Plant A,
filtered (What 2V). (Data shown
in Table 14-4).
-------
Table N-4. DETERMINATION OF LC5Q FOR FISH OF
MANEB MANUFACTURING WASTEWATEK (PLANT A)
Sample
Control
Fish
Concentration, ml/1 ^r»
fish
0
Unfiltered Wastewater 0.18
it
ii
Filtered Wastewater
ii
ii
Table N-5.
Sample
Control
0.56
1.0
1.8
10
18
32
DETERMINATION OF LC5Q FOR FISH
MANEB MANUFACTURING WASTEWATER
(PLANT B)
Concentration, ml/1 ,
fish
0
Unfiltered Wastewater 0.1
ii
ii
Filtered Wastewater
ii
ii
0.32
1.0
5.6
10.0
18.0
Surviving
% (Initial
= 10)
100
100
80
40
60
100
80
80
OF
Surviving
% (Initial
= 10)
100
70
0
0
100
0
0
at 96
no. of
at 96
no. of
227
-------
Wasteuater Concn., % (v/v)
0 12
Time, days
Figure N-3. Algal assay of Plant A wastewater
(Data shown in Table N-6) .
228
-------
Table N-6. EFFECTS OF FILTERED PLANT A WASTEWATER ON
ALGAL GROWTH (RANGEFINDING) EXPRESSED AS PERCENTAGE
OF ALGAL GROWTH IN CONTROL
Growth, Percent of Control
Plant A Wastewater Concentration,
Time (days)
1
2
3
A
5
6
7
8
9
10
11
12
13
1A
15
16
17
10
-
-
-
-
-
0
0
0
0
0
11
2
A
0
0
0
1.0
-
-
-
-
-
0
0
0
0
0
0
2
3
0
0
0
0.1
-
-
-
-
-
0
0
0
0
0
2
1
2
1
1
0
0.01
-
-
-
-
-
300
700
1100
183
23A
179
115
91
115
96
125
, in:
Percent (v/v)
0.001
-
-
-
-
-
150
650
1000
113
95
71
107
112
102
98
112
229
-------
JO
wastewater Concn., % (v/v)
0 (Control) •
V \-
23 45 67 8 9 10 11 12 13
E 10" •
10
Figure N-4. Algal assay of Plant B wastewater.
(Data shown in Table N-8).
230
-------
Table N-7. EFFECT OF FILTERED PLANT B WASTEWATER
SAMPLE 1 ON ALGAL GROWTH (RANGEFINDINC) EXPRESSED
AS PERCENTAGE OF ALGAL GROWTH IN CONTROL
Table N-3. EFFECTS OP1 FILTERED PLANT B WASTEWATER
SAMPLE 2 ON ALGAL GROWTH (RANGEFINDING) EXPRESSED
AS PERCENTAGE OF ALGAL GROWTH IN CONTROL
NJ
LO
Time (days)
1
2
3
4
5
6
7
8
1
10
11
12
13
14
Plant B
10
-
-
-
-
8
7
6
a
7
7
7
7
6
Growth, Percent of
Control ,
In:
Vaatewater Concentration, Percent
14
10
17
Concentration. Percent Cv/v)
0.1
-
-
-
-
40
13
0
29
12
9
A
3
2
5
13
13
13
0.01
-
-
-
-
120
113
100
111
190
104
96
109
96
74
111
90
U
0.001
-
-
-
-
40
88
100
71
200
99
134
91
10$
81
86
97
80
-------
Wastewater Concn., % (v/v)
01 23 45 678 9 10 11 12 13 14
10
10
Figure N-5. Algal assay of Plant B wastewater.
(Data shown in Table N-9).
232
-------
Table N-9. EFFECTS OF FILTERED PLANT B WASTEWATER SAMPLE 2 OH ALGAL
GROWTH (NARROW RANGE) EXPRESSED AS PERCENTAGE OF ALGAL
GROWTH IN CONTROL
Growth, Percent of Control, in:
Plant B Wastewater Concentration, Percent (v/v)
Time (days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0.1
-
—
—
-
150
150
140
100
129
135
98
49
34
25
34
0.056
-
—
—
—
100
150
185
141
416
184
174
75
70
42
S4
0.032
-
••
••
—
50
75
100
147
204
196
174
102
86
66
70
0.018
-
^
^
~
150
125
214
159
479
195
210
95
88
67
79
0.01
-
~
"
—
100
75
86
129
304
117
106
82
86
56
83
233
-------
Table N-10. EFFECT OF ACTIVATED CARBON TREATMENT
ON TOXICITY OF MANEB WASTEWATERS TO FISH
Sample
Control dilution water
(4 replicates)
Plant A Wastevater
Untreated
Filtered, Whatman 2V
GAC treated
Plant B Wastewater
Untreated
Filtered, Whatman 2V
GAC Treated
Concentration
ml/1
—
0.056
0.1
0.18
0.56
1.0
1.8
10
18
32
18
32
0.1
0.32
1.0
0.1
0.32
1.0
10.0
18.0
32.0
0.32
1.0
3.2
10
18
32
Fish Surviving at LC5n» ^6 hr.
96 hr, % (Initial no. nl/1
of fish = 10)
100
100
100
100 al
80
AC
60
100
80 >32
80
100 >32
90
70
0 'MD.IS
0
100
100
100 M.2
0
0
0
100
90
90
80 >32
60 C\42)
234
-------
01 23 456 7
10 -
10
10
Figure N-6. Algal assay of Plant B wastewater,
GAC treated. (Data shown in Table
N-ll).
235
-------
Table N-ll. EFFECT OF PLANT A WASTEWATER AFTER CARBON TREATMENT ON ALGAL
GROWTH EXPRESSED AS PERCENTAGE OF ALGAL GROWTH IN CONTROL
Growth, Percent of Control, in:
Plant A Wastewater Concentration,
Time (days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
0.1
-
^
—
-
—
_
_
14
0
1
0
0
0
0
0
0
0
0
0.032
-
_
-
-
-
-
_
128
120
87
58
145
104
116
106
114
95
109
Percent (v/v)
0.01
-
_
-
-
-
-
—
143
114
38
91
125
77
73
87
94
93
92
236
-------
10
7 -
Wastewater Concn., % (v/v)
0 123 45 67 8 9 10 11 12 13 14
10
Figure N-7. Algal assay of Plant B wastewater, GAC
treated. (Data shown in Table N-12).
237
-------
Table N-12. EFFECTS OF PLANT B WASTEWATER AFTER CARBON TREATMENT
ON ALGAL GROWTH (RANGEFINDING) EXPRESSED AS PERCENTAGE OF
ALGAL GROWTH IN CONTROL
Growth, Percent of Control, in:
Time
(days)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Plant
10
_
-
-
0
0
0
0
0
0
0
2
0
0
0
0
0
0
B Wastewater
1.0
—
-
-
0
0
0
0
0
15
9
18
7
8
14
13
19
14
Concentration
0.1
-
-
-
50
40
38
38
98
115
39
29
41
47
47
77
72
55
, Percent
0.01
-
-
-
50
60
63
46
131
167
124
96
107
99
80
104
86
94
(v/v)
0.001
-
-
-
50
40
63
62
74
85
110
97
50
78
86
123
95
86
238
-------
Wastewater Concn., 7. (v/v)
012 3 4 5678 9 10 11 12 13
10
Figure N-8. Algal assay of Plant B wastewater, GAC
treated. (Data shown in Table N-13).
239
-------
Table N-13. EFFECT OF PLANT B WASTEWATER AFTER CARBON TREATMENT ON ALGAL
GROWTH EXPRESSED AS PERCENTAGE OF ALGAL GROWTH IN CONTROL
Growth, Percent of Control, in:
Tine (days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Plant
0.1
_
-
_
100
50
86
100
417
212
137
69
63
36
25
38
28
B Wastewater
0.056
_
-
_
150
125
129
194
346
274
282
118
100
77
85
88
70
Concentration
0.032
_
_
•»
50
25
114
153
388
194
176
148
98
71
60
96
71
, Percent
0.018
—
_
_
100
125
143
153
617
241
210
164
124
77
97
106
79
(v/v)
0.01
_
,_
50
175
300
176
658
215
214
150
116
84
100
98
84
240
-------
Table N-14. EFFECT OF ACTIVATED SLUDGE TREATMENT ON TOXICITY OF
MANEB WASTEWATERS TO FISH
Sample
Control, dilution water, replicate 1
Control, dilution water, replicate 2
Primary sevage
Influent
Effluent
-Unit 1
-Unit 2
Primary sewage + 10% Plant A wastewater
Influent
Effluent
-Unit 1
-Unit 2
Primary sewage + 10% Plant B wastewater
Influent
Effluent
-Unit 1
-Unit 2
ml/1
—
-
100
180
180
180
100
180
180
180
100
180
180
180
%, v/v
10
18
18
18
10
18
18
18
10
18
18
18
% Fish Surviving at
96 hr, (Initial no.
of fish = 10)
100
90
100
100
90
100
40
70
f90
av. 70 <
I 50
0
0
f6Q
av. 45 <
L30
241
-------
Wastewater Concn., '/. (v/v)
10'
105J
10
0 (Control)
1 (influent)
0.1 (influent)
1 (effluent)
0.1 (effluent)
10 11 12 13 14
Figure N-9.
Algal assay of influent and effluent of
activated sludge units fed with Plant A
maneb manufacturing wastewater (10%).
(Data shown in Table N-15).
242
-------
Table N-15. ALGAL ASSAY OF INFLUENT AND EFFLUENT OF ACTIVATED SLUDGE UNITS
FED WITH PLANT A MANEB MANUFACTURING WASTEWATER (10%)
Growth, Percent of Control, in
Time
(days)
0
1
2
3
A
5
6
7
8
9
10
11
12
13
1A
15
Influent Concn.,
10 l.O
_ _
— —
_ _
_ _
__ _
_ _
- -
150
AO
75
9
A
3
2
5
17
% (v/v)
0.1
_
_
_
_
_ _
_
-
200
220
225
60
25
26
2A
35
AA
Effluent Concn., /
10 1.0
_ —
— —
- —
_ —
_ _
— —
-
50
AO
88
1A
9
10
A
7
9
I (v/v)
0.1
_
-
—
—
_
—
-
50
80
150
A9
27
A3
60
6A
61
2A3
-------
Wastewater Concn.. X (v/v)
0 (control) «
1.0 (influent)
0.1 (influent)
1.0 (effluent)
0.1 (effluent)
0123456 7 8 9 10 11 12 13
Figure N-10. Algal assay of influent and effluent
of activated sludge units fed with
Plant B maneb. (Data shown in Table
N-16).
244
-------
Table N-16. ALGAL ASSAY OF INFLUENT AND EFFLUENT OF ACTIVATED SLUDGE UNITS
FED WITH PLANT B MANEB MANUFACTURING WASTEWATER (10%)
Growth, Percent of Control, in
Time
(days)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Influent Concn.,
10 1.0
- -
-
- -
-
-
- -
-
200
100
138
36
31
35
1 31
48
86
% (v/v)
0.1
-
-
-
-
-
-
-
50
360
288
56
19
41
54
54
85
Effluent Concn.,
10 1.0
- -
-
-
- -
-
- -
-
50
-
25
14
4
4
4
5
8
% (v/v)
0.1
-
-
-
-
-
-
-
500
280
325
82
61
63
71
79
94
245
-------
APPENDIX 0
TESTS OF EFFECTS OF PESTICIDE WASTEWATERS ON DOMESTIC
SEWAGE ORGANISMS: SPOT TESTS
246
-------
Table 0-1. EFFECTS OF PESTICIDE WASTEWATERS IN SPOT TESTS
Zone of Inhibition, mm
Test Sample
Atrazine wastewater
-GAC treated
-Breakthrough
from GAC column
Oryzalin wastewater
-GAC treated
-Breakthrough
from GAC column
Oryzalin washwater
MSMA wastewater-grab
sample
MSMA wastewater
Maneb wastewater, Pit A
-Grab
-Composite, untreated
-Composite, GAC treated
Maneb wastewater, Pit B
-1st sample
-2nd sample
100
0
0
0
2
0
0
3
0
0
21
2
1-2
2-3
2
Wastewater Concentration, %
10 1.0 0.1 0.01
0
0
0
0
0
0
0
, 0
0
o2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
A second zone surrounding the first with colonies of reduced size was
6 mm wide
No clear zone existed but a zone 4-5 mm wide was present with colonies
of reduced size.
247
-------
a) Oryzalin Wastewater, Undiluted
b) Oryzalin Washwater, Undiluted
Figure 0-1. Spot tests showing toxicity of oryzalin wastewater
and washwater to domestic sewage flora.
-------
APPENDIX P
OXYGEN UPTAKE STUDIES WITH PESTICIDE WASTEWATERS
Figures in Appendix P present data on the 0 uptake studies performed
on pesticide wastewaters at various concentrations. Standard procedure was
followed as described in Section 3. Conditions tested were as follows:
Tapwater - 270 ml tapwater + 30 ml sludge
Sewage - 270 ml sewage + 30 ml sludge
10% Pesticide - 240 ml sewage + 30 ml sludge + 30 ml wastewater
1% Pesticide - 267 ml sewage + 30 ml sludge + 3 ml pesticide.
The tests are only moderately predictive of later results with activated
sludge units since the process of acclimitization cannot be expected to
occur with fresh sludge within the time limits of this test. Additionally
the test may give false positives where chemical oxidation occurs, a possibi-
lity with some industrial wastewaters. At the least, however, this test can
indicate concentrations showing gross toxicity.
While ex post facto interpretation can be overdone given the gift of
hindsight, certain patterns emerged from the oxygen uptake studies which
foreshadowed the results of the biological treatability efforts. As shown
in Figures P-l and P-2 MSMA and atrazine wastewater showed a pattern of non-
interference with bacterial processes. On the other hand, at 10% concen-
tration, oryzalin wastewater caused marked inhibition (Figure P-3). At 1%,
oryzalin wastewater caused much less inhibition, at least over the duration
of the test. It will be remembered, however, that 1% oryzalin eventually
disrupted the activated sludge process.
The results with maneb were more ambiguous (Figures P-4 and P-5).
Plant B wastewater was only moderately inhibitory at 10% concentration
249
-------
The oxygen uptake studies are of little predictive value for the
biological treatability of the pesticide component of the wastewater. While
the pesticide may not interfere with bacterial processes as is the case with
MSMA and atrazine wastewaters, it cannot be assumed that the pesticide is
amenable to biological degradation.
The oxygen uptake study, therefore, must be seen as a companion measure
which can provide for more intelligent use of the pilot activated sludge
systems, but cannot substitute for this process.
250
-------
fo
10.0-
9.5-
9.0-
r**
« 8.5.
UJ
O
S
VJ
0)
O.
O
Q
8.0-
7.0.
6.5-
6.0-
MSMA wastewater, 10%
MSMA wastewater, 1%
Domestic sewage control
8 10
Time (min.)
I
12
14
16 18 20
Figure P-l. Oxygen uptake studies with MSI1A wastewater
-------
to
Ul
to
DO
mg/1
Tdpw.-iU-r 107.
Sew.ipe
Atrazine 10% *•
MSMA 107. »-
0 12 34 56 7 8 9 10 11 12 13 14 15 16 17 18 19
Time (min.)
Figure P-2. Oxygen uptake studies of atrazine wastewater.
-------
KS
DO
mg/1
9
8
7
6
5
4
3
2
1
Tapw.iter
Sewage
Oryzalln 10Z
Atrazlne 1%
Oryzalin Wash
0 12 345 67 8 9 10 11 12 13 14 15 16 17 18 19
Time (min.)
Figure P-3. Oxygen uptake study of oryzalin wastewater.
-------
100
60-
55-
Maneb, Plant A - 10%
Maneb, Plant A - 1%
Control sewage *
\.
\
—T
20
0
T
2
T
4
T
6
T
8
10
—T
12
~T
14
T
16
18
Time (min.)
Figure P-4. Oxygen uptake study with maneb wastewater -
Plant A.
254
-------
100
c
cu
o
^
0)
O.
O
a
Maneb, Plant B - 10%
Maneb, Plant B - 1%
Control sewage
ill
20 22 2A
Figure P-5. Oxygen uptake study with maneb wastewater -
Plant B.
255
-------
TECHNICAL REPORT DATA
(Please read Inunctions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/2-80-043
4. TITLE AND SUBTITLE
Treatment Technology for Pesticide Manufacturing
Effluents: Atrazine, Maneb, MSMA, and Oryzalin
7. AUTMORIS)
L.W. Little, R.A. Zweidinger, E.G. Monnig, and
W.J. Firth
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
February 1980
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NOI
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
68-02-2612
13. TYPE OF REPORT AND PERIOD COVERED
Final: 3/77-9/78
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL-RTP project officer David K. Oestreich is no longer with
the Laboratory: for details, contact David C. Sanchez, Mail Drop 62, 919/541-2547.
16. ABSTRACT)
TJThe report gives results of laboratory and pilot studies of the treatability
of waste-waters generated by the manufacture of the pesticides maneb, oryzalin,
atrazine, and MSMAjWastewaters were characterized for pesticide content, routine
parameters, and toxicity to fish, algae, and activated sludge organisms. lEiological
treatability was evaluated in terms of abilityjof pilot activated sludge systems (l&oj
successfully\£perate on a mixture of municipal and pesticide waste waters] and (2) to
remove the pesticide and other toxic materials. Ability of activated cafoon to treat
the wastewaters was determined in adsorption isotherm tests and in granular acti-
vated carbon column tests. Study results showed that atrazine, oryzalin, and maneb
wastes could be treated successfully with activated carbon, although such treatment
had high cost potential. Oryzalin waste disrupted biological treatment. Atrazine and
MSMA waste did not disrupt biological treatment, but pesticide concentration was
not reduced by biological treatment. Maneb concentrations were reduced by biologi-
cal treatment, but additional work is needed to determine the fate of breakdown pro-
ducts from the biological treatment of maneb wastewaters.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI field/Group
Pollution
Pesticides
Industrial Processes
Waste Water
Water Treatment
Activated Carbon
Pollution Control
Stationary Sources
Atrazine
Maneb
MSMA
Oryzalin
13B
06H
13H
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This KepCftf
Unclassified
21. NO. OF PAGES
277
20. SECURITY CLASS (Thispage/
Unclassified
22. PRICE
EPA Form 2220-1 (t-73)
256
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