vvEPA
United States
Environmental Protection
Agency
industrial Environmental Research EPA^-BCMWa
Park NC 27711 6 . 2>
Research and Development
Treatability Studies of
Pesticide Manufacturing
Waste waters: Carbaryl
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RESEARCH REPORTING SERIES
gories were tabfe^t SeneS' Jhese nine bro^ en-
rthc
vironmental technology eton 5 ?«J7 ? 3 application of en-
planned to foster technology transfer °fHtrad'tlOnal 9rouPin9 was consciously
The nine series are: 9V 3nd * maxtmum inte--face in related fields
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
=rrn^~^
o. PoNution sources ^^J^SS^ *""
EPA REVIEW NOTICE
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EPA-600/2-80-077a
April 1980
TreatabilitV Studies of Pesticide
Manufacturing Wastewaters-. Carbaryl
by
Edward Monnig. M'«Jael Murphy.
Ruth Zweidinger, and Linda Little
Research Triangle Institute
P.O. Box12l94
Research Triangle Park, North Carolina 27709
Contract No. 68-02-3688
Task No. 109
Program Element No. 1BB610
EPA Project Officer. David C. Sanchez
Research Triangle Park,
Prepared for
u S ENVIRONMENTAL PROTECTION AGENCY
Slice of Research and Development
Washington, DC 20460
US Environmental Protection
Region V, Library
230 South Dearborn Sir
Chicago, Illinois 60604
n
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U,S- Environmental Protection Agency
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ABSTRACT
!„ February 1979 Research Triangle Institute (RTI) was requested by
the industrial Environmental Research Laboratory, Research Triangle Park
(IERX-RTP) of the U. S. Environmental Protection Agency (EPA) to conduct
Moratory and pilot studies of the treatability of pesticides manu ,c-
turing wastewaters. The project is designed to investigate the su.tabi-
U«, !f individual pesticide manufacturing vastewaters for discharge to
biological treatment systems, whether publicly o»ned treatment works
(POTW) or on-site systems.
The approach taken with each pesticide manufacturing vaste»ater
prioritised that is, less costly, more available methods of treatment
are investigated first. Tie preferred method of treatment „ assume to
b logic 1 treatment. If the pesticide is Judged suitable to hiolog,-
Cl treatment, a Judgement based on chemical and toiicoKgical evaluate
of the vaste before and after treatment, additional options were not
tbe results of the bench scale experimental work involved
in this study, both carbaryl manufacturing .abater *- -^™
part in nine parts municipal waste»ater, and carbaryl itself, when
rrr,rrr
of t ese p Lameters include combined hydrolysis and biodegradation of
and -apbthol, volatilation of toluene and biodegradat.on of
ir
from the biological units treating carbaryl manufacturing wastewater
ii
-------
Because tne technoloov r\f r,,-«- "
31, 1979. 3S ""Pted as of May
ill
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TABLE OF CONTENTS
Page
Section . .
- • • • •
Abstract
1 INTRODUCTION ...................... ' ^
2 CONCLUSION AND RECOMMENDATIONS ........ .......
3 CARBARYL . .................... '.'.'.'. 3
Chemical Information ............... _ 5
Manufacture ......... . ............. . 5
Current Waste Disposal Practice. . . . ........ ^ 5
Ecological Effects ......... ..... '....'. 6
Environmental Fate ................. 7
Health Effects .....................
4 TREATABILITY STUDIES ...... - • • • ; ; ' ......
Characterization of Wastewater from Carbaryl ..... g
Manufacture .................... 9
Biological Treatability Studies. . . - - - - ......
Effect of Biologically Treated Carbaryl Waste- ^
water on Algae, Fish and Daphnia ........ • • • Jg
Conclusions ..................
REFERENCES ......... .................
AP™nalytical Procedure for Determination of Carbaryl^and^ ^ ^ ^
a-Naphthol .....................
AP™nalytical Procedures for Routine Wastewater Characterization . 23
APPTrocedures for Conducting Activated Sludge Treatability ^ ^
Tests ...... ....................
APPENDIX D ..... 26
Procedures for Algal Assay Tests ..........
APPENDIX E . ... 28
Procedures for Fish Bioassay Tests ........ • •
AMIS2hod for Carbaryl Analysis as Reported by Hathaway ..... 30
for the Analysis of Carbaryl as Developed by ...... ^
Union Carbide .....................
iv
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LIST OF FIGURES
f°r Carbaryl
Activaed
3 Influent and Effluent COD Values 'for ' Control .......... 10
Activated Sludge Units . Control
Pesticide Reduction in Activated "sludge Units Fed ....... "
Municipal Sewage Spiked to 10 mg/1 with Carbarvl
C 1 Diagram of Swisher Bench Scale ActfvateTsiudge JnxV ! ! .' .' .' 25
LIST OF TABLES
Table
1 Ecological Effects Testing of Carbaryl
Sample". Cha"'te"Zati0n °f th£ Composiiei Carbaryl ..... '
3 Toluene Concen^ations'in Va^iou^ FracUon^ of ......... 9
Carbaryl Wastewater
5 sss s fig c '
and- Wastewatr
and
Treated
. «-ufacturing
8 Effect
on Fish Survival of carbaryi Manufacturing ....... 1?
9 Effect rerAiXed 10% With Municipal Wastewatef . 17
Effect on Fish Survival of Carbaryl Manufacturing ....... ?
IS^SifS-ffi with Municipal w— « -
10 Effect on Daphnia Survival of Ammonia Stripping of ....... 1?
Effluent Samples from Carbaryl Test Units
......... lo
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SECTION I
INTRODUCTION
In February 1979 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 waste-
waters. The project is designed to investigate the suitability of individual
pesticide manufacturing wastewaters for discharge to biological treatment
systems, whether publicly owned treatment works (POTW) or on-site systems.
The approach taken with each pesticide manufacturing wastewater is
prioritized, that is, less costly, more available methods of
treatment are investigated first. The preferred method of treatment is
assumed to be biological treatment. If the pesticide is judged suitable to
biological treatment, a judgment based on chemical and toxicological evalua-
tion of the waste before and after treatment, additional options are not
investigated.
If pesticide manufacturing wastewater disrupts biological treatment
systems, the possibility of pretreating the waste prior to biological treat-
ment is investigated. Pretreatment options may include pH adjustments,
filtration, flocculation, oxidation and others depending on the nature of
the waste and its chemical composition.
If pretreatment does not make the waste compatible with activated
sludge systems, adsorption techniques may be investigated. These may in-
clude both carbon and resin systems. The necessity for physical-chemical
treatment of wastewaters will again be evaluated as with the biological
treatment system.
This report details a study of the treatability of a wastestream re-
sulting from the manufacture of carbaryl, a product of the Union Carbide
Corporation manufactured at their Institute, West Virginia plant.
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SECTION 2
CONCLUSION AND RECOMMENDATIONS
Based on the results of the bench scale experimental work involved in
thxs study, both carbaryl manufacturing wastewater, when mixed one part in
nine parts municipal wastewater, and carbaryl itself, when spiked at 10 mg/L
xn municipal wastewater, appear suitable for biological treatment by accli-
mated systems if additional provision is made for removing ammonia in the
effluents from these biological treatment systems. Other parameters investi-
gated in this study including carbaryl, a-naphthol, and toluene concentrations
and the chemical oxygen demand (COD) all showed large reductions (90% or
greater). The mechanisms of reduction of these parameters include combined
hydrolysis and biodegradation of carbaryl and a-naphthol, volatilization of
toluene and biodegradation of species contributing to COD.
A large increase in ammonia concentration was noted in the effluent
from the biological treatment units relative to their influent. This ammonia
concentration made the toxicological evaluation of the effectiveness of
treatment problematic by rendering the effluent more toxic than the influent
Ammonia stripping lessened this toxicity. Because the technology of nitrogen
control has been extensively developed, these treatment options were not
pursued further.
The carbaryl manufacturing wastestream investigated in this study is
presently mixed with other manufacturing wastestreams and treated in a
manufacturer-operated aerated lagoon with approximately a 3-day retention
time. Based on the study detailed below, this treatment process should
provide an adequate treatment of the carbaryl manufacturing wastestream
provided there is no interference from the components of other wastestreams
and provided nitrification of ammonia occurs.
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SECTION 3
CARBARYL
CHEMICAL INFORMATION
CAS No.: 63-25-2
Category:
Synonyms:
Structure:
carbamate
Arylam, Atoxan, Caprolin, Carbaryl (DOT), Carbatox,
Carbatox-60, Carbatox-75, Capolin, Compound 7744,
Crag sevin, Denapon, Dicarbam, ENT 23, 969, Gamonil,
Germain's, Hexavin, Karbaryl, Karbatox, Karbosep,
Septene, Sevidol, SDK, Tricarnam, and others.
(Fairchild, 1977).
0-CO-NH-CH
Properties:
M.W. 201.24
1971).
PH
7.0
8.0
9.0
10.0
Carbaryl
half-life
10.5 days
1.8 days
2.5 hours
15 min.
-------
Cl,
NaOH
1
Hyd
PI
J
( H2° Naphthalene 0
I 1 1
rogen tt ^ Tetralin Tet
ant 2 Unit Ur
-
CO H. ' ,
J
.ralol
lit
Ve
t
nt
\
*1 Condenser |
v-
r
INaphthol
Unit
Phosgene
Unit
V
>
2 , Lt
\
' >
f
— 9
oformate
nit
» Carharyl
Unit
rcnt* Dust >
°nt* Collector < Pack
)
Proc
Jging
r
hict
H2°
->Vent-
— NaCl-
^
NaCl
»
*
2
>
Secoi
Wa
Trea
P1;
Flare
N t
Heavy Re
From Pro
Solvent
Son
idary
ste
tment
int-
•* Incinerator
FiRure 1. Production and Waste Schematic for Carbaryl (Sittig, 1977)
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Application:
Wide spectrun, insecticide for control of insects on cotton, vegetables,
fruits, rice, sugarcanes and ornamentals; used in agriculture, homes, anx-
mals, forests. Registered, 1959.
MANUFACTURE
Figure 1 presents a generalized production and waste schematic for
carbaryl manufacture.
CURRENT WASTE DISPOSAL PRACTICE
Carbaryl manufacturing wastewater is presently combined with the efflu-
ent of other manufacturing processes at the Institute, West Virginia plant
and treated in a system of aerated lagoons. This system consists of 3
aerated treatment basins run in parallel. Retention time of the entxre
system is reported to be approximately three days (plant engineer, personal
communication).
The major carbaryl-containlng wastestream is a continuous decantatxon
stream generated during a solvent recovery step in the carbaryl production
unit This stream was sampled for this study. Other carbaryl inputs to the
waste treatment systems include wash down from packing and cleaning procedures
which is intermittent in nature and was not sampled.
Carbaryl has apparently been detected in a sample of the effluent from
Union Carbide's waste treatment units at the Institute plant. Carbaryl
concentration in a sample taken on 4/11/78 was found to be 260 Mg/L (Hatha-
Way' Tpossible interference in some methods of analysis for carbaryl should
be noted. Routine in-plant analyses by Union Carbide personnel of products
vastestreams known to be free of carbaryl have shown a compound which elutes
at a similar retention time as carbaryl under the conditions for carbaryl
analysis. This compound has not been identified, though it resists hydrolys.s
at high PH which is not characteristic of carbaryl. The method of analysis
for carbaryl used by Union Carbide and the method used by Hathaway (1979)
are described in Appendices F and G.
ECOLOGICAL EFFECTS
Table 1 surcmarizes the published ecological effects data for carbaryl.
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TABLE 1. ECOLOGICAL EFFECTS TESTING OF CARBARYL
Species Duration Result (LC a)
Reference
Stone fly.
Pteronarcys
californica
Daphnia pulex
Brown trout
Gammarus lacustris
Fathead minnow
Bluegill
Daphnia magna
Gobio gobio
Red crawfish
Fathead minnow
Fathead minnow
— — , — _
48 hr
48 hr
48 hr
48 hr
96 hr
96 hr
48 hr
96 hr
48 hr
96 hr
Life cycle
ou
1.3 mg/L
6.4 mg/L
1500 mg/L
22 mg/L
12 mg/L
5.3 mg/L
0.1 mg/L
1.0 mg/L
3.0 mg/L
9.0 mg/L
0.21 to 0.68 mg/]
' • — — —
Bond and Straub,
1973
Bond and Straub,
1973
Bond and Straub,
1973
Bond and Straub,
1973
Surber and Taft,
1962
Surber and Taft,
1962
Ilisescu and
Stefanescu, 1974
Ilisescu and
Stefanescu, 1974
Muncy and Oliver,
1963
Carlson, 1971
- Carlson. 1Q71
3LC50-Concentration to kill 50% of a test population in the specified time
ENVIRONMENTAL FATE
Half life of carbaryl in soil is dependent on numerous variables.
Bollag and Lui (1972) state that a generally accepted half life of carbaryl
in the soil is one week though others have shown stability in soil from 25
to 60 days before appreciable decay (Caro, Freeman and Turner, 1974).
Bollag and Lui isolated fungi which were able to alter carbaryl by sidechain
and ring hydroxylation. or-Naphthol was shown to be more readily degraded by
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the marine fungi and bacteria studied than carbaryl (SiKKa, «iyazaki and
ts to separate the relative contribution .f chemical and
biological hydrolysis to the degradation of carbary!. Paris et .1 . O975),
report that bacterial removal or carbaryl was dependent upon the rate of
chemica! hydrous of carbary!. These authors also report that no sorpion
of carbaryl to microorganism was found in their studies, though thers have,
reported rapid sorption to saline sediments (Karinen et .1., 1967).
HEALTH EFFECTS
An extensive review of the toxicological literature on carbaryl is
contained in the vo!ume: Dr^n^WaterjniJieaUh (NRC, 1977). Ih. NHC
report classified the toxicity of carbaryl as moderate (1^ for male rats
500 mg/kg; no effect for man at 0.13 mg/kg for 6 «eeks). Carbaryl vas not
fold to"e either mutagenic, teratogenic, or carcinogenic after extens.ve
testing. The Mrak Commission IMC, 1977) concluded that c.rbaryl was one
of but three pesticides Judged "not positive for carcinogenicity by appropriate
tests in more than one species of test animals". The SEC report also concludes,
"In general, metabolism of carbaryl and the appearance of metabolites in water
syste«s would create no significant hazard in addition to that of carbaryl
itself".
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SECTION 4
TREATABILITY STUDIES
CHARACTER™* or WASTEWATER FROM CARBARYL
MANUFACTURE
tive dys.
t^e days during a normal winter operation perlod. „„ rate
t» ays of sa»pling. Plant personnel estiMted the flou "
-P Ung to be approximately 6-7 gpm and flow rate oo day 2 to be approxi-
" PeS
.
values according to plant personnel
s
run on this composited sample.
as anaT
^ -ate
-ult was noted in the deter«ination of tot.l dissolved
HW). The .etnod for the determination of TDS retires vacuim
f,l.r.t1M of the saBple through . 0:« „ filter (Millipore HA). After
fUtration of the carbaryl waste and subsequent drying at 105= an oily
rescue „. noted in the filtered sample that resisted further dessication.
Thls rescue »as not noted during the dessication of the who!e unfiitered
sample This ,rtlf.ct may arise ^ „ lnteraction ^^ «*
h was estrea. ,„„ the filter itse!f. The implication of these results on
the conduct of the algal assay will be discussed below.
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t,
TABLE 2. WASTEWATER
=====
Parameter (units)
OF THE COMPOSITED CARBARYL SAMPLE
Value
pH
Cl" (mg/L)
Alkalinity (mg/L as CaC03 to pH 4:5)
Total kjeldhal nitrogen (mg/L as N)
NH,-N (mg/L as N)
4
NO + N03 (mg/L as N)
COD (mg/L)
Total solids (mg/L)
Total dissolved solids, (mg/L)
Settleable solids (mg/L)
Carbaryl (mg/10
Toluene (mg/L)
8.2
120
385
1100
158
5.2
4100
100
75
Trace
4.3
160
BIOLOGICAL TREATABILITY STUDIES
°! (v/v) with municipal
diluted settled ..nicipal »aste«ater
units vas maintained at a
Mixed liquor volatile Su£pended .olids OU-VS , o_
MLVSS quantity a the test «t. » ^ ,wrMiBately
value of 3100 mg/1 on day 14. F/M ratios at
... d,/1 »ased on influent COD values
"-
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700
©
®-
®
®
G> Influent COD
• Unit#1 Effluent COD
A Unit #2 Effluent COD
Figure 2. Influent and Rrfluent COD ValuPs for T^, A^,..__ ,
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500
Influent COD
Unit #1 Effluent COD
*. -* Unit #2 Effluent COD
Mgurc 3. ,n.l«nt an, «fl«ent COD Value, for Control Actlv-fd Slud.e UnHs.
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the test un,ts. on day 12 lt had been noted ^
>n both test unit reactors had dropped belw 1 Air * > s
units was doubled on day „ £r- 2W) ^ the test
flow, coupled with the gradual increase in
-rease ln COD renoval. d tlc
. on COD rcduction
-fluent .verain 595 rag/L and fttlmt
Analysi, for carbaryl an a.naphthol revealed
e c taryl nanufacturing Msteuater cMposite ^ had e 1 „
was determined to be 0.06 mg/L instead of th
Illg/-L lnstead of the expected 0.10 me/L
Straight iajection of aqueous effluent sables by the method presented
: r;;tre:eaied n° carbaryi °r — — - «- -«•«» • -
"
h or a ' - ° •«*« -itb -thylene
chloride nd concentration of the extract likewise revealed no carbaryl „
" "1"6"1 "-overy of
s th: possibu roie ° «" "»^>
, sludge samples from the test units and control units were extracted
Pw:: rhyieM chioride -d -^ *- -^ - »-— - - 1
proble „ encountered Bith an ^^^ EMpies duri^ ^ ^
step. FUtration through glass »ool followed by fiUration through phase-
p.ra.ngfiHer paper aneviatea some of these problems. Hoover, recovery
•f carbaryl spiked at levels of 2 ,ne/L in municipal sludge was only 3»
Because of incomplete resolution of other compounds in sludge with
ei0n
ogr
used, an absolute determination of carbaryl ievels was not
possible. Carbaryl concentration was no greater than 0.01 mg/L in sludge in
the t«t units. Given the influent and effluent levels of c.rbaryl> tnis
concentration in the sludges wouid not represent any sorptive accumulation.
"-Naphthol was not detected in any of the sanples
12
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To test the possible role of air stripping in the removal of volatile
organic an air stripping control (ASC) unit .as run. Composite carbaryl
.aste.ater was nixed 10% in deionized vater (DIW) and pumped through an
activated sludge unit vhich contained only DIW. An eight hour retention
time and an air flo. of 400 .I/I. .as maintained in the ASC umt. COD
measurements .ere taken of the influent and effluent to the ASC units over a
t.o day period. No difference .as measured in the influent or effluent
values (420 mg/L for both influent and effluent). This value corresponds to
that expected of a 10% diiution of the composite carbaryl waste
Toluene analyses .ere performed on both the influent and effluent of
the biological treatment units and air stripping controls by the purge and
trap method (Bellar and lichtenberg, 1974; Bellar, Uchtenberg and Eicb.1-
berger 1976). Analysis of data provided in Table 3 sho.s that only m.nrmal
handling of carbaryl .aste .iU cause a substantial reduction in toluene
concentration. The routine handling retired to dilute sables and the
subsequent exposure of samples to the open air during the pumplng of in nt
over a 24 hour period is sufficient to reduce toluene concentrate by 85
95 percent. Additional reduction in toluene concentration occured after
passage through a S.isher unit. It .ill be noted that this reduction »
toluene concentration does not effect the COD determination. The d.chro.ate
digestion involved in COD measurement provides only minimal oxidate of
aromatic compounds.
To more adequately test the biodegradation of carbaryl, a .erxe. of
tests were run on municipa! »aste.ater spiked at a concentration of 10 mg/L
.ith technica! grade carbaryl. Three activated sludge units (test units)
.ere fed settled municipal .aste.ater diluted .ith carbaryl saturate de-
ionized .ater to give a final emulated carbaryl concentrate o 00m
compared .ith a carbaryl concentration of 4.3 mg/L in the composited carbary!
.aste.ater sample. Three activated sludge units (control units .ere e
.ith municipal .aste.ater diluted .ith a corresponding amount of unsp.ked
DIW. He. influent .as mixed every 48 hours.
Immediately upon mixing of test unit influent an .Uquot »•««*'»
for carbary! .naXysi.. Ali,uots .ere filtered through . 0.45M MilUpore HA
filter. Anaayses of influent over the period of the study sho.ed that
carbary! !e,els averaged 7.3 «g/L. Analyses of influent after its 48 hour
13
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Biological treatment units (10% carbaryl
waste in municipal waste)
Influent
Effluent
Air stripping control units (10% carbaryl
waste in deionized water)
Influent
Effluent
2.5
0.001
shelf life" showed that carbaryl levels averaged 7.0 mg/L. The difference
between the 10 mg/L spiked levels and the 7.3 mg/L analyzed levels probably
represents sorbtion of carbaryl to influent solids and its loss during the
filtration of samples prior to analysis by HPLC.
MLVSS levels were maintained between 1740 and 2300 mg/L. 0 85g/L of
NaHC03 was added to influent samples to maintain the PH in the units from
7-3 to 7.65. Residence time in the units was 8 hours. Dissolved oxygen was
Figure 4 presents data on percentage reduction in carbaryl concen-
tration over time in the test units. From day 7 on reduction was complete
except for a period around day 15 when aeration difficulties were experi-
enced in one unit. During the same period the COD reduction in the test
units averaged 83%, with the influent averaging 227 mg/L and the effluent
averaging 39 mg/L (range 24 to 60). The COD reduction in test units was 84%
with the influent averaging 230 and the effluent averaging 37 (range 28 to
48).
As these data indicate, carbaryl is readily degraded in activated
sludge systems after a short acclimation period.
EFFECT OF BIOLOGICALLY TREATED CARBARYL WASTEWATER ON ALGAE, FISH AND DAPHNIA
Algal assays were conducted in accord with the procedures outlined in
14
-------
Figure 4. Pesticide Reduction in Activated Sludge Units Fed
Municipal Sewage Spiked to 10 n,g/l with Carbaryl
-------
EPA manual: The Selenastrum Capricornutuni Printz Algal Assay Bottle J^st
and described in Appendix D. Samples were vacuum-filter sterilized through
a 0.45 (J filter.
Table 4 presents the results of an algal assay on the untreated carbaryl
manufacturing wastewater. The data on algal growth in test flasks are
presented in terms of percent of the growth in the control flasks on day 14
of the test. As can be seen in Table 4 the algal EC^ (concentration effective
in reducing growth to 50% of controls) for carbaryl wastewater lies between
0.01 and 0.1 mL per liter.
When mixed 10% with municipal wastewater, the toxicity to algae de-
creased remarkably. As shown in Table 5 the EC5Q for influent to the AS
units was approximately 1000 mL/L. On the other hand the effluent from the
AS units showed an increased toxicity over the influent. As shown in Table 6,
the EC5Q for the effluent samples was between 100 and 320 mL/L.
A similar pattern was exhibited by the fish bioassay using fathead
minnows. The bioassay procedure is described in Appendix E. As shown in
Table 7, the LC5Q (concentration lethal to 50% of the test population) of
carbaryl wastewater was approximately 100 mL/L. Table 8 shows the LC of
the influent to the test units was between 320 and 1000 mL/L. The LC of
the effluent from the AS units as shown in Table 9 was between 100 and°320
mL/L (Table 9).
It was hypothesized that the conversion of organic nitrogen to ammonia
by biologically mediated processes in the treatment units caused an increase
in the toxicity of the effluent from the AS unit. The ammonia levels in-
creased from 30 mg/L in the influent to 110 mg/L in the effluent.
To test the biological significance of this ammonia concentration an
additional bioassay was conducted comparing ammonia stripped samples with
unmanipulated samples. To strip the test unit effluent of ammonia, the
sample pH was raised from 7.2 to 14. Samples were aerated for 2 hours and
pH readjusted to 7. Due to sample volume limitations this bioassay was
conducted with Daphnia pulex. The results of this bioassay are presented in
Table 10. As can be seen, the toxicity of the ammonia stripped effluent was
less than that of the unmanipulated sample effluent or the influent. It
could, of course, be argued that the stripping process may have removed some
other volatile, toxic component of the effluent. However, these samples
16
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TABLE 4. EFFECT ON ALGAL GROWTH OF CARBARYL MANUFACTURING WASTEWATER
Carbaryl wastewater (mL/L)
Growth (% of control on day 14)
TABLE 5. EFFECT ON ALGAL GROWH OF CARBARYL MANUFACTURING
WASTEWATER MIXED 10% WITH MUNICIPAL WASTEWATER
Carbaryl wastewater (mL/L)
Growth (% of control on day 14)
TAB!* 6. EFFECT ON ALGAL GROWH OF' CARBARYL MANUFACmiNG WASTEWATER
MIXED in Mli miSpALWASTEWATER AND BIOLOGICALLY TREATED
Carbaryl wastewater (mL/L)
Growth (% of control on day 14)
TABLE 7. EFFECT ON FISH SURVIVAL OF CARBARYL MANUFACTURING WASTEWATER
Carbaryl wastewater (mL/L)
Fish surviving 96 hr (%)
TABLE 8. EFFECT ON FISH SURVIVAL OF CARBARV1 MANUFACTOJNG WASTEWATER
MIXED 10% WITH MUNICIPAL WASTEWATER
Carbaryl wastewater, mL/L
Fish surviving 96 hr (%)
TABLE 9. EFFECT ON FISH SURVIVIAL OF CARBARYL t^FACTURING WASTEWATER
WASTEWATER ASD BIOLOGICALLY TREATED
Carbaryl wastewater, mL/L
Fish surviving 96 hr (%)
~" = — ""-
aTest population, 10 fish per concentration.
17
-------
-_ ^ tinuent Influent
f^^tr^edunmanipulated uiunanipul.ted
" —• _
Survival of Daphnia at
had previously been subjected to , hours of air stripping under neutral p«
cond^ons during p.sssge through an AS unit. This aeration would elininate
:::CL L" crunds which d°not sh°-a —«"<->< ->—hiP
characteristic of ammonia.
CONCLUSIONS
Based on the initial examination involved in this study, carbaryl
manufacturing w.t«.t« and carbary! appear suitab!e for biological treat-
ment by acclimated systems if addition provision is made for ammonia
reduction. The production of a^onia in the digestion of this »aste could
prov.de toxicity problems if some form of a^onia removal is not employed or
»f he effluent is not diluted substantially. Because this technology is
well established, extensive study in this area Uas not undertaken The
reader is directed to the EPA Technology Transfer Manual: Process Design
Manual for Nitrof.n Control for further information on these" systems
The execution and interpretation of various bioassays conducted on
multi-component wastestreams, particularly those containing volatile compounds
should recognize certain sources of uncertainty. A primary concern is the
ma.ntenance of sample integrity through the manipulations »hich are a part
of many bioassay procedures.
The filter sterilization step required by algal assays can be a particu-
larly important, especially if done under a vacuum. The loss of volatile
components in the sample during vacuum filtration is an obvious result In
•dditxon, the filter itself might provide active sites for the chemical
formation of compounds not found in the unfiltered sample. This possibility
18
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was noted in conjunction with the discussion of the determination of dissolved
solids in carbaryl wastewater.
The sorption of toxic components to particulate portions of samples and
their subsequent removal in the filtration step also provides a source of
interference. This process could account for the reduction in toxicity to
algae of carbaryl wastewater mixed 10% in municipal wastewater. This reduc-
tion in toxicity is greater than that expected by a simple 1:9 dilution.
While the fish or daphnia bioassays require much less sample manipu-
lation than the algal assay, the maintenance of sample integrity can still
be a problem. The loss of volatile compounds over the 96 hour test period
will occur as the samples are exposed to open air. It might be argued that
this loss represents an environmental reality; the volatile components of a
waste will become less available over time. However, as with many of the
factors involved in biological testing, the problem remains one of adequate
laboratory accounting of environmental processes.
19
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REFERENCES
t
2
3
Sci. Technolo:926-3o 1976
-w " \ Eichelber*e- Determination
" " ^ G" Ch*™^Ora. Environ.
; 236:177°ld78S;
«f Carbaryl by Soil Fungi.
' Voi
Ohi 1973?
°f
Treatment> CRC Press, Cleveland,
Survival
prolelas) J
promeiasj. j.
°f i°n«-Tera ExP°su" to Carbaryl (Savin) on
^"r^ °f the Fathead Minno«
Res. Bd. Canada. 29:583-587, 1971.
11 '
c
i E' J' Ced°- Agricultural Chemicals and Pesticides- A
MOS\Re8if ry,?f IOX1C E""" °f CheMcal sSst.*
blication Ko. 77-180, National Institute for Occuna
tional Safety and Health, Cincinnati, Ohio, 1977. P
20
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12. Hathaway, J. L. Compliance Evaluation and Wastewater Characterization:
Union Carbide, Institute, West Virginia, EPA-303/2-79-014A, U.S. Environ-
mental Protection Agency, Denver, Colorado, 1979.
13. Ilisescu, A., and L. Stefanescu. Cercetari Privind Biodegradabilitatea
si Toxicitatea unor Impuritati Existente in Apele Uzate Evacuate de
Industria Petrochimica (Research on the Biodegradability and Toxicity
of Pollutants in Wastewaters Discharged by the Petrochemical Industry).
Stud. Epurarea Apelor 16:76-98, 1974.
14. Karinen, J. F., J. G. Lamberton, N. E. Stewart, and L. C. Terriere.
Persistence of Carbaryl in the Marine Estuarine Environment. Chemical
and Biological Stability in Aquarium Systems, J. Agric. Food Chem.,
15(1):148-156, 1967.
15. Matsumura, F. Biological Effects of Toxic Pesticidal Contaminants and
Terminal Residues, pp. 525-548, in F. Matsumura, G. M. Boush, and
T. Misato, eds. Environmental Toxicology of Pesticides. Academic
Press, N. Y., 1972.
16. Miller, W. E., J. C. Greene and T. Shiroyama. The Selenastrum Capri-
cornutum Printz Algal Assay Bottle Test, EPA-600/9-78-018, U.S. Environ-
mental Protection Agency, Corvallis, Oregon, 1978.
17. Muncy, R. J. and A. D. Oliver. Toxicity of Ten Insecticides to Red
Crawfish, Procambarus clarki (Girard). Trans. Amer. Fish. Soc. 92(4):
428-431, 1963.
18. National Research Council. Drinking Water and Health. National Academy
of Sciences, Washington, D. C., 1977.
19. Paris, D. F., D. L. Lewis, J. T. Barnett, Jr., and G. L. Baughman.
Microbial Degradation and Accumulation of Pesticides in Aquatic Systems,
EPA-660/3-75-007, U. S. Environmental Protection Agency, Corvallis,
Oregon, 1975.
20. Sikka, H. C., S. Miyazaki, and R. S. Lynch. Degradation of Carbaryl
and 1-Naphthol by Marine Microorganisms. Bull. Envir. Contam. Toxicol.,
13(6):666-672, 1975.
21. Sittig, M. Pesticides Process Encyclopedia. Noyes Data Corporation,
Park Ridge, N. J., 1977, 524 pp.
22. Sparacino, C. M. and J. W. Hines. High Performance Liquid Chromato-
graphy of Carbamate Pesticides. J. of Chrom. Sci., 14:549-556, 1976.
23. Surber, E. W. and R. A. Taft. Water Quality Criteria for Freshwater
Fishes. Proc. 16th Annual Conf., S. E. Assoc. Game and Fish Comm.,
Oct. 17, 1962.
24. Swisher, R. D. Surfactant Biodegradation. Marcel Dekker, Inc. N. Y.,
1970.
21
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APPENDIX A
ANALYTICAL PROCEDURE FOR DETERMINATION OF CARBARYL AND a-NAPHTHOL
The procedure for the analysis of carbaryl and a-naphthol was adapted
from Sparacino and Hines (1976) and involves the separation and quantitation
of compounds by high-performance liquid chromatography (HPLC) with a reverse
phase column and an ultraviolet absorption detection system.
A modular liquid chromatographic system was used for analyses. The
basic system consisted of the following components: 2 M6000 pumps with an
M660 solvent programmer and a U6K injector (Waters Assoc.); Model SF 770
variable wavelength detector (Schoeffel Inst.). A reverse phase column,
packed in our laboratory, was employed. The column was packed with Partisil
10 bonded with octadecyl trichlorosilane in the conventional manner. The
mobile phase consisted of acetonitrile mixed 40% in distilled water. A
wavelength of 222 nm was used for the detection of both carbaryl and a-naphthol.
Flow rate of mobile phase was 2 mL/min. Sample injection size was either 10 ML
or 100 ML. Samples were directly analyzed by HPLC. Separate calibration curves
were run for each injection size. Detection limit of the system at these
conditions was 0.5 nanograms carbaryl and 1.0 nanograms of a-naphthol. Standard
deviation of carbaryl determination at 0.25 mg/L was 5.6% and at 1.0 mg/L was 7.5<
All samples were filtered through a 0.45 p Millipore HA filter prior to
analysis.
22
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APPENDIX B
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 (N02~N,
NO--N) were determined by the Devarda's alloy method (419 F).
COD—
Chemical oxygen demand (COD) was determined by Method 508.
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.
23
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APPENDIX C
PROCEDURES FOR CONDUCTING ACTIVATED SLUDGE TREATABILITY TESTS
For biological treatability studies the bench scale, complete-mix, con-
tinuous-feed, activated sludge unit designed by Swisher (1970) was employed
(Figure C-l). This unit has an aerator capacity of 0.3 L and a settler
capacity of 0.075 L. The unit is made entirely of glass, avoiding the
possibility of contamination by organics leaching from the container.
Continuous feed to the units was supplied through Teflon tubing by a peris-
taltic pump to give the nominal retention time of 8 hours.
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 wastewater from the Chapel Hill
Treatment Plant. When a steady-state condition was reached, as indicated
by consistent effluent quality in terms of COD and^mixed liquid suspended
solids levels, the feed to the test units was spiked with pesticide waste-
water. Control units were fed only primary wastewater.
The pesticide spiked wastewaters were prepared by adding pesticide
wastewater to the primary municipal wastewater which had been allowed to
settle for a 120 min to simulate primary settling. Routine determinations
were made of dissolved oxygen, pH, mixed liquor volatile suspended solids
in the aerator and COD, and pesticides. Dissolved oxygen was determined
with an oxygen probe (Yellow Springs Instrument Co.).
-------
ro
INFLUENT
FEED
RESERVOIR
EFFLUENT
COLLECTION
AIR
Figure C-l. Diagram of activated sludge pilot unit.
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APPENDIX D
PROCEDURES FOR ALGAL ASSAY TESTS
Algal bioassays were conducted according to the freshwater algal assay
procedure described in the report The Selenastrum Capricornutum Printz Algal
Assay Bottle Test (Miller, Greene, and Shiroyama, 1978). The test alga was
Selenastrum Capricornutum Printz, obtained from the National Eutrophication
Research Program, EPA, Corvallis, Oregon. This test was designed to measure
algal response to changes in nutrient concentrations and to determine toxi-
city or inhibition.
Wastewaters to be tested were filter sterilized through a sterile
prewashed membrane filter (Millipore Filter, 0.45 [im 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
cell concentration of 10 cells/mL.
In each set of experiments, algal growth in the presence of a series of
concentrations of the wastewater added to the nutrient medium was compared
to algal growth in the nutrient medium alone. Growth was determined by
direct counts 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 cell yield. Direct cell counts were performed by an automated procedure
utilizing a Fisher Scientific Model FO 16 particle counter.
The tests were conducted in water bath shakers at 24 ± 2° C and at approxi-
mately 80 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.
The 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.
26
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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 subcultur-
ing into fresh medium free of the test material.
27
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APPENDIX E
PROCEDURE FOR FISH BIOASSAY TESTS
The fish bioassay procedure chosen was the standard 96-hour static
bioassay (APHA, et al., 1976; Duke et al., 1977). The static method has
been criticized as being rather simplistic, and more complex alternate
methods have been suggested. 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 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 aeration devices and
recirculating filtration. The water was Durham tapwater which was passed
through a combined selective ion exchange and activated carbon system which
removes 99+% of the organics and ionics present in the water. The water was
then reconstituted by the addition of 48 mg/L NaHCOg, 30 mg/L CaS04«2H20,
30 mg/L MgSO,, and 2 mg/L KC1. 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 laboratory bioassays were conducted to determine the range
of concentration 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 con-
tainer was used.
28
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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 bisec-
tion of intervals of the logarithmic scale, such as 1.0, 1.8, 3.2, 5.6, and
10.0 percent, multiplied 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 con-
sidered invalid if more than 10% mortality occurred among the control fish.
In the large scale tests, test containers were 10-gallon glass aquaria
containing 15 liters of test solution. To test each experimental concen-
tration, 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.
LC values were estimated by interpolation after plotting the data on
semilogarithmic coordinate paper with concentrations plotted on the loga-
rithmic and percentage dead plotted 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.
29
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APPENDIX F
METHOD FOR CARBARYL ANALYSIS AS REPORTED
BY HATHAWAY (1979)
Methodology: Carbaryl Analysis
A liter of the sample was extracted serially with three 50 ml portions
of methylene chloride. The extracts were combined and passed through Na2S04
into a 250 mL round bottom flask. 50 ml of ethyl acetate was added to the
flask and the solvents were concentrated to 10 mL in a rotary evaporator at
45° C. The extract was passed through a cleanup column of 3 cm Florisil
topped with 1 cm of Na2S04. The Carbaryl was eluted with 20 mL of ethyl
acetate. The 30 mL of ethyl acetate was concentrated to 10 mL on a hot
plate under a gentle stream of carbon filtered air.
The extract was analyzed on a Waters 204 Liquid Chromatograph with a
M Bondapak C18 column. A methanol-1% acetic acid gradient was used over
25 minutes at a flow rate of 2.0 mL/min. The gradient was run from 0 to 80%
methanol. The dual channel UV detector was operated at wave lengths of
254 run and 280 nm.
Quality Control: A blank and a spike were analyzed along with the samples.
The blank did not contain any interferences at the retention time of Carbaryl.
The spike was at a concentration of 250 pg/L of Carbaryl and the recovery
was 117%.
The presence of Carbaryl in the samples was established by the coinci-
dence of retention time and confirmed by the ratio of the 254 to 280 response.
30
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APPENDIX G
METHOD FOR THE ANALYSIS OF CARBARYL AS
DEVELOPED BY UNION CARBIDE
Samples were extracted serially with methylene chloride which was then
dried with Na2S04. The extract was analyzed on a Varian 825 Liquid Chromato-
graph with a Micropak CN-10 column. The mobile phase consisted of N-propanol
10% in iso-octane. A single UV detector was operated at a wavelength of
25A run.
31
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TECHNICAL REPORT DATA
(Please read Inunctions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/2-80-077a
4. TITLE AND SUBTITLE
Treatability Studies of Pesticide Manufacturing
Wastewaters: Carbaryl
7.AUTH0R(s) Edward Monnig, Michael Murphy, Ruth
Zweidinger, and Linda Little
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
April 1980
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
68-02-3688, Task 109
13. TYPE OF REPORT AND PERIOD COVE
Task Final; 2/78-3/80
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES T.ERL-RTP project officer is David C. Sanchez, Mail Drop 62,
919/541-2547.
The report gives results of a bench-scale, experimental treatability stud
of wastewaters from the manufacture of the pesticide carbaryl. Results indicate tt
both carbaryl manufacturing wastewater (mixed one part in nine parts municipal
wastewater) and carbaryl itself (spiked at 10 mg/L in municipal wastewater) appea
suitable for biological treatment by acclimated systems if additional provision is
made for removing ammonia in the effluents from these biological treatment sys-
tems. Other parameters investigated in this study--including carbaryl, alpha-
naphthol, and toluene concentrations and the chemical oxygen demand (COD)—all
showed large reductions (90% or greater). The mechanisms of reduction of these
parameters include combined hydrolysis and biodegradation of carbaryl and alpha-
naphthol, volatilization of toluene, and biodegradation of species contributing to O
A large increase in ammonia concentration was noted in the effluent from the bio-
logical units treating carbaryl manufacturing wastewater. This ammonia concentr;
tion made the toxicological evaluation of the effectiveness of treatment problemati
by rendering the effluent more toxic than the influent. Ammonia stripping lessenec
this toxicity. Because the technology of nitrogen control has been extensively deve
oped, these treatment options were not pursued further.
17. KEY WORDS AND DOCUMENT ANALYSIS
a DESCRIPTORS
Pollution Nitrogen
Pesticides Naphthols
Industrial Processes
Waste Water Toluene
Waste Treatment Toxicity
Ammonia Oxygen Demand
18. DISTRIBUTION STATEMENT
Release to Public
b. IDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Carbaryl
Treatability
Alpha-naphthol
Chemical Oxygen De-
mand
19. SECURITY CLASS (This Report)
Unclassified
20. SECURITY CLASS (This page)
Unclassified
C. COSATI
13B
06F
13H
07B
Field/Groi
07C
06T
06F
21. NO. OF PAGES
33
22. PRICE
EPA Form 2220-1 (9-73)
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