svEPA
United States
Environmental Protection
Agency
Environmental Research
Laboratory
Athens GA 30605
EPA-600 4-78-056
September 1978
Research and Development
Organic Compounds in
Organophosphorus
Pesticide
Manufacturing
Wastewaters
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1 Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161.
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ORGANIC COMPOUNDS IN ORGANOPHOSPHORUS PESTICIDE
MANUFACTURING WASTEWATERS
by
M. Marcus
J. Spigarelli
H. Miller
Midwest Research Institute
Kansas City, Missouri 64110
Contract No. 68-03-2343
Project Officer
Arthur W. Garrison
Analytical Chemistry Branch
Environmental Research Laboratory
Athens, Georgia 30605
ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ATHENS, GEORGIA 30605
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DISCLAIMER
This report has been reviewed by the Environmental Research Laboratory,
U.S. Environmental Protection Agency, Athens, Georgia, and approved for publi-
cation. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does men-
tion of trade names or commercial products constitute endorsement or recommen-
dation for use.
ii
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FOREWORD
Nearly every phase of environmental protection depends on a capability
to identify and measure specific pollutants in the environment. As part of
this Laboratory's research on the occurrence, movement, transformation,
impact, and control of environmental contaminants, the Analytical Chemistry
Branch characterizes chemical constituents of water and soil.
The toxicity and persistence of pesticides and their decomposition
products are problems of major importance to those concerned with environ-
mental quality. In addition to evaluating potential problems associated
with the application of pesticides, environmental concern has been directed
toward identifying and quantifying specific compounds associated with pesti-
cide manufacturing effluents. This report examines organophosphorus pesti-
cide plant wastes, which are of particular importance because these pesticides
are among the most toxic compounds produced in appreciable quantities in the
United States.
David W. Duttweiler
Director
Environmental Research Laboratory
Athens, Georgia
iii
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ABSTKACT
The major goals of this program were to develop preliminary survey in-
formation on the organophosphorus pesticide industry wastewater streams and
to develop analytical methods to monitor levels of organic compounds present
in these streams. The identification and quantification of organophosphorus
compounds were emphasized, but nonphosphorus chemicals were also included in
the survey. A secondary goal of the program was to use the survey information
to evaluate the efficiency of various waste treatment processes.
The wastewater from five pesticide plants that produced eight organophos-
phorus pesticides was sampled. The pesticides were: diazinon; methyl para-
thion; azinphos-methyl and disulfoton; fonofos, phosmet and bensulide; and
EPN. Samples were taken at pre-, mid- and posttreatment locations.
The analytical methodology included extraction and partitioning, gas chro-
matography with specific element detection, thin-layer chromatography, infra-
red spectroscopy and gas chromatography/mass spectrometry.
Methods and procedures were developed by analysis of (a) distilled water
samples fortified with model compounds and (b) an actual wastewater sample
from the azinphos-methyl/disulfoton production plant.
The 116 compounds identified included organophosphorus pesticides, re-
lated organophosphorus esters, organophosphorus acids, volatile organic com-
pounds, thiocarbamate pesticides, triazine herbicides, and miscellaneous ex-
tractable process chemicals, by-products, and compounds of unknown origin.
The levels of parent pesticides in the final effluents were below 0.005
mg/liter. Oxygen analogs of the pesticides were not a significant degradation
product of any of the waste treatment processes. Phosphorothioates and organo-
phosphorus acids were only partially removed by the treatment processes, and
were observed at the parts per million levels in some final effluents. Phenyl-
phosphonate esters closely related to the parent pesticides were observed in
a final effluent sample at parts per billion levels. Volatile organic compounds
were effectively removed by the treatment systems with the exception of one
totally enclosed system. One effluent which was disposed in an injection well
contained over 150 mg/liter organic disulfides, almost 200 mg/liter thiocarba-
mate pesticides and over 100 mg/liter organophosphorus acids.
IV
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Recommendations were made regarding further work in treatment system eval-
uation, synergistic toxicity studies of organophosphorus compounds, analytical
method development, and the fate of wastewater in injection well systems.
This report was submitted in fulfillment of Contract No. 68-03-2343 by
Midwest Research Institute under the sponsorship of the U.S. Environmental Pro-
tection Agency. This report covers the period June 30, 1975, to November 29,
1977, and the work was completed as of April 17, 1977.
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CONTENTS
Foreword ill
Abstract iv
Figures , viii
Tables ix
Acknowledgments xi
1. Introduction 1
2. Conclusions 2
3. Recommendations 4
4. Experimental 6
Sampling 6
Analytical procedures 7
5. Selection and Sampling of Production Facilities 19
Site selection criteria , 19
Pre samp ling surveys , 19
Field sampling summary 19
6. Results and Discussion. 21
Identified compounds 21
Production sites , 30
Methods development 67
References 75
Appendices
A. Nomenclature 76
B. Mass spectra of identified compounds not present in the MSSS
library 81
vii
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FIGURES
Number Page
1 General sample fractionation scheme 9
2 Analytical scheme for organophosphorus compounds 10
3 Wastewater treatment sampling points for diazinon production • • 31
4 Wastewater treatment sampling points for parathion production. . 37
5 Wastewater treatment sampling points for disulfoton and azinphos-
methyl production 45
6 Wastewater treatment sampling points for fonofos, phosmet and
bensulide production 52
7 Wastewajter treatment sampling points for EPN production 62
Vlll
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TABLES
Number Page
1 Gas Chromatographic Parameters 13
2 Instrumentation for Analysis 13
3 Gas Chromatographic Parameters for Parathion Analysis 14
4 TLC Solvent Separation Characteristics 14
5 Gas Chromatographic Parameters for VOA 17
6 Field Sampling Summary 20
7 Concentration of Compounds Identified by Sample Location
Concentration 22
8 Priority Pollutants Detected in Phosphorus- and Nitrogen-
Containing Pesticide Wastewater Samples 30
9 Concentration of Identified Compounds in Diazinon Production
Plant Wastewater 34
10 Acid Analogs of Identified Esters in Diazinon Production Plant
Wastewater 35
11 Concentration of Identified Compounds in Parathion Production
Plant Wastewater 40
12 Acid Analogs of Identified Esters in Parathion Production Plant
Wastewater 41
13 Concentrations of Identified Compounds in Azinphos-Methyl and
Disulfoton Production Plant Wastewater 47
14 Acid Analogs of Identified Esters in Azinphos-Methyl and
Disulfoton Production Plant Wastewater 48
ix
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TABLES (continued)
Number Page
15 Concentration of Identified Compounds in Fonofos, Phosmet
and Bensulide Wastewater 56
16 Acid Analogs of Identified Esters in Fonofos, Phosmet and
Bensulide Wastewater 57
17 Concentrations of Identified Compounds in EPN Production
Plant Wastewater 64
18 Acid Analogs of Identified Esters in EPN Production Plant
Wastewater , '. 66
19 Distribution and Recovery of Organophosphorus Compounds 68
20 Pesticide Recovery Data 69
21 Rf Matches for "Protocol" Sample (2004) 72
22 Organophosphorus Compounds Identified in Protocol Samples. ... 74
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ACKNOWLEDGMENTS
The authors appreciate the support, useful suggestions and efforts of
Dr. A. W. Garrison of the Athens Environmental Research Laboratory.
The following staff members contributed to this program: J. Downss J.
Middleton, M. Woodfin, G. Radolovich, G. Vaughn, P. Kuykendall, D. Sauter,
and M. Serrone. Their assistance is gratefully acknowledged.
The cooperation of the personnel from all five pesticide production fa-
cilities is very much appreciated and was necessary for the success of the
program.
xi
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SECTION 1
INTRODUCTION
The possible hazardous effects of many chemical pollutants have stimu-
lated efforts to identify and quantify specific compounds associated with var-
ious industrial effluents. The nature of organophosphorus pesticide plant ef-
fluents is of particular importance because organophosphorus pesticides are
among the most toxic compounds produced in appreciable quantities in the
United States.
The major goals of this program were to develop preliminary survey in-
formation on the organophosphorus pesticide industry wastewater streams and
develop analytical methods to monitor levels of compounds present in these
streams. The identification and quantification of organophosphorus compounds
were emphasized, but nonphosphorus chemicals were also included in the survey.
A secondary goal of the program was to use the survey information to evaluate
the efficiency of various waste treatment processes.
Presented in this report are the following: the conclusions and recom-
mendations resulting from this study; the experimental methods; the selection
and sampling of production facilities; and a discussion of results. The results
are discussed for each class of compound identified, each production facility,
and analytical method development. Appended to this report are nomenclature
and structural information for organophosphorus compounds and the mass spectra
of the compounds identified that were not contained in the Mass Spectral Search
System (MSSS)* at the time of this study.
* Mass Spectral Search System, ADP Network Services, Cyphernetics Division,
Copyright 1975.
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SECTION 2
CONCLUSIONS
* The analytical methodology developed and applied in this study was
successful in identifying and quantifying organic compounds present in pre-,
mid- and posttreatment samples of five organophosphorus pesticide manufactur-
ing plants. The compounds identified were classified as follows: organophos-
phorus compounds, 47 of them ranging in concentration from 0.01 to 50 mg/liter,
including organophosphorus pesticides and oxygen analogs, and organophosphorus
esters and acids; volatile (purgeable) organic compounds, 24 of them ranging
in concentration from 0.004 to 1,400 mg/liter, including alcohol precursors,
process solvents, chlorinated hydrocarbons, alkyl sulfides and disulfides,
and miscellaneous compounds; nonpurgeable nonphosphorus compounds, 45 of them
ranging in concentration from 0.01 to 120 mg/liter, including triazines and
thiocarbamate pesticides, precursors and by-products, and compounds of unknown
origin.
* The levels of organophosphorus pesticides in the final effluents were
low, generally below 0.005 mg/liter, indicating effective removal by the waste
treatment systems that were studied.
* Oxygen analogs of the pesticides were generally not a significant deg-
radation product of any of the treatment processes.
* In general, low molecular weight alkyl phosphates, phosphorothioates
and phosphorodith.ioates were effectively reduced in concentration by the waste
treatment systems. Several methyl phosphorothioates actually increased in con-
centration across the treatment systems, which might be indicative of biomethy-
lation of phosphorothioic acids. Organophosphorus acids were also identified
in final effluent samples and appear to be only partially removed by the treat-
ment systems.
* Phenylphosphonates, chlorophenylphosphonates, and phosphonothioates
(all of which were involved in only one of the plants studied) were partially
removed by the waste treatment system; however, many of these compounds per-
sisted in the final effluent at low levels. It is significant that several of
these compounds are not simple alkyl esters but are closely related to the
parent pesticides (leptophos and EPN), and are potential cholinesterase in-
hibitors.
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* Volatile (purgeable) organic compounds were effectively removed by the
waste treatment systems that were studied; an exception was one plant with a
totally enclosed biodegradation system.
* The injection well sample studied contained relatively high levels of
organophosphorus acids (over 100 mg/liter), thiocarbamate pesticides (approxi-
mately 200 mg/liter), and organosulfur compounds (over 150 mg/liter) after pre-
treatment by base hydrolysis. This method of waste disposal cannot be evaluated
until the fate of this injected wastewater is known.
* The overall analytical methodology was successful in identifying many
compounds in the wastewater. However, methods in a few analytical areas should
be improved prior to further work on these types of effluents. These areas in-
clude: analysis of nonvolatile compounds, preservation of samples, and chro-
matography of selected pesticides.
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SECTION 3
RECOMMENDATIONS
* Although the pesticides were effectively removed by the treatment sys-
tems observed, the mechanism of removal, i.e., degradation or adsorption, is
unknown. Since solids from biotreatment systems are usually landfilled, the
disposal of these solids is a potential problem if they contain adsorbed pes-
ticides. The mechanism of pesticide removal should be determined.
* The rates of hydrolysis of all organophosphorus compounds identified
in the final effluents should be determined.
* Individual and synergistic toxicities of all organophosphorus com-
pounds identified in the final effluent should be determined.
* Open aeration ponds should be evaluated as a possible fugitive air
emission source for volatile organic compounds.
* Additional methods development should be conducted in the areas of:
- Analysis of nonvolatile compounds by derivatization or alternative
procedures such as HPLC.
- Concentration of organic compounds from the wastewater by accumula-
tor columns.
- Preservation of VOA samples, aqueous composites and organic extracts
to minimize further degradation and chemical reactions prior to analy-
sis.
- Improved chromatographic systems for selected pesticides, e.g., azin-
phos-methyl and bensulide.
* The presence of organophosphorus compounds at parts per million lev-
els in the injection well sample is of concern until the ultimate fate of the
wastewater is known. The organophosphorus pesticide manufacturers who dispose
of wastewater in this manner should be identified. A study of wastewater mi-
gration rates and directions should be made to determine the safety of this
disposal method in each separate case.
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* It is important to verify the identification of the 0-alkyl-0-(sub-
stituted aryl) phenylphosphonates because of their apparent long-term (> 1
year) persistence and probable high toxicity. These compounds should be syn-
thesized for, mass spectral confirmation of identifications that were based on
manual interpretations.
* Recommended procedural modifications are described in the Methods De-
velopment Section of this report.
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SECTION 4
EXPERIMENTAL
The experimental portion of the program is discussed in two sections,
sampling and analytical procedures. The sampling section specifies the equip-
ment and procedures used to collect 24-hr composite and volatile (purgeable)
organic samples and describes the safety aspects of field sampling. The ana-
lytical procedure discussion is divided into six sections which include: ex-
traction and partitioning; gas chromatography (GC); thin-layer chromatography
(TLC); frustrated multiple internal reflectance infrared spectroscopy (FMIR);
gas chromatography/mass spectrometry (GC/MS); and volatile organic analysis
(VOA).
SAMPLING
The goal of the sampling protocol was to obtain contamination-free waste
effluent which is representative of both the stage of treatment sampled and
of the discharge for an average 24-hr production period. The protocol was de-
signed to provide a 5 |ig/liter (ppb) detection limit for parent pesticides in
final (treated) effluents. Sampling point selection was based on the following
criteria: characterization of major phases of treatment, cooperation of plant
personnel, and physical accessibility. The sampling equipment and procedures
selected to meet this goal are discussed; safety procedures followed during
this sampling are presented at the conclusion of this section.
Equipment
Brailsford Model DU-2 effluent samplers were used to collect the 24hr
composite waste samples. The 2-gal. Nalgene sample jug was replaced with a 4-
liter glass Erlenmeyer flask. The uptake and delivery tubing was replaced with
Teflon tubing. After collection, the effluent was transferred to 32 oz plain
amber Saniglass® bottles for shipping and storage prior to analysis. The paper
cap-liner was replaced by a Teflon liner. All glassware was washed with
AIconox® followed by rinses with tap water, , 10% (v/v) HG1, tap water, 1 N NaOH,
tap water, acetone and deionized water. The glassware was air-dried and sealed
for shipment to the production site.
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Grab samples of the waste effluent to be analyzed for volatile (purge-
able) organics were taken in 6 ml Pierce Hypo-Vials™ (actual held volume, 11
ml) sealed with Canton Bio-Medical Microseps® F-174 (silicone rubber with Tef-
lon film). The glass vials were put through the same wash cycle as the compo-
site sample bottles and then heated in a muffle^ furnace at 50(f G overnight.
When cool, the vials were sealed with Microseps® and tear-away aluminum seals
to prevent contamination prior to field sampling. This easily removable clo-
sure was replaced with the standard seal after sample collection. The volatile
organic vials were kept cool in insulated containers with Divajex Blue Ice®
during period of sampling and shipment back to laboratory.
Procedures
A 2-liter sample was collected at each of the selected points. When con-
sistent with selection criteria, the production site's on-line sampling equip-
ment was utilized. In cases when the production facility had no compositor
capabilities, effluent was collected at ambient conditions with the Brailsford
samplers, in combination with 8-hr grab sampling when necessary. Following the
sampling period the wastewater pH was measured and adjusted to 7 with sodium
hydroxide or hydrochloric acid. The sample bottles were then packed with Blue
Ice® for refrigerated shipment to MRI's laboratories.
Samples for volatile organic analysis were taken at the same locations
as the composite samples. At regular intervals over an 8-hr period the pre-
sealed vials were opened, filled to overflow, re sealed with a minimum of head-
space and refrigerated.
Safety
Because of the toxic nature of the compounds under study, care was taken
to protect those directly or indirectly involved with the samples. Field crews
wore disposable gloves and rubber overshoes as well as safety shoes, glasses
and hard hats. All contaminated disposable items (gloves, wipes, broken sample
vials, etc.) were closed in plastic bags and placed in the company's toxic
waste containers. The glass sample bottles were sealed in plastic bags and
carefully packed to avoid damage and/or leakage during shipment.
ANALYTICAL PROCEDURES
The analytical procedures for this program were designed to obtain maxi-
mum information about the complex mixtures of organophosphorus compounds ex-
pected in pesticide production wastewater.
A general detection limit of 0.005 mg/liter for the parent pesticides in
treated effluents was used as guideline for sample volume, extract concentra-
tion and instrumental sensitivity. This limit was met for most pesticides and
related organophosphorus esters; exceptions included azinphos-methyl and
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bensulide for which detection limits were higher due to difficulty in eluting
these compounds from the chromatographic systems used.
The quantification and detection limits of parent pesticides and most
volatile (purgeable) compounds were based on comparisons with authentic stan-
dards. Quantification of nonphosphorus extractable compounds was based on
comparison of mass spectral total ion current response for a diazinon ex-
ternal standard. Therefore, the concentration estimates for the latter group
of compounds (nonphosphorus nonpurgeable) are less accurate than the concen-
trations determined for the pesticides and volatile (purgeable) compounds and
may vary within an order of magnitude. Organophosphorus esters other than the
parent pesticides were quantified against authentic standards when they were
available; otherwise, they were compared to diazinon standards. If an organo-
phosphorus compound was detected but not identified, it was classified in as
much detail as possible including solubility, degree of hydrolysis and chemi-
cal class. The general sample fractionation and analysis schemes are graphi-
cally outlined in Figures 1 and 2.
The analytical scheme was designed with an emphasis on the identifica-
tion and quantification of organophosphorus compounds. As outlined in Figure
2, only sample fractions in which organophosphorus compounds were detected
would be further analyzed by GC/MS. Only those nonphosphorus nonpurgeable
compounds which partitioned into fractions that contained detectable or-
ganophosphorus compounds would be detected by mass spectrometry; therefore,
the results obtained from this protocol should not be considered a total
characterization of organic content of analyzed wastewater.
Specific techniques described in detail in the following sections are:
extraction and partitioning; gas chromatography (GC); thin-layer chromatog-
raphy (TLC); frustrated multiple internal reflectance spectroscopy (FMIR);
gas chromatography/mass spectrometry (GC/MS); and volatile organic analysis
(VGA).
Extraction and Partitioning (for nonpurgeable compounds)
To aid in the chemical classification of compounds contained in waste-
water an extraction-partitioning scheme (Figure l) was developed to separate
compounds into solubility groups: water soluble compounds at pH 7 (Fraction
A); organic bases (Fraction D); and neutral water insoluble compounds (Frac-
tion J).
One liter of each sample was adjusted to pH 7 and extracted three times
with 200-ml portions of diethyl ether. The water phase was concentrated to
not less than 5 ml in a rotary evaporator, yielding Fraction A. The ether
phase was concentrated to 50 ml in a Kuderna-Danish (K-D) evaporator and par-
titioned three times with 25-ml portions of 1% HGl/H20. The ether phase was
concentrated to 5 ml in a K-D evaporator, yielding Fraction J. The aqueous
phase was adjusted to pH 9 and partitioned three times with 50-ml portions of
8
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Sample
1
Adjust Water to
pH 7 & Partition
with 3 x 200ml
Diethyl Ether
Concentrate Ether
to 50ml & Partition
with 3 x 25ml
1% HCI
Evaporate Ether
Phase in K-D Evap.
to 5ml (neutrals)
Fraction (Jj
Volatile
(Purgeable)
Analysis
I
Evaporate Water
Phase in Rotary
Evaporator to 4
5ml (water solubles)
Fraction (A)
I
Derivatize
with
Diazomethqne
Fraction (AD)
1
I
OP Analysis
OP Analysis
i
Adjust Water to
pH 9 & Partition
with 3 x 50ml
Ether
I
OP Analysis
Discard
Water
Phase
Evaporate Ether
Phase in K-D Evap.
to 5ml (bases)
Fraction (D
I
OP Analysis
Figure 1. General sample fractionation scheme.
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TLC/Spot Test
+
-
OP
Confirmed
Classified
Identified
GC - FPD
Retention Time
S/P Response
Ratio Only
LEGEND
TLC -Thin Layer Chromatograpliy
GC/FPD - Gas Chromotography,
Flame Photometric Detection
OP - Organophospliorus
MS - Mass Spectrometry
IR - Infrared Spectroscopy
Dl - Direct Inlet
S/P - Sulfur/Phosphorus
Figure 2. Analytical scheme for organophosphorus compounds.
10
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diethyl ether. This ether phase was concentrated to 5 ml in a K-D evaporator,
yielding Fraction D. Two milliliters of dry methanol was added to the ether
solutions of Fractions D and J. Just prior to analysis, the volume of Frac-
tions D and J was adjusted to 2 ml either by evaporation of residual ether or
the further addition of dry methanol.
The high concentration of inorganic salts associated with the A fractions
led to difficulty in concentrating these water phases to 5 ml. When volumes
dropped below 100 ml, copious amounts of solid precipitated, often accompanied
by severe frothing. At this point further concentration was halted to avoid
problems with gas chromatographic analyses. The exact volumes were recorded
and concentration values were calculated accordingly.
Nonvolatile hydrolyzed esters (predicted process degradation products)
partitioned into Fraction A. In order to chromatographically analyze for these
compounds, a portion of Fraction A was reacted with diazomethane to produce
volatile methyl ester derivatives of these organophosphorus (OP) acids.
A 0.5 ml portion of Fraction A was derivatized with diazomethane accord-
ing to a method reported by G. W. Stanley.—' The aqueous solution was taken to
dryness under a nitrogen stream. Dry methanol (0.5 ml) was added to the solid
residue to extract the organophosphorus compounds from any inorganic salts.
The solution was decanted from any remaining material. One drop of 1:1 HCl-
ethyl acetate was added to this solution followed by the addition of .diazo-
methane-ether solution until the yellow color persisted. The solution was al-
lowed to stand for a few minutes and then evaporated to less than 0.5 ml under
a nitrogen stream. The final volume was adjusted back to 0.5 ml with dry meth-
anol. This solution was designated Fraction AD.
Gas Chromatography (for nonpurgeable compounds)
Fractions A, AD, D, and J were characterized by gas chromatographic (GC)
separation coupled with element specific detection (see Figure 2). A phosphorus-
sulfur profile was obtained for all sample extracts using flame photometric
detection. Samples were submitted for nitrogen-specific alkaline flame ioniza-
tion detection (AFID) when evaluation of the production and waste treatment
processes suggested the usefulness of such a screening. Standard glass columns
(6 ft x 2 mm ID) and equivalent temperature programs (allowing for variation
of parameter selections of different instrument manufacturers) were used to
correlate results with data obtained from GC/MS chromatograms.
Two chromatographic liquid phases (Carbowax 20M-TPA and OV-l) were se-
lected to best cover the range of polarities and volatilities of compounds ex-
pected to be detected in sampled.wastewaters.
11
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Table 1 lists recommended gas chromatographic parameters for the analysis
of intermediately volatile organic compounds. Specific instruments used in all
analyses are given in Table 2.
Retention times were calculated relative to diazinon. Approximate concen-
trations of organophosphorus, sulfur and nitrogen compounds were determined
by GC based on element specific response to diazinon external standards.
The GC analysis of samples for two of the five sites required a modifica-
tion in the standard OV-1 temperature program because the pesticides under
study did not elute or chromatographed poorly under the standard conditions.
In one case it was only necessary to extend the final hold time period an ad-
ditional 10 min. However, to obtain well-resolved chromatographic peaks for
parathion and its oxygen analog it was necessary to use the temperature pro-
gram given in Table 3.
Thin-layer Chromatography (TLC)
The sample extracts were developed in three solvent systems. These sys-
tems were selected to separate the organophosphorus species anticipated in the
effluent samples. The plates were visualized by spraying with a modified molyb-
date reagent.
Solvent Systems--
The solvent systems and their separation characteristics are summarized
in Table 4.
Plates--
The TLC plates (Analtech, Inc., Uniplate, 250 u, Silica Gel G) were se-
lected on the basis of resolution requirements, low background after visuali-
zation, glass thickness, and ability to withstand temperatures required to con-
vert organophosphonates to the visualized orthophosphate species. The plates
were developed in 95% ethanol prior to use to reduce the residual background
and to improve the reproducibility of standard Rf values.
Visualization Reagents--
Preparation of the visualization reagents was as follows:
Potassium persulfate reagent--Dissolve 2 g of potassium persulfate in
100 ml NH^OH. This reagent is stable for about 2 weeks.
Ammonium molybdate reagent—Dissolve 2 g of ammonium molybdate in 92 ml
of water and add 8 ml of concentrated HCl. This reagent is stable for about
2 weeks.
12
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TABLE 1. GAS CHROMATOGRAPHIC PARAMETERS
____—^ Column ^ Program
3% OV-1 on Supelcoport 80/100 mesh 5 min hold at 120°C, 7.5°C/min pro-
2 mm ID x 6 ft glass grammed temperature, increased to
220°C, 10 min hold at 220°G
57. Carbowax 20M-TPA on Supelcoport 5 min hold at 120°C, 5°C/min pro-
80/100 mesh 2 mm ID x 6 ft glass grammed temperature, increased to
200°C, 10 min hold at 200°G
TABLE 2. INSTRUMENTATION FOR ANALYSIS
Instrument Analysis
Tracor Model 550 gas chromatograph Phosphorus-sulfur screen
equipped with dual flame photometric
detectors for phosphorus (526 nm filters)
and sulfur (394 nm filter)
Perkin-Elmer 3920 gas chromatograph Nitrogen Screen
equipped with rubidium bead thermionic VOA screen and quantitation
detector and flame ionization detector
Wilks Model 8B Multiple Internal IR of preparative TLC
Reflectance spectrophotometer isolates
Varian/MAT CH-4 magnetic sector Gas chromatography/
mass spectrometer with Tracor 2000-R mass spectrometry
gas chromatograph
Varian/MAT 311-A double focusing
mass spectrometer with Varian Aerograph
Model 2740 gas chromatograph
Varian 620/i minicomputer
13
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TABLE 3. GAS CHROMATOGRAPHIC PARAMETERS
FOR PARATHION ANALYSIS
Column
Program
3% OV-1 on Supelcorport 80/100 mesh
2 mm ID x 6 ft glass
Initial temperature 100°C, 25°C/min
programmed temperature, increased
to 220°C
TABLE 4. TLC SOLVENT SEPARATION CHARACTERISTICS
Solvent system
Compounds separated (Rf)
Ethanol 95%
Acetone/ethyl acetate (.1/1, v/v)
Methylene chloride
Inorganic P (< 0.2)
Organic P (> 0.2)
Mono-alkylated esters
Di-alkylated esters
Tri-alkylated esters
[increasing)
Hydrolyzed esters (0.0)
Alkyl phosphonates (0.15-0.40)
Alkyl phosphates (> 0.4)
Hydrolyzed esters (0.0)
Pesticides
14
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"Benzidine" reagent—Dissolve 0.065 g of 3,3',5,5'-tetramethylbenzidine
(a noncarcinogenic analog of benzidine) in 8 ml of glacial acetic acid, add
20 ml of water, warm the solution and add slowly 20 g sodium acetate trihy-
drate. Dilute this solution to 100 ml with water. This reagent is stable for
about 2 weeks.
TLC Procedures—
Twenty microliter portions of each extract were applied to TLC plates
and developed in each of the solvent systems. The plates were visualized by
spraying until wet with potassium sulfate reagent, heating on a hot plate at
235 C for 3 min and allowing to cool. The process was repeated, the plates
were sprayed with ammonium molybdate reagent and heated at 180°G until vapors
were no longer visible above the plate. The cooled plate was next sprayed with
tetramethyl-benzidine reagent. Organophosphonates, organophosphates and thio-
phosphates, and orthophosphate compounds gave a blue spot on a white back-
ground. The detection limit for organophosphorus compounds is 1 to 5 p,g.
For preparative TLC, the samples were streaked or spotted across the
width of a chromatoplate to obtain sufficient quantities of sample for fur-
ther studies. After development in the solvent (Table 4) which gave the best
separation in the initial development, the plate was divided into two parts:
the first was used for visualization of the component bands, the second for
recovery of the components at locations corresponding to positive Rf on the
visualized plate. Each band was transferred to a disposable micropipet and
the compound eluted from the silica gel with several drops of dry methanol.
.The methanol solutions of these isolated compounds were respotted and devel-
oped in the three solvents (Table 4). The resulting three Rf values were then
matched against Rf values for standard compounds in the data base, i.e. stan-
dards of compounds expected to be detected in the effluent sample.
The isolated phosphorus-containing extracts were characterized further
by FMIR, GC/FPD, MS and/or GC/MS (Figure 2). The method used for further char-
acterization was selected on the basis of spot intensity (quantity) and Rf
value. For example, a compound with an Rf value equal to zero in acetone/ethyl
acetate would be considered nonvolatile and further characterized by FMIR
rather than GC.
Frustrated Multiple Internal Reflectance Infrared Spectroscopy (FMIR)
Nonvolatile phosphorus-containing compounds that had been separated and
recovered by preparative TLC were characterized by FMIR. The minimum detect-
able quantity of most organophosphorus esters by FMIR is on the order of
5 Hg. The reflectance spectrum of each compound was determined in the range
of 4000 to 625 cm"1. Methanol solutions were applied to a 50 x 20 x 2 mm KRS-
5 plate for analysis.
15
-------
FMIR results were used for chemical classification by detecting various
functional groups within a molecule and for compound identification by match-
ing unknown spectra with the spectra of standard organophosphorus compounds.
Functional groups and associated absorption bands common to organophos-
phorus pesticides are listed below.
Functional group Characteristic absorption bands (cm"l)
P=0 1170-1285
POC (G is aliphatic) 990-1080
770-860
P=S 600-700
Gas Ghromatography/Mass Spectrometry (GG/MS)
The standard GG columns and conditions listed in Table 1 were used for
GG/MS. The helium carrier gas flow was adjusted so that the retention time of
a diazinon standard matched as closely as possible that obtained during the
GC/FPD runs.
Mass spectra were taken for all peaks seen on the total ion current (TIG)
reconstructed gas chromatograms. Two criteria were used to select a spectrum
for interpretation: peak intensity and organophosphorus character. The organo-
phosphorus character was based on a relative retention time window (+ 0.05)
determined by GC/FPD response and on intensities of characteristic fragments.
All mass spectra taken in these windows were chosen as candidates for inter-
pretation, and spectra in these windows with estimated extract concentrations
of 200 ppm (approximately 1 ppm in the wastewater sample) as determined by GC/
FPD response were given priority.
Spectra from all GC/MS runs were grouped by molecular ion and similar
fragmentation patterns, and the best representatives of these groups were sub-
jected to manual interpretation. Spectra of well-resolved compounds were sub-
mitted for computer assisted (Biemann Search) mass spectral matching.
Compound identifications were based on one or more of the following:
manual interpretation, similarity index matches, comparison of sample spectra
with reference spectra from laboratory standards or from the literature, and
matches from the Eight Peak Index of Mass Spectra. Mass Spectrometry Data Cen-
ter, Aldermastun, Reading, U.K. (1970). If an identification was made only by
a similarity index or "Eight Peak" match, the identification is considered
tentative and the listed compound is indicative of the type or class of com-
pound only.
16
-------
Volatile Organic Analysis (VOA)
Equipment —-
The purging system consisted of a 10 x 180 mm chromatography column with
Teflon stopcock and a $24/42 glass joint at the top. A very fine pore glass
frit cylinder, 10 x 1 mm, was press fit into the top of the Teflon stopcock.
A glass £24/42 reducing union to 3 mm was placed at the top of the purging
column. A 1/4 in. Teflon union was attached to the 3 mm glass tube at the top
of the column. A 3 in. x 1/4 in. stainless steel tube was pressed into the
open end of the Teflon Bunion and tightened until gastight. The stainless steel
tube was filled with Tenax GG®.
A Bendix Model 10 Flasher was used to thermally desorb the volatile com-
ponents from the Tenax GG®absorbent.
Procedures--
A number (N) of sealed VOA samples were obtained from each location at
regular intervals during 8 hr of the 24-hr sampling period. Equal portions
(5/N ml) were withdrawn by syringe from each sealed septum vial and combined
to obtain a 5 ml representative composite sample.
This composite was placed in the system described above and was purged
with nitrogen at 20 ml/min for 10 min at ambient temperature. The adsorbed
volatiles were desorbed at 185°C.
All samples were analyzed by gas chromatography with flame ionization de-
tection (GC/FID) before mass spectral analysis to determine the number of com-
pounds in the sample and estimate the concentrations. If insufficient concen-
tration or too large a concentration for mass spectral analysis was observed,
the sample volume was adjusted to obtain the optimum sample for the next purg-
ing to be used for mass spectral analysis.
The VOA GG conditions are given in Table 5.
TABLE 5. GAS CHRQMATOGRAPHIC PARAMETERS FOR VOA
Column
Program
Chromosorb 101 80/100 mesh
1/8 in. OD x 6 ft stainless
steel
4 min hold at 120°C, 4°C/min
programmed temperature, increase
to 200°C, 8 min hold at 200°C
17
-------
Quantisation after mass spectral analysis was performed by preparing
aqueous standards, purging and determining peak height by FID. Three to five
different concentrations were analyzed for each component in the sample. Stan-
dards were prepared to bracket the concentration range of that component in
the sample. The calibration curves were linear in the concentration range of
interest. During work on the protocol sample, it was noted that purging and
trapping onto Tenax was not 100% efficient. The method used to quantify the
samples assumes reproducible recovery of standards and of standards relative
to samples if purging rates and times are carefully controlled. Because linear
calibration curves can be obtained by this method, it appears that this is a
good assumption.
18
-------
SECTION 5
SELECTION AND SAMPLING OF PRODUCTION FACILITIES
The discussion of production facilities is divided into three sections:
site selection criteria; presampling surveys; and a field sampling summary.
SITE SELECTION CRITERIA
To characterize the organophosphorus pesticide manufacturing effluents
on an industry wide basis, the most important selection criteria were total
annual production volume, chemical class, toxicity of organophosphorus pesti-
cides produced and type of waste treatment used. After representative com-
pounds (parathion, methyl parathion, diazinon, malathion, phorate, disulfoton,
azinphos-methyl, fonofos, bensulide, phosmet, and leptophos) were selected,
manufacturers of these compounds were contacted to determine the accessibility
of production sites.
PRESAMPLING SURVEYS
Site visits were made to all the consenting facilities to assess the
suitability of each location for characterization of the waste effluent before
and after treatment. The information needed at each location included the
indentification of organophosphorus pesticides produced or formulated; the
identification of other organic compounds produced; production methods for
the organophosphorus pesticides; production volumes; locations of waste streams;
waste treatment technique; location of possible sampling points; and possible
problems with the disclosure of identified compounds and their concentrations
in the wastewater. Sites were disqualified for the following reasons: refusal
of permission to sample, lack of treatment prior to disposal, e.g., ocean dump-
ing, and discontinuation of pesticide production. Facilities that manufacture
malathion and phorate did not meet the sampling criteria. EPN was being manu-
factured at the former leptophos manufacturing facility that was studied, and
methyl parathion was being manufactured at the time of sampling the plant that
alternates the production of parathion and methyl parathion.
FIELD SAMPLING SUMMARY
Field sampling information is summarized in Table 6.
19
-------
TABLE 6. FIELD SAMPLING SUMMARY
Date
OP Production
sites
Estimated national
production in 1974
(million
Sample description
Waste treatment
2-76 Diazinon
3-76 Methyl parathion
7-76 Disulfoton
Az inp ho s -methyl
10-76 Phosmet
Fonofos
Bensulide
11-76 EPN
12
51
10
5
10
3
Not listed
Not listed
1. Untreated segregated OP waste
2. After acid destruct, segregated
OP waste
3. Discharge to river mixed with
non-OP waste
1. Untreated acidic waste
2. Combined pH adjusted waste
3. Discharge to city sewer
1. Before biotreatment (mixed
with non-OP waste)
2. After biotreatment (mixed
with non-OP waste)
1. Runoffk' untreated
2. Runoffk/ after aeration
3. Base-treated for deep-well
injection
1. Runofffe/ untreated
2. Treated runoff^/ mixed with
35 unknown waste effluents
Acid hydrolysis, acti-
vated, sludge, aera-
tion, clarifiers
pH Adjusted, activated
sludge aeration,
clarifiers
pH Adjustment, polymer
reactor, activated
sludge, clarifiers
Runoff:k/ pH adjust-
ment, organic skimming,
aeration; production
waste: base hydrolysis,
deep-well injection
Aeration, activated
sludge, chlorination
clarifier
a/ Kelso, G. L., R. Wilkenson, T. L. Ferguson, and J. R. Maloney, "Development of Information on Pesti-
cides Manufacturing for Source Assessment," Final Report, Midwest Research Institute, EPA Contract
No. 68-02-1324, July 30, 1976.
b/ Primary production waste disposed by deep-well injection.
-------
SECTION 6
RESULTS AND DISCUSSION
The results are discussed in three major sections: identified compounds;
production sites; and methods development.
The identified compounds section contains a list of all compounds identi-
fied in this program and a discussion of these compounds by chemical class.
The production site section contains a description of each waste treatment fa-
cility, the pesticide synthesis methods, a summary of compounds identified at
each site, the origin of the compounds identified, and a discussion of the ef-
fect of the waste treatment system. The methods development section describes
the work carried out on fortified water solutions containing model compounds
and on one "protocol" sample taken from the azinphos-methyl/disulfoton produc-
tion plant.
IDENTIFIED COMPOUNDS
All compounds identified in this study are summarized in Table 7. The
identified compounds* and their concentrations are given for each sample lo-
cation. The compounds are divided into organophosphorus, volatile (purgeable),
and intermediately volatile nonorganophosphorus groups. The sample locations
are grouped by production site and location of the sample in the waste treat-
ment system (see Table 6). A detailed description of each sample location is
given in the Production Site section.
Organophosphorus Compounds
The organophosphorus compounds listed in Table 7 are divided into three
groups according to compound class: parent pesticides and oxygen analogs
(compounds 1-6); organophosphorus esters (compounds 7-29) and organophospho-
rus acids (compounds 30-46)«
The common names of the pesticides are listed in Table 7; the correspond-
ing trade names, chemical names and structures are given in Appendix A,
along with general ITJPAC nomenclature and structures for organophospho-
rus compounds.
21
-------
TABLE 7. CONCENTRATION OF COMPOUNDS IDENTIFIED BY SAMPLE LOCATION
Azinphos-methyl and Fonofos, phosmet, and bensulide
Diazioon productioa Parathioa production disulfoton production ~ production—
Pre- Mid- Post- Pre- Mid- Post- Mid- Post- Pre- Post- Injection
No. Compound identified treatment treatment treatment treatment treatment treatment treatment treatment treatment treatment well
Organophosphorus compounds
1 Diszinon 2.0 < 0.006 < 0.006
2 Methyl parathion 2.0 3.2 < 0.004
3 Methyl paraoxon < 0.002 0.01 < 0.002
4 Ethyl parathion 0.24 < 0.006 < 0.006
5 Fonofos 0.001 0.001 0.6
6 EFN
7 0,0,0-Trimethyl < 0.002 0.80 < 0.002
phosphate
8 0,0,0-Trlethyl phosphate 0.75 < 0.002 < 0.002
9 0,0-Diethyl phenylphoe-
phonate
10 0-(Chloroaminophenyl)-0-
methyl phenylphofiphonate
lla O-(Chlorobromoamlnophenyl)-
0-methyl phenylphosphonate
lib O-(Chlorobromoaminophenyl)-
0-ethyl phenylphosphonate
12 0,0,0-Trimethyl phosphoro- 2.7 3.9 4.4
thloate
13 0,0,0-Triethyl phosphoro- < 0.002 0.03 < 0.002 < 0.02 0.5
thloate
14 0,0-Dlmethyl-O-ethyl < 0.002 < 0.002 3.5
phosphorothloate
15 0,0-Dlmethyl phosphors,- < 0.002 2.1 2.8
midothloate
16 0,0-Dimethyl-N-methyl- < 0.002 < 0.002 0.16
phosphoroainidothioate
17 0,0-Diethyl ethylphos- 0-75 0.02 < 0.01
phonothioate
18 0,0-Dimethyl phenylphos-
phonothloate
19 0,0-Diethyl phenylphos-
phono thloate
20 0,S-Dlethyl phenylphos-
phonothioate
21 0-Mathyl-S-ethyl phenyl-
phosphoiiothioate
EPN production—'
treatment treatment
9 < 0.004
1.2 < 0.004
0.12 < 0.004
0.007
0.22 0.002
0.04 < 0.004
0.12 < 0.004
4 < 0.004
0.04 < 0.004
(continued)
-------
ho
10
No.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
Diazinon production
Pre- Mid- Post-
Compound identified treatment treatment treatment
0,0-Diethyl chloro-
phenylphosphono-
thioate
0-Ethyl phenylphos-
phonochlorothioate
0-(4-Nitrophenyl)-0-
ethyl chlorophenyl-
phosphonothioate
0,0-Dimethyl-S-methyl
phosphorodithioate
0-tfethyl-S , S-dimethyl
phosphorodithioate
0,O-Diethyl-S-ethyl
phosphorodithioate
0 ,0-Diethyl-S-methyl
phosphorodithioate
0,0-Diisopropyl-S-methyl
phosphorodithioate
OjO-Dlmethyl-o-hydrogen
phosphate^
0,0-Diethyl-O-hydrogen DNQ^
phosphateS''
0-Ethyl-O- hydrogen
ethylphosphonate£/
0-Methyl-O-hydrogen .
phenylphosphonate~~
0-Ethyl-O-hydrogen
phenylphosphonate^'
0 ,0-Diraethyl-S-hydrogen
phosphorothioate^
0,O-Dimethyl-0-hydrogen
phosphorothioate—
0,0-Diethyl-O-hydroeen DNEJ^'
phosphorothioate^'
O.O-Diethyl-S-hydroeen DNQ^'
Azinphos-methyl and Fonofos, phosmet, and bensulide
Parathion production disulfoton production production—' EPN production—
Pre- Mid- Post- Mid- Post- Pre- Post- Injection Pre- Post-
treatment treatment treatment treatment treatment treatment treatment veil treatment treatment
0.61 < 0.004
0.29 < 0.004
0.3 0.002
2.3 2.3 0.25 5 0.2
0.02 0.3 0.002 6 < 0.02
0.09 0.12 0.05
0.80 0.76 0.16 3 0.3
< 0.01 < 0.01 4
0.07 2.7 < 0.008
< 0.01 < 0.01 12
1.4 < 0.004
1.4 0.04
3.5 2.3 0.03
1.0 7.0 0.02 25 40 < 0.01 < 0.01 50
< 0.02 6
phosphorothioato
(continued)
-------
No.
39
40
41
42
43
44
45
46
47
Azinphoi-raethyl and Fonofos, phosmet, and bensulide
Diazinon production Parathion production disulfoton production production—
Pre- Mid- Post- Pre- Mid- Post- Mid- Post- Pre- Post- Injection
Compound identified treatment treatment treatment treatment treatment treatment treatment treatment treatment treatment well
0-Methyl-O-hydrogen-O- < 0.008 0.69 < 0.002
(4-nitrophenyl) phos-
phorothioateS''
S-Ethyl-0-hydrogen
pnenylphosphono-
thioateS'
0-Methyl-S-hydrogen
pheny Iphosphono-
thioateS/
' 0-Ethyl-S-hydrogen
pheny Iphosphono-
thioate^
0,0-Dimethyl-S-hydrogen 4.1 3.1 < 0.008 21 < 0.02
pho8phorodlehioate£/
0,0-Diethyl-S-hydrogen 2.7 < 0.004 < 0.008 6 4
p hosp horodi toioate£
0,0-Oiisopropyl-S- < 0.01 < 0.01 50
hydrogen phosphoro-
dithioataE.'
O.S-W.iBOpropyl-0- 0.04 < 0.01 < 0.01
hydrogen phosphoro-
dithloateS'
S,S-Dinethyl hydrogen < 0.02 0.08
phosphite
EPN production^
Pre- Post-
treatment treatment
1.4 < 0.004
0.04 < 0.004
0.94 0.008
Volatiles
48
49
50
51
52
53
54
55
56
57
58
59
Methanol 1,300 1,000 230 98 29 8 0.1 0.1
Et Hanoi 1,400 1,400 < 0.05 0.3 0.2 1 < 0.05 620
Propanol < 0.05 < 0.05 6
Acetone 300 170 16 250 370 0.9 0.5 0.1 18 17 < 0.05
Diethyl ether
Chloroform 140 25 3 0.02 0.02 < 0.01 1.5 1.5 0.6 0.9 < 0.01
Methylene chloride 0.6 0.5 13 11 < 0.01
Benzene 1.4 5 2 0.07 0.03 0.005 0.04 0.04 634
Toluene 3 < 0.05 < 0.05 0.10 0.53 0.009 0.01 0.01 0.6
Xylene 0.08 0.004 < 0.002
Heptane 60 6 < 0.05
Cyclohexane < 0.01 < 0.01 0.07
31 < 0.05
22 12
0.8 0.6
< 0.01 6
7 5
0.8 0.02
< 0.005 0.01
(continued)
-------
Mo.
Diazinon production
Pre- Mid- Post-
Compound Identified treatment treatment treatment
60 1,2-Dichloroethylene
61 1,2-Dichloroethane
62 1,1,1-Irichloroethane 300 < 0.05 < 0.05
63 1,1,2,2-Tetrachloroethane
64 Dimethyl sulfide
65 Dimethyl disulfide
66 Methyl ethyl sulfide
67 Diethyl disulfide
68 Ethyl isobutyrate < 0.005 3 < 0.05
69 Pinacolone
70 Phenyl acetate
71 Chlorobenzene
Intermediately volatile
no&organophosphorus
72 Atrazine > 10 0.04 NA4/
73 Simazine 0.30 NA^
74 Propazine 0.06 H**-'
75 EPIC
76 Vernolate
77 Holinate
78 Pebulate
79 Cycloate
80 2-Isopropyl-4-methoxy- DNO^' DBO^' HA4-'
6-methyl pyriraLdine
81 2-Isopropyl-4-ethoxy- 1.5 0.08 NA^'
6-methyl pyrimldine
82 2-lsopropyl-6-methyl- > 10 DHO^' UA4/
4-pyrimldone
83 £-Methoxynitrobenzene
84 £-Hitrophenol
85 £-chlorophenol
86 £-Chloronitrobenzene
87 £-Chloroaniline
88 Hexachlorobenzene
89 Dlphenyl disulfide
90 1-Ihiol diethyl disulfide
91 1- (Methyl mercapto)-
dlethyl disulfide
92- Phenyl ethyl disulfide
Azinphos-methyl and Fonofos,
Parathion production disulfoton production
Pre- Mid- Post- Mid- Post- Pre-
treatment treatment treatment treatment treatment treatment
0.4 0.4 0.6
6 6 0.4
0.02 0.02
< 0.01
0.45 0.60 < 0.01
< 0.01
< 0.01
24 10
< 0.01
0.3 0.3 0.76
1.1
0.2
0.1
< 0.05
0.3
3 1 < 0.01
< 0.01 9 < 0.01
3 < 0.01 < 0.01
0.3 0.4 < 0.01
0.6 2 2
< 0.01 < 0.01 0.1
< 0.05
< 0.05
< 0.05
< 0.05
phosmet, and bensulide
production^
Post-
treatment
0.5
0.3
< 0.01
< 0.01
< 0.01
< 0.01
0.02
< 0.05
0.38
< 0.05
0.07
< 0.05
< 0.05
< 0.05
< 0.05
Injection
well
< 0.01
< 0.01
0.08
0.3
8
0.03
80
58
12
0.1
27
42
4
120
0.4
EPN production-'
Pre- Post-
treatment treatment
0.3 0.2
0.3 0.44
0.04 < 0.01
0.02 < 0.01
(continued)
-------
TABLE 1^ (cjjntimied^
Dlazinopproduction
Parathion production
Pre- Mid- Post- Pre- HJ.U-
Mo. Compound identified ^jiu treatment^ ^Teatment treatmeut treatjaent treatmei
93 m-Dichlorobenzene
94 £-Dichlorobenzene
95 lYichlorobenzene
96 2,4-Dichlorophenol
97 Ethyl isothiocyanate
96 N-Cyanodimethylamioe
99 4,4-Dimethy1-2-penten-
2-aI«/
100 Alpha terpineoL*^
101 Terpinoi*:'
102 6-Cyclohexylhexan-l-ol
103 Secondary butyl iodide^ ,
104 Methyl tridecyl octonate^
105 2,2-Dimethyl propanoic
acid*7
106 p-Ch.
Azinphos-methyl and Fonofos, phosmet, and bensullde
d i s u 1 f o ^oj^pjcoduc t ion p^rffdjucutilonS{ _mm^.jQj.JP.^.P4.M-^t_ionfe.
Mid- Post- Pre- Post- Injection Pre- Post
Mid- Post- Mid- ..
int treatment treatment treajtmejqt _ _ treatment treatment
__^___ r .gb/
Injection Pre- Post-
well t re a tmen t. t re atme n t
«#
0.3
0.1
< 0.02
< 0.02
0.09
< 0.02
0.01
0.1
0.03
< 0.02
0.06
0.3
0.03
0.08
< 0.02
0.28 < 0.005
1.3 < 0.005
0.02 < 0.005
0.01 < 0.005
107
108
109
110
111
112
113
114
115
116
Dlethyl aniline
PyrrolizldineS' .
Methyl palmltate2
Methyl oleateS'
Methyl N-tetradeconate^'
Cyclohexanol
Biphenyl
Cresol homolo^'
2-Chlorobiphenyl
Diisobutylphthalate
< 0.
15
0.
0.
0.
< 0.
05
6
3
1
05
<
<
<
<
<
<
0.05
0.05
0.05
0.05
0.05
0.05
0.
< 0.
.1
.05
< 0.05
< 0
< 0,
4
.05
.05
2 < 0.01
0.01 < 0.005
0.01 < 0.005
0.01 < 0.005
a/ Pretreatroent and posttreatment samples were surface water runoff from the production area; the injection well sample was process wastewater.
b/ Both ffampl*ff were surface water runoff from the production area. Process wastewater is deep well injected off site.
c/ Identified as the methyl ester of the indicated compound.
d/ DMQ indicates a compound was detected but not quantified; HA indicates a sample was not analyzed.
e/ Ifce identification is based on a similarity index match or on the Eight Peak Index of Mass Spectra. 1st ed., Mass Spectrometry Data Center, Aldermaston, Reading, UK (1970),
~ and not on a match with a full reference spectrum. The identification is unconfirmed and should be considered tentative.
-------
The parent pesticides were detected in pretreatment and midtreatment sam-
ples. Pesticide concentrations in final effluents were below the detection
limit (~ 0.002 mg/liter). The injection well sample did have detectable levels
of fonofos but this sample is not considered a final effluent. Gas chromato-
graphic methods were not successful for azinphos-methyl, phosmet and bensulide,
therefore detectin limits of these pesticides were much higher (~ 1 mg/liter),
and none of them were identified in any sample. (Bensulide was tentatively
identified by TLC in the pretreatment sample.) The oxygen analogs of the pes-
ticides were expected products of the waste treatment systems. Identification
of the oxygen analogs is important because of their increased toxicity over
the parent pesticide. Methyl paraoxon, the only compound of this type detected,
was found in a midtreatment sample but not in the final effluent. Diazoxon,
ethyl paraoxon, and fonofoxon were not detected at low parts per billion lev-
els. Standard solutions of these compounds were chromatographed with the sam-
ple from the corresponding production sites. Extracted ion current plots were
obtained from the GG/MS data for these compounds to establish detection lim-
its at low parts per billion levels. The absence of parent pesticides and
their oxygen analogs in final effuents indicates that the five waste treatment
systems studied are effective in the removal of these compounds.
Organophosphorus esters (compounds 7-29, Table 7) are either formed as
by-products during the synthesis process or during the waste treatment process
by solvolysis with alcohols. Phosphate and phosphonate esters (compounds 7-10)
were not detected in the final effluents indicating their instability. Phos-
phorothioate esters (compounds 12-16) appear to be stable in the waste treat-
ment systems studied. Compounds 12, 13, 15, and 16 increased in concentration
across the waste treatment systems. This increase might be due to methylation
of organophosphorus acids by the biomass treatment. The high water solubility,
observed increase in concentration across the waste treatment system, and pos-
sible toxic potentiation of the phosphorothioate esters^/ are of concern for
this class of compounds. Although phenylphosphonothioate esters (compounds 18-
24) decreased, they were detected in the final effluent (all from the EPN pro-
duction plant). Of particular significance is that several of the nonhydrolyzed
phenylphosphonates and phenylphosphonothioates (compounds lla,b, 23 and 24) that
were detected in the final effluents were not simple alkyl esters. These com-
pounds are probably the most toxic compounds detected in the final effluents.
Phosphorodithioate esters (compounds 25-29) were also detected at decreasing
concentrations across waste treatment systems. The efficiency of removal is
not as high as that for the parent pesticides. Phosphorodithioates have also
been indicated as potentiators in toxicity studies and may be of concern in
the final effluents.
Organophosphorus acids (compounds 30-46) are formed by the hydrolysis of
the parent pesticides and other alkylphosphorus esters. The phosphorodithioate
acids (compounds 43-46) are also precursors for pesticide synthesis. Few acid
hydrolysis rates have been reported; however, the hydrolysis from the ester
to the monoacid is generally faster than the hydrolysis from the monoacid to
27
-------
the diacid. Therefore, the monoacids have moderate stability in aqueous solu-
tions. Four acids (compounds 35-37, and 44) were detected in posttreatment
samples; three others (compounds 32, 36, and 45) were detected at 10 to 50
ppm levels in the injection well sample. Although these compounds are not con-
sidered cholinesterase inhibitors, their potentiation effects are not known.
Because of the levels at which some of the acids were present, the synergistic
toxicity of these compounds should be determined. 0-Methyl-0-hydrogen(4-nitro-
phenyl) phosphorothioate (compound 39), which results from the hydrolysis of
the methoxy group from methyl parathion, was identified in a midtreatment sam-
ple. This product is unexpected because the usual degradation route is a nu-
cleophilic attack on the phosphorus atom which results in the loss of the most
acidic leaving groups, i.e., the 4-nitrophenyl group. The analogous acids of
other pesticides were not identified but this observed degradation pathway for
other pesticides should be studied.
Volatile Compounds
The discussion of volatile compounds as listed in Table 7 is divided
into four groups according to chemical class: alcohol precursors (compounds
48-50); production solvents (compounds 51-59); chlorinated hydrocarbons (com-
pounds 60-63); alkyl sulfides and disulfides (compounds 64-67); and miscellan-
eous (compounds 68-71).
The alcohol precursors methanol, ethanol and propanol were expected com-
pounds in the wastewater. These compounds are water soluble, polar and gen-
erally resistant to the waste treatment techniques (ethanol was greatly re-
duced at two plants).
The production solvents (compounds 51-59) are generally volatile materi-
als and are effectively removed by the waste treatment systems. The method of
removal is likely to be vaporization in open aerated treatment basins. Those
compounds identified in the azinphos-methyl/disulfoton production wastewater
are exceptions. Little or no decrease in concentration was observed because
the system is enclosed between the midtreatment and posttreatment sampling
locations. The biological treatment had no effect on these solvents.
The origin of the chlorinated hydrocarbons (compounds 60-63) is unknown.
These identified compounds are not apparent precursors, by-products, or sol-
vents for organophosphorus pesticide production. A treatment system with good
aeration is effective in removing the compounds, as indicated by the decrease
in trichloroethane (compound 62) across the diazinon treatment system.
Alkyl sulfides and disulfides (compounds 64-67) are by-products from or-
ganophosphorus synthesis. The waste treatment systems are effective in remov-
ing these compounds. The injection well sample had significant levels of di-
ethyl disulfide which may be useful in tracking the fate of this wastewater
discharge.
28
-------
The origin of the miscellaneous volatile compounds (68-71) is unknown ex-
cept for chlorobenzene which is a precursor for methyl parathion production,
and was present at a moderate level (0.7 rag/liter) after treatment. The other
compounds were identified from MSSS Biemann searches with low similarity index
matches and their identification is considered only tentative.
Intermediately Volatile (Nonpurgeable) Nonorganophosphorus Compounds
The compounds as listed in Table 7 are discussed in three groups: non-
organophosphorus pesticides (compounds 72-79); expected precursors and synthe-
sis by-products (compounds 80-96); and compounds of unknown origin (compounds
97-116).
Triazines (compounds 72-74) and thiocarbamate pesticides (compounds 75-
79) were detected in the samples taken from the organophosphorus waste treat-
ment systems. These compounds were also produced at the sites that were stud-
ied. The final effluents had low or undetectable levels of thiocarbamate
pesticides except molinate (compound 77). The final effluent of the diazinon
production site was not monitored for triazine herbicides. The injection well
sample had significant amounts of the thiocarbamate pesticides and may be rea-
son for concern until the ultimate fate of this wastewater is known.
Nonorganophosphorus precursors and synthesis by-products (compounds 80-
96) were effectively treated in the systems studied. p_-Chloroaniline (compound
87) was an exception, but it is an expected biodegradation product of j^-chloro-
nitrobenzene (compound 86). Hexachlorobenzene (compound 88) was also observed
in a final effluent in moderate concentration (0.1 mg/liter) but was not ob-
served in the pre- and midtreatment samples. High levels of disulfide com-
pounds were identified in the injection well sample, and were probably re-
sponsible for its strong odor.
Concentrations of nonorganophosphorus compounds of unknown origin (com-
pounds 97-116) were generally decreased by the wastewater treatment systems.
Each compound was identified from a MSSS Biemann search and had a low simi-
larity index match. Therefore, the identification of these compounds is only
considered tentative. The listed compound should be considered representa-
tive of a compound class rather than a verified compound identification.
Priority Pollutants Identified
Table 8 lists the priority pollutants* that were identified, along with
their location in the treatment system and number of times the compounds were
Those compounds listed in "Sampling and Analysis for Screening of Indus-
trial Effluents for Priority Pollutants," U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio, Revised April 1977.
29
-------
TABLE 8. PRIORITY POLLUTANTS DETECTED IN PHOSPHORUS- AND
NITROGEN-CONTAINING PESTICIDE WASTEWATER SAMPLES
Compound
Benzene
Chlorobenzene
HexachLorobenzene
1,2-Dichloroethane
1, 1,1-Trichloroethane
1 , 1 , 2, 2-Tetrachloroethane
Chloroform
1,3-Dichlorobenzene
1 , 4-Dichlorobenzene
2 , 4-Dichloropheno 1
Methylene chloride
4-Nitrophenol
Toluene
1,2-Dichloroethylene
Compound
No. in
Table 7
55
71
88
61
62
63
53
93
94
96
54
84
56
60
Number of
times iden-
tified in
pretreatment
4
2
0
2
1
0
4
1
1
1
1
0
4
2
Number of
times iden-
tified in
midtreatment
4
1
0
2
1
1
4
0
0
0
2
1
2
1
Number of
times
identified
in final
effluent
5
1
1
2
1
1
3
0
0
0
2
0
3
3
identified; concentrations are given in Table 7. These compounds were identi-
fied using the analysis protocol developed for this study and not the recom-
mended priority pollutant protocol (developed March 1977). Therefore, the list
of priority pollutants given in Table 8 should not be considered complete.
PRODUCTION SITES
The wastewater treatment systems for five organophosphorus production
sites producing eight organophosphorus pesticides were studied. Each produc-
tion site is discussed individually in this section as follows: diazinon pro-
duction; parathion production; azinphos-methyl and disulfoton production;
fonofos, phosmet and bensulide production; and EPN production. The discussion
of each site includes the wastewater treatment system and sampling locations;
pesticide synthesis methods; compounds identified at each sampling location;
and a discussion of each compound's origin and persistance across the waste
treatment system.
Diazinon Production
Wastewater Treatment System--
The wastewater treatment system is shown schematically in Figure 3. The
wastewater from the diazinon production unit enters the acid destruct holding
30
-------
u>
(Cyanuric Chloride)
Toxic Waste [T7
Acid Destruct
Holding Pond
02
f*
Cyanide
Removal
*
Equali-
zation
i
All Other Plant Waste
Bio
Treatment-
Clarify
pH Adj.
River
Figure 3. Wastewater treatment sampling points for diazinon production.
-------
pond. This wastewater stream does not include cooling water from the diazinon
production and therefore is not diluted. The total flow for the 24-hr sampling
period at the pretreatment sample point (01 on Figure 3) was 91,560 gal. at a
pH of 10.6. The acid destruct pond was at pH 1.0. As indicated in Figure 3, an
additional wastewater stream labeled "Acid Waste" (cyanuric chloride) also
enters the acid destruct holding pond. The pretreatment sample was taken from
an in-line flow dependent composite sampler used by the production site for
their own samples.
The diazinon wastewater has a several day hold-up in the acid destruct
pond. Diazinon is relatively unstable (T^g at pH 3.1 is 12 hr)!/ to acid hy-
drolysis when compared to other dialkyl phosphorothioates. The acid treatment
is intended to be the primary destruction method for diazinon. The acid hy-
drolysis of diazinon minimizes the formation of diazoxon.
The effluent from the "Acid Destruct Holding Pond" was sampled at Loca-
tion 02 (Figure 3). The total flow for the sampling period was 250,000 gal.
This resulted in about a threefold dilution of the "Toxic Waste" (diazinon)
by the "Acid Waste" stream.
Cyanide, when present, is removed by caustic chlorination, the pH is ad-
justed to 6.5, and wastewater from other production units is mixed before the
combined waste stream enters an aerobic biological treatment system. The water
is then clarified and pH adjusted before river discharge. The "Posttreatment"
sample (03) was taken at this location. The 24-hr composite sample was taken
from an in-line flow proportional sampler. The flow volume for the final efflu-
ent during 24-hr sampling was 1.4 million gallons. This implies a 15-fold dilu-
tion of the "Toxic Waste" (diazinon) stream.
The waste treatment system for diazinon wastewater is designed to remove
material by the following method: acid hydrolysis, neutral hydrolysis, bio-
logical degradation, adsorption onto biomass, and vaporization. Additionally,
compounds detected at low levels in the pretreatment (01) sample may be below
the detection limits in the final effluent due to the dilution resulting from
additional wastewater inputs into the treatment system.
Pesticide Synthesis Method--
The synthesis of diazinon is a simple condensation reaction between 0,0-
diethyl phosphorochlorothioate and 2-isopropyl-6-methyl-4-pyrimidinol as shown
in Eq. 1.
s
(C2H50)2PC1
N CH(CH3)2 K2C03 (C2HsO)?P-0X^t^V-CH(CH3)2
(Eq. 1)
32
-------
The precursor 2-isopropyl-6-methyl-4-pyrimidinol is synthesized in three
steps shown by Eqs. 2 through 4. 0,0-Diethyl phosphorochlorothioate, the other
precursor for diazinon, is not synthesized at this location but is shipped to
the production site. This accounts for the relatively low number of phosphoro-
thioates in the wastewater streams.
QCH3
(CH3)2CHCN + CH3OH » (CH3)2CHONH-HC1 (Eq. 2)
HC1
OCH3 NH2
(CH3)2CHC=NH-HC1 + NH3 » (CH3)2CH-i-NH-HCl (Eq. 3)
NH2 00
(CH)CHC=NH-HC1 + CHCCHCOCH - > (Eq. 4)
32
NaOH
Compounds Identified--
All compounds identified by GC/MS in the three samples taken from this
site are listed in Table 9. The compounds are listed in the following order:
organophosphorus (1-4), miscellaneous (5-12) and volatiles (13-21). Organophos-
phorus esters that were detected in the derivatized fraction are listed as the
underivatized compounds. Table 10 lists the methyl esters detected and the pos-
sible acid analogs of these esters.
Diazinon (1) was detected in the pretreatment sample as expected. It was
not detected in the midtreatment sample which indicates the effect of acid hy-
drolysis on this compound. The decrease in concentration is more than can be
accounted for by the factor of 5 dilution across the acid destruct pond. Di-
azoxon is an expected by-product of the synthesis and a possible degradation
product. Its absence (< 0.006 mg/liter) in the pretreatment sample indicates
the absence of 0,0-diethyl phosphorochloridate impurity in the 0,0-diethyl
phosphorochlorothioate precursor. Diazoxon's absence in the midtreatment sam-
ple indicates that the acid catalyzed hyrolysis of the pyrimidinyl group is
more rapid than oxidation of the thion group or that diazoxon also undergoes
rapid acid catalyzed hydrolysis of the pyrimidinyl group. Neither compound
was detected in the final effluent as was expected from their absence in the
midtreatment sample.
33
-------
TABLE 9. CONCENTRATION OF IDENTIFIED COMPOUNDS IN
DIAZINON PRODUCTION PLANT WASTEWATER
Concentration, mg/£ (ppm)
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Compound identified
Diazinon
0 , 0-Diethyl-S-hydrogen
phosphorothioate3-'
0 , 0-Diethyl-O-hydrogen
phosphorothioateiL/
0 , 0-Diethyl-O-hydrogen phosphate3-/
2-Isopropyl-4-methoxy-6-
me t hy Ipyr imid ine
2-Isopropyl-4-ethoxy-6-
methylpyrimidine
2-Isopropyl-6-methyl-4-pyrimidone
Ethyl isothiocyanate
N-Cyanodimethyl amine
Atrazine
Simazine
Propazine
Methanol
Ethanol
Acetone
Chloroform
1,1, 1-Trichloroethane
Benzene
Toluene
Heptane
Ethyl isobutyrate
Pre-
treatment
2.0
DNQ^-/
DNQb/
DNQk/
DN(£/
1.5
< 10
DNOW
DNQb/
< 10
0.30
0.060
1,300
1,400
300
140
300
1.4
3
30
< 0.05
Mid-
treatment
< 0.006
DNQ^
0.08
w«v-
0.04
1,000
1,400
170
25
< 0.05
5
< 0.05
6
3
Post-
treatment
< 0.006
NAS/
*
NAS/
NA£/
NA£/
NA£/
NAS/
NA£/
NA£/
230
< 0.05
16
3
< 0.05
2
< 0.05
< 0.05
< 0.05
a/ Detected as 0-methyl or S-methyl derivatives of indicated acid (see
Table 10 for acid analogs).
b/ DNQ = Detected but not quantitated.
c_/ NA = Not analyzed.
34
-------
TABLE 10. ACID ANALOGS OF IDENTIFIED ESTERS IN DIAZINON
PRODUCTION PLANT WASTEWATER
Compound identified Acid analog
0,0-Diethyl-S-methyl phosphorothioate 0,0-Diethyl-S-hydrogen phosphorothioate
0,0-Diethyl-O-methyl phosphorothioate 0,0-Diethyl-O-hydrogen phosphorothioate
0,0-Diethyl-O-methyl phosphate 0,0-Diethyl-O-hydrogen phosphate
(2) 0,0-Diethyl-S-hydrogen phosphorothioate and (3) 0,0-diethy1-0-hydro-
gen phosphorothioate are both expected synthesis by-products. The hydrolysis
of 0,0-diethyl phosphorochlorothioate yields 0,0-diethy1-0-hydrogen phosphoro-
thioate. 0,0-Diethyl-O-hydrogen phosphorothioate undergoes tautomerism to form
0,0-diethyl-S-hydrogen phosphorothioate. The equilibrium favors the 0-hydrogen
isomer which is indicated by its higher concentration in the pretreatment sam-
ple. Neither compound was detected in the midtreatment or post treatment sam-
ples, because of dilution or possible acid hydrolysis.
(4) 0,0-Diethvl-O-hydrogen phosphate was detected in the pretreatment
sample. The origin of this compound is the oxidation of either 0,0-diethyl-
S-hydrogen phosphorothioate or 0,0-diethyl-0-hydrogen phosphorothioate. The
absence of this compound in the midtreatment sample indicates acid hydrolysis
of the 0-ethyl ester groups.
(5) 2-Isopropvl-4-methoxv-6-methyl pyrimidine, (6) 2-isopropyl-4-ethoxv-
6-methyl pyrimidine and (7) 2-isopropvl-6-methyl-4-pyrimidone are reaction by-
products from the synthesis of 2-isopropyl-6-methyl-4-pyrimidinol (Eq. 4).
These compounds are not affected by the acid destruct pond as indicated by
their presence in the midtreatment sample at about the factor 5 dilution from
the cyanuric chloride waste (Figure 3). Because of the addition of nonorgano-
phosphorus wastewater between midtreatment and posttreatment, nonorganophos-
phorus compounds were not analyzed in the posttreatment sample.
(8) Ethyl isothiocvanate and (9) N-cyanodimethylamine were identified in
the pretreatment sample. The exact origin of these compounds cannot be ex-
plained. They are structurally related to reaction intermediates for the prep-
aration of the precursor 2-isopropyl-6-methyl-4-pyrimidinol (Eqs. 2 through
4).
(10) Atrazine, (ll) Simazine and (12) Propazine were detected in the pre-
treatment sample. This was a surprising result because the diazinon wastewater
system is segregated from the rest of the plant. Although the compounds are
35
-------
produced at this site, they should not be present in the pretreatment sample.
Atrazine was detected at reduced concentration in the midtreatment sample, in-
dicating that it is somewhat stable to acid hydrolysis or also present in the
cyanuric chloride wastewater.
(13) Methanol and (14) ethanol are used in the synthesis of diazinon (Eq.
2). The waste treatment system was not expected to be effective for these two
alcohols. These compounds could also be added from other waste streams. The
decrease in both compounds could result from dilution, evaporation, or degra-
dation.
(15) Acetone, (16) chloroformm (18) benzene, (l9) toluene, and (20) hep-
tane are all likely process solvents for the production of diazinon and the
other compounds at this facility. The specific solvents used for diazinon are
unknown because they were classified as proprietary information. The waste
treatment system is effective in decreasing the concentration of these low
molecular weight nonpolar compounds. The likely removal process is evaporation
during the aeration in the biological treatment as is indicated by the de-
crease in concentration between the midtreatment and posttreatment samples.
The presence of (17) 1,1,1-trichloroethane and (21) ethyl isobutyrate
cannot be explained. Both compounds are removed before the final effluent.
Parathion Production
Wastewater Treatment System--
The wastewater treatment system is shown schematically in Figure 4.47 The
chlorinated acid wastewater from parathion production was sampled at location
2201 (pretreatment). Neutral wastewater from parathion production was sampled
at location 2202 (midtreatment). The combined wastewater passes through aero-
bic biodegradation lagoons, clarifiers and finally at point 2203 (posttreat-
ment) enters the city sewer system.
Twenty-four hour composite samples were taken at the pretreatment and
midtreatment sampling locations. An 8-hr composite was made from grab samples
taken at the posttreatment location. The pH's at the pretreatment, midtreat-
ment and posttreatment samples were 0.7, 6.4, and 7.1, respectively. The flow
at the pretreatment location is not measured. The flows at midtreatment and
posttreatment are considered classified information by the production plant
personnel.
It is difficult to determine the effect of the waste treatment process
between the pretreatment and midtreatment samples because the volume of the
pretreatment effluent was not measured and the water is diluted with nonacid
wastes before the midtreatment sample location. The wastewater is not diluted
beyond this point; the volumes of water leaving the midtreatment sampling lo-
cation and the posttreatment location are monitored and are of nearly equal
36
-------
LIQUID PARATHION WASTE TREATMENT PLANT
Chlori nation
Chlorination
Pumps'
10
Liquid |[ f
***—*J
2201
v . •••/
\
*__ ._/! J
2202 \j
r zr.1 ' " ' "
ft , I
Jj_
/ / / ' /
Raw Waste Lagoon Limestone pH Adjustment .Blending
Neutralization with Soda Ash Hold Tank
or Caustic
n /
QJ /
Compres
Biological
Oxidation
\
it — P \ . .
JL_ iiil'lijMigii
II
Returning Sludge
Clarific
>rs
\ P
][
^ /-^|
f\^
2203
r-i, 1 lo City oewers
Waste Excess Sludge
Pumps
Figure 4. Wastewater treatment sampling points for parathion production.
-------
volume. Concentration differences between midtreatment and posttreatment can
be attributed to the effects of the biotreatment process. This process can
remove organophosphorus compounds by several mechanisms which include: aero-
bic biodegradation, air oxidation, adsorption onto the biomass, neutral hy-
drolysis, and vaporization.
Pesticide Synthesis Method--
The synthesis of methyl parathion is a simple condensation reaction be-
tween 0,0-dimethyl phosphorochlorothioate and sodium £-nitrophenoxide, as
shown in Eq. 5.
LJ
(CH-OKP-Cl +
NaO
a
(CH30)2P-0
N0? (Eq. 5)
Both precursors for methyl parathion synthesis are also made at this lo-
cation. The preparation of 0,0-dimethyl phosphorochlorothioate is a two-step
process shown in Eqs. 6 and 7.
4CH3OH
LJ
2(CH,0)~P-SH
(Eq. 6)
2(CH30)2P-SH + C12
2(CH30)2P-C1
(Eq. 7)
The preparation of sodium ^-nitrophenoxide is a three-step process shown
in Eqs. 8, 9, and 10.
C1
Cl
(Eq. 8)
Cl
+ HNOc
(Eq. 9)
NO + NaOH
NaO
(Eq. 10)
38
-------
This production site makes ethyl parathion during part of the year and
methyl parathion during the remainder of the year. The plant had switched from
ethyl to methyl parathion just prior to our sampling. Because of this conver-
sion, ethyl esters and methyl esters of the organophosphorus compounds were
detected in the wastewater treatment system. The synthesis of ethyl parathion
is identical to the synthesis of methyl except that ethanol is used in Eq. 6.
Compounds Identified--
All compounds identified by GC/MS in the three samples taken from the
parathion production site are listed in Table 11. The compounds are grouped
according to chemical class: organophosphorus (1-18), miscellaneous (19-25)
and volatiles (26-34). Organophosphorus esters that were detected in the de-
rivatized fractions are listed as the underivatized compounds. Table 12 lists
the methyl esters detected and the possible acid analogs of these esters.
(1) 0,0,0-Trimethyl phosphate (TMP) is produced from the reaction between
0,0-dimethyl chlorophosphate and methanol. 0,0-dimethyl chlorophosphate is a
likely by-product formed during the generation of precursor 0,0-dimethyl phos-
phorochlorothioate. TMP was detected only in the midtreatment sample. The bio-
treatment process is effective in removing the compound from the water.
(2) 0,0,0-Trimethyl phosphorothioate is produced during the synthesis of
0,0-dimethyl-S-hydrogen phosphorodithioate by the further addition of methanol
and displacement of hydrogen sulfide. 0,0,0-Trimethyl phosphorothioate was
found at increasing concentration from pretreatment to posttreatment. This
compound is either stable to acid hydrolysis or is added at midtreatment. The
compound is resistant to the biotreatment process.
(3) 0,0-Dimethvl-S-methyl phosphorodithioate is produced from the pre-
cursor 0,0-dimethyl-S-hydrogen phosphorodithioate and methanol with the elim-
ination of water. This compound was detected at nearly the same concentration
in the pre- and midtreatment samples. It was detected in the final effluent
but at one-tenth the concentration indicating that the compound is partially
removed by the biotreatment process.
(4) O-Methyl-S.S-dimethyl phosphorodithioate is generated by the reaction
of starting material, phosphorus pentasulfide, with 0,0,0-trimethyl phosphate
(compound 1 in Table 11). The highest concentration of the compound in the
waste treatment stream was detected in the midtreatment samples. The concen-
tration decreased to one-hundrth bf its midtreatment concentration in the fi-
nal effluent.
(5) 0.O-Dimethyl-O-hydrogen phosphate, (6) 0.0-dimethy1-0-hydrogen phos-
phorothioate, and (7) 0.0-dimethyl-S-hydrogen phosphorothioate are expected
hydrolysis products of Compounds 1 and 2. They decrease in concentration from
midtreatment to posttreatment, which indicates the biotreatment process is
effective in degrading partially hydrolyzed organophosphorus esters.
39
-------
TABLE 11. CONCENTRATION OF IDENTIFIED COMPOUNDS IN PARATHION PRODUCTION PLANT WASTEWATER
-P-
O
Concentration, mg/i
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Compound Identified
0,0,0-Trimethyl phosphate
0,0,0-Trimethyl phosphorothioate
0,0-Dimethyl-S-methyl phosphorodithioate
0-Methyl-S,S-dimethyl phosphorodithioate
0,0-Dimethyl-O-hydrogen phosphateS'
0,0-Dimethyl-O-hydrogen phosphorothioate9.'
0,0-Dimethyl-S-hydrogen phosphorothioate0.'
0 , 0- Dime thy 1-S- hydrogen phosphorodi thioateS'
0,0- Dimethyl phosphoramidothioate
0, 0- Dime thyl-N- methyl phosphoramidothioate
Methyl parathion
Methyl paroxon
/
0-Methyl-0-hydrogen-0-(4-nitrophenol)phosphorothioateS'
0,0,0-Triethyl phosphorothioate
0,0-Diethyl-S-methyl phosphorodithioate
0,0-Diethyl-S-ethyl phosphorodithioate
0,0-Diethyl-S-hydrogen phosphorodithioateS'
Ethyl parathion
j>-Methoxynitrobenzene
£-Nitrophenol
Chlorobenzene
£-Chlorophenol
j>-Chloronitrobenzene
£-Chloroaniline
Hexachlorobenzene
Acetone
Chloroform
Benzene
Dimethyl disulfide
Toluene
£-Xylene
m-Xylene
Methanol
Cyclohexane
Pretreatment
< 0.002
2.7
2.3
0.02
0.07
1.0
3.5
4.1
< 0.002
< 0.002
2.0
< 0.002
< 0.002
< 0.002
0.80
0.09
2.7
0.24
2.6
-
0.3
3.1
0.28
0.64
-
250
0.02
0.07
0.45
0.10
0.08
0.015
98
-
Midtreatment
0.08
3.9
2.3
0.3
2.7
7.0
2.3
3.1
2.1
< 0.002
3-2
0.01
0.69
0.03
0.76
0.12
< 0.004
< 0.006
1.0
8.8
0.3
-
0.42
1.7
-
370
0.02
0.03
0.60
0.053
0.004
0.004
29
-
(ppm)
Posttreatment
< 0.002
4.4
0.25
0.002
< 0.006
0.02
0.03
< 0.008
2.8
0.16
< 0.004
< 0.002
< 0.002
< 0.002
0.16
0.05
< 0.008
< 0.006
-
-
0.76
-
-
2.3
~ 0.1
0.9
-
0.005
-
0.009
-
-
8
0.07
a/ Detected as 0-methyl or S-methyl derivative of Indicated acid (see Table 12 for other possible compounds).
-------
TABLE 12. ACID ANALOGS OF IDENTIFIED ESTERS IN PARATHION PRODUCTION PLANT WASTEWATER
Compound identified Acid analog
0,0,0-Trinethy1 phosphate 0,0-Dimethyl-O-hydrogen phosphate^/
0-Methyl-0,0-dihydrogen phosphate
0,0,0-Trimethyl phosphorothioate 0,0-Dimethyl-0-hydrogen phosphorothioate^'
0-Methyl-O,0-dihydrogen phosphorothioate
0,0-Dimethyl-S-methyl phosphorothioate 0,0-Dimethyl-S-hydrogen phosphorothioateS'
0-Methyl-S-methyl-O-hydrogen phosphorothioate
S-Methyl-0,0-dihydrogen phosphorothioate
0-Methyl-O-hydrogen-S-hydrogen phosphorothioate
0,0-Dimethyl-S-methyl phosphorodithioate 0,0-Dimethyl-S-hydrogen phosphorodithioateS'
0-Methyl-S-methyl-O-hydrogen phosphorodithioate
0,0-Dihydrogen-S-methyl phosphorodithioate
0-Methyl-O-hydrogen-S-hydrogen phosphorodithioate
0,0-Dimethyl-0-(4-nitrophenyl) 0-Methyl-O-hydrogen-O-(4-nitrophenyl)phosphorothioate
phosphorothioate 0,0-Dihydrogen-0-(4-nitrophenyl)phosphprothioate
0,0-Diethyl-S-methyl phosphorodithioate 0,0-Diethyl-S-hydrogen phosphorodithioateS'
aj The acid analog which is listed in Table 11; the true identity could be any of the listed
analogs.
-------
(8) 0,0-DimethyI-S-hvdrogen phosphorodithioate is a precursor in the
production of methyl parathion. It is formed from the reaction of methanol and
phosphorus pentasulfide. The high concentration in pre- and midtreatment indi-
cates that it does not undergo acid hydrolysis or that it is contained in the
wastewater stream entering at the midtreatment location. The absence of 0,0-
dimethyl-S-hydrogen phosphorodithioate in the final effluent indicates effici-
ent removal by the biotreatment process.
(9) 0,0-Dimethyl phosphoramidothioate is an unexpected material to be
found in methyl parathion wastewater. Its formation is possible by the addi-
tion of ammonium hydroxide to 0,0-dimethyl-S-hydrogen phosphorodithioate or
OjO-dimethyl chlorophosphorothioate. The source of ammonium hydroxide in the
wastewater is unknown. 0,0-Dimethyl phosphoramidothioate concentration is not
significantly affected by the waste treatment as evidenced by the negligible
change in concentration from mid- to posttreatment. A related compound, (lO)
0,0-dimethyl-N-methyl phosphor amidothiate was detected in the final effluent
sample. It appears that the biological treatment results in some methylation
of the amido group during treatment.
(ll) Methyl parathion was detected in the acid waste pretreatment and in
the midtreatment samples at similar concentrations. This indicates that either
it does not undergo significant hydrolysis or the additional wastewater enter-
ing at this location contains methyl parathion. The final biotreatment process
is very effective in removing methyl parathion from the water.
(12) Methyl paraoxon was detected in the midtreatment sample. Methyl par-
athion from the pretreatment sample could be oxidized to methyl paraoxon in
the acid or limestone lagoons. The methyl paraoxon could also be introduced
in the nonacid wastewater. Methyl paraoxon was not detected in the final ef-
fluent, indicating effective treatment.
(13) 0-Methvl-0-hvdrogen-0-(4-nitrophenyl) phosphorothioate is produced
by the hydrolysis of a methoxy group from methyl parathion. This compound was
only detected in the midtreatment sample, indicating that hydrolysis of methyl
parathion occurs prior to or at this location. The absence of this compound in
the final effluent indicates that additional degradation occurs in the bio-
treatment process.
(14) 0,0.0-Triethyl phosphorothioate, (15) 0.0-diethyl-S-methvl phosphor-
odithioate, (16) 0,0-diethyl-S-ethyl phosphorodithioate, and (17) 0.0-diethyl-
S-hydrogen phosphorodithioate are ethyl analogs of Compounds 2, 3, and 8 from
Table 11. The presence of these ethyl compounds is probably due to carryover
in the acid waste holding pond from ethyl parathion production. The formation
of these compounds can occur in the same manner described for the methyl ana-
logs. The waste treatment has the same effect on their concentrations as that
described for the methyl analogs.
42
-------
(18) Ethyl parathion was detected in the acid waste holding pond but at
no other location. The presence of ethyl parathion again indicates carryover
from ethyl parathion production and some resistance of ethyl parathion to acid
hydrolysis.
(19) £-Methoxynitrobenzene is produced from the reaction between £-nitro-
chlorobenzene and methanol or from the reaction of 0,0,0-trimethyl phosphoro-
thioate with sodium £-nitrophenoxide. The £-nitrochlorobenzene and sodium £-
nitrophenoxide are precursors for the manufacture of methyl parathion. The
0,0,0-trimethyl phosphorothioate is an identified impurity (3) detected in
these samples at parts per million levels. £-Methoxynitrobenzene is eliminated
during the waste treatment. jD-Methoxyaniline, a primary biodegradation product,
was not detected in the final effluent. This indicates that more extensive deg-
radation is occurring.
(20) £-Nitropheno1 can be formed from the hydrolysis of parathion or from
the reaction between water and sodium ^-nitrophenoxide. The most likely source
is hydrolysis of the precursor sodium ^-nitrophenoxide.
(21) Ghlorobenzene is an intermediate product in the production of para-
thion. It is produced by the chlorination of benzene. The concentration of
this compound was slightly increased by the waste treatment process. This
could occur because of the chlorination of the wastewater, or the biodegrada-
tion of jD-nitrochlorobenzene to remove the nitro but not the chloro group.
(22) 2.-Chlorophenol could be generated during methyl parathion synthesis
if during chlorination of benzene some dichlorobenzene were formed. The di-
chlorobenzene would react with sodium hydroxide to generate £-chlorophenol.
It is only detected in the acid waste stream (pretreatment sample). This is a
surprising result because £-chlorophenol is expected to be relatively stable
and would be expected at the other two sampling locations.
(23) p.-Ghloronitrobenzene is an intermediate product in the synthesis of
parathion. It is produced by the nitration of chlorobenzene. The waste treat-
ment process is effecient in removing this compound. The probable degradation
product is (24) £-chloroaniline which appears at increasing concentration
across the waste treatment system.
The presence of (25) hexachlorobenzene in the posttreatment sample can-
not be easily explained. One possible source is the chlorination of benzene
during the synthesis of sodium ^-nitrophenoxide. However, if this were the
case, hexachlorobenzene would be expected in the pre- and midtreatment sam-
ples.
(26) Acetone. (28) benzene, (31) £-xylene (32) m-xylene, and (33) meth-
anol are expected solvents or starting materials used during the manufacture
of parathion. They are found in highest concentration in the pretreatment
43
-------
sample and decrease through the waste treatment system. The aeration basins
are most efficient in removal of these compounds. The removal is likely to oc-
cur by vaporization during the aeration process.
The presence of (27) chloroform can result from chlorination of the
wastewater. The chloroform concentration increased slightly with storage time,
which indicates the possibility of sample contamination above the amount ob-
served for the initial GC screen.
(29) Dimethyl disulfide is generated when methyl sulfide dimerizes in the
presence of oxygen. The methyl sulfide is produced from hydrolysis of 0,0-
dimethyl-S-methyl phosphorodithioate. It is efficiently removed during the
final treatment process.
The source of (30) toluene and (34) cyclohexane is not obvious. Toluene
is a possible contaminate from Chromosorb 101 which is used as a GC column for
VOA, but toluene did not elute during blank program runs.
Disulfoton and Azinphos-MethylT Production
Wastewater Treatment System--
The wastewater treatment system is shown schematically in Figure 5. This
system treats disulfoton and azinphos-methyl manufacturing wastewater and
waters from nonorganophosphorus (nitrogen-containing) agricultural chemical
production. The wastewater treatment system consists of: solvent removal;
gross pH adjustment; polymer reaction tank of unspecified function; an equal-
ization tank which has a 3-day hold to adjust for variations in flow and con-
centration fluctuation; dilution to 60% with well water as the wastes leave
the equalization tank; a splitter tank which directs wastewater to either one
or both biotrains; biotrains which are aerobic liquor mass digesters; and a
final clarifier before discharge.
The production site personnel would not permit sampling of the raw produc-
tion wastewater. A midtreatment sample was taken from the site composite sam-
pler after the splitter tank (2302 on Figure 5). This sample was at pH 7.6 and
the average flow rate during the sampling period was 1,430 gal/min. The post-
treatment sample was taken from the site's composite sampler after the final
clarifier (2303 on Figure 5). This sample was at pH 7.3 and the average flow
rate during the sampling period was 1,260 gal/min.
The wastewater treatment system at the site is designed to remove or-
ganic compounds by the following mechanism: solvent stripping; adsorption
onto sludge and polymer; neutral hydrolysis, aerobic biodegradation, oxidation,
and adsorption to secondary sludge. Because a pretreatment sample could not be
taken, an overall evaluation of the treatment system could not be made. Analy-
ses of the midtreatment and posttreatment samples allow an evaluation of the
aerobic biodegradation and secondary clarifier.
44
-------
Production
Sites
Solvent
Remova I
Caustic
H2SO4
Primary Clarifier
Primary Sludge
Pumps
pH
Adjustment
Equalization
Tank
Well
•Water
Dilution
Dewatered
Sludge
Lime Slurry
Ferric
Chloride
Mix
2303
Final
Clarifier
Sludge
Thickeners
Bio Train I
Bio Train II
2302
Splitter Tank &
pH Adjustment
Figure 5. Wastewater treatment sampling points for disulfoton and
azinphos-methyl production*
-------
Pesticide Synthesis Methods--
Azinphos-methyl is prepared in a one-step synthesis from benzazimide,
formaldehyde, and 0,0-dimethyl phosphorodithioic acid as shown in Eq. 11.
(CH30)2PSH
CH20
H1
-HoO
(CH30)2PSCH2-
(Eq. 11)
0,0-Dimethyl phosphorodithioic acid is prepared by the following synthesis
(Eq. 12).
CH3
-------
TABLE 13. CONCENTRATIONS OF IDENTIFIED COMPOUNDS IN AZINPHOS-METHYL
AND DISULFOTON PRODUCTION PLANT WASTEWATER
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Compound identified
0,0,0-Triethyl phosphorothioate
0,0-Dimethyl-S-methyl phosphorodithioate
0,0-Diethyl-S -methyl phosphorodithioate
0-Methyl-S, S-dimethyl phosphorodithioate
0,0-Dimethyl-S-hydrogen phosphorodithioate3-'
0,0-Dimethyl-O-hydrogen phosphorothioate3-'
0,0-Diethyl-S-hydrogen phosphorodithioate3-'
0,0-Diethyl-O-hydrogen phosphorothioate3-'
S,S-Dimethyl hydrogen phosphite
4,4-Dimethyl-2-penten-2-ol
Alpha terpineolk/
Terpineolk'
6-Cyclohexylhexan-l-ol—
Secondary butyl iodide-
Methyl tridecyl octonoate—'
2, 2 -Dimethyl propanoic acid—'
p -Chlorobenzand.de
Methanol
Ethanol
Acetone
Methylene chloride
1 , 2-Dichloroethylene
Chloroform
1,2-Dichloroe thane
Benzene
Pinacolone
1,1,2, 2-Tetrachloroethane
Concentration
Midtreatment
< 0.02
5
3
6
21
25
6
< Oo02
<0.02
2
0.3
0.1
< 0.02
< 0.02
0.09
< 0.02
0.01
0.1
0.3
0.5
0.6
0.4
1.5
6
0.04
24£/
0.02
, mg/£ (ppm)
Posttreatment
0.5
0.2
0.3
< 0.02
< 0.02
40
4
6
0.08
0.1
0.03
< 0.02
0.06
0.3
0.03
0.08
< 0.02
0.1
0.2
0.1
0.5
0.4
1.5
6
0.06
10£/
0.02
a/ Methyl analogs detected. See Table 14 for other possible acids.
b/ The identification is based on a similarity index match or on the Eight
Peak Index of Mass Spectra, 1st ed., Mass Spectrometry Data Center,
Aldermastun, Reading, U.K. (1970), and not on a match with a total ref-
erence spectrum. The identification is unconfirmed and should be consid-
ered tentative.
c/ Estimated concentration based on benzene response.
47
-------
TABLE 14. ACID ANALOGS OF IDENTIFIED ESTERS IN AZINPHOS-METHYL AND DISULFOTON
PRODUCTION PLANT WASTEWATER
Compound identified
Acid analog
oo
0,0-Dimethyl-S-methyl phosphorodithioate
0,0,0-Trimethyl phosphorothioate
0,0-Diethyl-S-methyl phosphorodithioate
0,0-Diethyl-O-methyl phosphorothioate
0,0-Dimethyl-S-hydrogen phosphorodithioate^'
0-Methyl-S-methyl-O-hydrogen phosphorodithioate
0,0-Dihydrogen-S-methyl phosphorodithioate
0-Methyl-0-hydrogen-S-hydrogen phosphorodithioate
0,0-Dimethyl-O-hydrogen phosphorothioatea/
0-Methyl-0,0-dihydrogen phosphorothioate
0,0-Diethyl-S-hydrogen phosphorodithioate^/
0,0-Diethyl-O-hydrogen phosphorothioate3-'
a/ The acid analog which is listed in Table 13; the true identity could be any of the listed analogs,
-------
The effectiveness of the entire wastewater treatment system cannot be
determined because an untreated sample could not be obtained. However, com-
parison of the compound concentrations at two sampling points (midtreatment
and posttreatment) allows an evaluation of the biotrain and clarifier on the
removal of organic compounds. The water volumes at the two sample locations
are nearly the same, allowing direct comparison of solution concentrations.
The biotrain and clarifier can remove organic compounds by several mechanisms,
which include: aerobic biodegradation; chemical oxidation; adsorption on the
biomass; neutral hydrolysis; and vaporization from the clarifier. The exact
mechanism of removal cannot be determined, but neutral hydrolysis of organo-
phosphorus compounds and vaporization of the high boiling compounds are not
likely removal mechanisms. The possible source of each compound and the effi-
ciency of the biotreatment process for removal of each compound are discussed
below.
Neither azinphos-methyl nor disulfoton were identified in either sample.
However, the analytical methodology for these compounds resulted in rather
high detection limits. Azinphos-methyl was not eluted from either gas chroma-
tographic column in a reasonable time; therefore the detection limit for this
compound was established by TLG, i.e., approximately 0.25 mg/liter. The re-
covery of disulfoton was not consistent in the sample concentration step re-
sulting in a detection limit of 0.050 mg/liter.
Known precursors account for all organophosphorus compounds (except the
dimethyl phosphite) detected in the two samples. 0,0-Dimethyl-S-hydrogen phos-
phorodithioate is a precursor in azinphos-methyl production. Solvolysis of
this compound by methanol accounts for the methyl substituted compounds. 0,0-
Diethyl-S-hydrogen phosphorodithioate is the precursor in disulfoton produc-
tion. Solvolysis of this compound by ethanol accounts for the ethyl substituted
compounds.
(l) 0,0.0-Triethyl phosphorothipa.te is produced during the synthesis of
0,0-diethyl-S-hydrogen phosphorodithioate by the further addition of ethanol
and displacement of hydrogen sulfide. The presence of this compound only in
the final effluent sample indicates that it is formed during biotreatment.
The likely precursor is 0,0-diethyl-S-hydrogen phosphorodithioate, which was
present in the posttreatment sample.
(2) P.P-Dimethyl-S-roethyl phosphorodithioate is produced from the pre-
cursor 0,0-dimethyl-S-hydrogen phosphorodithioate and methanol with the elim-
ination of water. The concentration of this compound was decreased by the bio-
treatment process.
(3) 0,0-Diethyl-S-methyl phosphorodithioate is produced from the pre-
cursor 0,0-diethyl-S-hydrogen phosphorodithioate and methanol with the elim-
ination of a water molecule. The concentration of this compound decreased by
a factor of 10 through the biotreatment process. The likely degradation
49
-------
product is 0,0-diethyl-O-hydrogen phosphorothioate (8), which was detected in
the posttreatment sample.
(4) 0-Methyl-S,S-dimethyl phosphorodithioate is generated by the reaction
of phosphorus pentasulfide (starting material) with 0,0,0-trimethylphosphate.
This compound was not detected in the final effluent, indicating efficient re-
moval by the waste treatment system.
(5) 0,0-Dimethyl-S-hydrogen phosphorodithioate and (6) 0.0-dimethyl-O-
hydrogen phosphorothioate are expected hydrolysis products of compound (2).
Compound (5) decreases in concentration across the waste treatment system.
Compound (6) increases from midtreatment to final effluent.
(7) 0,0-Diethyl-S-hydrogen phosphorodithioate and (8) 0.0-diethyl-O-
hydrogen phosphorothioate are expected hydrolysis products of compounds (1)
and (3). Compound (7) decreases in concentration and compound (8) increases
in concentration across the biotreatment in the same manner as the methyl an-
alogs (compounds (5) and (6)).
(9) S,S-Dimethyl hydrogen phosphite is not an expecte-1 degradation prod-
uct or precursor for the synthesis of disulfoton or azinphos-methyl •
The identification of compounds (10) 4.4-Dimethvl-2-penten-2-ol. (ll)
alpha terpineol. (12) terpineol. (16) 2.2-dimethvl propanoic acid, and (26)
pinacolone are tentative and based on a similarity index match or on the
Eight Peak Index of Mass Spectra. 1st ed., Mass Spectrometry Data Center,
Alderraastun, Reading, U.K. (1970), and not on a match with a total reference
spectrum. These compounds are all structurally related compounds which could
result from hydrolysis of the parent compound limonene. Limonene is used as
a wetting and dispersing agent for water-insoluble compounds, and could be
used during the formulation of pesticides. Limonene itself was not detected
at the two sampling locations but alpha terpineol (ll) was identified; it is
the first hydrolysis product of limonene. Further hydrolysis of alpha terpin-
eol (ll) results in the formation of terpineol (12). Additional hydrolysis re-
sults in ring opening of the cyclohexane ring with minor rearrangements and
would account for the presence of 4,4-dimethyl-2-penten-2-ol (10), pinacolone
(26), and 2,2-dimethyl propanoic acid (16).
(17) p_-Chlorobenzamide is not associated with the production of azinphos-
methyl or disulfoton.
(13) 6-Gvclohexylhexan-l-ol. (14) secondary butyl iodide, and (15) methyl
tridecyl octanoate were tentatively identified in the samples and not con-
firmed by matching with total reference spectra. Their presence in the waste-
water treatment system cannot be attributed to the production of either pesti-
cide.
50
-------
(18) Methanol and (19) ethanol are expected starting materials for the
synthesis of azinphosmethyl and disulfoton. Their concentrations do not de-
crease across the biotreatment because the wastewater system is enclosed from
midtreatment to posttreatment sampling points.
(25) Benzene and (20) acetone are both expected process solvents used in
the manufacture of organic compounds.
(21) Methylene chloride. (22) 1.2-dichloroethylene. (24) 1.2-dichloro-
ethane, (23) chloroform, and (27) 1,1,2.2-tetrachloroethane are expected sol-
vents and nonorganophosphorus intermediates used in pesticide manufacturing.
These compounds could also result from the chlorination of wastewater that oc-
curs during the synthesis step in which 0,0-dimethyl-S-hydrogen phosphorodi-
thioate and 0,0-diethyl-S-hydrogen phosphorodithioate are converted to 0,0-
dimethyl chlorophosphorothioate and 0,0-diethyl chlorophosphorothioate, re-
spectively. The chlorination of methanol and ethanol could account for the
chloromethanes and chloroethanes.
Fonofos, Phosmet and Bensulide Production
Wastewater Treatment System--
The wastewater treatment system is shown schematically in Figure 6. Rain-
water runoff from the plant grounds is sent to the "Upset Sump." Other water
from production activities may be periodically discharged into this "Upset
Sump." This water is pH adjusted and the organic phase skimmed. The pretreat-
ment sample (2401 on Figure 6) was taken at the inlet to the aeration pond.
The water is aerated in an open, polyolefin-lined pond. There is some micro-
bial growth in this pond but it is not designed for biotreatment. The pre-
treatment sample was a 24-hr composite sample. It had a pH of 10.5 and the
volume for sampling period was 234,000 gal. The posttreatment sample (2402
on Figure 6) was a 24-hr composite sample. It was at pH 7.0. The flow was not
metered at this location, but it is assumed to be the same as that at the pre-
treatment sample location because no additonal water is added and the aeration
pond is maintained at constant volume. The pretreatment and posttreatment sam-
ples are not representative of the three pesticide production wastewaters
which are injected into a deep well. The wastewater from the various produc-
tion units are combined, and the pH is adjusted to 13 prior to injection into
the deep well. The injection well sample (2403) was taken after the pH adjust-
ment. A 24-hr composite sample was taken. The flow was measured at 66,000 gal.
during the sampling period.
Production of phosmet, fonofos, thiocarbamates, thiophenol, and phospho-
rus trichloride occurred during the sampling period. The bensulide unit was
in the process of coming back on-line during the sampling period. A power
failure occurred during the sampling period for about 1 hr, which interrupted
sampling and some poduction processes.
51
-------
Lab
IMP
PCL
Carba mates
Bensulide
D
Storm Sewer
pH
Adj
Injection
Well
Phosgene
Upset
Sump
pHAdj
&
Organic
Skim
Aeration
Pond
River Discharge
Figure 6. Wastewater treatment sampling points for
fonofos, phosmet and bensulide production.
52
-------
The water treatment across the aeration pond can remove compounds by any
of the following methods: hydrolysis; air oxidation; adsorption onto sus-
pended solids; and vaporization. The organophosphorus compounds would not be
expected to be removed by vaporization and most undergo slow neutral hydroly-
sis*
The injection well is a waste disposal rather than waste treatment method.
However, the sample is treated by pH adjustment prior to injection. The sample
remained an average of 12 hr at pH 13 before neutralization of the composite
sample. This exposed the organophosphorus compounds to base hydrolysis and any
compounds detected in high concentration must be reasonably stable to this base
hydrolysis.
Pesticide Synthesis Method--
The origin of the identified compounds can be best discussed if the syn-
thesis steps for the parent pesticides are known. The reactions for a possible
synthesis of fonofos are shown below»2/ The phosphorus-containing precursor
is ethylphosphorothioic dichloride, which can be synthesized as shown in Eq.
15.
PC13 + l/3Al(G2H5)3
H90
C2H5PC13»1/3A1C13
S
II
C2H5PC12
C2H5PC12'1/3A1C13
(Eq. 15)
The synthesis of fonofos is given in Eq. 16.
S
ii
-OH
HS-
S
> 021151-^1
OC2H5
\=Z/ (C2H5)3N
v
C2H5P-S
fonofos
(Eq. 16)
A possible synthesis for the two precursors of phosmet is given in Eqs. 17
and 18. The synthesis of phosmet is given in Eq. 19.
53
-------
3
or
2 t01^ if
J ^
X>
ii
1 1
0
JNjtio
j ,
naphthalene
CHO
u
II
NCH2OH
S
0
™ > if
X = Cl ^
Br
0
II
^Cc>CH2X
II
0
(Eq. 17)
P2S5
4CH3OH
-H2S
^f
-* 2(CH,0),P-SH
3W2J
NaOH S
» (CH30)2P-SNa
(Eq. 18)
ij
(CH-0)9P-SNa
XCH,
X = Cl
Br
-S-CH2-N
phosmet Q
(Eq. 19)
The synthesis of bensulide is similar to that of phosmet because it is
also a phosphorodithioate. The precursor preparation is shown in Eq. 20 and
the final synthesis in Eq. 21.
S NaOH
2(i-C3H70)2P-SH
tj
(i-C3H70)2P-SNa
(Eq. 20)
54
-------
f
(i-G3H70)2P-SNa + C1CH2CH2NHS02G6H5
bensuLide (Eq. 21)
Trimethyl phosphite and triethyl phosphite are also produced at this
site. The expected synthesis for these compounds is shown in Eq. 22.
PG13 + 3ROH + 3NR3 - > (RO)3P + 3R3NHC1 R = GH3, G2H5 (Eq. 22)
Compounds Identified--
All compounds identified by GC/MS in the three samples taken from this
site are listed in Table 15. The compounds are grouped into organophosphorus
(1-10), thiocarbamates (11-15), miscellaneous (16-25), and volatiles 26-38).
Organophosphorus esters that were detected in the derivatized fractions are
listed as the underivatized compounds. Table 16 lists the methyl esters de-
tected and the possible acid analogs.
The identification of organophosphorus compounds in samples from this lo-
cation is complicated by the fact that methyl, ethyl, and propyl esters of
phosphonates and phosphorothioates are possible. The potential number of com-
pounds is very large and precludes prediction of all the possible compounds
that might be present in the wastewater.
(l) 0,0,0-Triethyl phosphate is produced from the oxidation of triethyl
phosphite (Eq. 22). The concentration dropped significantly from pretreatment
to posttreatment, indicating efficiency of the waste treatment system. It is
surprising that this compound was not detected in the injection well sample.
(2) 0,0-Dimethvl-O-ethvl phosphorothioate in the injection well sample
may be due to the reaction of methanol and ethanol with phosphorus pentasul-
fide in the wastewater. The addition of ethanol to 0,0-dimethyl phosphorodi-
thioate (Eq. 18, phosmet precursor) with the elimination of hydrogen sulfide
is another possible explanation for its presence.
(3) 0,0-Diisopropvl-S-methyl phosphorodithioate is produced from the ben-
sulide precursor 0,0-diisopropyl-S-hydrogen phosphorodithioate (Eq. 20) and
methanol with the elimination of a water molecule. This compound was detected
in the injection well sample which indicates stability to base hydrolysis.
(4) 0,0-Diethyl ethylphosphonothioate is produced from 0-ethyl ethylphos-
phonochlorothioate (intermediate Eq. 16) by addition of ethanol and removal
of hydrochloric acid. The waste treatment system is effective in the removal
of this compound.
55
-------
TABLE 15.
CONCENTRATION OF IDENTIFIED COMPOUNDS IN FONOFOS,
PHOSMET AND BENSULIDE WASTEWATER
Concentration, me/liter (ocm)
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
Compound identified
0,0,0-Triethyl phosphate
0,0-Dimethyl-O-ethyl phosphorothioate
0,0-Diisopropyl-S-methyl phosphorodithioate
0,0-Diethyl ethylphosphonothioate
Exo-2-dimethyl phosphono-2-hydroxynorbornene
Fono f o s
0, 0-Diisopropyl-S -hydrogen phosphorodithioatek/
0,0-Dimethyl-O-hydrogen phosphorothioatek/
0-Ethyl-O-hydrogen ethylphosphonatek/
0,S-Diisopropyl-0-hydrogen phosphorodithioatek/
EPTC
Vernolate
Molinate
Pebulate
Cycloate
Diphenyl disulfide£/
1-Thioldiethyl disulfide
1 (Methyl mercapto)diethyl disulfide
Die thy 1 aniline^/
Pyrrolizidine£id/
Methyl palTn-ttaroC.d/
Methyl oleateSii'
Methyl N-tetradeconate£ii/
CyclohexanolS./
Phenyl ethyl disulfida£./
Ethanol
Propanol
Acetone-ethyl ether
Methylene chloride
1,2-Dichloroethylene
1,2-Dichloroethane
Chloroform
Benzene
Toluene
Dimethyl sulfide
Methyl ethyl sulfide
Diethyl disulfide
Phenyl acetate
Pre-
treatment
0.75
< 0.002
< 0.01
0.75
1
- o.ooia./
< 0.01
< 0.01
< 0.01
0.04
1.1
0.2
0.1
< 0.05
0.3
< 0.05
< 0.05
< 0.05
< 0.05
15
0.6
0.3
0.1
< 0.05
< 0.05
1
NDS/
18
13
0.6
0.4
0.6
6
0.01
NDS./
ND£/
NDS/
NDS/
Post-
treatment
< 0.002
< 0.002
< 0.01
0.02
< 0.01
~ 0.001 a/
< 0.01
< 0.01
< 0.01
< 0.01
0.02
< 0.05
0.38
< 0.05
0.07
< 0.05
< 0.05
< 0.05
< 0.05
< 0.05
< 0.05
< 0.05
< 0.05
< 0.05
< 0.05
NDS/
NDS/
17
11
0.5
0.3
0.9
3
0.01
NDS/
NDS/
NDS/
NDS/
Injection
well
< 0.002
3.5
4
< 0.01
< 0.01
0.6
50
50
12
< 0.01
80
58
12
0.1
27
42
4
120
0.1
< 0.05
< 0.05
< 0.05
< 0.05
4
0.4
620
6
ND!/
ND!/
ND!/
NDi/
Noi/
4
0.55
0.08
0.3
8
0.03
a/ Concentration estimated from extracted ion current plots.
b_/ Detected as methyl derivatives of the corresponding hydroxy or thio compounds.
c/ Concentration estimated from GC/MS response and calculated relative to diazinon
standard.
d/ The identification is based on a similarity index match or on the Eight Peak Index
of Mass Spectra, 1st ed., Mass Spectrometry Data Center, Aldermastun, Reading, U.K.
(1970), and not on a match with a total reference spectrum. The identification is
unconfirmed and should be considered tentative.
s/ Not detected; detection limit not established.
56
-------
TABLE 16. ACID ANALOGS OF IDENTIFIED ESTERS IN FONOFOS. PHOSMET AND BENSULIDE WASTEWATER
Compound identified
Acid analog
Ul
0,0-Diisopropyl-S-methyl phosphorodithioate
0,0,0-Trimethyl phosphorothioate
0-Ethyl-O-methyl ethyl phosphonate
0,S-Diisopropyl-0-methyl phosphorodithioate
0,0-Diisopropyl-S-hydrogen phosphorodithioate
0,0-Dimethyl-O-hydrogen phosphorothioate^'
0-Methyl-0,0-dihydrogen phosphorothioate
0-Ethyl-O-hydrogen ethylphosphonate
0,S-Diisopropyl-0-hydrogen phosphorodithioate
a/ The acid analog which is listed in Table 15; the true identity could be either of the listed
analogs*
-------
(5) Exo-2-dimethyl phosphono-2-hydroxy norbornene was identified tenta-
tively from a low similarity index match only and is probably not present in
the sample.
(6) Fonofos is one of the pesticides produced at this location. It was
detected at low levels in the pretreatment and posttreatment samples. The
concentration in the injection well sample was higher but below 1 ppm.
(7) 0,0-Diisopropyl-S-hvdrogen phosphorodithioate was found at high lev-
els in the injection well sample. The compound is a precursor for the synthe-
sis of bensulide (Eq. 20). It is also an expected base hydrolysis product of
bensulide.
(8) 0,0-Dimethvl-O-hvdrogen phosphorothioate is an hydrolysis product of
the phosmet precursor 0,0-dimethyl-S-hydrogen phosphorodithioate (Eq. 18). It
could also be formed from the hydrolysis of phosmet at the P-S bond. It was
detected only in the injection well sample. This compound appears to be stable
to base hydrolysis.
(9) O-Ethyl-O-hydrogen ethylphosphonate is an expected degradation prod-
uct of the precursor 0-ethyl ethylphosphonochlorothioate and a hydrolysis
product of fonofos (Eq. 16).
(10) 0,S-Diisopropyl-O-hydrogen phosphorodithioate could be produced from
a rearrangement reaction of compound (7) and therefore a by-product of the
precursor for bensulide. It does not appear to be stable to base hydrolysis
because it is absent in the injection well sample. The waste treatment system
is efficient in the removal of the compound.
(11) EPTG. (12) vernolate, (13) molinate. (14) pebulate. and (15) cvclo-
ate are all thiocarbamates produced at this location. Small amounts of EPTC,
vernolate, molinate, and cycloate were detected in the pretreatment sample.
EPTC, vernolate, molinate, and cycloate were detected at high concentration
(12 to 80 ppm) in the injection well sample indicating stability to base hy-
drolysis (see Appendix A for structures).
(16) Diphenyl disulfide, (17) 1-thioldiethyl disulfide. (18) l-(methyl
mercapto)diethyl disulfide and (25) phenyl ethyl disulfide are sulfur-
containing compounds associated with the manufacture of organophosphorus and
thiocarbamate compounds. Thiophenol is synthesized at this site for use in
the production of fonofos (Eq. 16). Oxidation of the phenol would produce di-
phenyl disulfide. 1-Thioldiethyl disulfide and l-(methyl mercapto)diethyl di-
sulfide may be formed from the various methyl and ethyl mercaptans that are
base hydrolysis products in the injection well sample in the same manner as
diphenyl disulfide .
58
-------
(19) Diethyl aniline and (20) pyrrolizidine are nitrogen-containing com-
pounds which may be by-products from the thiocarbamate synthesis. Pyrrolizi-
dine identification was based on a similarity index match only and is consid-
ered to be tentative.
(21) Methyl palmitate, (22) methyl oleate, and (23) methyl N-tetradeca-
nate are methyl esters of high molecular weight carboxylic acids that were
tentatively identified. Their presence in the pretreatment sample cannot be
explained.
(24) Cyclohexanol can be readily associated as a synthesis precursor.
Cyclohexanol is an expected starting material for the production of cycloate.
(26) Ethanol and (27) iso-propanol are precursors for fonofos and ben-
sulide production (Eqs. 16 and 19, respectively). Ethanol was detected in
pretreatment and not posttreatment, indicating efficient removal.
(28) Acetone/ethyl ether. (29) methylene chloride. (32) chloroform. (33)
benzene, and (34) toluene are all likely process solvents. All of these com-
pounds are found at about the same concentration in the pretreatment and post-
treatment samples, indicating inefficient removal.
(30) 1.2-Dichloroethylene and (3l) 1,2-dichloroethane are both detected
in the pretreatment and posttreatment samples. Their origin is not apparent.
It is possible that they are formed during the reaction of phosphorus tri-
chloride and triethyl aluminum if excess phosphorus trichloride is present.
This is not confirmed because of the absence of either compound in the injec-
tion well sample.
(35) Dimethyl sulfide. (36) methyl ethyl sulfide and (37) diethvl disul-
fide are all expected by-products from the synthesis of organophosphorus and
thiocarbamate compounds. The high concentration of diethyl disulfide, along
with other disulfides, accounted for much of the strong unpleasant odor ex-
hibited by the injection well sample.
(38) Phenyl acetate, which was detected in the injection well sample, is
not a known process chemical.
The major constituents of the injection well sample were unidentified
disulfide compounds of MW 218, which were similar to diphenyl disulfide .
These compounds were not observed in the other two samples.
Bensulide would not chromatograph on either Carbowax or OV-1. A chromat-
ographic system was not developed for-this single compound. The GC/MS data
for J fractions on OV-1 were analyzed for mass characteristic peaks but no
59
-------
bensulide was detected. Bensulide was tentatively identified in the pretreat-
ment sample by TLC indicating a concentration above 20 ppm. It was not present
in sufficient concentration to obtain IR spectra for further confirmation.
Failure to detect bensulide in the injection well sample by TLC indicates the
base hydrolysis is effective in decreasing its concentration below the 20 ppm
level.
No phosmet standard was available at the time these samples were analyzed.
It was not known prior to sampling that this facility was producing phosmet.
It is not listed in Chemical Sources as a compound made at this location and
there was no indication during the presite selection visit that this compound
was being made.
Literature values^/ suggest that phosmet would have a relative retention
value of approximately 2.5 (diazinon = 1.0) on OV-1 under the chromatographic
conditions used for these analyses and would have been detected if present.
The GC/MS results for J fractions on OV-1 were checked for more characteris-
tic peaks, but phosmet was not detected. Phosmet was not in MRI TLC data of
standards; therefore, TLC confirmation of results was not possible.
EPN Production
Wastewater Treatment System—
The EPN production site employs two different waste disposal systems
that handle their chemical and process wash stream waste separately from the
effluent consisting primarily of rain runoff, blowdown and washdown waters.
Primary production waste is disposed of by off-site deep-well injection; sam-
ples were not taken of this material. The site discharges the runoff-washdown
effluent into the Bio-San channel of an industrial area's central waste treat-
ment plant that treats wastes from approximately 35 plants of various types.
This system is shown schematically in Figure 7. It consists of: preaeration,
activated sludge treatment with clarification and sludge recycle, chlorina-
tion, and final polishing where additional natural biological stabilization
occurs. The pretreatment sample was taken of the EPN effluent just prior to
discharge into Bio-San channel. There was no information to indicate waste
processing prior to this discharge point. The posttreatment sample was taken
following chlorination but prior to the final polishing stage.
Pesticide Synthesis Methods-
According to information provided by personnel from the production site
EPN was being produced during the sampling period and leptophos, which also
had been manufactured at this site, had not been in production for at least a
year prior to sample collection. The synthesis methods for EPN and leptophos
are outlined in Eqs. 23 and 24, respectively.
60
-------
C2H5OH
NaO
-NaCl
EPN
(Eq. 23)
CH OH
(CH3)3N
(toluene)
OCH-
leptophos
Cl
(Eq. 24)
61
-------
NJ
Discharge from
•"Approximately
35 Industries
oo
c
o
JB
u
CO
Monitor
2501
Filter Cake
to Landfill **"
EPN Manufacturing Plant
Equalization
Basin
Equalization
Basin
Spill Basin
Aeration Units
(Biotreatment )
Sltid
Filter Press
10-Fold Increased Excess
Clo During Sampling Period
Polishing
Basin
Aerobic
Sludge Digestor
Clean Stream
Diverted During /
Sampling Period A
Stabilization Basins
Additional
Natural
Biological
Stabilization
Occurs
Final
Holding
Basin
Discharge
Figure 7. Wastewater treatment sampling points for EPN production.
-------
Compounds Identified—
All compounds identified by GC/MS in the two samples are listed in Table
17. Because of the additional wastewater stream from other industries that
enter between the two sampling locations, only organophosphorus compounds were
analyzed in the posttreatment sample. The compounds in Table 17 are grouped
into organophosphorus (1-19), miscellaneous (20-27) and volatiles 28-39). Or-
ganophosphorus esters that were detected in the derivatized fractions are
listed as the underivatizedcompounds. Table 18 lists the methyl esters de-
tected and the possible acid analogs.
All the organophosphorus compounds, with the exception of 0(chlorobromo-
aminophenyl) 0-methyl phenylphosphonate, identified in the treated sample
were also present in untreated effluent. In general, the reduction in their
concentration across the waste treatment system is approximately equivalent
to the dilution factor (l to 250) across the system. A discussion of the iden-
tified compounds follows.
(2) 0-Ethyl S-hydrogen phenylphosphonothioate could result from partial
alkaline hydrolysis of 0-(4-nitrophenyl) 0-ethyl phenylphosphonothioate (EPN)
in the pH 8.8 untreated effluent. Further hydrolysis would be retarded under
the neutral conditions at the central waste treatment facility.
(4) 0-Ethyl 0-hydrogen phenylphosphonate is an expected hydrolysis prod-
uct of the oxygen analog of EPN. Chemical oxidation of EPN is likely to occur
during the production process. The stability of this compound in the neutral
environment between sampling points is predictable as is the case with (2).
The para nitrophenyl group is the preferred leaving group under nucleophilic
attack.
(17), (18) 0-(4-Nitrophenyl) Q-ethyl chlorophenylphosphonothioate iso-
mers may be reaction products of EPN with a strong halogenating agent such as
NaOCl (formed from Cl2 in the presence of base). The persistence of this com-
pound might be explained by increased stability to alkaline hydrolysis induced
by addition of a halogen to the ring attached directly to the phosphorus.
(13), (14) O-(Ghloroaminophenyl) 0-methyl phenylphosphonate isomers, (16)
0-(chlorobromoaminophenyl) dimethyl phenylphosphonate, and (19) 0-(chlorobromo-
aminophenyl) 0-ethyl phenylphosphonate can more easily be associated with the
production of leptophos than that of EPN. The aminophenyl moities might be in-
termediates in the Sandmeyer reaction for preparation of aryl halides. In this
procedure, the amino group is diazotized and the diazonium salt group is re-
placed by a halogen. However, since the published!/ industrial production syn-
thesis uses potassium 4-bromo-2,5-dichlorophenolate as a starting material,
the origin of compounds (13), (14), (16), and (19) is still in question.
63
-------
TABLE 17. CONCENTRATIONS OF IDENTIFIED COMPOUNDS
IN EPN PRODUCTION PLANT WASTEWATER.2/
Concentration,
me/liter (ppm)
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Compound identified
0-Hydrogen S-ethyl phenylphosphonothioate-^'
0-Ethyl S-hydrogen phenylphosphonothioateH'
0-Methy 1-0 -hydrogen phenylphosphonateE'
0-Ethyl 0 -hydrogen phenylphosphonate£'
0-Methyl S-hydrogen phenylphosphonothioateE'
0-Methyl S-ethyl phenylphosphonothioate
0,0-Diethyl chloro phenylphosphonothioate
0,0-Diethyl phenylphosphonothioate
0,0 -Dimethyl phenylphosphonothioate
0-Ethyl phenylphosphonochlorothioate
0,S-Diethyl phenylphosphonothioate
0,0-Diethyl phenylphosphonate
O-(Chloroaminophenyl) 0-methyl phenylphosphonate
Isomer of 13
0-(4-Nitrophenyl) 0-ethyl phenylphosphonothioate
(EPN)
O-(Chlorobromoaminophenyl) 0 -methyl phenyl-
phosphonate
0-(4-Nitrophenyl) 0-ethyl chlorophenylphos-
phonothioate
Isomer of 17
O-(Chlorobromoaminophenyl) '0-ethyl phenyl-
phosphonate
m-Dichlorobenzene
Pre- Post-
treatment treatment
1.4
0.94
*U4d/
jfr b.042
0.61
0.12
0.04
0.29
4.08
1.25
0.06
0.06
9. 16./
2l!/
ND£/
0.29
0.13
0.22
ND£/
0.008
ND£/
0.04
7 ND£/
ND£/
NE£/
ND£/
ND£/
ND£/
ND£/
ND£/
ND£/
ND£/
0.007
0.002
0.002
•
0.28S' ND£/
0.008J1/
21
£-Dichlorobenzene
1.3s7 ND£/
o.oiaii/
22
23
24
25
26
27
28
29
30
31
32
Trichlorobenzene
Biphenyl
Cresol homo log
2-Chlorobiphenyl
2 ,4-Dich loropheno 1
Diisobutylphthalate
Ethano 1
Diethyl ether
1,2-Dichloroethylene
1 ,2-Dichloroethane
Chloroform
0.02
2.08
0.01
0.01
0.01
0.10
31
22
0.3
0.3
0.8
ND£/
ND£/
ND£/
ND£/
ND£/
ND£/
ND£/
12
0.2
0.44
0.6
(continued)
64
-------
TABLE 17 (continued)
Concentration,
No.
33
34
35
36
37
38
39
Compound identified
Benzene
Toluene
Chlorobenzene
Diethyl disulfide
Methylene chloride
m-Xylene-i'
£-Xylen©i'
mg/liter
Pre-
treatment
7
0.8
0.02
0.04
ND£/
ND£/
(ppm)
Post-
treatment
5
0.02
ND£/
ND^
6
0.01
0.01
aj Not process wastewater; these samples were surface water runoff from the
production area. Process wastewater is deep well injected off-site.
b_/ Methyl ester detected (see Table 18 for other possible acids and the methyl
esters).
c/ Not detected by MS or not confirmed by matching relative retention times
on two columns.
d/ Detected as mixture.
e/ Corrected for 81% recovery.
fj Value from rapid determination procedure.
g/ Detected as extractable organic compound.
h/ Detected as volatile organic compound.
if Not associated with EPN production process.
65
-------
TABLE 18. ACID ANALOGS OF IDENTIFIED ESTERS IN EPN PRODUCTION PLANT WASTEWATERS/
Compound identified
Acid analog
0-Methyl-S-ethyl phenylphosphonothioate
0-Ethyl-S-methyl phenylphosphonothioate
0,0-Dimethyl phenylphosphonate
0-Ethyl-O-methyl phenylphosphonate
0,S-Dimethyl phenylphosphonothioate
0-Hydrogen-S-ethyl phenylphosphonothioate
0-Ethyl-S-hydrogen phenylphosphonothioate
0,0-Dihydrogen phenylphosphonate
b/
0-Methyl-O-hydrogen phenylphosphonate—
0-Ethyl-O-hydrogen phenylphosphonate
0,S-Dihydrogen phenylphosphonothioate
0-Methyl-S-hydrogen phenylphosphonothioate—
0-Hydrogen-S-methyl phenylphosphonothioate
b/
a/ Not process wastewater.
b/ The acid analog which is listed in Table 17; the true identity could be any of the listed
analogs.
-------
(10) 0-Ethyl phenlyphosphonochlorothioate is an intermediate in the EPN
production process which would not be expected to be stable for extended peri-
ods in an aqueous system.
(l) 0-Hydrogen S-ethyl phenylphosphonothioate. (3) 0-methy1-0-hydrogen
phenyIphosphonate, (5) 0-rnethyl S-hvdrogen phenylphosphonothioate, (6) O^methyl
S-ethylphenylphosphonothioate, (8) 0,0-diethyl phenylphosphonothioate, (9) 0,0-
dimethy1 phenyIphosphonothioate, (11) 0,S-diethyl phenylphosphonothioate, and
(12) QjO-diethyl phenylphosphonate are all expected from the hydrolysis and/or
oxidation of EPN or the side products of the synthesis reaction.
The two concentration values reported for (15) 0-(4-nitrophenyl) 0-ethyJL
phenylphosphonothioate (EPN) are evidence of degradation during a month's
storage at 4°€«
The presence of (7) 0,0-diethyl chlorophenylphosphonothioate, (20), (21)
dichlorobenzene, (22) trichlorobenzene, (25) 2-chlorobiphenyl, (30) 1,2-di-
chloroethvlene. (31) 1,2-dichloroethane, (32) chloroform, and (35) chloroben-
zene is strong evidence for the existence of a strong chlorinating agent in
the untreated effluent.
(29) Diethyl ether, (33) benzene, and (34) toluene are process solvents
associated with the manufacture of organic compounds.
(28) Ethanol is a starting material for the synthesis of EPN.
(36) Diethyl disul.fi.de might result from the dimerization of ethyl sul-
fide, a hydrolysis product of S-ethyl phenylphosphonothioates.
(26) 2,4-Dichlorophenol is a predicted degradation product of 0-dichloro-
phenyl phenylphosphonothioate, a compound closely related to leptophos.
(23) Bipheny1 cannot be directly associated with the EPN production pro-
cess but might have resulted from an upset condition involving heat-transfer
fluid.
METHODS DEVELOPMENT
The bulk of analytical methods development for this program was carried
out on synthetic samples consisting of water solutions of model compounds rep-
resentative of various compound classes expected to be in actual waste efflu-
ent and one "protocol" sample taken from the azinphos-methyl/disulfoton pro-
duction plant. Improvements and modifications in procedures, e.g., adjustment
of gas chromatographic parameters, mass spectral extracted ion current plots,
and the use of a nitrogen selective detector, required by differences in pro-
duction and treatment processes were made throughout the project.
67
-------
Extraction and Partitioning of Model Compounds
The partitioning scheme (Figure 1) was designed both to give some prelim-
inary chemical characterization, and to simplify gas chromatographic analyses
by isolating specific classes of compounds. Examples of such compound classes
are: hydrolyzed esters which require derivatization (Fraction A) and nitrogen-
containing organic bases (Fraction D).
The model compounds and their distribution and recovery from a synthetic
sample as determined by GG/FPD detection are shown in Table 19.
TABLE 19. DISTRIBUTION AND RECOVERY OF ORGANOPHOSPHORUS
COMPOUNDS
Recovery (%)
Fraction
Compound A D J AD Total
Pesticides
Ethion - 4 144 148
Azinphos-methyl^/ - 0
Demeton 0 72 30 102
Alkyl esters
Triethyl phosphate 46 30 18 - 94
0,0-Diethyl ethyl 4 3 100 - 107
phosphonothioate
Hydrolyzed esters
0-Methyl-0,0-dihydrogen - - 96 96
phosphate
0-Ethyl-0,0-dihydrogen - - - 65 65
phosphate
0-Ethyl-S-hydrogen - 118 118
methylphosphonothioate
a/ The inability to recover azinphos-methyl was due to the poor
chromatographic properties of this pesticide on the columns
used.
68
-------
In addition to the recovery data obtained on model compounds prior to
sampling, distilled water was fortified with the pesticide produced at each
site and analyzed in parallel with the wastewater samples. The results are
summarized in Table 20.
TABLE 20. PESTICIDE RECOVERY DATA
Product Level of fortification% Recovery
Diazinon
Methyl parathion
Disulfoton
Fonofos
EPN
10 ng/liter
10 |j,g/liter
10 u,g/liter
10 |jbg/liter
100 ng/liter
69
76
IIS/
85
81
a/ The 117o recovery value was obtained for the fortified sample run
in the same manner as the wastewater. Further studies showed
that the partitioning efficiency was 85% but that even with slow
controlled concentration in Kuderna-Danish evaporators, losses at
this step reduced the overall recovery to 347o.
In general, the results indicated a quantitative partitioning of hydro-
lyzed esters and the pesticides into Fractions A and J, respectively. The re-
sults of the partitioning of the nonhydrolyzed esters indicated that triethyl
phosphate was present in all fractions with approximately 50% in Fraction A
(water soluble) whereas the phosphonothioate was detected (100% of 107% total)
in Fraction J (water insoluble). The hydrolyzed esters were not detected in
Fraction A because they do not elute from the chromatographic column unless
derivatized; hence the recovery of the acids are indicated by the results of
the derivatized A fraction (AD) only.
The hydrolyzed alkyl esters used in the model sample, and their diazo-
methane esterification products, were analyzed by GG/MS to determine what
impurities were present in the standards and to verify the identity and num-
ber of esterification products observed by GC/FPD.
No chromatographable compounds were observed in the nonesterified acids
(Fraction A).
The results of the GC/MS analysis of esterified acids indicated that the
esterification with diazomethane yielded the expected products. Minor quanti-
ties of other esters were detected in the esterified methyl phosphate and
ethyl phosphate. These compounds were most likely due to esterification of
69
-------
impurities originally present in the standards and not due to multiple prod-
ucts from pure monoalkyl phosphates.
TLC procedures were also used to determine the partitioning of the model
compounds in a fortified water sample. The results generally agreed with the
GG/FPD with respect to the distribution of the model compounds among the three
fractions. The few exceptions are discussed below.
0,0-Diethyl ethylphosphonothioate was not detected in any of the frac-
tions. This compound volatilized from the plate prior to visualization. Azin-
phos-methyl was detected in Fractions A and J whereas the GC/FPD results
showed azinphos-methyl only after derivatization. The TLC results for azinphos-
methyl was verified by FMIR and suggests that the GC analysis was anomolous
rather than loss of azinphos-methyl during extraction.
TLC is useful in the analysis of nonvolatile phosphorus-containing com-
pounds. The following information may be obtained for individual compounds
isolated from matrix interferences by preparative TLC.
Result
Rf values in three solvent systems
Rf standard data base match
Preparative TLC/FMIR of isolated compound
Preparative TLC/FMIR standard match
Preparative TLC/Direct inlet mass spectrum
Derivatization of Qrganophosphorus Acids
Compound information
Chemical classification
Tentative identification
Tentative identification
Confirmation
Identification/confirmation
Hydrolyzed organophosphorus esters, major pesticide degradation products,
are not sufficiently volatile for direct GC analysis. A portion of each model
extract was derivatized with diazomethane to produce methyl esters of these
hydrolysis products. Prior to analysis of these derivatized extracts the ef-
ficiency of the esterification reaction was determined for the following com-
pounds.
Compound
0-Me thy1-0,0-dihydrogen pho sphate
0-Ethyl-0,0-dihydrogen phosphate
0-Ethyl-S-hydrogen methyl phos-
phonothioate
Conversion product
Conversion
0,0,0-Trimethyl phosphate 96
68
O-Ethyl-0,0 dimethyl
phosphate
0-Ethyl-S-methyl
methylphosphonothioate
45
70
-------
The efficiencies are based on the standards being 100% pure. TLC analy-
ses of each of the standards showed at least one major impurity in the ethyl
phosphate and the phosphonothioate which might explain the apparent low con-
version rate.
Several problems were associated with the GC analysis of hydrolyzed
esters. Poor chromatographic separation and questionable stability of methyl
derivatives, have been investigated by Shafik et al.*L/ Synthesis of amyl de-
rivatives was recommended for better chromatographic resolution. However, the
longer retention times of the amyl esters might cause coelution with other
higher molecular weight phosphorus compounds. Amyl esterification would pro-
vide an esterifying agent whose carbon number exceeds that of the pesticides'
alkyl groups and allow one to distinguish between monoalkyl and dialkyl phos-
phates after derivatization.
The presence of the organophosphorus acids has an adverse effect on the
analysis of the water soluble esters which also partition into Fraction A.
Deposition of the acids on the head of the chromatographic column often pre-
vents the elution of the normally volatile esters. Because the esters are at
least partially lost during evaporative steps in derivatization, attempts were
made to separate these compounds from the acids prior to esterification. Pre-
liminary efforts to partition the water-soluble esters from protocol Fraction
A into ether resulted in incomplete separation of the two compound classes. A
different approach might be to extract both esters and acids into a nonaqueous
medium compatible with the esterification reaction to thus avoid evaporative
losses and differentiate between the derivatized esters and those present be-
fore derivatization by prudent choice of the aklylating agent. The most pro-
mising approach would be to separate the acids from the water soluble esters
with a strong ion-exchange resin. Verweij and Boter have reported^/ the sep-
aration of methylphosphoric acids on BIORAD AG 1-X8.
Analysis of the "Protocol" Sample,
All fractions of the "protocol" sample (2004) were developed in three
TLC solvents: ethanol, acetone/ethyl acetate, and methylene chloride/cyclo-
hexane.
Fraction A was found to contain at least 10 phosphorus-containing com-
pounds at an approximate concentration of 20 ppm each with respect to the
original effluent sample; Fraction J had a minimum of three phosphorus com-
pounds at this concentration level; and no phosphorus compounds were detected
in Fraction D. The Rf matches in all three solvents with standards in the MRI
data base are summarized in Table 21•
Phosphonothioates and dithioates predicted for this site were entered
into a data matching program. Identification based on matching Rf values is
71
-------
TABLE 21. Rf MATCHES^/ FOR "PROTOCOL" SAMPLE (2004)
Fraction Matching standard
2004 A Methyl phosphonic acidV
Monomethyl phosphate
Dimethyl phosphate
Ethyl methyl phosphonic acid—'
Diethyl phosphate
Triethyl phosphate
Diethyl ethylphosphonatek'
Diisopropyl methylphosphonateJl/
c/
2004 AD— Dimethyl phosphate
Diethyl ethylphosphonatek-'
0-Ethyl S-methyl methylphosphonothioateH/
Triethyl phosphate
2004 D None
2004 J Dimethyl phosphate
Tri-N-butyl phosphate
Azinphos-methyl
al The listed compounds have matching Rj values in three developing sol-
vents: ethanol, acetone/ethyl acetate, and methylene chloride/cyclo-
hexane.
Jj/ Not expected at this site.
£/ Derivatized with diazomethane.
Note: All compounds detected in Fraction A were not detected in AD be-
cause the more volatile esters are lost during evaporation to dry-
ness. The AD fraction is designed to detect only the compounds
that are originally present as acids.
72
-------
the least reliable identification in the analytical scheme. Generally, Rf
matching was used as supporting information for GC/FPD, EMIR, and GC/MS iden-
tification.
"Protocol" Fraction A (2004 A), derivatized Fraction A (2004 AD) and the
methanol eluate of a preparative TLC band from 2004 A at Rf 0.73, ethanol, and
0.35 to 0.45, acetone/ethyl acetate, were analyzed by GC/MS using the Carbowax
20M column. The organophosphorus compounds identified in these extracts are
listed in Table 22.
Other fractions of the protocol sample were not analyzed by GC/MS because
of the additional time and effort involved. The purpose of the protocol sample
was to test and evaluate the analytical methodology. The results obtained on
the limited number of extracts analyzed indicated that compounds could be iden-
tified and wastewater effluents characterized by the methodology applied to
the protocol samples.
Recommended Procedural Modifications
In addition to the modifications to specific procedures already mentioned
in this section, some general recommendations can be made to improve the over-
all sampling and analysis scheme.
Studies should be done to determine evaporation and degradation losses
in both the aqueous sample and the organic extract during storage prior to
analysis. Efforts should be made to preserve the integrity of those compounds
most likely to impact on the .environment.
Sufficient final effluent sample should be collected either in volume or
by means of accumulators to compensate for the dilution factor commonly seen
between untreated waste streams and the treated discharge. In addition, all
samples collected from streams should be on a flow proportional rather than
time proportional basis.
In a survey project where all samples are to be characterized by GC/MS
with emphasis given to specific element-containing (e.g., phosphorus) com-
pounds, a GC prescreen employing a column effluent splitter with FID and FPD
detectors would be desirable. This would allow determination of concentration
ratios of phosphorus and nonphosphorus-containing compounds. These data would
facilitate decisions on the need for further extract concentration and/or
cleanup prior to GC/MS analysis and in turn maximize the number of interpret-
able spectra of organophosphorus compounds. It is also suggested that a FPD
detector be used in parallel with the GC/MS in identification of phosphorus
compounds.
73
-------
TABLE 22. ORGANOPHOSPHORUS COMPOUNDS IDENTIFIED IN PROTOCOL SAMPLES
Sample
Compounds identified
2004 A
U
CH-0-P-SCH
J i
OCHo
74
C0H,.0-P-SCHo
2 5 i J
OC2H5
(major peak)
C2H50-^>-SC2H5
OC2H5
2004 A, Rf 0.73, ethanol, and
Rf 0.35 to 0.45 acetone/ethyl acetate
C2H50-PI-SCH
25
5
(major peak)
c2H5
S
ti
C2H50-|-SCH3
OCoHe
2004 AD
CH30-p'-OCH3
OCHo
S
ii
C2H50-P-OCH3
S
CH30-P-SCH3
OCHc
C2H50-P-SCH3
-------
REFERENCES
1. Stanley, C. W. Journal of Agricultural and Food Chemistry, 14:321, 1966.
2. Pellegrini, G. and R. Santi, Journal of Agricultural and Food Chemistry,
20:944-950, 1972.
3. Eto, M. Organophosphorus Pesticides: Organic and Biological Chemistry,
CRC Press Inc., Cleveland, Ohio, 1974. p. 72.
4. Stutz, C.N. Chemical Engineering Progress, 62:82, 1966.
5. Eto, M. Organophosphorus pesticides: Organic and Biological Chemistry,
CRC Press Inc., Cleveland, Ohio, 1974. p. 50.
6. Analytical Methods for Pesticides and Plant Growth Regulators, Vol. VI,
Gas Chromatographic Analysis, G. Zweig, ed. Academic Press, New York, 1972.
7. Pesticide Manual, 5th ed. Hubert Martin and Charles Worthing, eds. issued
by British Crop Protection Council, 1977. p. 233.
8. Shafik, T., D. E. Bradway, H. F. Enos and A. R. Yobs, Journal of Agricultural
and Food Chemistry 21:625-629, 1973.
9. Verweij, A., and H. L. Boter, Chemical Laboratorium TNO Report No. 1976-19,
Rijswijk, The Netherlands, 1976.
75
-------
APPENDIX A: NOMENCLATURE
GENERAL IUPAC NOMENCLATURE FOR ORGANOPHOSPHORUS COMPOUNDS
0,0-Dialkyl phosphorous acid
Trialkyl phosphite
0,0,0-Trialkyl phosphate
0,0,0-Trialkyl phosphorothioate
0,0-Dialkyl S-alkyl phosphorothioate
0,0-Dialkyl S-alkyl phosphorodithioate
0,0-Dialkyl phosphoroamidate
0,0-Dialkyl phosphoroamidothioate
0,0-Dialkyl phosphorochloridate
R-
R-
R-
R-
R-
R-
R-
R-
R-
R-
R-
R-
R-
,/
P-OH
P-O-R
V
-R
R
-R
-R
R-
R-
R-O Cl
(continued)
76
-------
GENERAL IUPAC NOMENCLATURE FOR ORGANOPHOSPHORUS COMPOUNDS (concluded)
0,0-Dialkyl phosphorochlorothioate
0,0-Dialkyl phosphonate
0,0-Dialkyl phosphonothioate
0-Alkyl phosphonochloridate
0-Alkyl phosphonochlorothioate
0-Alkyl phosphinate
0-Alkyl phosphinothioate
R
V.
R-Cr 0-R
R-Cf Cl
V,
-R
77
-------
NOMFNCLATURE OK i'LSTIClUtS. RELATED OXYGENATED COMPOUNDS OKCANOPH-'SPHDHUS O-HHUUNDS
C_ommon___ndBic
Diazinon
Trade name
Spcctracidt-
Chemical name
0,O-DJethyL 0-[6-methyl-2-(l-methylethyl)]
pyriinidinyl phosphorothioate
ij
(C2H50)2PO
Diazoxon
0,0-Diethyl 0-[6-raethyl-2-(l-methylethyl)]-4-
pyrimidlnyl phosphate
00
Ethyl parathion
Methyl parathion
Methyl paraoxon
Niran
Metacide
0,O-Diethyl 0-(4-nitrophenyl) phosphorothioate
0,0-Dimethyl 0-(4-nitrophenyl) phosphorothioate
0,0-Dimethyl 0-(4-nltrophenyl) phosphate
(C2H50)2lo—ff \—NO
(CHjO)
(CH30)
NOo
Disulfoton
Oxydlsulfoton
Disulfoton sulfone
Di-Syston
Di-Syscon sulfoxide
Di-Syston sulfone
0,0-Dlothyl S-f2-(ethylthio)ethyl] phosphorodlthioate
O,0-Diethyl S-{2-(ethylsulfinyl)ethyl]
phosphorodithioate
O»O-Dierhyl S-[2-(ethylsulfonyl)ethyl]
phosphorodithioate
(C2H50)2ls(CH2)2SC2H5
(C2H50)2PS(CH2)2SC2H5
s b
AzInphos-methy1
Fonofoa
Guthion
Dyfonate
0,0-Dimethyl S-[(4-oxo-1.2,3-ben2otriazin-3(4H)-yl>-
methyl] phosphorodithioate
0-Ethyl S-phenyl ethylphosphonodithioate
C2H3OPSC6H5
42»5
(continued)
-------
Common name
Fonofoxon
NUMF.HCIATDKE OF PESTICIDES. RJJ.ATED OXYGENATED .COMPOUNDS AMI) ORCANOl'IIOSPSI'IRIIS CfVII-fUINDS (coiitjnuud)_
Trade name Chemical name Structure
0-Ethyl S-phenyl ethylphosplionothioate
8
H'tOPSC'/' Hr
J I O J
Bensullde
rhosmet
Betasan
Imidan
0,0-bls(l-Methyl) S-{2-[(phenylsulf onyDamlno Jethyl)
phosphorodithloate
S-[(1,3-Dihydro-l,3-dloxo-2H-lsoJndul-2-yl)methyl)
O,0-dimethyl pliosphorodithiuace
Phosmet oxygen analog
VO
EPN
Leptophos
Leptophoxon
Propazine
Phosvel
Milogaid
N-(Hercnptomethy1)phthalimlde S-(0,0~dimethy1)
phoaphorothioata
0-(4-nitrophenyl) 0-ethyl phcnylphoephonothtoate
O-(4-Bromo~2,5-dichlorophenyl) O-methyl
pheuylphoaplionotliioate
0-(4-Bromo-2,5-dichloropI»enyl) O-methyl
phenylphosphonate
2-Chloro-A,5-bls(isoj> ropy land no) -S-triazine
-L-/~
ic.
'2^5
-HO^
/M^^H
T
(cont inued)
-------
NOMENCLATURE OF PES'J'iCIDKS, RKLAIliU UXYUtNAt'KD COMPOUNDS AND DKuANUPHuSPHiMUS COMPOUNDS icimr jnu> .1)
Coiaroon name Trade name Chemical name Structure
Atrazine Aatrex 6-ChIoro-N-ethyl-N'-(l-methyletliyl)-l,3,5-trlaz1ne-
2,4-diamine Clv-
CO
° Simazlne Prlncep 6-Chloro-N,N'-dietliyl-l,3,5-trizine-2,A-dJainine ,,
C1I >J
f. II r il
EPTC Eptam S-Ethyl dlpropylcarbaiuothioate O
C2H3s!;N(C.jH7)2
-------
APPENDIX B; MASS SPECTRA OF IDENTIFIED COMPOUNDS NOT PRESENT IN THE MSS*
LIBRARY""
Compound
Figure B-l. Mass spectrum of S,S-dimethyl hydrogen phosphite
Figure B-2. Mass spectrum of 0,0-dimethyl phosphoramidothioate
Figure B-3. Mass spectrum of 0-methyl-S-methyl phosphoramidothioate
Figure B-4. Mass spectrum of 0-methy 1-0-ethyl ethylphosphonate
Figure B-5. Mass spectrum of 1-thiol diethyl disulfide
Figure B-6. Mass spectrum of £-chlorobenzamide
Figure B-7. Mass spectrum of 0,0,0-trimethyl phosphorothioate
Figure B-8. Mass spectrum of 0,0-dimethyl-S-methyl phosphorothioate
Figure B-9. Mass spectrum of 0,0-dimethyl phosphorochlorothioate
Figure B-10. Mass spectrum of 2-isopropyl-4-methoxy-6-methyl pyrimidine
Figure B-ll. Mass spectrum of 0,0-dimethyl-O-ethyl phosphorothioate
Figure B-12. Mass spectrum of 0,0-dimethyl-S-methyl phosphorodithioate
Figure B-13. Mass spectrum of 0-methyl-S,S-dimethyl phosphorodithioate
Figure B-14. Mass spectrum of 2-isopropyl-4-ethoxy-6-methyl pyrimidine
Figure B-15. Mass spectrum of 0,0-diethyl ethylphosphonothioate
Figure B-16. Mass spectrum of 0,0,0-triethyl phosphate
Figure B-17. Mass spectrum of 0,0-diethyl-O-methyl phosphorothioate
Figure B-18. Mass spectrum of 0,0-diethyl-S-methyl phosphorothioate
Figure B-19. Mass spectrum o-f 0,0-dimethyl phenylphosphonate
Figure B-20. Mass spectrum of S-ethyl hexahydro-lH-azepine-1-carbothioate
(molinate)
Figure B-21. Mass spectrum of 0,0-diethyl phosphorochlorothioate
Figure B-22. Mass spectrum of S-ethyl dipropyl thiocarbamate (EPTC)
Figure B-23. Mass spectrum of 0,0-diethyl-S-ethyl phosphorothioate
Figure B-24. Mass spectrum of 0,0-diethyl-S-methyl phosphorodithioate
Figure B-25. Mass spectrum of 0-methy1-0-ethyl phenylphosphonate
Figure B-26. Mass spectrum of 0,0-dimethyl phenylphosphonothioate
Figure B-27. Mass spectrum of 0-methyl-S-methyl phenylphosphonothioate
Figure B-28. Mass spectrum of S-propyl dipropyl thiocarbamate (vernolate)
Figure B-29. Mass spectrum of S-propyl butyl ethyl thiocarbamate (pebulate)
Figure B-30. Mass spectrum of 0,0-diethyl-S-ethyl phosphorodithioate
Figure B-31. Mass spectrum of 0,0-diethyl phenylphosphonate
Figure B-32. Mass spectrum of S-ethyl cyclohexylethyl thiocarbamate (cycloate)
Figure B-33. Mass spectrum of 0-ethyl-S-methyl phenylphosphonothioate
Figure B-34. Mass spectrum of 0-methy1-S-ethyl phenylphosphonothioate
*Mass Spectral Search System, ADP Network Services, Cyphernetics Division,
Copyright 1975.
81
-------
Compound (coneluded)
Figure B-35. Mass spectrum of 0-ethyl phenylphosphonochlorothioate
Figure B-36. Mass spectrum of 2,4-bis(ethylamino)-6-ethylmercapto-S-triazine
Figure B-37. Mass spectrum of 0-methyl-0,S-diisopropyl phosphorodithioate
Figure B-38. Mass spectrum of 0,0-diisopropyl-S-methyl phosphorodithioate
Figure B-39. Mass spectrum of 0,0-diethyl phenylphosphonothioate
Figure B-40. Mass spectrum of 0,S-diethyl phenylphosphonothioate
Figure B-41. Mass spectrum of 0-ethyl-S-phenyl ethylphosphonodithioate (fonofos)
Figure B-42. Mass spectrum of 2,6-di-tertbutyl-4-methoxymethyl phenol
Figure B-43. Mass spectrum of 0,0-diethyl chlorophenylphosphonothioate
Figure B-44. Mass spectrum of 0-(chloroaminophenyl)-0-methyl phenylphosphonate
Figure B-45. Mass spectrum of 0-(4-nitrophenyl)-0-ethyl phenylphosphonothioate
(EPN)
Figure B-46. Mass spectrum of 0-(4-nitrophenyl)-0-ethyl chlorophenylphosphono-
thioate
Figure B-47. Mass spectrum of 0-(chlorobromoaminophenyl)-0-methyl phenylphos-
phonate
Figure B-48. Mass spectrum of o-(chlorobromoaminophenyl)-0-ethyl phenylphos-
phonate
82
-------
00
Lo
S.S-Diwelhyl hydrogen phosphite
f-20
•1 C
0 SO 100
SPECit 15675 LS 15b?SLH lSb?3LH
150
800 2!SO 300
STEP HflSS'l, I/B-'S • i
350
400
Figure B-l. Mass spectrum of S,S-d±methyl hydrogen phosphite.
-------
CO
1 00-
90-
80-
70-
60-
50-
HO-
30-
20-
1 0-i
,,,..|..L
0 50
, 1,
1 00
1
0,0 -Dime thy 1 phosphoramldothloate
CH,0 S
P-NH2
CH,0
3
M+ - 141
ISO 200 250 300 350 1
30
£0
1 0
oc
6PECO 1126! LS
- I12S9LI1
STEP
Figure B-2. Mass spectrum of 0,0-dimethyl phosphoramidothioate.
-------
00
Ul
1 00
ISO
O-Methyl-S-methyl phosphoraraldothioate
CH 0-P-SCH
141
200
SPECS 7188 LS
I"""""! '"I 7-r-ri"-
aso
STEP riass'i.
300
350
-I—i""l ."i"'
400
\y.
Figure B-3. Mass spectrum of 0-methyl-S-methyl phosphoramidothioate.
-------
OO
I 00-
90-
eo-
70-
60-
50-i
HO-i
30-j
1 0-j
-------
00
100-
90-
80
70
to
50
10
30
80
10
0
154
l-thlol diethyl dlsulftde
0 SO 100
SPEC!) 80838 JS 20832JM - 20829JM
150
800
-| i I r | . | . i . | • ( . | . | . | .
850 300
STEP ttnSS'l, IxB'S • \Y.
350
ttt
Figure B-5. Mass spectrum of 1-thiol diethyl disulfide.
-------
00
oo
00-=
80-j
70-\
*.j
SO-j
HO-i
Z6-.
1 0-.
0
J I
5
•Wjrt1l|Jltjin-Jn
0
14
-------
CO
100-
90-i
60-
?0-i
60-
50-
40-
30-
20-
.10-
0 —
M
0 50
•
100
150
0,0,0-Trlmethyl phosphorothloate
s
CH30-|-OCH3
3
+
H a 156
1
£00 £50 300 350 HI
•
:
-
-30
.
.
'.
•SO
1 0
10
SPEC8 S67S LS 567SIH - S67MLM
STEP MfiSS'l,
• IK
Figure B-7. Mass spectrum of 0,0,0-trlmethyl phosphorothioate.
-------
1 00-
80-
70-1
50H
E
30-j
zo-i
1 0-j
0-=
J,o~
0 50
SPECS 1343 LS M3M3LI1
»T—r-."-f™!"1 "••••
i oo
H33SLM
0,0-Dlraethy 1-S-raethyl phosphorothloate
CH^O^ O
3 \u
cn3o
i | i r i |
150
200 850 --00
STEP nfiss= i, I/B/S • i;:
350
40
Figure B-8. Mass spectrum of 0,0-dimethyl-S-methyl phosphorothioate.
-------
100-
vo-
60-
70-
60-
50-
HO-j
30-j
eo-i
H
OJ:
ECtt
..„,.. .J.,..
0
E67
1
L
1 i , . T"1
3 LS £
• i
"P'T ^ I""1'
50
I673LI1 -
|
' T"'
5b?
I'T '"f"
1 00
ILH
""i
"'""'""I"'™'
ISO
0,0 -Dimethyl phosphorochlorothloate
CI10 S
XP-C1
CH-0
3
4.
M = 160
, I I I I . | 1 1 I 1 i I ' 1 I | 1 I ' 1 I I I 1 1 , > I > I r 1 1 , -I f . | , | i | i , r
EUI) 250 300 350 f 0
STEP HhSS=J, ~L/B'S - IK
Figure B-9. Mass spectrum of 0,0-dimethyl phosphorochlorothioate,
-------
to
100"
90-
80-
70-
HO-
30-
80-
10-
,|,n,Mll|.<,|u..rJ..rJlru,u,|KllT4l.if*rHl
0 EO 100 I
BPECB e9^lo us EIOI-J ecus H n. 3-29-76
2-isopropy1-4-methoxy-6-methyl pyrimidine
CH,
M+ = 166
BOO 850 300
STEP MRSS'l, I^-B/'S • IK
-20
-I 0
350
400
Figure B-10. Mass spectrum of 2-isopropyl-4-methoxy-6-methyl pyrimidine.
-------
Co
100-:
90-!
70-
to-
50-
10-i
0
SO
j. ,
J:
"T"1')"
Ll
fnyn.p
100
ll
r*,
it, , ,
r
ISO
ll
V'-i
0,0-dlraethyl-O-ethyl phoaphorothloate
GH 0-Lc H
M*" • 170
,!,.P,.r.l..,.,,,.,,.,.r..r<.r..r..t,..r,Y..l....|....,....(....,..T,,,1,,.,)1,,T,,,|,.n,,.,., i,.,,..,,,,.,,,,.,,,,,,,,,,..,..,,,,,.,, ,j ,„ , .„,,„.,.„.,,.„,..,,„.,,„
EOO E50 3CO 350 4
•1 1
1 °
4CC
SPECO C5908 JS ES908JH - 2S917JI1
Figure B-ll. Mass spectrum of 0,0-dimethyl-O-ethyl phosphorothioate.
-------
1 00-
90-
80-
70-j
60-
5(H
30H
ao-i
:
1 0-i
J
III
11^1
!t,
. 1
1. __
1 I ' | '
,' II
L
0,0-dla»ethyl-S-methyl phosphorodlthloate
CH30 S
Np-scii3
3
M+ - 172
mrpn| mj,,.n ^^^^^oj....^ ....j.-.^.p,.^^..,,..^,,.,....^,....^,..^....,...^™.,....^,..,..^,...,™^^^^
0 50 100
SPECS S93H LS S93MIM - 55>3iiLI1
150
eoo eso . 300
STEP MASS* i > I/B^S - i:•:
Figure B-12. Mass spectrum of 0,0-dimethyl-S-methyl phosphorodithioate.
-------
vO
100-
90-
BO-
70-j
60-
50-
<»0-
30-
20-
)0-|
0-
SPEC)'
' I ' J I I
50
100
150
O-methyl-S,S-dlraethyl phosphorodlthloate
0/SCH3
800 250 300
STEP MflSS'l, I/B/S ' I.'!
350
1 0
H «tl
Figure B-13. Mass spectrum of 0-methyl-S,S-dimethyl-phosphorodithioate.
-------
2-isopropyl-4-ethoxy-6-methyl pyrimidine
1 00-
i
90-
eo-
ro-
60-
50-
to-
30-j
eon
10-
0-
*•
1 j
.1 J lull
0 SO
ECtt 28865 LS 2101-0 6CMS
CHoCHoCX M -CH(CH3)2
•J £~ ^v J1^»'»">w. rf^*^ •* *•
1 T
V
L
OHo
J
M+ = 180
1 1
J
100 ISO 200 250 300 350 4
so
•
•
-10
•
•
•
0
00
H. MILLER 3-29-76 3TEP MflSS-1, I/B/S « IZ
Figure B-14. Mass spectrum of 2-isopropyl-4-ethoxy-6-methyl pyrimidine.
-------
100-;
90-
60-
70-
60-
10-
10-i
30-
20-
10-i
0"
<-i > r i i < i
0
•
jJl
1
J I J
i | 1 i ' 1 •> 1
g.
I
J In
i '
1 1
1
r 1 ' r '
II
I
0,0-olecnyl ctny ipnospnonocnioace
|
C2"5Jc?"5
M+ = 182
""l"7™ i~T-T™r™T •"T™i"'|-^~T"T"|-T~T"'r^™'^""'-T"T"T-'™T1'n~T'7"1~T~r~r~'""r i— i—r-fi-T-i-T-r- r"1'1"1!
50 100 ISO 800 850 300 350 HI)
ECS 21131 JS 80H3MJH - 30433jn STEP ttftSS-1^ I/-B/S » 1 ;<
Figure B-15. Mass spectrum of 0,0-diethyl ethylphosphonothioate.
-------
00
100-
90-
80-
70-i
60-
so-i
30-|
1 0-:
1
-i i r r ' i ' i • f T^ 1 *" i
0 50
LiLbm
•^r1
i
00
»iThnnift%
tJ I
' ' T '"T
ISO
' ' y V V
R
C.H.O-P-OC,!!,
25 25
i >C.H
2 5
M+ = 182
1 il
200 250 300 350 HI
-eo
->o
SPEC» £0467 JS
STEP
* i;:
Figure B-16. Mass spectrum of 0,0,0-triethyl phosphate.
-------
VO
joo-a
:
90-i
80-
70H
to-
50-:
40-
30-
20-
1 0-
'
EC 8
T
0
578
L,
[•"Y^F
B L
I,
,•"1 1 1
8 S
1 i f I
50
738Lr
I '
1
mf
1 00
57ai>LH
1
UmM-M
150
0,0-dlethyl-O-methyl phosphorothloate
C^HcO S
\15
c2i.5ox "°C"3
M+ = 184
i i 1 ' i i i i i ' i i 1 i i i i i i i-i i 1 '•-! ' i i i i , . 1 . i . j . i i i i
200 250 300 350 -II
STEP MfiSS'l, I-'BxS ' \7.
•
•10
•
3D
Figure B-17. Mass spectrum of 0,0-diethyl-O-methyl phosphorothioate.
-------
100-
90-
60-
70-
60-
50-
)_. 40-
O
o
30-
EOH
1 OH
0J
1 I "• i^
0
.
1
[j
bo
U,
J
1 o,0-diethyl-S-raethyl phosphorothloate
C2H5°^lsCH2
C2»50/
^fl = 184
L-iJiJ
1
i lUlil i
, 1, ..
100 ISO 200 250 300 350
SPEClt 29701 LS 2101-flO 6CMS H M 4-2-76 STEP I1ASS*1> l/fs/S • IK
' I
4 o •;
Figure B-18. Mass spectrum of 0,0-diethyl-S-methyl phosphorothioate.
-------
I 00-3
90-
60-
70-j
6CH
50-
HO-
30-
EO-
1 0-
0-
jUr^-tU
0 50
rc« 301MH tIS 30144JM -
1
I b
1 11^ H 1 flllfll 1 1 VlUJI^ lullltlfUl^l''!!!
1 00 150
O.O-Di methyl phenylphosphonate
0 OCH3
(fV^OCH'
"k^
M^ - 186
SOfi £50 300 3SO
301M3JI1 STEP Pin'SS'l. IxB^'S > I ;;
Figure B-19. Mass spectrum of 0,0-dimethyl phenylphosphonate.
•in.
-------
100-
96-
e°H
60-
50-
O u ,-, J
Ni ' :
30-i
i o-4
(i
50
160 1 i> i)
SPECS 39559 .IS 29559.111 - H'^51 Ul
S-F.tliy I hexahydro-lH-azepine-1-carbothtoate
(mollnate)
Mf = 187
••HO
300
H 00
STEP MH'5S= 1 • I-'B'
Figure B-20. Mass spectrum of S-ethyl hexahydro-lH-azepine-1-carbothioate (molinate).
-------
100-j
90-
80H
70-
60-
50-
0 HO-
Ui
30-
20-
10-
9-
•
nJLj
0
In |l
50
I, ,1
^Ti^r
SPECI! 5733 US S783LI1 -
Lu,l
L
NI""I""IH •j'—i—'i
1 00
S78SLM
i
i""
,
,1
i
1 i li
0,0-Dl ethyl phoapliorochlorothloate
C^5\lcl
C2H50
M* - 188
I
150 BOO 350 300 350
STEP «fl33>l. I''B .'•-. = IK
Figure B-21. Mass spectrum of 0,0-diethyl phosphorochlorothioate.
-------
I 00-
90-
80-
70-;
frOH
E01
40-j
3D-]
I 0-\
0'
0
L -j
in ..i|,,,i|t
SO
1 00
S-Ethyl dipropyl thiocarbamate (EPTC)
Cll CPH ff II ^
f^lt ir DLiW ^Lcill-y )
-------
o
Ul
1 6 0 -j
t
90-
eo-l
70-
60-i
60-
HO-!
30-
eo-
10-
j l|, ,L
'^•.T-IIiJniffll1 m(|iih|h>
0 50
6PECIS 10376 LS 103."CLri
III
100
I 03?t)Lt1
ISO
O,O-Dlethyl-S-eChyl phoaphorothioate
C2H5
M+ - 198
.t.ii.^.T lp .ij.iyi. |- -| ", t.j .• |l |.'l
600 SB (>
SIEP Mfii? - 1 . ) .
3 l.n
' i
•jr-.ii
Figure B-23. Mass spectrum of 0,0-diethyl-S-ethyl phosphorothioate.
-------
1 00-
90-
60-
70-
fcO-
i
BOH
40H
30-i
20-j
1 0-i
:
o-i
•l|l 1 VI H fl IftlltM jt|
| ,
r*'T
J
w 1
yl i J
ll
I
.11.
,
It, ,
'H *¥ I11"1"'! 1 | I1"'""!"
T™1 i |
II
r»nrt
OtO-Diethyl-S-methyl phosphorodithioate
/i U f\ ^Z
C2H50/ 3
M+ = 200
. .
P^^^^V-,
"
.
-1 0
•
-
•
0
SPECS
0 50 100
3171 LS 3171LM - 3169LII
50
800 £50 300
STEP IIHSS' 1 , I/B^S ' I
350
400
Figure B-24. Mass spectrum of 0,0-diethyl-S-methyl phosphorodithioate.
-------
100-;
90-
80-
70-
50-
HO-;
30-;
£0-
1 0-
0
SPECS 3014'^ J3
ijintm tqmiU «ftrrt|n .1
150
" 'i
a oo
0-Methyl-O-ethyl phenylphosphonate
>OCU3
OCH
200
STEP
3 i) 0
•• •?. ' !;:
350
T-I- --i-'j—.
H J
Figure B-25. Mass spectrum of O-methyl-0-ethyl phenylphosphonate.
-------
100-|
90-
80
70-
60-
SO-
,_, HO-
o
oo ;
30-:
eo-
,o-
__ jul
' i i i i i ' V '
I
1 Jtltiiflin .It ilifflllll. il
4Li|
ltlLl»P>.,ffl llji J,
r1!"1 rili|"Tnr^
i
O^O-Dimethyl phenylphosphonothioate
S DC1I3
OT XOCH3
M+ = 202
l""l I....I""!""!""!""!""!""!""!""!1'")""!""!""!""!""1""!""1""!""'""!""1""!""!""! '|»"l""|' T'"|""l»»f"T"(""l""
-
-
-JO
•
-
•
0 50 100
6PECU 5598 JS 5S98JH - S59SJH
150
800 £50 300 350
STEP HflSS=l, I'-B/'S - IK
HOC1
Figure B-26. Mass spectrum of 0,0-dimethyl phenylphosphonothioate.
-------
100-:
90-
80-
70-
60-
50-
10-
30-
20-
10-
0}.
\
1
In
JlL
1
i it
^-JiKik..^
..,..,.,,...,.,• |....|..,.j..,.
Uilin
MTnTritmnftfmtn
| ^mj^1j,|_^
1 ' 1 I i ' 1 '
O-Methyl-S-methyl phenylphosphonothioate
M+ = 202
I
SPECK
0 50 100
30197 JS 30197JM - 30J95JI1
ISO
a 0 0 250 30 D
STEP t1F»S3=l, I/B'S =
350
Hi)
Figure B-27. Mass spectrum of 0-methyl-S-methyl phenylphosphonothioate.
-------
1 0(1-,
90-
80-
70-
SO-i
:
i
HO-i
10-;
T
J^-^4Jr^J|M|J»rr41'
S-Propyl dipropyl thiocarbamate (vernolate)
\t
c3H7sc-N(c3n7)2
M+ - 203
a so 100
SPECt! 20514 J:3 2051HJM - £051 UK
ISO
•"'""l""i""l I '"I -|".r"T"T"|'"T"'|""i""p""|""i""f"i""| p-r^pr
£00 250 300 350
STEP HflS5=l, I-'BxS = IK
•1 0
H 0 (i
Figure B-28. Mass spectrum of S-propyl dipropyl thiocarbamate (vernolate).
-------
7«J
60-
so-i
HO-
30-
ao-
«"
~
0
S-Propyl butyl ethyl thlocarbamat^ (pebulate)
P C2H5
3 1 Xc«"9
M+ - 203
lllljllll |lll 1 ll | II
50 100 150 800 850 300 350 Ml
C8 81315 JS ai315Jt1 - ei311JH STEP MASS -I, I'P^S ' IK
Figure B-29. Mass spectrum of S-propyl butyl ethyl thiocarbamate (pebulate).
-------
0,0-Dlethyl-S-ethyl phospliorodithioate
C2H50 S
C2HO
SPEC* 11396 LS
1 00
1 13-90UI
ISO
£00 £50
STEP
300
= i::
350
Figure B-30. Mass spectrum of 0,0-diethyl-S-ethyl phosphorodithioate.
-------
100-g
90-
eo-
70-
60-
50-
1
HO-
30-
80-
10-
|.l.|M.|l»TH.|....,...|.U.|,..l|l..l|A..p,..|,.,r,.l,l...r..T|ll
nr
NlUpmpJ
8PEC8 56H3 JS
SO 100
56H3JH - S6HIJM
0,0-DJethyl phenylphosphonate
'-(OCH2CH3)2
214
ISO
ZOO £50 300
STEP HRSS'i, I-'B^-S = IK
...|..^....|....l,.,,|,n ,...T^r.~|...
350
rntnj*«TT F
40
Figure B-31. Mass spectrum of 0,0-diethyl phenylphosphonate.
-------
100-
90-
60-
*0-
50-i
40H
30H
BO-i
i
I 0-i
tcs
JJ. ll
0 5C
20599 JS gOSS
J,
"'T ' 1
1
>9JM
44*
- 2
1 , I,J
100 ISC
OS94JM
S-Ethyl cyclohexylethyl thlocarbamate (cycloate)
0
T
M+ - 215
I
1 800 ESO 300 350 4
STEP MflSS = l, I-'B'-S • IX
-
-30
\
-eo
-
10
00
Figure B-32. Mass spectrum of S-ethyl cyclohexylethyl thiocarbamate (cycloate).
-------
100-
90-j
60-
70-
60-
50-
HO-
30-i
BO-:
1 0-
O.J
'"'""I" 1 "'|""i"'l
0
,1
1 1
5
,
jl,
0
j
*
, 1,1)1,1 1
„., ,flp.p.
I 00
LUJLj,
1 1
150
0-Ethyl-S-methyl phenylphoephonothloate
s**J'*™*
Qj X°C"2CH3
M+ =216
iiJ Jiii. i iii i
£00 850 300 350 HO
SPECtt 30209 JS 30309JI1 - 30£1£JM
STEP ttflSS'l , IVB,"S = IV.
Figure B-33. Mass spectrum of 0-ethyl-S-methyl phenylphosphonothioate.
-------
100-
90-
eo-
70-
60-
50-
SO-
1
ao-i
1 O-j
i
0, •
*•*
.
I.I
* 1 1 1 1 1 1 'i ' 'i
|||
i,
i 1 1 i 1 i • ( i |
1
HL_L,J|
rni|iiii|iiii|i|«rt
i ,li
.,... |
O-Methyl-S-ethyl phenylphosphonothioate
l, ,„
0
M
IL^J SCH2C^3
M* = 216
i ...1. 1 1,
"1 1 ''""I1 " 1""' I11"' T'">""r 1"" | 1""'"" 1"" |""l""|-T~f | f "T.v,""| ...|.«!-j..| ..|...,r,|..,— p. ,. ..,. „,.,..
0 50 100 150 a 00 350 300 350 Hi]
ECB SOH9 JS 5049JM - SOMHJM STEP hflSS=l, I/-B/S = 1 X
Figure B-34. Mass spectrum of 0-methyl-S-ethyl phenylphosphonothioate.
-------
100-3
80-
SOr
HO-
30-
80-
4t
0 SO
6PECIS 5617 JS 5617JH
100
"T"
150
0-Ethyl plienylphosphonochlorothloate
ri
M+ - 220
|n^h|U|:..+.d|in|.nr_r.~|.-T-r..,~j.-l..T~,..-|...,....|..-,..,.|-.^....|.._l...
"T
EDO £BO 300
STEP llflSS'lr I/BxS = 1
3SO
-1 0
40D
Figure B-35. Mass spectrum of 0-ethyl phenylphosphonochlorothioate.
-------
00
100-
90-i
70-
60-i
SO-:
MO-J
£H
IMMIIIIf UUI j
o c
0
ImlmillllhliUHllIB'
"T ' f ' I
j, i\
SO
I It .itk
i tli iiiii iMmhiiHr'i
I
1 ll
00 150
J
mipmjitr
1! Illl 1
r -i-| •• i
800
2,4-Bis(ethylamino)-6-ethylraercapto-S-
trlazlne
SCH2CH3
Mx^s.M
N ^N
CjHjNH^^T^ HHCjBg
M+ - 227
i II i 1
850 300 350 HI
6PECO 88996 LS 3101-D GCHS H MILLER 3-S9-76
STEP rinss-i,
Figure B-36. Mass spectrum of 2,4-bis(ethylamino)-6-ethylmercapto-S-triazine.
-------
IOO-:
80
70-
60-
50-
10-
30-
ao-
1 0-
0-
i i i i i i i
1
I
1
I
1 1
1,
i li
I i| i
1 Jjil |IL.,|,M tltf^
50
100
O-Hethyl-O.S-dlisopropyl phosphorodlthloate
OC3H7
H1" - 228
6PEC« £2089 JS
s o o e 5 u 3 o ft
STEP nnss=i, i-'B.-s = i:r
1! BO
40 0
Figure B-37. Mass spectrum of 0-methyl-0,S-diisopropyl phosphorodithioate.
-------
100-
90-
80-
70-
60-j
so-j
HO-!
80-]
:
1 0-=
0
0 50
SPECK £3114 JS 23114JM -
1 00
150
0 , 0-Diisopropy 1-S-me thy 1 phosphorod i thioa te
-1 0
M4" - 228
200 £50 300
STEP MRSS'i, I-'B^S « t
350
HOC
Figure B-38. Mass spectrum of 0,0-diisopropyl-S-methyl phosphorodithioate.
-------
JOO-
90-
eo
70-
60-i
50-
30-
20-
1 0-
0,
_
EC It
0 SO
5670 JS S6/-OJM -
10
EbbBJI
...j...r{If.-t--n-|-— |-t«j
3
1
0,0-Diethyl phenylphoBphonothloate
S
X^^x^ (OCH2CB3) 2
M* - 230
1
'••••('•••il"1'"!" T""''-| i-'|"-r -I-T • c-i-if I- ,•-•, | - r™|""i""|""l""|""l'"T" i-'j""!""!'"'!""!""1"' l""'"'T'"i""|""l''"|"1i""r "'""I1 '!"
150 200 E50 300 350
STEP nnssM, IXB--S = ir.
•30
-ao
i D
-------
(S3
too
90
60
60
50
tlJfnVitntl
0,S-Diethyl phenylphosphonothionte
P-SCH2CH3
OCH2CH3
M+ - 230
u,
0 50 tOO
5687 JS 5627JM - S625.JM
150
i i | i i i j i r"i ,
200 £SO 300
STEP nnss=i, ixBx-s • t;;
£SO
•yi *t, .1. J,ju AJ, .. -i.. i. j,, ..r-j,|. ti.p-T- j... .|....
350
4 0 0
Figure B-40. Mass spectrum of 0,S-diethyl phenylphosphonothioate.
-------
CO
100-:,
09 *O
O O
70-
60-
50-
40-
30-
eo-
1 0-
0-
L
1 1
• I ' I ' I '*""
0
EC« 9S70 US
1
, 1
1
JJjUljl
50
1
L
i
j 1 1 ii ii
100 150
01 - 1 0-T4
J
1
jjJLL
0-Ethyl-S-phenyl ethylphosplionodlthioate
(fonofos)
C2H5foC2H5
If1" = 246
800 SSO 300 3 '.'.(•
STEP ttfiSSM, I^B-'S « I'/.
4 UU
Figure B-41. Mass spectrum of 0-ethyl-S-phenyl ethylphosphonodithioate (fonofos).
-------
NJ
•P-
i 00-
i
eo-j
i
70-j
so-i
MO-i
:
30-j
£0-1
I 0-1
50
104
ll
150
JujijJ JL
2,6-Di-tertbutyl-4-methoxymethyl phenol
Oil
CH2
OCII3
M4^ • 250
''""r"!11")1" i"V |""i»"|»''p'i""i""i i i""'""i "T i '!"" i i -rTT"'" 'i i i i
£00 350 30fl 35 ii H
EPECB 88'?30 US 3101-0 GCMS H.MJLLER 3-39-7fc
STEP MflSS= 1 , I^B^'S
Figure B-42. Mass spectrum of 2,6-di-tertbutyl-4-methoxymethyl phenol.
-------
K3
too
90-i
eo-
?o-i
bO
50-
•«0-
30-
eo-
10-
o
0 SO
SPECS 5663 JS S663JM -
0,O-Dlethyl chlorophenyl-
phoaphonothioate
Cl
M+ - 264
250 300
STEP IIBSS'J , I -B'-S * IK
350
•to
400
Figure B-43. Mass spectrum of 0,0-diethyl chlorophenylphosphonothioate.
-------
N3
1 OO-g
»OH
SO
>H
60-
EO-j
10-i
30-j
£0-j
I 0-=
.^,.|l(n|ml|niT|lnl}llT.|....fi1li|knJ. ..i.tlll^
SPECS
50 100
OS S749JM - B6H7JM
150
O-(Chloroamlnophenyl)-O-methyl
phenyIphosphonate
M+ = 297
200 850
STEP nnss«i,
300
I 0
r.|.^j....1,tHjf,..(,...j.,,,1.,,,j...,,,l,j,,.,|,,^j,inp™^mY'"|"'Y"T'^^"'J1TT'1
350
4 0 il
i::
Figure B-44. Mass spectrum of 0-(chloroaminophenyl)-0-methyl phenyl phosphonate.
-------
0-(4-Nitrophenyl)-O-etliyl phenylphosphonothioate (EPN)
100-3
90-
eo-
?°1
t,0-
50r
HO-
80-
1 0-
0-
I
1
1. ,,
,.,....,. , .., ..., ...,....,. . , . ,. Jf , .., , ( , , | j. , y-,
0 50 100
ECtt 5,'Sa JS 578SJI1 S780jrt
h-i,.t..i..HiM......j.lifl
U4
i
8X0
Qf^ ^
^
j
tf ' 323
, „ 1. 1 I, .
IH.|,.I.I,WJI j...,,, p,,^ ,. ,Y"T"T'"r"Y"r'"('n'ri'^""i""f-'N'"-j"ii'"^"i""('''i"^p'"i"^"T"'T"i^""Pmp^T""j"'r^^
J50 200 050 300 350 4 d
STEP MflSS=l, I--B^S = I.1:
Figure B-45. Mass spectrum of 0-(4-nitrophenyl)-0-ethyl phenylphosphonothioate (EPN).
-------
0-(4-Nitrophenyl)-0-ethyl chlorophenylphosphonothloate
ho
00
t 00-:
90-
eo
60
50
MO-
30-
^o-.
lo-i
o
-T"—"r^fW^S
0 50
SPEC9 5385 JS 588SJI1
M+ • 357
£00 £EO 300
STEP tlflSS'l- I^BXS = IK
350
HO
Figure B-46. Mass spectrum of 0-(4-nitrophenyl)-0-ethyl chlorophenylphosphonothioate.
-------
ro
vo
00-.
1
90-|
i
80-.
70-i
4,0-
EO-
HO-
30-i
eo-
10-
0-
1
^^.dlbiii
I L,
1
.nil i l.i „!. .1 i. , 1. 1.
T 1 1 1 1 1 1 I 1 f 1 T ' 1 • 1 ' 1 ' | ' 1 ' 1
l.,1|..ll|.rti
0 50
SPEC!! 86730 JS 36730JM -
100
150
0- (Chlorobromoamlnopheny 1 )-O-methyl phenyIpliosphonate
M+ = 375
a 0 0 £50
SIEP nnss= i ,
300
10
350
S 0
i;:
Figure B-47. Mass spectrum of 0-(chlorobromoaminophenyl)-0-methyl phenyIphosphonate.
-------
1 00-
90-
eo-
70-
fcO-
50-
f 0-j
30-;
£0-;
P,-
CIS
1
,1.1.
D SO
5303 JS S803JM -
I
1 OD
5850. .1(1
150
0- (Chlorobromoarainoplienyl)-O-ethy 1 pheny Ipli
91
(II OCH2CH3 ™«2
-
M+ - 389
|| [ 1 ! }l 1 1 |r 1 1 | ! it t i i '*iM i 1 1 1 i h - ill Jtr f i Ir nil i i
300 SSO 300 35 f
S TEP Mfl:3S= 1 , I--e-'S = i ::
r ' i i
Figure B-48. Mass'spectrum of 0-(chlorobromoaminopheriyl)-O-ethyl phenyIphosphonate.
-------
TECHNICAL REPORT DATA
(f lease read Instructions on the reverse before completing)
REPORT NO.
EPA-600/4-78-056
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Organic Compounds in Organophosphorus Pesticide
Manufacturing Wastewaters
5. REPORT DATE
September 1978 issuing date
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
M. Marcus, J. Spigarelli, and H. Miller
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Boulevard
Kansas City, MO 64110
10. PROGRAM ELEMENT NO.
1BD713
11. CONTRACT/GRANT NO.
68-03-2343
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Research Laboratory - Athens, GA
Office of Research and Development
U.S. Environmental Protection Agency
Athens, GA 30605
13. TYPE OF REPORT AND PERIOD COVERED
Final. 6/75-10/77
14. SPONSORING AGENCY CODE
EPA/600/01
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Preliminary survey information on the organophosphorus pesticide industry
wastewater streams and analytical methods to monitor_ levels of organic compounds pre-
sent in these streams are presented. The identification and quantification of organo-
phosphorus compounds was emphasized, but nonphosphorus chemicals were also included in
the survey. A secondary goal of the program was to use the survey information to
evaluate the efficiency of various waste treatment processes.
The wastewater from five pesticide plants that produced eight organophosphorus
pesticides was sampled. The pesticides were diazinon; methyl parathion; azinphos-
methyl am?*disulfoton; fonofos, phosmet and bensulfide; and EPN.
The 116 compounds identified included organophosphorus pesticides, related
organophosphorus esters, organophosphorus acids, volatile organic compounds, thiocar-
bamate pesticides, triazine herbicides, and miscellaneous extractable process chemi-
cals, by-products, and compounds of unknown origin.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Chemical analysis
Organic compounds
Pesticides
Wastewater
Water pollution
Water quality
07C
68D
68E
3. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
143
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
131
ft U.S. GOVERNMENT PRINTING OFFICE: 1978— 657-060/1507
------- |