&EPA
United States
Environmental Protection
Agency
Environmental Monitoring and Supporf /
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S4-81 -017 Jan, 1982
Project Summary
Development of Analytical
Test Procedures for Organic
Pollutants in Wastewater—
Application to Pesticides
Hope Miller, Paul Cramer, Arbor Drinkwine, Alice Shan, Glenn Trischan,
John Going, Edward Kerns, and Thomas Pressley
Test procedures were developed for
monitoring concentrations of 58 pes-
ticides in industrial discharge waste-
water, the procedures involved: (a)
solvent extraction, (b) extract concen-
tration, (c) adsorbent column cleanup,
and (d) gas or high pressure liquid
chromatographic determination. The
procedures were developed and eval-
uated using relevant industrial waste-
water. Based on the results of this pro-
ject, methods have been written and
are available from EPA.
This Project Summary was devel-
oped by EPA's Environmental Moni-
toring and Support Laboratory, Cin-
cinnati. OH. to announce key findings
of the research project that is fully
documented in a separate report of
'the same title (see Project Report
ordering information at back).
Introduction
The Clean Water Act of 1977, Section
304(h), stimulated research on analyt-
ical procedures for monitoring toxic
compounds in industrial and municipal
wastewater discharges. Pesticides are
an important group of toxic compounds
which have come under scrutiny for
control by the National Pollutant Dis-
charge Elimination System (NPDES)
permits program. The purpose of this
project was to develop procedures for a
select group of pesticide compounds.
Objectives were to minimize the cost of
performing the analysis and maximize
the probability of obtaining accurate
results.
Method Development and
Validation
In order to minimize the cost of per-
forming the analysis, three, ideas were
incorporated in the philosophical
approach to the method development:
(a) multiresidue methods, wherein sev-
eral compounds may be determined by
one analysis, were favored, (b) standard
analytical techniques and instruments,
in common use, were incorporated in
the methods, and (c) techniques used in
approved EPA procedures were favored
because of their future side-by-side use
with these pesticide methods.
Preliminary development work util-
ized diluted standard reference mate-
rials for chromatography and cleanup
studies and spiked distilled water for
extraction recovery work. Then, sam-
ples of wastewater from pesticide manu-
facturing plants were subjected to the
respective preliminary methods to test
the method validity with relevant sam-
ple matrices. Aspects of the methods
were altered if acceptable recovery and.
selectivity were not obtained. Success-
ful methods were assigned a prelimi-
-------
nary EPA method number, written in
EPA format, and scheduled for proposal
use under the NPDES program.
Generally all the final methods used
the same procedure. A 1 -liter water
sample near pH 7 was extracted three
times with 60 mL of methylene chlo-
ride. The extracts were combined, dried
by anhydrous Na2S04, and concentra-
.ted by Kuderna-Oanish (K-D) technique.
After the solvent was exchanged into
Table 1. Pesticide Method Details
hexane and reduced to less than 100
mL by K-D, the extract was cleaned up
by solid adsorbent chromatography in a
glass column. The column effluent was
concentrated by K-D, then analyzed by
gas chromatography or high pressure
liquid chromatography using selective
detectors when possible. Exceptions
were dinoseb which was extracted at
pH 2, benomyl which was hydrolyzed.to
carbendazime by addition of 10 mL of
concentrated HCI and stirring of the
sample overnight prior to extraction,
and aldicarb which was oxidized to the
sulfone with peracetic acid prior to
extraction.
Table 1 is an outline of much of the
pertinent analytical information from
the developed methods. More detail
may be found in the report available
from NTIS or the methods available
from EPA.
Method*
604 Addendum
608 Addendum
619
622
Compound
Dinoseb
Chlorobenzilate
Chloroneb
Chloropropylate
Dibromochloropropane
Etridiazole
PCNB
Ametryn
Atrazine
Prometon
Prometryn
Propazine
Simetryn
Simazine
Terbuthylazine
Terbutryn
Azinphosmethyl
'Bolster
Coumaphos
Demeton-O
Demeton-S
Disulfoton
Fensulfothion
Fenthion
Phorate
Trichloronate
Chlorpyrifos
Ronnel
Stirofos
Naled
Cleanup*
_
/
;
/
/
/
/
2
2
2
2
2
2
2
2
2
/
;
;
-
-
/
-
-
/
/
;
;
;
-
Column'
1
3
2
3
3
3
3
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
,5
5
5
5
—f-- • f
Detector*
FID
ECD
ECD
ECD
ECD
ECD
ECD
TSD
TSD
TSD
TSD
TSD
TSD
TSD
TSD
TSD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
FPD
Parameter
160°C
215°C
150°C
215°C
100°C
140°C
160°C
200°C
200°C
200°C
200°C
200°C
200°C
200°C
200°C
200°C
150 to220°Ca
at 25°C/min
150 to 220°C*
at 25°C/min
150 to 220°C°
at 2S°C/min
150 to 220°CQ
at 25°C/min
150 to 220°C9
at 25°C/min
150 to 220°C9
at 25°C/min
150 to 220°C°
at 25°C/min
150 to 220°C°
at 25°C/min
150 to 220°Ca
at 25°C/min
150 to 220°C°
at 25°C/min
160 to 220°C
at 25°C/min
160 to 220°C
at 25°C/min
170to220°C
at 20°C/min
170to220°C
at 20°C/min
DL"
W/L
20
0.001
0.001
0.001
0.001
0.003
0.02
0.06
0.03
0.03
0.03
0.03
0.07
0.05
0.03
0.05
1.5
0.15
1.5
0.25
0.25
0.20
1.5
0.1
0.15
0.15
0.3
0.3
0.5
0.5
Wastewater1
Recovery
(%)
82
91
68
130
67
97
N/A
111
122
119
93
103
182
106
107
102
90
92
213
82
17
114
95
46
58
42
96
75
112
81
-------
Table 1. (Continued)
Chromatography '
Method*
623
628
629
631
632
633
*
*
*
*
Compound
Mevinphos
Dichlorvos
Diazinon
Ethoprop
Parathion, methyl
MOCA
Carbofuran
Cyanazine
Carbendazin
Benomyl
Duiron
Fluometuron
Linuron
Methomyl
Oxyamyl
Propachlor
Propoxur
Bromacil
Hexazinone
Terbacil
Metribuzin
Triadimefon
DEET
Tricyclazole
Piperonyl butoxide
Tokuthion
Piperalin
Aldicarb
Cleanup*
-
-
1
1
1
-
1
1
3
3
3
1
3
3
3
6
1
5
4
5
4
4
4
4
3
1
-
3
Column"
5
5
5
5
5
6
7
7
7
7
7
7
7
7
7
7
7
9
9
&
8
8
8
9
7
5
10
4
Detector" Parameter
FPD 170to220°C
at 20°C/min
FPD 170to220°C
at 20°C/min
FPD 190°C
FPD 190°C
FPD 190°C
TSD 260°C
HPLC-UV CHaCN/HtO
HPLC-UV CHaOH/HaO
HPLC-UV CHaOH/HaO
HPLC-UV CHaOH/HaO
HPLC-UV CHaCN/HaO
HPLC-UV CHaCN/HaO
HPLC-UV CHaCN/HaO
HPLC-UV CHaCN/HaO
HPLC-UV CHaOH/HaO
HPLC-UV CHaCH/HaO
HPLC-UV CHaCH/HaO
TSD 210-25O°C
at 10°C/min
TSD 210-2SO°C
at 10°C/min
TSD 210-250°C
at 10°C/min
TSD 240°C
TSD 240°C
TSD 180°C
TSD 240°C
HPLC-UV CHaCN/HaO
FPD 150 to 220°Cfl
TSD 200°C
TSD 150°C
DL'
ug/l
0.3
0.1
0.8
0.03
0.8
1.0
5
6
3
3
0.3
0.5
0.3
3.5
1.5
16
16
0.2
0.5
0.5
0.7
0.7
0.1
0.1
6
0.5
0.3
0.4
Wastewater1
Recovery
(%)
94
107
116
79
67
114
129
128
85
74
108
95
78
67
106
106
99
53
83
107
87
99h
40*
79
46
*EPA preliminary method number; methods available from EMSL. Cincinnati, OH 45268.
''Cleanup methods used: (1) Florisil adsorbent ethel ether (ee)/petroleum ether (pa) solvent. (2) alumina-10% deactivated, ee/pe
solvent, (3) Florisil, acetone/hexane solvent, (4) Florisil-2% deactivated, acetone/hexane solvent, (5) Florisil-5% deactivated,
acetone/hexane solvent, and (6) Florisil-20% ether/hexane, then acetone/hexane.
"Chromatography column: (1) 1% SP-1240DA, (2) 1% SP-2250, (3) 1.5% SP-2250/1.95% SP-24O1, (4) 5% Carbowax 20M TPA,
(5_I5%SP-2401. (6)3%SP-2250-DB, (7) u Bondapak Ci«, f8l3%SP-2401, (9) 3% SP-2250 DB, and (10) 3% SP-2340.
Detector: FID = flame ionization, ECD = electron capture. TSD = thermionic nitrogen selective, FPD = flame photometric, UV =
ultraviolet.
* DL =.detection limit estimate.
* Aver age of four analyses.
'One meter column.
hAver age of six analyses.
* Method number to be assigned.
-------
Hope Miller, Paul Cramer, Arbor Drinkwine, Alice Shan, Glenn Trischan, and
John Going are with Midwest Research Institute, Kansas City, MO 64110;
Edward Kerns and Thomas Pressley (also the EPA Project Officers, see
below) are with the Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45268.
The complete report, entitled " Development of Analytical Test Procedures for
Organic Pollutants in Wastewater—Application to Pesticides," (Order No.
PBS1-172 629: Cost: $ 10.50, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield. VA 22161
Telephone: 703-487-4650
The EPA Project Officer (Thomas Pressley) can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
•ft U S GOVERNMENT PRINTING OFFICE, 1982 — 559-017/7435
-vv
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300
PS Q000329
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