Development of Analytical Test
Procedures for Organic Pollutants in
Wastewater - Application to Pesticides
Midwest Research Inst.
Kansas City, MO
Preparec for
Environmental Monitoring and Support Lab.
Cincinnati, OH
November 31
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service

-------
P 8 R 2—13 25 07
EPA 600/4-81-017
November 1981
DEVELOPMENT OF ANALYTICAL TEST PROCEDURES FOR ORGANIC POLLUTANTS IN
WASTEWATER - APPLICATION TO PESTICIDES
By
Hope Miller
Paul Cramer
Arbor Drinkwine
Alice Shan
Glenn Trischan
John E. Going
Midwest Research Institute
Kansas City, Missouri 64110
EPA Contract No. 68-03-2711
Project Officer
Edward H. Kerns, Chemist
Environmental Monitoring and Support Laboratory
Cincinnati, Ohio 45268
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268

-------
NOTICE
THIS DOCUMENT HAS BEEN REPRODUCED
FROM THE BEST COPY FURNISHED US BY
THE SPONSORING AGENCY. ALTHOUGH IT
IS RECOGNIZED THAT CERTAIN PORTIONS
ARE ILLEGIBLE, IT IS BEING RELEASED
IN THE INTEREST OF MAKING AVAILABLE
AS MUCH INFORMATION AS POSSIBLE.

-------
TECHNICAL REPORT DATA
(Please read Instruction: on the reverse before comnlettng)
1. REPORT NO. 2.
EPA-600/4-81-017
3. RECIPIENT'S ACCESSION NO.
Pt)82 1 3 2 507
4. TITLE ANO SUBTITLE
Development of Analytical Test Procedures for Organic
Pollutants in Wastewater - Application to Pesticides
S. REPORT DATE
November 1981
6. PERFORMING ORGA^II^A^Cj^^j}^
7. AUTHOR(S)
Hope Miller, Paul Cramer, Arbor Drinkvine, Alice Shan,
Glenn Trischan, John E. Going
8. PERFORMING ORGANIZATION REPORT NO.
4586-A1
9. PERFORMING ORGANIZATION NAME ANO ADDRESS
Midwest Research Institute
425 Volker Boulevard.
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2711 •
12. SPONSORING AGENCY NAME ANO AOORESS
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati. Ohio 45268
13. TYPE OF REPORT ANO PERIOO COVERED
Final 9/78 - 5/79
14 SPONSORING AGENCY COOE
15. supplementary notes
This camera copy is latest revision and supercedesEPA 600/4-81-017, NTIS PB81 -172629
Project Officer: Edward Kerns
16. A3STRACT
The Environmental Protection Agency's Environmental Monitoring and Support Labora-
tory at Cincinnati has been engaged in the development of test procedures for a multi-
tude of organics in water. "Midwest Research Institute was contracted to perform in a
development program directed toward a group' of 58|pesticides. The objective was to de-
velop procedures that were as similar to each other as possible and were sensitive to
1 ug/liter. By using a standard method, at least as a starting point, and making ad-
justment as necessary, the number of unique procedures was kept to a minimum.
The experimental approach was to test each pesticide against the standard method,
e.g., methylene chloride extraction—Kudema-Danish evaporation—Florisil cleanup—gas
chromatographic determination. Problem areas such as poor recovery, inadequate cleanup,
etc., were identified and modifications to circumvent these problems were devised. One
major deviation was the use of HPLC for several classes of pesticides.
The general classes or individual pesticides studies (and the number of compounds
in the classes) were: organochlorine (6); organonitrogen (7); organophosphorus (19);
triazines (9); carbamates and ureas (7); carbendazin and benomvl; cyanazine; carbofuran;
4,4'-aethylene-bis(2-chloroaniline); dinoseb; tokuthion; piperalin; piperonyl. butoxide;
and aldicarb.
17 KEY WORDS ANO DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENOEO TERMS
c. COSATi l-ieid/Group
Chemical analysis
Organic compounds
Pesticides
'./astewater


18. DISTRIBUTION STATEMENT
1
Release to public
19. SECURITY CLASS /This Report/
Unclassified
3 £5
20. S6C'JfllTv CLASS iThuptiqci |22 ?fllCE
Unclassified |
£PA Fo»m 2220-1 (R«v. 4-77) p = Eviovjj e:i:ion h obsol£'e

-------
Abstract (concluded):
Generally speaking, recoveries for clean water extraction, 7-day stability, and
spiked wastewater were good. The greatest deviation from a single method and the
sajor source of reduced recovery was in the area of cleanup.
The sensitivity goal of the basic protocol (1 yg/liter detection limit) was
achieved for 80% of the studied pesticides.
|-0^

-------
DISCLAIMER
This report has been reviewed by the Environmental Monitoring and
Support Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily re-
flect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
ii

-------
FOREWORD
The Environmental Protection Agency is charged with improving the con-
dition of the environment for the benefit of people and the natural world
which surrounds them. Several laws have been enacted which focus the at-
tention of the Agency on specific environmental concerns and initiate ac-
tion for their solution. The Clean Water Act of 1977 concentrates on en-
suring the high quality of the nation's natural waterways.
In support of this effort the Environmental Monitoring and Support
Laboratory-Cincinnati conducts research on laboratory procedures to measure
the presence and concentration of chemical pollutants in water. Of particu-
lar interest are monitoring methods for toxic organic compounds in wastewater
which is discharged from manufacturing plants.
This report describes the development of methods for certain selected
pesticides in aqueous samples, particularly in manufacturing wastewater.
These methods use common gas chromatography and high pressure liquid chro-
matography detection following common wet laboratory preparation techniques.
Robert L. Booth, Acting Director
Environmental Monitoring and Support
Laboratory-Cincinnati
iii

-------
ABSTRACT
The Environmental Protection Agency's Environmental Monitoring and
Support Laboratory at Cincinnati has been engaged in the development of
test procedures for a multitude of organics in water. Midwest Research
Institute was contracted to perform a development program directed
toward a group of 58 pesticides. The objective was to develop procedures
that were as similar to each other as possible and were sensitive to 1 pg/
liter By using a standard method, at least as a starting point, and making
adjustment as necessary, the number of unique procedures was kept to a min-
imum.
The experimental approach was to test each pesticide against the stan-
dard method, e.g., methylene chloride extraction--Kuderna-Danish evaporation-
Florisil cleanup—gas chromatograpic determination. Problem areas such as
poor recovery, inadequate cleanup, etc., were identified and modifications
to circumvent these problems were devised. One major deviation was the use
of HPLC for several classes of pesticides.
The general classes or individual pesticides studied (and the number
of compounds in the classes) were: organochlorine (6); organonitrogen (7);
organophosphorus (19); triazines (9); carbamates and ureas (7); carbendazin
and benomyl; cyanazine; carbofuran; 4,4'-methylene-bis(2-chloroaniline);
dinoseb; tokuthion; piperalin; piperonyl butoxide; and aldicarb.
Generally speaking, recoveries for clean water extraction, 7-day sta-
bility, and spiked wastewater were good. The greatest deviation from a
single method and the major source of reduced recovery was in the area of
cleanup.
The sensitivity goal of the basic protocol (1 |jg/liter detection limit)
was achieved for 80% of the studied pesticides.
This report was submitted in partial fulfillment of Contract No. 68-03-
2711 by Midwest Research Institute under the sponsorship of the U.S. Environ-
mental Protection Agency.
iv

-------
TABLE OF CONTENTS
Foreword	iii
Abstract		iv
Figures		vi
Tables	viii
Acknowledgements		x
1.	Introduction 		1
2.	Conclusions and Recommendations		4
3.	Materials		5
Apparatus 		5
Reagents		5
4.	Procedure		6
Chromatography		6
Extraction and Concentration		6
Cleanup 		6
Stability 		7
Application to Wastewater 		7
5.	Results and Discussion 		8
Chromatography		10
Extraction and Concentration		10
Stability		16
Cleanup		19
Wastewater Analyses 		20
References		26
Appendix - Chemical Information on Studied Compounds	 66

-------
FIGURES
Number	Page
1	Flow, diagram'of protocol for development of test procedure. .	3
2	GC/FID chromatogram of the dinoseb standard (168 ng)		27
3	GC/ECD chromatogram of chloroneb standard (3 ng)		28
4	GC/ECD chromatogram of the chlorobenzilate standard (3 ng). .	29
5	GC/ECD chromatogram of the chloropropylate standard (3 ng). .	30
6	GC/ECD chromatogram of dibromochloropropane standard
(0.3 ng)		31
7	GC/EC chromatogram of etridiazole standard (100 pg) 		32
8	GC/EC chromatogram of pentachloro'nitrobenzene standard'
(1 ng)		33
9	GC/TSD chromatogram of mixed triazine pesticide standard
(1.1 ng) on a Carbowax column		34
10	GC/FPD chromatogram of mixed orgnophosphorus pesticide stan-
dard (~ 5 ng)		35
11	GC/FPD chromatogram of diazinori standard (10 ng)		36
12	GC/FPD chromatogram of methyl parathion and methyl paraoxon .	37
13	GC/FPD chromatogram of mixed pesticide standard (1 ng). ...	38
14	GC/FPD chromatogram .of ethoprop standard (0.6 ng)		39
15	GC/FPD chromatogram of ronnel, chloropyrifos methyl and
chlorpyrifos standard (2 ng)		40
16	GC/TSD chromatogram of MOCA standard (250 ng)		41
17	HPLC chromatogram of carbofuran standard (500 ng)		42
18	GC/TSD chromatogram of the mixed triazine standard (1.1 ng)
on a SP-2250 column		43
vi

-------
FIGURES (continued)
Number	Page
19	HPLC chromatogram of cyanazine standard (0.5 pg)		44
20	HPLC chromatogram of oxamyl and carbendazim standard
: (100 ng)		45
21	HPLC chromatogram of methomyl (1 |Jg), diuron (0.1 ng) and
linuron (0.-1 ^g)		46
22	HPLC chromatogram of fluometuron standard (20 ng)		47
23	HPLC chromatogram of propachlor standard (400 ng)		48
24	HPLC chromatogram of propoxur (1 pg)		49
25	GC/TSD chromatogram of DEET standard (500 ng)		50
26	GC/TSD chromatogram of terbacil (500 ng), bromacil (500 ng),
and hexazinone (100 ng) standard		51
27	HPLC chromatogram of carbendazim standard (20 ng)		52
28	GC/TSD chromatogram of metribuzin (1.4 ng) and triadmefon
(1.1 ng) standard		53
29	GC/TSD chromatogram of tricyclazole standard		54
30	GC/FPD chromatogram of tokuthion in a mixed pesticide
standard		55
31	GC/TSD chromatogram of piperalin (8.45 ng)		56
32	HPLC chromatogram of piperonyl butoxide standard		57
33	GC/TSD chromatogram of aldicarb sulfone standard (4 ng) ...	58
34	Chromtograms of extract for chloroneb analysis before and
after cleanup (manufacturing site C)		59
35	Chromatograms of extract for etridiazole analysis before and
after cleanup (manufacturing site E)		60
36	Chromtograms of extract for PCNB analysis before and after
cleanup (manufacturing site E)		61
37	Chromatograms of extract for cyanazine analysis; upper GC/TSD
after florisil cleanup, lower HPLC/UV without cleanup ...	62
vii

-------
FIGURES (continued)
Number	Page
38	Chromatograms of extract for propachlor analysis before and
after cleanup (manufacturing site G)	 63
39	Chromatograms of extract for propoxur analysis before and
after cleanup (manufacturing site F)	 64
40	Chromatograms of extract for metribuzine analysis before and
after cleanup, (manufacturing site F)	 65
viii

-------
TABLES
Number	Page
1	Compounds Studied; Grouped by EPA Method Numbers		8
2	Chromatographic Systems and Parameters Developed for Studied
Compounds		11
3	Extraction Efficiency and 7-Day Stability Results 		17
4	Column Cleanup Systems		19
5	Percent Recovery of Studied Compounds from Selected Sorbent
Cleanup Systems 		21
6	Percent Recovery of Studied Compounds from Relevant Wastewater.	24
ix

-------
ACKNOWLEDGMENTS
We wish to thank Mr. Gary L. Westberg, Assistant Director, Morse .
Laboratories, Inc., Sacramento, California, and Dr. H. Anson Moye, Professor,
Institute of Food and Agricultural Sciences, University of Florida. These
two experts in the field of pesticide residue analysis contributed construc-
tive review and comment during the preparation of this report.
x

-------
SECTION 1
INTRODUCTION
Pursuant to Section 304(h) of the Clean Water Act, as amended in 1977,
the Environmental Monitoring and Support Laboratory (EMSL) in Cincinnati has
been assigned the responsibility for providing test procedures for the mea-
surement of organic pollutants in wastewaters. These procedures are designed
for use in monitoring direct discharges from industrial and publically owned
treatment works (POTW) sources under the National Pollutant Discharge Elimi-
nation System (NPDES) permit system and discharges into a POTW system under
pretreatment.
On December 3, 1977, a series of 14 new test procedures were proposed in
the Federal Register, for the quantitative measurement of specific organic
materials commonly referred to as the "priority pollutants."1 These 14
methods were developed through in-house and contracted research.
In this study a new group of toxic compounds was addressed. Fifty-eight
pesticidal compounds of high interest were selected for method development.
As with the priority pollutants some analytical information was available in
the literature, but in most cases previous methodology was neither sensitive
nor selective enough. The project set guidelines of 1 (Jg/liter minimum de-
tection level and modern chromatographic separation quality with specific de-
tection.
Another concern also shaped the approach to this project. The Environ-
mental Protection Agency is interested in placing the minimum cost burden on
users of these methods while maintaining high quality procedures. To reduce
costs, everyday analytical procedures were applied where possible, and costly
state-of-the-art techniques were avoided. A "multiresidue" method approach
was also followed, wherein several compounds of a given chemical class may be
analyzed in a certain sample by one run of the procedure. Extending this
idea further, commonality of steps of separate multiresidue procedures can
decrease cost by reducing the number of procedural repetitions. For example,
incorporation of liquid extraction with methylene chloride followed by
Kuderna-Danish extract concentration in as many procedures as possible allows
the user to handle a sample just once for analysis of several compound classes
covered by different multiresidue procedures. Separate class-selective de-
termination procedures can then be performed.
In concert with the multiresidue method approach, the pesticides were
grouped according to chemical and analytical characteristics. Groupings (see
Table 1, p. 8) were not always the same after the work was concluded because
of what was learned.
1

-------
This study investigated chromatography, liquid extraction, cleanup, and
application to relevant wastewater for each compound. Figure 1 is a flow di-
agram of the protocol used during the study. A brief investigation of ana-
lyte stability in aqueous medium was also performed.
2

-------
Figure 1. Flow diagram of protocol for development of test procedure.

-------
SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
This group of 58 pesticides performed well under methylene chloride ex-
traction, absorbent column cleanup, gas chromatography (GC), or high pressure
liquid chromatography (HPLC). About 60% of the pesticides could be recovered
from activated Florisil using standardized diethyl ether/petroleum ether elu-
tion mixture. Less active sorbents and more polar elution solvents were re-
quired to obtain satisfactory recovery values. As would be expected, samples
from sites with multiproduct integrated waste streams posed both detection
and interference difficulties. The methods were most successfully applied to
final effluents and to untreated waste which was segregated by the production
process.
The study of the applicability of these methods to manufacturing waste-
water samples has suggested some areas for improvements or future work. Stor-
age stability studies indicated that even in the benign clean water matrix
some pesticides were seriously degraded. Further effort should be directed
toward investigation of matrix effects on the integrity of the analyte. This
work should also include the development of preservation systems or conditions
which allow minimal change to be effected in the overall character of such
complex mixtures as waste streams. Alternate methods for extract cleanup in-
cluding liquid-liquid partitioning or the use of HPLC sorbents should be eval-
uated for compound classes such as organophosphorus pesticides where recover-
ies from Florisil are generally poor. Ultimately, there will be a need to
assess the environmental impact of the by-products of waste treatment pro-
cesses. Consequently, analytical methods will be needed both to identify and
quantify these decomposition or metabolic products.
4

-------
SECTION 3
MATERIALS
APPARATUS
Gas chromatography studies were performed using a Varian Model 3700
equipped with electron capture, nitrogen-specific thermionic, and phosphorus-
specific flame photometric detectors. Columns were 2-mm ID glass of 1.8 or
1.0 m length. High pressure liquid chromatography studies were performed us-
ing a Waters Associates Model 6000A pump, 600 solvent programmer, and 440 de-
tector. The analytical column was 4 mm ID x 30 cm packed with (jBondapak C18,
10-(jm particle size, from Waters Associates. The guard column was 4 mm x
7 cm packed with CO:PELL 0DS from Whatman Company.
Kuderna-Danish apparatus had a volume of 50 ml. Cleanup columes were
20-mm ID x 300-mm pyrex with a coarse fritted disc at bottom and a Teflon
stopcock. Solvent drying columns were 19-mm ID x 600-cm (nominal) glass.
REAGENTS
All solvents used were "Distilled-In-Glass" from Burdick and Jackson
Company. Anhydrous sodium sulfate was from Supelco Company. Flocisil and
alumina from Supelco Company were activated for at least 16 hr at 130°C in an
open tray prior to use. Florisil was deactivated by adding a measured volume
of distilled water to a portion of activated Florisil, followed by agitation
for 4 hr prior to use.
5

-------
SECTION 4
PROCEDURE
CHROMATOGRAPHY
The first step in the development of each test procedure was experi-
mental determination of a detection system to meet the sensitivity require-
ments (1 pg/liter DL*) for each one of the compounds to be analyzed in a
given group. Those chromatographic columns and operating parameters were
selected which would separate the compounds expected to co-occur in a given
industrial waste sample. The separation had to be sufficient for quantita-
tion while keeping the analysis time under 1 hr.
Because GC was considered to be a more common and less expensive tech-
nique than HPLC, GC procedures were first investigated. Many compounds, how-
ever, were known to be heat labile so these were investigated by HPLC. Chro-
matographic conditions in common use were investigated. Dilute standards in
solvent were injected into the chosen chromatographic system. Retention time
and response factors were calculated.
EXTRACTION AND CONCENTRATION
One-liter aliquots of deionized water at pH 7 were spiked with one or
more analytes. Three consecutive extractions with 60 ml of methylene chlor-
ide were performed in a 2-liter separatory flask. Extracts were combined and
passed through a drying column filled with 5 to 10 cm of anhydrous sodium
sulfate. The dried extract was concentrated to less than 5 ml by Kuderna-
Danish technique. Fifty milliliters of'hexane was added to the extract, and
it was reconcentrated to less than 10 ml final volume. This extract was
chromatographically analyzed for recovery. Several compounds were found to
require unique extraction conditions, as discussed in the section "Results
and Discussion" (p. 8). A goal of 85% recovery was set for^this step.
CLEANUP
Twenty grams (nominal) of activated Florisil were placed in a cleanup
column and prewet with 60 ml of petroleum ether. The entire extract was
added to the column. Initial studies were performed with four sequential
200-ml elutions of 6%, then 15%, then 50%, and finally 100% ethyl ether in
" DL = detection limit. Defined as five times the noise background when
5 (Jl of a 1-liter sample extract concentrate (5 ml, final volume) is
analyzed.
6

-------
petroleum ether. Fractions were separately concentrated and- chromatograph-
i^ally analyzed for recovery.
Poor recoveries of certain compounds were solved by eluting with stronger
solvent (acetone), deactivating the absorbent with water, or using a different
absorbent (alumina).
STABILITY
One-liter aliquots of deionized water, fortified with given pesticides
were stored in the light at room temperature and neutral pH for at least 7
days; then the compounds were extracted and concentrated according to the
verified procedure. Losses during storage were documented, but no experi-
ments were run to isolate the causes or determine satisfactory storage condi-
tions .
APPLICATION TO WASTEWATER
Samples of process or final effluent wastewater were collected from
plants which manufacture the compounds of interest. These were adjusted to
near pH 7 and stored at 4°C in the dark until use. To serve as a realistic
challenge to the preliminary method, aliquots were analyzed by procedures
developed using deionized water. Spiked aliquots were also analyzed for re-
covery. Often such studies indicated problems in recovery or with chromato-
graphic interference. As a result, modifications were initiated in chroma-
tography, extraction,and cleanup.
7

-------
SECTION 5
RESULTS AND DISCUSSION
Table 1 lists the multiresudiue methods developed and the 58 compounds
studied. Method numbers were assigned by EPA for purpose of regulatory ci-
tation. The structures and CAS nomenclature for the compounds are given in
Appendix A. In the following discussion the results for each procedural step
are presented.
	TABLE 1. COMPOUNDS STUDIED; GROUPED BY EPA METHOD NUMBERS	
Method 604 - Phenols
Dinoseb
Method 608 - Organochlorine Pesticides and PCB's
Chlorobenzilate
Chloroneb
Chloropropylate
Dibromochloropropane
Etridiazole
PCNB
Method 619 - Triazines
Ametryn
Atrazine
Prometon
Prometryn
Propazine
Simetryn
Simazine
Terbutylazine
Terbutryn
Method 622 - Organophosphorus Pesticides
Az inpho sine thy,1
Bolstar
Chloropyrifos
Coumaphos
Demeton-0
Demeton-S
Diazinon
Dichlorvos
Disulfoton
Ethoprop
(continued)
8

-------
TABLE 1 (continued)
Fensulfothion
Fenthion
Mevinphos
Naled
Parathion, methyl
Phorate
Ronnel
Stirofos
Trichloronate
Method 623
4,4'-methylene bis(2-chloroaniline) [MOCA]
Method 628
Carbofuran
Method 629
Cyanazine
Method 631
Carbendazim and benomyl
Method 632 - Carbamate and Urea Pesticides
Diuron
Fluormetron
Linuron
Methorny1
Oxamyl
Propachlor
Propoxur
Method 633 - Organonitrogen Pesticides •
Bromacil
DEET
Hexazinone
Metribuzin
Terbacil
Triadmefon
Tricyclazole
Method 634
Piperalin
Method 635
Piperonyl butoxide
Method number assignment pending
Aldicarb
Tokuthion
9

-------
CHROMATOGRAPHY
The chromatographic columns, detectors, and operating parameters were
selected to separate and detect specified groups of compounds in the presence
of one another and other interferences associated with the wastewater analyzed.
The chromatographic conditions, detection limits, and retention times
for each compound are summarized in Table 2. The compounds whose separation
was considered during column and operating parameter selection are listed in
the last column. All GC analyses were performed with 2-ram x 1.8-m ID glass
columns with the exceptions noted for the first 10 organophosphorus compounds
listed for Method 622. The 1-ra column and rapid program rate were used in
this instance to reduce on-column residence time for azinphosmethyl, which
apparently decomposed on the longer column.
Initially an attempt was made to develop an HPLC method for the analysis
of aldicarb in manufacturer's wastewater. The extraction efficiency, 7-day
stability and column chromatography cleanup data were satisfactory for deion-
ized water and.hexane fortified with aldicarb. However, when the wastewater
was extracted and the residue eluted from a Florisil column, the background
interferences persisted and prevented the quantitation of aldicarb. Modifica-
tion of the HPLC method from an isocratic system to a gradient system was also
unsuccessful in obtaining the necessary resolution of aldicarb from the back-
ground. At this point, MRI began adapting a gas chromatographic residue
method for the analysis of the wastewater.
In order to analyze aldicarb by gas chromatography, the compound was
first oxidized to aldicarb sulfone by treatment with peracetic acid. The al-
dicarb sulfone was then thermally .degraded in the injection port to produce
the volatile species 2-methyl-2-(methylsulfonyl) propionitrile.
Two sets of operating parameters are given for cyanazine, dinoseb, and
DEET. The second cyanazine method using HPLC was required to separate a
wastewater interference which could not be removed by solid sorbent cleanup
techniques. Method .604, developed prior to this work, was specified for the
analysis of dinoseb. In the absence of interfering phenols, analysis time
was reduced by operating at 160°C isothermal. A thermionic nitrogen specific
detector, which might also improve sensitivity, was not evaluated for this
analysis. It should be noted that gas chromatography of dinoseb is demanding.
The column must be properly conditioned and devoid of active sites. Waste-
water interferences required modification of the isothermal conditions ini-
tially developed for the analysis of DEET. Temperature programming was re-
quired to effect the necessary separation. Figures 2 through 33 (pp. 26
through 57) are copies of the GC or HPLC chromatograms of standard solutions
of the studied compounds. The detection limit goals of 1 (Jg/liter GC and 10
(Jg/liter HPLC were met for 51 of the 58 compounds.
EXTRACTION AND CONCENTRATION
The goal of 85% extraction efficiency was met for 95% of the studied com-
pounds. All the studied compounds were successfully extracted from water at
pH 7 with three 60-ml portions of methylene chloride with the exception of
10

-------
Cutnpouud
TABLE 2. CMKOhlATOCKAI'llIC SVS'lbHS AHO HAKAHKTKKS WV£l,Om) H)H SIMDIKH rOHIHJUNDS
Delect iou
liioil (mb/8) Selector
Opera! ing |>«ir«iueLeib
lleieulion tine Chromatography developed l"«.r
(volume)	«d

  • -------
    TAIH.E 2 (continued)
    Met hot)	Compound
    I'ropuznie
    Siioctryn
    Terhut y 1 aziite
    T»'i butryn
    622 Az i nphobtuclhy 1
    Uulection
    limit (|'g/£) Dctcrtor
    Operating parameters
    51 Caihowj* 20H-TPA
    on 100/120 Supelco-
    port
    51 Curbowa* 20M-TPA
    on 100/120 5upc)co-
    I'Oi L
    5X Caihownx 20N-TPA
    nil 100/120 Supclco-
    |»o»t
    5X Carbowjx 20H-TPA
    on 100/120 SiijicIco-
    f>Ol t
    51 Ca i howitx 20M-1PA
    on 100/120 Supelco-
    poi i
    5% SP-2401 on 100/120
    SupcIcopoit
    200° ibothcraal
    200° Isol hernia I
    200° i botlierma I
    200° isothermal
    200° isothermal
    KctCfltjOd I IBM?
    (volume)
    1 min at ISO®, 25t>/mlr» in-
    crease to 220°, 9 rain hold
    ot 220° (1 meter column
    )<;ii£lh)
    16 3 nin
    15.4 oiin
    Chromatography developed lot
    add it loiu 1 compounds
    Same as above
    Sauic ab above
    Same as above
    Sane us above
    Same! as 
    -------
    lAtif.E 2 (continuedJ
    Detection	Kutvniion Lime Chromatography dcvclo|>ed (or
    Compound	limit (|ig/f) Detector	Column	Operating pjraoetcrn	(volume)	additional compounds
    Distilfoton
    Feosultot hi on
    Fenthiou
    Trichloronaie
    SX SP-2401 on 100/120
    Snpclcoporl
    51 Si'-2401 on 100/120
    SupelcoporL
    5% SP-2401 on 100/120
    SupcIcoport
    5% SP-2401 on 100/120
    Supclroporl
    51 SP-2401 on 100/120
    Supelcopoi I
    I ain at ISO*, 2S°/inin in-
    crease to 220°, 9 mill hold
    at 220® (1 atcter column
    length)
    I niu ul 150°, 2S°/aiu in-
    crease to 220°, 9 min hold
    at 220° (I meter column
    length)
    I tain at 150°, 25°/m»n in'
    crease to 220°, 9 min hold
    at 220• (1 meter column
    length)
    I niii at 150°, 2S°/oin in-
    crease to 220®, 9 o>iu hold
    at 220° (I meter column
    length)
    I oiu aL 150°, 25®/min In-
    cieasc to 220°, 9 bin hold
    at 220° (I ttcler column
    length)
    J.I mui
    1.4 min
    SJtne as above
    Sbm as above
    S«*me as above
    Saw as above
    Same as above
    Chloropyri fos
    Mt«v i iijthofl
    Oichlorvos
    FPU	5X SP-2401 on 100/120
    SupelcoporL
    FPU	5% 3P-240I on 100/120
    Supelcopoit
    FPU	5% SP-2401 on
    100/120 Stipe 1 co*
    port
    Fl'O	5X ST-2401 on
    100/120 Stipe lco-
    |IO| t
    HI) s% SP-2'.0I UII
    100/120 Supclco-
    |>urt
    FPU	SX SP-2401 on
    100/120 Sujm Jco-
    poi I
    10°/oin increase from
    160 to 220°
    10°/©)i» i/icrcjbe from
    160 La 220°
    2 win hold at 170°
    20A/min iuctease to
    220®» hold for 10 cam
    2 tain hold at 170° 20°/mij>
    increase lo 220°, hold
    for 10 min
    2 mui hold at 170° 20°/mlu
    iucieat»c to 220°, hold
    for 10 min
    2 min hold at 170° 20°/min
    Increase to 220°, hold
    lor 10 mill
    U .9 mi"
    2.4 min
    Chloropyrifos
    Siirolos
    Mcvinplios
    Dichloivoa NoJcd
    St i rofou
    Mevinplias
    Diclilorvos Nalcd
    St i ro fos
    Hcviuphos
    Dicblorvos Hulcd
    Siiiofos
    Hevi uphos
    Dichlorvob N.il«;il
    (cout inurd)
    

    -------
    TABLE 2 (coin unictl)
    Crwumiiml
    Oia£tciQ(t
    Flhuprnfi
    I'ataLliicn, iwlliyl
    clJ HOCA
    fcJB CQLbof«iran
    629 Cyanazjuc
    631	Crt i lieu J J'i ii* and
    lu*aue*y(
    UJ2	Diuran
    McUiuwyl
    Pi u|iat.h1 u C
    Pi
    Di'lectiou
    lrnil (ifg/J)
    I.O
    5
    OCA
    lb
    16
    WUl-UV
    24(1 tin
    5) Sl»-24Ul on
    IOO/120 Stvp«]co-
    pocl
    53. SL*-240 1 on
    ICO/120 Supi-Uo-
    I'C-ri
    mci
    Uu/liO Siij'e1 Ico-
    porL
    J* SP-2250 DB or,
    100/ 120 .Snpel ca-
    )'U i I
    \iltuiKUyak
    SP -22SO o«i
    ICQ/I 20 Su^lco-
    ,-urL
    IH'I.C-IJV (lUou^p.ikt €,«
    2SC lllB
    lll'I.C — IJV 1111^K C,4
    2H0 m
    LLL'l.C-U'p1 |iBui«Jnpa|i Cl&
    25UV	C,
    2!>4 iiw
    jji'ij:- Lrv |iBu.nid]»dk c: I
    2 54 ruo
    III'IjC-IIV iilluiMlipA c,
    iiA wg
    IIPI.IXJV |ill<->rii|^{j.'ilf Cti
    2*0 iinj
    t>pina\.jng
    Rrf** cm I I un I i a
    (.vulumrO
    £>)rii^>)lugr«i|il»y 'luvc! u|i[ J for
    4.Id11 j-un«jl L0in|hjMiu1a
    110® iBuChemiil
    13U" ,le,L.tht:r«j|
    ty&° isoifrcticai
    50:50 C»3CIJ;HvU
    -2 tnl/mict
    Sll.50 ll2U.CII30!l
    1	ml/mi"
    50 50 ll^O-OljOII
    2	nI/k¦n
    itix CflaC|tf/Hal> ti* IQUS ClIjCN,
    thirjr gradient in 3Hi £>'it
    wl 1 li 2 mJ /mm i Low
    lot. CMzCft/ll.J} to 200% aijC.H,
    hutav ^cadicui. iu "JO bin
    with 2 in I/whi flow
    Kit CHjLK/rr/i La 100* CHaCM,
    I mi'iir	in JL) u»iii
    vilh 2 at f mitt flow
    50.5U ll^O'SlljUl
    1	Hjl/tnfn
    SO 5il II^O.CII^CH
    2	m//uit((
    4.4 ei 11
    3.5 tnln (/ »l)
    5 2 ram
    10.2 lubu
    (10.2 »))
    3.9 aiii (T.« «U
    15.5 «hi CM nl)
    Avl-L tryn, At r*z i nt
    FroiMeifrii, )*rotiH-t ryu
    Pi.opa-zi.nc, Slaietryn.
    Sioazliie, Te rtiui jlai iw
    ' ItcbuL ryn
    He t-Jiuuy J j l. 1 iKii or 1.
    17.9 u> J it (1S.B)	Mit L In >aiy I, IHuioh
    6.5 oiiti t I I nl)	QUiton, Liiivmn
    U . ~i m 11« t9 . U }
    3.4 ariii	Nu
    &.» -.O
    (i'o*il j uur:'! J
    

    -------
    TABLE 2 (continued)
    Helhod
    Compound
    Detection
    iiffiil (pg/t) Detector
    Operating parameters
    RelculIon line
    (votlKQc)
    Chromatography developed lor
    add illona1 compounds
    Fluometuron
    Oxamyl
    633 Hetribiizin
    Triadmefon
    DEET
    634
    635
    Tricyclazole
    Bromaci 1
    llexazinone
    TerbaciI
    Pi perjI in
    Piperonyl buioxide
    Aldicat b
    0.5
    1.5
    0.7
    0.7
    0. I
    0.1
    0.2
    0.5
    0.5
    0.3
    6
    0 4
    5
    0.5
    IIPLC-UV pUondupjK Cl8
    254 ni
    IIPLC-UV pUondapak C18
    254 nn
    TSD
    TSD
    TSD
    1IPI.C-UV
    280 nia
    IIP I.C-UV
    254 urn
    FIH)
    31 SP-2401 on 100/120
    Supeicoport
    31 SP-2401 on 100/120
    Supeicoport
    3X SP-2401 on 100/120
    Supeicoport
    31 SP-2250 Dl) on
    100/120 Supeicoport
    31 SP-2250 l)fi on
    100/120 Supeicoport
    31 SP-2250 DB on
    100/120 Supeicoport
    31 SP-2250 DB on
    100/120 Supeicoport
    3X SP-2340 on
    Supelcopoit 100/120
    pliundapak C|g
    5X Carbowax 20H-TPA
    on Supeicoport 80/100
    phuiidapak C|8
    5% SP-2401 on
    Supeicoport 100/120
    50:50 l|20:CllaCN
    2 tal/ain
    25:75 Cll30ll:H2O
    1 ml/(sin
    240° isothermal
    240° IsoLhermal
    160° isothermal
    1	niu at 130° 12°/min
    increase to 200°
    240° isothermal
    2	min at 210° 10°/oin
    increase to 250*
    2 rain ol 210° 10°/ain
    increase to 250°
    2 aln at 210° 10°/ioin
    increase to 250°
    200°, isothermal
    65X CI13CN.35X 11*0
    1.5 ul/min
    150° , i sot hi: rma I
    (1)	50% C1I3CN:5OX 11*0
    2 ml/mtn
    (2)	2OX CII3CN/I120 to
    70X CI?3CN/ll20
    Linear gradient In
    20 mhi, 2 ul/miii
    I mill hold at 150°
    25°/miu incieaae to 220°
    9 nin hold at 220°
    (1 is column length)
    3.6 nin
    (7.2 ®1)
    8 oin (8 ml)
    2.4	nin
    4.1 nin
    1.6 niu
    4.6	nin
    3.5	nin
    3.7	nin
    7.6	min
    2.1	nin
    3.2	min
    14.3 ml
    (9.5 min)
    2	5 uin
    5.6 mn
    IB.1 nin
    3	4 nin
    a	Detection limit - nanograms needed to give a signal 10 times the noise level
    h	FLU - flume ionization detector.
    c	ECU - electron captutc detector,
    d	TSU - thermionic nitrogen specific detector,
    e	fPD - flame phoLometiic detector.
    *	EPA method uiuuhei to be assigned.
    No
    No
    Triadmefon
    Hetnbuztn
    No
    Developed for waste-
    water interferences
    Terbaci1
    llexazinone
    6runaci1
    Terbaci 1
    llexazinone
    Bromaci1
    No
    No
    No
    No
    No
    

    -------
    carbendazim and benomyl and dinoseb. An increase in solvent volume from 60
    to 350 ml resulted in an increase in the recovery of carbendazim from 15 to
    83%. Since benomyl slowly hydrolyzes to carbendazim,2 it was decided to de-
    velop the method for benomyl around the total conversion to carbendazim. One
    liter of neutral wastewater and 10 ml of HC1 were stirred for 24 hr to assure
    the complete hydrolysis of benomyl to carbendazim. The pH was then raised to
    7 for sample extraction with three 350-ml portions of methylene chloride.
    The previously developed test procedure for phenols (604) was evaluated
    for the analysis of Dinoseb. Method 604 requires an initial extraction (3 x
    60 ml CH2C12) at pH 11 to remove basic interferences and a final extraction
    at pH 2 for the partitioning of Dinoseb and other acidic phenols.
    As discussed in the previous section, aldicarb was oxidized to aldicarb
    sulfone for chromatographic purposes. Prior to extraction the water was
    treated with peracetic acid and allowed to stand 15 min. The oxidized sample
    was neutralized with 10% sodium bicarbonate and then extracted with three
    60-ml portions of methylene chloride. The combined extracts were concentrated
    and taken completely to dryness, until no peracetic acid odor remained. This
    must be done to eliminate background interferences during the GC/TSD analysis.
    Two significant losses of piperalin occurred during the sample workup
    procedure. The first of these losses involved the extract drying step and is
    presumably dependent upon the activity and amount of the anhydrous sodium sul-
    fate used to dry the methylene chloride extract. Studies showed that recovery
    of piperalin from a water-saturated methylene chloride extract after drying
    with a 10-cm column of anhydrous sodium sulfate (y 20 g) was quantitative.
    However, when a dry extract spiked with piperalin was passed through a similar
    column, a recovery of about 35% was observed. No specific studies were under-
    taken to determine the maximum amount of sodium sulfate which could be used in
    drying an extract; however, a 10-cm 20 g) column proved to be adequate to
    dry the extract and not cause any significant losses of piperalin. Alterna-
    tively, the drying step.could be eliminated and the final solvent exchange
    could be made into acetone rather than hexane.
    The second and perhaps most dramatic loss of piperalin during the sample
    workup occurred during the solvent evaporation step. Silanization of the two
    lower portions of the Kuderna-Danish evaporator was necessary to prevent ad-
    sorption of any piperalin present in the extract to the surface of the glass.
    Studies indicated that adsorption of piperalin to unsilanized glass surfaces
    occurred only during the extract concentration step and not during the extrac-
    tion or extract drying step.
    STABILITY
    Deionized water fortified with each compound was extracted on day 0 and
    day 7 after storage at ambient conditions and neutral pH. The percent recov-
    ery values are included in Table 3. Comparison of the two values would in-
    dicate a need for some means of preservation for Bolstar, Demeton-S, Disulfo-
    ton, Fenthion, Phorate, Trichloronate, Ronnel, Dichlorovos. tokuthion, and
    piperalin. It should be noted, however., that no effort was made to determine
    the cause of analyte losses during storage.
    16
    

    -------
    
    TABLE 3. EXTRACTION EFFICIENCY AND 7-DAY
    STABILITY
    RESULTS
    
    
    
    
    Concentration
    1
    Recovery
    
    Method
    Compound
    (Mg/^)
    Day 0 Day 7
    604
    Dinoseb
    100
    94,
    95
    92
    608
    Chloroneb
    5
    87,
    73
    70
    
    Chlorobenzilate
    5
    96
    
    96
    
    Chloropropylate
    5
    91
    
    94
    
    Dibromochloropropane
    
    86,
    84
    84
    
    Etridiazole
    1
    99
    
    100
    
    PCNB
    1
    68
    
    65
    619
    Ametryn
    1
    103,
    100
    90
    
    Atrazine
    1
    101,
    101
    92
    
    Prometon
    1
    96,
    99
    94
    
    Prometryn
    1
    96,
    101
    93
    
    Propazine
    1
    97,
    100
    94
    
    Simetryn
    1
    102,
    102
    93
    
    Simazine
    1
    94,
    103
    91
    
    Terbutylazine
    1
    95,
    102
    96
    
    Terbutryn
    1
    93,
    93
    93
    622
    Azinphosmethyl
    1
    96
    
    87
    
    Bolstar
    1
    100
    
    79
    
    Coumaphos
    1
    99
    
    97
    
    Demeton-0
    1
    91
    
    75
    
    Demeton-S
    1
    97
    
    0
    
    Disulfoton
    1
    111
    
    71
    
    Fensulfothion
    1
    102
    
    91
    
    Fenthioa
    1
    87
    
    61
    
    Phorate
    1
    89
    
    29
    
    Trichloronate
    1
    107
    
    55
    
    Chloropyrifos
    1
    78
    
    70
    
    Ronnel
    1
    91
    
    58
    
    Stirofos
    1
    83
    
    80
    
    Naiad
    1
    95
    
    91
    
    Mevinphos
    1
    92
    
    88
    
    Dichlorvos
    1
    110
    
    70
    
    Diazinon
    1
    91
    
    89
    
    Ethoprop
    1
    101
    
    100
    
    Parathion, methyl
    1
    99
    
    94
    623
    MOCA
    200
    80
    
    90
    
    
    10
    55
    
    ND3
    
    
    
    56
    
    NDa
    628
    Carbofuran
    10
    101,
    101
    102
    629
    Cyanazine
    
    88,
    101
    94
    A
    631
    Carbendazim
    10
    83
    
    ND
    
    Benomyl
    150
    81,
    72
    M)3
    
    
    
    
    (continued)
    
    
    17
    
    
    
    

    -------
    TABLE 3 (continued)
    Concentration	% Recovery
    Method	Compound	(|Jg/£)	Day 0	Day 7
    632
    Diuron
    10
    95,
    89
    93
    
    Linuron
    10
    91,
    92
    96
    
    Methomyl
    100
    78,
    77
    95
    
    Propachlor
    100
    104,
    109
    104
    
    Propoxur
    100
    91,
    89
    91
    
    Fluometuron
    10
    98,
    87
    -99
    
    Oxamyl
    10
    98
    
    82
    633
    Metribuzin
    1
    95,
    100
    102
    
    Triadmefon
    1
    93,
    93
    88
    
    DEET
    1
    97
    
    96
    
    Tricyclazole
    1
    100,
    100
    81
    
    Bromacil
    1
    91
    
    100
    
    Hexazinone
    1
    102
    
    83
    
    Terbacil
    1
    97
    
    99
    634
    Piperalin
    1
    95
    
    60
    635
    Piperonyl butoxide
    10
    96,
    102
    87
    
    Aldicarb
    1
    70,
    72
    60
    *
    Tokuthion
    1
    92,
    95
    63
    a ND - value not determined.
    * EPA method number to'be assigned.
    18
    

    -------
    CLEANUP
    Since manufacturer's wastewater generally contains structurally similar
    compounds (i.e., starting materials, by-products and degradation products)
    the development of a cleanup for extracts of this matrix is most important
    but is also most difficult.
    Modifications of the preliminary cleanup procedure were made when neces-
    sary and possible. In some cases GC or LC parameters were varied instead of
    or in addition to modifying the cleanup system in order to achieve adequate
    resolution from the wastewater interferences. Column materials and elution
    mixtures were evaluated using the predetermined order given in Table 4. Be-
    cause of the use of selective detector systems, it was only necessary to
    cleanup the extracts of seven wastewaters representative of 13 of the 58 stud
    ied compounds. It was observed that the adsorptivity varied greatly between
    determinations made with fortified hexane and actual wastewater extracts. It
    is advisable to retain all fractions and determine the elution pattern of the
    compound in the presence of any new set of matrix interferences. Chromato-
    grams of wastewater extracts before and after cleanup are shown in Figure 34
    to 40 (pp. 58 through 64).
    TABLE 4. COLUMN CLEANUP SYSTEMS
    System
    no.
    Solid
    sorbent
    Elution mixtures
    Percentages
    Florisil
    Florisil
    2% water de-
    activated
    Florisil
    6% water de-
    activated
    Florisil
    10% water de-
    activated
    Alumina
    Ethyl ether/petroleum ether 6, 15, 50, 100
    Acetone/hexane	6, 15, 50, 100
    Acetone/hexane	6, 15, 50, 100
    Acetone/hexane
    6, 15, 50, 100
    Ethyl ether/petroleum ether 6, 15, 50, 100
    Since the existing phenol Method 604 evaluated for dinoseb does not in-
    clude a cleanup step, no method was developed.
    Triazines containing the functional group S-CH3 could be successfully
    recovered only from 10% deactivated alumina. Although nonsulfonated tria-
    zines, with the exception of cyanazine, were recovered from Florisil with
    ether-petroleum ether, the alumina column was used because both types of tri-
    azine were present in the wastewater.
    Organophosphorus pesticides as a class exhibited extremely poor recovery
    from Florisil. Because of the specificity of the flame photometric detector
    19
    

    -------
    solid sorbent cleanup was not required in the analysis of wastewater, and
    only system 1 was evaluated for those compounds because of time considera-
    tions .
    All the solid sorbent cleanup systems given in Table 4 were evaluated
    for piperalin. None were successful due to 100% retention of piperalin by
    the adsorbents.
    No cleanup method was developed or required for the analysis of MOCA.
    Satisfactory recovery of labile compounds such as carbamates and ureas
    generally required substitution of the more polar acetone/hexane mixture as
    would be expected. No solid sorbent technique was successful in both recov-
    ering cyanazine and removing the interferences which appeared in a relevant
    wastewater. An HPLC method was developed for this purpose.
    Caution must be used when attempting to apply a cleanup developed for
    one matrix to another matrix.
    Table 5 summarizes the recovery results from solid sorbents and indicates
    which compounds were determined in wastewater without the need for cleanup.
    WASTEWATER ANALYSES
    When possible, wastewater was obtained from industrial sites that manu-
    factured one or more of compounds studied. These water samples were utilized
    to allow for needed method modifications due to matrix effects and to verify
    the efficiency of final procedures. First, the preliminary method developed
    with fortified reagents was tested on a relevant sample and any necessary
    changes were made. Percent recovery values for the final procedure were then
    determined on wastewater that had been fortified with levels relevant to
    those observed in the background. Table 6 provides recovery data at speci-
    fied spiking levels.
    20
    

    -------
    TAIII.K 5. I'tUCKNT HfcXOVt.hY UK STUUlhl) COM*nUNI>.S KHOTI SKI.KCTF.I) SOI.II) SOKHENT CIJ-'.ANUp SYS IV. MS
    ttu'Uiml
    604
    608
    619
    622
    Cooi|>oui}«|
    a
    System
    Ailllt'il UUHHIIIt
    ll'g)
    6
    X Recovery Infraction
    15 50 100° I001'
    Tot j |
    Recovery
    Diitoscl)
    
    
    
    NOT UKVKlCf'KI)
    
    
    Cltluroiich
    1
    10
    o:i
    -
    -
    -
    93
    Oil orolmiiz i laic
    1
    10
    
    15
    70
    -
    85
    Ch 1 orO|>ro|>y late
    1
    10
    
    32
    6|
    -
    93
    UJbroMocliloro|>i opane
    1
    10
    60
    10
    1
    -
    71
    Etrldiazol*:
    1
    I
    100
    -
    -
    -
    100
    rcNu
    1
    1
    75
    -
    -
    -
    75
    Awetryo
    1
    
    -
    -
    7
    -
    7
    
    5
    1
    
    70
    21
    -
    91
    Alrazinc
    1
    1
    
    3
    93
    -
    96
    
    5
    1
    -
    99
    -
    -
    99
    I'roooioii
    1
    1
    -
    -
    -
    66
    66
    
    5
    1
    -
    84
    -
    -
    84
    ProtscCryii
    1
    1
    -
    7
    3
    -
    10
    
    5
    1
    -
    13
    98
    -
    til
    Proflavine
    1
    1
    
    5«
    33
    -
    91
    
    5
    1
    
    5J
    41
    -
    94
    Siatcltyit
    1
    1
    -
    -
    -
    21
    23
    
    5
    1
    
    89
    -
    -
    89
    SmiazJnc
    1
    1
    -
    -
    92
    -
    92
    
    5
    1
    -
    94
    -
    -
    94
    Terbuly la/.iikc
    1
    1
    -
    16
    75
    -
    91
    
    5
    1
    -
    35
    57
    -
    92
    Tci Ixi I ryii
    1
    1
    -
    -
    -
    -
    0
    
    
    1
    -
    -
    H5
    -
    85
    Aziii|»lio(> ineihyl
    1
    1
    -
    -
    -
    33
    33
    Uitl si m
    1
    1
    35
    -
    -
    -
    35
    CoiuuaphuS
    1
    1
    
    -
    -
    
    44
    llc.wel
    1
    1
    
    -
    -
    -
    0
    toa-S
    1
    
    -
    -
    -
    -
    0
    l)i Lit 11 olon
    1
    1
    26
    16
    10
    -
    52
    hiibiil lothion
    1
    1
    
    -
    -
    -
    0
    Kenl lii on
    1
    1
    16
    9
    -
    -
    25
    ttu<|ui ft'
    -------
    	iji.fi
    Ad«t<:*l utnminl
    Method	Compound	Syblcw"	(J'k)
    Hum ale	1	1
    Tricliloroiialc	I	1
    Cliloro|tyi i (us	I	I
    Runnel	1	1
    SLirofoa	I	I
    Nil I ed	I	I
    Mevitiphos	I	)
    L>i cliiurvos	1	I
    Diaziiion	I	I
    Ell»oproj>	I	I
    f'.tral li ion, uicUiyl	!	I
    62 1 flOCA
    628 Coxuc*	1	100
    Fluoiuelorou	I	10
    (coiit
    X Recovery t»v Ir.-Mtton ....	,, , , ,
    	i. j		 lol.il 11 cd foi
    15 SO	100*'	(00* Recoveiy w.istew.ittM'
    34 - - - -	34	no
    67 -	6?	no
    100 -	100	no
    B2 -	B2	no
    63 - -	63	no
    -----	0	no
    J 4 -	14	no
    no
    24	-	24
    30 .16 10	-	76	no
    70	-	70	no
    !)0	90	no
    HOT DtVKl.Ol'KI)
    43 61	-	104	no
    83	-	8 )	yc* *
    29	-	29
    46	-	46	no
    24 58 -	-	82	no
    14 82	-	96	no
    84	-	H4	no
    94	-	94	yt-'tJ
    92	-	92	no
    89	-	89	yt-s
    63	32	95	yes
    (i Olll I IHH'd)
    

    -------
    TAULK 5 (continucd)
    
    
    
    Added amount
    
    % Recovery by
    f ract ion
    a It
    
    Required for
    Hclliod
    Compound
    System3
    (i»r)
    6
    15
    50
    100 100
    Total
    wastewater
    633
    Met ri biizin
    3
    1
    22
    45
    _
    _
    67
    yes
    
    Triadmefon
    3
    1
    -
    100
    -
    -
    100
    yes
    
    IJEKT
    3
    1
    21
    60
    -
    -
    81
    no
    
    Tricyclnzole
    3
    I
    20
    22
    35
    18
    101
    no
    
    llexazinone
    3
    1
    -
    -
    82
    -
    82
    no
    
    Terbaci L
    4
    1
    -
    62
    -
    -
    62
    no
    
    Bromacj1
    4
    1
    -
    10
    38
    -
    48
    no
    634
    Fipet al in
    
    
    Not Developed
    
    
    
    
    635
    Piperonyl but oxide
    2
    10
    10
    -
    -
    -
    100
    yes
    is
    Aldicarb
    2
    1
    -
    -
    86
    -
    86
    no
    *
    Tokuthion
    I
    1
    65
    7
    -
    -
    72
    no
    a Systems Sorbent	Elut ion mixture
    1	Florisil	ethcr/petrolenm ether
    6, 15, 50, 100a, 100b
    2	Florisil	acetone/hexane
    W	6, 15, 50, 100
    3	2% water de-	acetone/hexanc
    activated	6, 15, 50, 100
    FlorisiI
    U 6% water de-	scetone/hcxane
    activated	6, 15, 50, 100
    F1ori s LI
    5	10% water de-	ether/petroleum ether
    activated	6, 15, 50, 100
    Almuiua
    6	Florisil	20% ether/hcxane, then
    6, 15, 50, 100 acetone/hexaiie
    h No solid sorbent evaluated was effective in removing a wastewater interference und
    analysis was completed by HPLC.
    * EPA method number to be assigned.
    

    -------
    	 ..
    		 	 TAH1.1l
    
    COMf'OUHOS
    MtO!1 KF.I.KVANl
    WASThWATl-R
    . 	
    
    
    
    
    
    lllf Incut
    
    
    fif t Jiient
    
    
    
    
    MiiMifdCt tiring Hai kground
    
    
    lid4 fcgf 0«(II<1
    
    
    
    H.-llio.l
    
    Site3 (|*g/£)
    
    X R
    
    (mis/*)
    X K
    604
    IllllOSfl)
    A 460
    840
    86, 98
    30
    420
    69,
    74
    60S
    Clilorobcuzi lute
    U 99
    ion
    26, 48
    5.2
    4
    118,
    172
    
    Clilur(i|>ropylaLe
    11 < 1 .0
    
    
    < 1.0
    10
    129,
    130
    
    Clt)oroite|>
    C 33
    16
    46
    0.3
    0. I
    63
    
    
    |)iiu owui It Joro)>rt>|jaue
    D < 0.005
    1.2
    74, 87
    < 0.007
    1.2
    73,
    32
    
    Kir itliazole
    E 0.010
    1
    81, in
    < 0.006
    1
    92,
    100
    
    IM^NU ^
    e so
    100
    20, 16
    
    -
    
    
    619
    Atuci i yn
    B 16,000
    20,000
    111, 96
    31,000
    40,000
    125,
    1 I 1
    
    Ai rail»e
    B 1,500
    1 ,500
    m, 100
    1, 100
    1,200
    142,
    129
    
    ProiucLoit
    ft 140
    150
    126, 98
    164
    200
    135,
    117
    
    fa omulryu
    It 9, .100
    10,000
    80, n
    955
    1 ,000
    123,
    91
    
    Fl ojia^ilkC
    U 90 0
    ] , 000
    105, 11
    280
    300
    122,
    109
    
    Simclryii'
    H 130
    ISO
    198, 168
    270
    300
    194,
    169
    
    Sicnazifte
    B 420
    500
    122, 103
    180
    200
    104,
    93
    
    Terbutyluzine
    n 450
    500
    126, 101
    230
    300
    105,
    94
    
    Toihid ryn
    11 . 440
    500
    111, 10)
    140
    200
    91 ,
    83
    622
    c±:\
    Aziii|ilio& (uc'Lliyl
    V
    *'•
    1.
    6
    101
    
    <*
    i.
    
    6
    69,
    101
    bu 1 bl »i r
    ¥
    &
    1.
    10
    77,
    1 1 1
    i.
    
    5
    85,
    94
    Cuuwcjihns
    V
    il>
    lt
    9
    131,
    256
    1,
    
    9
    213,
    255
    Deujctoii-0
    V
    A"
    8
    v:»,
    78
    i-
    
    a
    rit
    80
    IVou'loii-S
    V
    
    2.6
    i/
    
    .. u
    i.
    
    2.6
    o.
    0
    |)» so 1 I oi on
    F
    A1'
    17
    129,
    141
    i.
    
    17
    93,
    9 1
    Fc!I81I 1 f Ol i| i OU
    F
    *b
    l.
    360
    89,
    139
    .~ i>
    i.
    
    360
    72,
    78
    ( Clllfl 1 IM|
    F
    .. **
    8
    43.
    41
    
    
    8
    60,
    42
    litAr.ilc
    F
    i1*
    10
    47
    
    i.
    
    10
    57,
    69
    Ti i ilt 1 (it y i'i /os
    0
    1,
    3
    l)l*
    81
    
    
    3
    104 ,
    102
    liounc 1
    0
    J u
    3
    93,
    80
    
    
    3
    68,
    60
    Jij .iziiion
    U
    41
    15
    110,
    13/
    1
    1
    4.3
    108,
    108
    hi i:hlorvos
    0
    < 2
    4
    120,
    1 10
    <
    2
    4
    89,
    1 10
    Mcvtii|'hos
    1)
    , < 2
    4
    86,
    92
    <
    2
    4
    120,
    78
    N-l.-.l
    1)
    7.2
    4
    60,
    80
    <
    2
    4
    95,
    90
    ill. 1 toftlH
    0
    < 2
    /,
    1 10,
    120
    <
    2
    4
    120,
    98
    tlOCA
    If
    212
    200
    45 ,
    56
    < )
    0
    20
    87,
    93
    
    
    
    
    
    
    
    
    10
    /y.
    44
    (< mil ifulfil)
    

    -------
    TABLE 6 (continued)
    Influent		Affluent
    
    
    Manufacturing
    Background
    Added
    
    
    Background
    ! Added
    
    
    Method
    Compound
    Site3
    (Ms/«)
    (Mg/i)
    t K
    
    (M8/*)
    
    1 R
    628
    Carbofuran
    I
    600,000
    -
    -
    
    < 5
    13
    120,
    108
    629
    Cyanazine
    n
    -
    
    lusul ficienL
    sample tor
    quantitation
    
    
    631
    Caibendaziw
    J
    6 ,000
    -
    -
    
    190
    230
    138,
    120
    
    Benotnyl
    C
    164
    
    Insufficient
    sample for
    quanli talion
    
    
    632
    Diuron
    C
    240
    250
    108,
    212
    110
    100
    91,
    101
    
    Limuon
    C
    47
    50
    66,
    130
    21
    50
    56,
    42
    
    HeihoutyJ
    C
    300
    250
    148,
    170
    41
    100
    59,
    55
    
    Kluorioetron
    U
    880
    1,460
    90,
    94
    870
    1,280
    80,
    76
    
    Oxdnty 1
    J
    "h
    -
    -
    
    *>'81
    200
    93,
    97
    
    Propachlor
    G
    aO
    " 1,
    200
    56,
    68
    
    100
    98,
    89
    
    Propoxur
    F
    •v"
    100
    63,
    68
    
    100
    71
    
    633
    Droiuaci 1
    C
    5,990
    6,450
    102,
    88
    2,433
    2,700
    109,
    126
    
    ]|exo2 inonc
    C
    1,715
    2,000
    137,
    83
    767
    900
    95,
    108
    
    Teibacil
    C
    <1,165
    -
    
    
    1,675
    1,800
    104,
    119
    
    DKKT
    K
    270.000
    270,000
    110,
    110
    590
    540
    106,
    103
    
    Met ribiizin
    F
    
    200
    79.
    41
    *D
    K
    200
    41.
    50
    
    Triadmefon
    F
    *b
    92
    74,
    63
    jul)
    92
    100,
    94
    
    Tricyclazole
    L
    960
    684
    82,
    74
    < 0.2
    0.8
    94,
    97
    634
    Piperalin
    1.
    334d
    375
    75,
    58
    °f
    7.1
    
    
    
    
    
    
    
    
    0
    162, 101
    95,
    87
    635
    Piperony] bntoxi de
    K
    270
    240
    103,
    115
    0
    10
    96.
    101
    **
    Aldicatb
    D
    u'1
    50
    28
    56
    h26
    20
    50f
    50
    ¦kit
    Tokutbion
    F
    
    21
    43d
    
    A
    64
    36
    
    a Identification of site on file at KHSL-Cin.
    b Data 011 file at ENSI,-Cin.
    c Mean of triplicate analyses.
    d Sample collection point designated only by number 7.
    e Sample collection point designated only by number 4.
    f Sample collection point designated only by number 6.
    ** EPA method number to be assigned.
    

    -------
    REFERENCES
    1.	Federal Register, Vol. 44, No. 233, p. 69464 (December 3, 1979).
    2.	Austin, D. J., A. Lord, and I. H. Williams, Pesticide Science, Vol. 7,
    p. 211 (1976).
    26
    

    -------
    Figure 2. GC/FID chromatogram of the dinoseb standard (168 ng).
    27
    

    -------
    Figure 3. GC/ECD chromaCogram of chloroneb standard (3 ng).
    28
    

    -------
    Figure 4. GC/ECD chromatogram of the chlorobenzilatie standard (3 ng) .
    

    -------
    Figure 5. GC/ECD chromatograw of the chloropropylace standard (3 ng) .
    

    -------
    Figure 6. GC/ECD chromatogram of dibromochloropropane standard (0.3 ng) .
    31
    

    -------
    Response @ 16 x 10"^
    Injection
    
    "Etridiazole
    
    ' I l
    1 2 3
    Minutes
    Figure 7. GC/EC chromatogram of etridiazole standard (100 pg).
    32
    

    -------
    Figure 8. GC/EC chromatogram of pentachloronitrobenzene standard (1 ng).
    33
    

    -------
    0	5	10	15	20	25
    Minutes
    Figure 9. GC/TSD chroma'togram' of mixed triazine pesticide standard
    (1.1 ng) oti a Carbowax column.
    34
    

    -------
    Figure 10. CC/Fl'D cliroinatogram of mixed organophosphorus pesticide standard 5 ng) .
    

    -------
    Diaiinon Standard
    (lOng)
    '-Injection
    Minufes
    Figure 11. GC/FPD chromatogram of diazinon standard (10 ng)
    36
    

    -------
    Response @
    lO^x 16
    Figure 12. GC/FPD chromatogram of methyl parathlon and methyl paraoxon.
    

    -------
    Diclilorvos
    Figure 13. CC/FPD cliroinatogram oE mixed pesticide standard (1 ng) .
    

    -------
    Figure 14. GC/FPD chromatogram of ethoprop standard (0.6 ng).
    39
    

    -------
    figure 15. GC/FPD chromatogram of ronnel, chlorpyrifos methyl
    and chlorpyrifos standard (2 ng).
    

    -------
    MOCA
    (250ng)
    3
    I
    O
    c
    o
    0.
    V)
    V
    Injection
    Figure 16. GC/TSD chroraatogram of MOCA standard (250 ng)
    41
    

    -------
    0.018
    0.016
    0.0U
    0.012
    0.010
    5 0.008
    "5
    0.C06
    0.C04
    0.002
    1
    VJ
    , ¦ • ^
    Injecnon
    Minu fes
    Figure
    17. HPLC chromatogram of carbofuran standard (500
    42
    

    -------
    Min'jfw
    Figure 18. GC/TSD chromatogram of mixed tirazine standard
    (1.1 ng) on the SP-2250 column.
    43
    

    -------
    3
    <
    U")
    O
    o
    @)
    c
    o
    Q.
     "
    0)
    Cyanazine
    t_ In!
    Injection
    5	10
    Minutes •
    15
    Figure 19. HPLC chromatogram- .of cyanazine standard (0.5 yg).
    44
    

    -------
    Oxamyl
    "D
    <
    m
    o
    o
    o
    <§>
    c
    o
    CL
    l/l
    v .
    J
    L
    
    Carbendazim
    
    
    J
    0	5	10
    Figure 20. HPLC chromatogram of oxamyl and carbendazim standard (100
    45
    

    -------
    Mefhomyl (1/i.g)
    /
    Diuron 0. i^ig
    Linuron 0. \pg
    /
    Figure 21. HPLC chromatogram of rnethorayl (1 lig) , diuron (0.1 pg) ,
    and linuron (0.1 ug) standard.
    46
    

    -------
    0.004 -
    0.003
    a
    T
    4
    0
    1
    0.002
    0.001
    Minute
    Figure 22. HPLC chromatogram of fluotneturon standard (20 ng),
    47
    

    -------
    W)
    LU
    ZD
    <
    UO
    O
    o
    c
    o
    a
    
    -------
    a Solvenr
    zi
    <
    '=>
    u
    2
    J
    t_ Injection
    I	I
    
    Propoxur
    ( 'M9)
    1
    Minures
    Figure 24. HPLC chroraatogram of propoxur (1 ug).
    49
    

    -------
    JV
    !n|ecfion
    t I I
    ! 	I
    12 3 4
    Minufes
    Figure 25. GC/TSD chronatogram of DEET standard (500 ng),
    50
    

    -------
    Terbacil
    500 ng
    I	L	I	I	I	I I I I I
    0123456789
    Minutes
    Figure 26. GC/TSD chromatogram of terbacil (500 ng), bromacil (500 ng),
    and hexazinone (100 ng) standard.
    51
    

    -------
    Carbendazim
    0	10
    Minutes
    Figure 27. HPLC chromatogram of carbendazim standard (20 ng).
    52
    

    -------
    Mef ribuzi n
    t
    Hnjecfion
    I	I	I	!	I	I
    0 12 3 4 5
    Minures
    Figure 28, GC/TSD chromatogram of metribuzin (1.4 ng) and
    triadmefon (1.1 ng) standard.
    53
    

    -------
    Tricyclazole
    118 ng
    
    -------
    — Injection
    10	12
    U
    Minutes
    Figure 30. GC/FPD chromatogram of tokuthion in a
    mixed pesticide standard.
    55
    

    -------
    Figure 31. GC/TSD chromatogram of piperalin (8.45 ng).
    56
    

    -------
    CO
    u.
    D
    <
    o
    o
    o
    @
    o
    Q.
    M
    £
    
    200 ng
    Piperonyl
    Butoxide
    Standard
    0
    10
    15
    Minutes
    Figure 32. HPLC chromatogram of piperonyl butoxide standard.
    57
    

    -------
    C-l
    ©
    X
    03
    o
    3»
    0
    a
    u
    OS
    
    -------
    Ufar* Civonue
    
    Tigure 34. .Chromatograms of extract for chloroneb analysis before
    and after cleanup (manufacturing site C).
    59
    

    -------
    3*'*ot C'venva
    o	>	i	6	j	»o	i;	:•»
    Tim* Miaui»i
    Figure 35. Chromatograms of extract for etridiazola analysis
    before and after cleanup (manufacturing site E).
    60
    

    -------
    Sefore CWanvO
    *
    *
    I
    JV
    
    Figure 36. Chromatograms of extract for PCNB analysis before and
    after cleanup (manufacturing site E).
    61
    

    -------
    Xfttt
    rlontil
    CIwxjO
    /
    —IniMh'or
    0	2
    Hm*. Mjmrfti
    -'^A'
    Aftvr HPVC
    C/ana«llW
    I
    figure 37. Chromatograms of extract for cyanazine analysis; upper GC/TSD
    after Florisil cleanup, lower HPLC/UV without cleanup.
    62
    

    -------
    Before Cleanup
    "Injection
    10
    Time. Minute!
    12
    After Cleanup
    -Injection
    Time, Minutes
    10
    Figure 38. Chromatograms of extract for propachlor analysis before
    and after cleanup (manufacturing site G).
    63
    

    -------
    Ctonuo
    Aff«f Cleanup
    
    Mnj#eriOft
    I	L.
    0	3	10
    Tim*. Mi(Vfi
    0	5
    TIm. MIihitm
    Figure 39. Chromatograms of extract for propoxur analysis
    before and after cleanup (manufacturing site F).
    
    

    -------
    *
    V
    Figure 40. Chromatograms of extract for netribuzine analysis
    before and after cleanup (manufacturing site F).
    65
    

    -------
    APPENDIX
    CHEMICAL INFORMATION ON STUDIED COMPOUNDS
    OH CH3
    1 ,1 H
    NO?
    OiS tfocanciacura: 2-<'Sac-ScvrLi -
    iimirsonenai
    Trada !fasas: Cr.ecox, Sabiiiss. ?r
    N.-.c x-Vasa, 5 :c T-«
    Sucerssvca::
    Jhioroneo
    .ia-icuiar .'d^sn::
    0Ci:
    CA3 :iace_=-cii:--ri: L,--ci;r.ij7
    :er.:ar.e
    "rada :.'ac:as: ^a^sar., tirsan
    :raiic-ii.ir ;r.:: Z j
    Lnicr3oen:^j.it;
    —i"—]
    ChlorooroovLacs
    CAS :io=er.ila:-ri. Zz?".
    iicsijrssar.iilaca
    Trua :!a=es: Acari=ir.. .icarzi
    Aicar "oiiax.
    >'.OL4Cvu.ar
    
    CAS h'csar.ciazura: IjOTrrc/l -
    3-aniiiac2
    Trads Vases: Ac^rslara, "ssa-'.
    r.csw ir.. ^-2-1:3
    Jtoiacuiar "aLir.z: ]3C
    66
    

    -------
    Jibroaochlars^rjoar.e
    C2->3r-G-3r-CHiCl
    CAS Moaenclacure: L,2-01bromo-3-
    chloroFropane
    Trade Mames: Nemabcom, D3C?, Tuxazone,
    Neaatame, Maaa?on, OS-1397
    Molecular Vaigac: 236
    la:sle
    1CC>e;
    CAS XoaancIacur9: 5-«choxy-3-(cri-
    cnloronechyD-L,2,i-
    cniadiazol
    T*ada names: xqaan, Tarrasole, Truoan
    Molecular '.'eight: H7.i3
    ?^acachlor3P.i:roaen2ane
    CI
    CI
    CAS ttomeaclacure: ?ancachloronicro-
    benserte
    Trade Manes: Terracloc, Brassicol,
    Tricisari
    Molecular Weigne: -95
    ::o-
    
    CAS .vromenciacure: il-«cayl->T-( l-^echvl-
    achyL)-o-(oechvichio)-
    l,J,5-cria2ine-i,--
    diaaine
    trade Maaes: Cesapax; G-}t*rioZ\ I"IX
    Molecular Veighc: 227
    Airaziae
    
    CAS "anaaciacura:
    S-cr.iora—tf-ec'nyi-j'-
    (I-aeer.yLaer.yD-i.J.j-
    tnaziae-J, Wlaaiae
    Traaa "aaa: AacrsaO
    A:rac3 i.'S
    3esasris-5
    ?r-_=a;oi.-3
    1 ar	Xi . 3
    67
    

    -------
    CAS ifoceiciiZ'ira:
    ??caegr''ti8
    '! '
    a
    
    CAS :>oaa-c-ar^ra:
    )l .^T-bis (l-aechvLacnyl) -9-
    (2aciivL;r.io)-i,3, j-
    criasisa-Z, diasiza
    Trade Xdse: Cararci.
    •3asa$ari
    ?73©ecr/-a
    'lalacuiar	;•!.
    CAS tfoaeaciacuTs:
    5-chiar^-i^,.r--5131' 1-cacr.vL-
    ¦icr.vi.) -L. J, j-snasisa-
    
    i| 1
    Sv^JT
    Trada '.'aze: G-!G023^
    '	C^SaS!,!"—
    68
    

    -------
    azir.e
    I
    
    CftS ^ocer.c-acora:
    5-cr.ioro-'{ .I'-du ".-•.* 1- L. J,
    :riA2iiQ- i>laaisa
    .riaa ..aae:
    ^.w .
    err
    •Z*i 37-17592
    'r^sasaiV
    ^lalacuiar tfeijhc: Z0L.3
    ¦seer^ne
    -. - -•	CA3 Matneaciacurs:
    i
    :i x-*	St:T-4iaca7L-o-(sechyi5hio)-
    1, J, cri42t2®'~2 * i-^iiasiiiia
    :rac2a5
    Trada "Jaca: 0-329II _
    SiiecTvr.c?
    I'.oLacuiar '.'aishc: -13
    iriucvi32ir.a
    .j
    CAS MoceEciac'-jra:
    i-:.-.iorc-\J-\ 1.l-cinac.-.v
    acr.vi) -S—sc.r/L-1, j ,i-
    :riasir.e-i, iiasisa
    Trace '.lane:- 33—L3529
    ^oiacuiir "reijh;: I-?
    
    ..r.—. ,a.
    CJ%S :fotspr.cl2C^ra:
    :i-(if.-di3ecr.7iacn^L)-y-
    dchvl-6-	) -
    3 ~i-criasiia-2, —
    iiarn-e
    "race Mane: JS-1-260
    Ir.?ran^
    Prabac,^
    lla L±cular '*-ii?r.c: Z-I
    69
    

    -------
    kz.T.s ho sea : * v I
    
    ci-,f ^3 :r
    
    CAS liocanciacur*:
    0,0-dira :hv i. : no S3 ho rc ci ;hia-
    -i;a 5-sacer vi::i 3-(3ar;aiC3
    -sachv!.)-!, 2,3-oaniocriazii
    Trada "ara: Guaashion^
    'ju:r.iaa®
    Cj tr.lJr.-ca I'""
    Maiacuiar Veijhe: 317
    Boljcar
    CAS '.ioEar.cia:-irs:
    hc~l~(~V :--C.
    \ss/	s	2'—3 >„i-Csecr.ylcr.io)ohassyl j 5-
    srsoyl ?hossr.crcci;r.icaca
    Trace "Taae: 3cl3:ar
    3aZ '.mi ? 2C6
    Molecular	IZZ
    CAS Horer.clic'-ri '•
    0 .C-iiacxyl 0-\>cnl:r3-^-
    2ecr.^l-*-c3usarin''l)
    raoscho ro cr.iaaca;
    .-,£-0	^		3-cni3rs-«-secr.,irL-"-':c'i=arir-vl
    : C^) I I j	ciecr.yi snoschorachiaaca;
    3-cr.lor3-7-"ivcr3:c*-i-2acr.7l
    C3u=ari.i O—ascar *.i:h 0,0-
    disac.v/l pr.csohorocr.ijaca.
    Trada 'lace: .;-Sun;2
    1 Cj-Sar® _
    ^useacax7
    P-asiux'S
    7 — tj-rai'—
    3-:i/199
    Moiicvilar •¦ej.?.-.:: ;S2
    70
    

    -------
    a ^iic-ura of:
    	desasan - 0
    ¦>	5—C
    cI?.j3-^"**0
    ia=at3ti - S
    "crsail/ tsr.taizs about:
    6i.T o: C-ijccer
    3;^ of S-ijoinar
    CAS irane=sia:-jra:
    ieaetan-O: 0,3—iiathyl 0-[2-
    (athylthio)atnyl!
    jnoaafcorstnioaca
    iasatan-S: 0,3—iiathyl 5-,'t-
    (sthylthialathyll
    ?tiasono-3Cnicaca
    'race :iica: sertaotaanos
    Syszox&
    3-3173
    i'siicular Vai?r.c: 253
    -JoU_T3t3n
    CiS ttoeaaciacura:
    :-.SsO'
    0,0-diathyl S-fZ-(athy
    athyl] pnoaohorjc.-ijaci;
    3 - (; —st.-.y 1 :hi j-s shy 1;: r-.c s o r.s
    ot.-.ijlachitnata.
    Crada :iaaa: Si-iystrr.^
    r^L5tir,a^ "run:
    iolnrsx ~
    3-;5-jl9
    :iaiac-iiar ¦'ai?.-;: 17-
    z-ar.sulutr.loa
    CAS Mo^aaciatura:
    ^ —3c_,-^3	0,0—aiath7i 0-f'--<=ecr.ylaul-
    		iiayDanaarl lahosar.arsthuata:
    diethyl i-CsachyLjuiiisvL)
    pr.snyl ahosonorathioaata.
    trada Maaa: Oaaar.it^
    tarrac'jr 5^?
    3-Zfl-L
    2;'£?
    llalacular "aij":
    71
    

    -------
    : sair ion.
    /^Tv _
    3
    CSt
    ?'-.or3ia
    
    CAS v'ouaaciacura:
    0,0-
    -------
    .OKUCniO^
    
    CAS Somenclacure:
    C-i;nyi-0-(3, --diir.lcra-
    ?r.aayL)-5-9r:oyi3cios-
    pr.orsaiihijaea
    Trad a Jfaco:
    3ay JiTII 35i»
    Moi.ecui.ir "signs: jii
    Diaziaoti
    ;:;h3o):?o-^
    CAS >Ioaacciac-jra: Q,C-4iasayi.
    0-fS-aBCiyl-i-Cl-caca/LacIiyi)-
    1-n-v—	-- ^--y' j pr.osjnoro
    Trada Manas: 3asudii, "acciioi
    Mucicoi, Soectraciia
    Molecular '.Jeignc: 304
    :i
    ; 3-0)-fCCS-CCl,
    CAS '.ToEenciacura: 3.;i;r.Z.3rc-
    aehacyl dizecivL pnossnaca
    Trade :iaaas : Har'ioi, llojos , ??uvan
    Phesui:, 7a?otia
    Molecular Valine: 230.98
    CAS Xozaaelacura: Maciiyl 3C(ci
    aacr.yL3:ty?r'-oapaix'I!oxy; -1-
    •? -i,	jucaaoace
    ¦I /" •>
    ,C2-0).."3C :
    ^CiCOCiT	Trsda :iaae: .-hosmn
    Mclacular Vaij.ic: 32i
    73
    

    -------
    ::alad
    ^ . 3R	?r.ossr_aca
    II
    E3O)??OCH
    Stirafas (cacrschlorvinphos)
    -:.",Q3roo
    
    CAS ;Tooetici3C'-r3: '-,2—iiircca-
    2,2~iicr.isT3acn?l iirecr.yl
    ,C1	Trade Mara: Dibron
    Vc^:i
    ^3^	MoLecular Vaighc: 380.30
    CAS N'onecclacura: (Z)-2-chi3rc-
    iccao, PTrcnos
    - "''s
    Molacuj.ar ^eigr.t:
    CAS lloaenclacura: 0,C—Diascr.yi-
    C1	0-(2f-,i-":r--r.i3r3or.aayi) ?hos-
    1
    mcrcc-isasa
    \ 11
    CH-0) -rrC^sy	tride liaces: Korlaz. '.lowacr.
    Troiesa
    Molacuiar Veignc: 321
    74
    

    -------
    Chlor3vrizo3
    Cia :roB«sclieura: O.r-Olaair.vL
    0-<3,3,3-criciior;-2-?7Ticir.v
    phosphorschioaca
    .1 | I
    -la5-')	Tr»• :ihc:ch->
    i J
    0
    CA3 :tccar.siacurj: Mac;:
    amir.21 carsacvl [ - iZ-baMisi;a;
    :¦• L jara " a
    Traca Manes: 3eniica, Tar jar.
    Ma lic-ilar	290
    75
    

    -------
    Carjanaaila
    ^^>_rH-CCCK3
    CAS ManeaciiC^ra: '.•',a:.v?L l-r>
    3emi=ida:ai-ivi.iar:aci;i
    Traie :taaes: 3a::i3Ci=. jsrssal
    Molacular 7eigr.:: 191
    0:car.v'i
    0 3 'c
    CAS Scaanciacura: Ma:r.yi
    -aci'/iiai-3)[ (;a:.v/l iair.3)-
    carioayi Jo?:/; - ^-oxae^ham^icocsio-
    ata
    "raaa 'lace: Vvaaca
    :!olecular VaLghc: 119.3
    . J	\ 'I
    CAS Moaaaciac-ra:
    3-( 3, i—iichisrochar.vi) -L, 1—ii-
    ^ochvluraa
    Msiacuiar = : 233.i
    -ir.ur^n
    / V 1
    \ Vrr:ci(C23)-.:-C2j
    „«-v-s .ioaescia:ura:
    ir* — ^ 3, i^cniaroanenv Li -.f-chore* ¦
    i'-tecr.vluraa
    Molecular V^ijnc: 2-9.1
    Ma: hoc i
    CAS 'loaanclac^ra:
    MechvL i* (zscr.vi.asir-c") ;ar:cTiyl
    i:r/; achac-^iiocr.icazs
    .race lianas: .ar.na;a
    Molacula; 'U-ir.c: lil
    76
    

    -------
    CAS Maicer.ciacura: l,l--ji:^c.-.Ti-3-
    (a,	uraa
    CA3 :lo.: 2154-17-2
    Traea :ta=«s: Cocaran, CI3A-I05?
    Molacuiar '."eij.-i:: 231
    jcac.ilor
    CXS '.Iomeaci.ac.i-s: 2' -ciiiora-M-
    iioarapy'.acecanilida
    Trada '.Tanas: Rasrsc
    '.'.aiicuiir Vaijl-.c: lli.T
    CAS :ioaecciac-ira: 2-(L-ca civ 1 ache :c
    jr.anyi -eccivl iarjasaca
    Trad a "anea: 3a7jon, 3Ia::a=ex,
    '.laUcuiar Vaijiic: 209
    CAS "oner.clirura: M,:i-3iacr./i-i-rac
    banzamia
    Traca Maces: Caac, Oaiphesa, '.iaca^a
    Hoiacular j'eij.-se: 151.3
    77
    

    -------
    Tir^aell
    
    V ''""3' 3
    CAS !tonancj.ae\ir#: j.-Chiara-
    2-(i,l-
    -------
    La£-a:an
    Ca3 '.Tocaaciicura: l-(--r-.l2r35r.ar.5x:.')
    3, j-diarchy1-1-(IE-1.1.
    1-/1) -2-oucanooe
    .0-C3-C-:(C3->,
    i	J -
    ^ rk;:
    Trade iTaaa: 3ayljcon
    X9iae-ii.ir	133.!
    .ric-.-ilazola
    CAS Mocaaciainra: j-Mac-Tl-L.I,
    triisaLo-i 3 .--0
    Triis Macs: Tricyslaisii
    Xclaciiar	1:9.:
    -2H5O ^ 3
    J — Q.
    - C j K 7 3
    \J~a
    CAS Mooeaciacuce: 0-*tavi~3-(2.i-
    dicaiaropaeayi )-5-?ropylpr.o$pnoro*
    diiaioaca
    Trade Samel: Toiuthioa; 3Ai" NTM 3629
    Molecular Veigac: 3^4
    Plperalin
    ,CHn
    , , 33 0
    ! 1	'(
    CVS Noneaciature: J-fZ-fletliylpxper-
    idiao)prooyi-i,
    dicUocooeczodce
    Trade Names: Piproa
    Molecular Veijsc: 230
    Pigerop.yL 3ucaxi.de
    C3H7 CH^OCotf^CC^OC^Hg
    \	/
    //
    0 0
    CAS ^omeaciacure: i-f[2*(2-buco*7-
    ecaoxyjecioxy laewyi j-6-pr)pyl-
    l ,J-oea2odioxole
    trade Haass: 3utocide
    Molecular Veijat: 338
    0 CH3
    fi3C-'/H-j-0-VsCH-C	3-:h3
    ch3
    CAS Voneaciacurs• (^echylainifto)-
    (carboayi))oxiae
    Trade Mames: Tenik
    Molecular Veight: 190.3
    79
    

    -------