EPA-660/2-74-032
April 1974
Environmental Protection Technology Series
Movement
I
55
UJ
O
Office of Research and Development
U.S. EnvironmentaI Protection
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five bread
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
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2. Environmental Protection Technology
3. Ecological Research
i*. Environmental Monitoring
5. Socioeconomic Environmental studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
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technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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PESTICIDE MOVEMENT FROM CROPLAND INTO LAKE ERIE
By
Dr. Acie C. Waldron
Ohio State University
Columbus, Ohio 43210
Project 13020 EBL
Program Element 1BB039
Project Officer
Dr. George W. Bailey
Agro-Environmental Systems Branch
Southeast Environmental Research Laboratory
Athens, Georgia 30601
Prepared For
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
LIBRARY
Environ. Prot. Agency, WQO
Edison, Msw Jersey 08817
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.40
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ABSTRACT
Gas chromatographic analysis of water and bottom mud sediment samples
collected monthly during a one-year period from sites on the Maumee, Portage,
Sandusky, Huron, and Grand River systems indicated only very infrequent and
sporatic occurrence of minute concentrations of pesticide residues. Samples
were analyzed for organochlorine and organophosphate insecticides and for
triazine and chlorophenoxy acid herbicides.
Concentration of residues in the few positive analyses were generally less
than 10 parts per billion for detected insecticides and less than 50 ppb
for triazine herbicide. Diazinon, dieldrin, and the DDT family of compounds
were the most common insecticides detected. Atrazine was the most often
detected herbicide. An indication of chlorophenoxy acid herbicide residue
in one water and one bottom sediment sample was very questionable. The
insecticide residues were generally associated with bottom sediment, whereas
atrazine was associated with both water and sediment samples.
The association of pesticide residues with particular river sites and sampl-
ing periods was inconsistent although limited correlation between residue
occurrence and the early spring agricultural soil preparation and planting
season was observed at one or two sites on two rivers. No valid basis
was provided to adequately assess the agricultural versus municipal sources
of pesticide contamination. During the period of this study, it appeared
that pesticide contamination of northern Ohio rivers was negligible and
the contribution to pesticide pollution of Lake Erie was insignificant.
This report was submitted in fulfillment of Project No. RF 3256-Al and
Contract No. 13020 EBL under the sponsorship of the Office of Research
and Development, Environmental Protection Agency.
ii
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CONTENTS
Section
I
II
III
IV
V
VI
VII
VIII
IX
Conclusions 1
Recommendations 3
Introduction 4
Sample Collection 7
Sample Preparation and Analysis 9
Results and Discussion 10
Acknowledgements 14
References 15
Appendices 18
iii
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TABLES
No. Page
1 Sampling Sites 20
2 Soil Characteristics and Cropping at Sampling Sites 23
3 Sample Collection 27
4 River Flow Data: Auglaize River near Fort Jennings 31
5 River Flow Data: Auglaize River near Defiance 33
6 River Flow Data: Maumee River near Defiance 35
7 River Flow Data: Tiffin River near Stryker 37
8 River Flow Data: Maumee River at Waterville 39
9 River Flow Data: Portage River at Woodville 41
10 River Flow Data: Sandusky River near Mexico 43
11 River Flow Data: Sandusky River at Fremont 45
12 River Flow Data: Huron River at Milan 47
13 River Flow Data: Grand River near Madison 49
14 Organochlorine Insecticide Residues in River Water and 67
Bottom Sediment Samples
15 Triazine Type Herbicide Residues in River Water and 79
Bottom Sediment Samples
16 Chlorophenoxy Acid Type Herbicide Residues in River 84
Water Bottom Sediment, and Mussel Samples
17 Organophosphate Insecticide Residues in River Water 89
and Bottom Sediment Samples
iv
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SECTION
CONCLUSIONS
Based upon the experimental design and the analytical results of this
study, the contribution of agricultural and municipal sources to the
pesticide residue pollution of Lake Erie in 1971-1972 was negligible
and insignificant. The results of the study provided no real basis for
comparing the pesticide pollution contribution from agricultural use of
pesticides to that attributed to municipal, residential, and industrial
use. Termination of the study after only one year of sample collection
seriously curtails the reliability of making any valid evaluation of the
actual situation. A certain percentage of the experience, technique, and
data of the first year could have very profitably been utilized in making
adjustments so that subsequent year's procedures, etc., would have pro-
vided for more valid and meaningful evaluation.
The data indicate that at the times of the sampling on the five rivers
there were no significant problems with pesticide contamination. The very
few positive residue values obtained for atrazine or simazine at generally
less than 50 ppb and for diazinon and dieldrin at less than 10 ppb indicated
some association of residue in the streams during the spring soil prepara-
tion and corn planting season. If pesticide residues were to drain from
agricultural land due to runoff from rainfall, etc., this is one particular
season of the year that some contamination of water ways could be expected
because it is the season during which a large percentage of pesticides are
used and the vegetative cover offering protection from soil erosion during
rainfall is at a minimum. Only in the case of occurrence of triazine herbi-
cides was there noticeable correlation of residues between water and bottom
sediment samples and with subsequent sampling at the particular sites at
the later 2 week or 1 month interval.
The data obtained in this study produced no indication of pesticide pollution
problems from any of the insecticides and herbicides involved. Generally
the insecticides from these categories that might be of concern because of
use in Ohio agriculture are aldrin-dieldrin, heptachlor-h<>ptachlor epoxide,
diazinon, and parathion. Triazine, 2,4-D and dicamba herbicides are used in
weed control programs. DDT and consequently its metabolities and 2,4,5-T
are no longer used in Ohio agriculture and in fact have had very limited
previous use for a period of several years. Residential use of all of
these materials would be considerably curtailed because of recommendations
and restrictions. Some industrial use in municipalities might occur. In
most cases, pesticide residues could be present in the streams originating
from agricultural land only in period of excessive rainfall and subsequent
movement of soil into the streams through runoff.
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As indicated previously, the data provide no basis for assessing the
contribution of agricultural versus municipal, residential, and indus-
trial sources to pesticide pollution of waterways. Nor with the limita-
tion of data presently available from this study is it possible to
accurately relate pesticide residues in streams with soil characteristics,
topography, cultivation, and cropping practices.
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SECTION II
RECOMMENDATIONS
It is very unfortunate that this study was terminated after only year
and not permitted to continue for the three-year period designated in the
proposal. The criteria for a one-year program would probably have been
considerably different than that of the three year agreed upon by EPA and
The Ohio State University in that the collection and concentration of
effort would probably have been changed in order to provide for more
meaningful sampling and consequent evaluation of the situation. We learn
considerably during the first year of a relatively long-range program of
the adjustments in proposal design and techniques that will make subse-
quent procedures more adequate to meet the goals of the project.
At the present time, the data gives no basis for assessing any particular
problems in the use of pesticide chemicals either in agricultural or
municipal surroundings. Therefore, no recommendations are made herein to
affect pesticide use practices as long as they are used in accordance
with the registration, label,and necessary precautions befitting the situa-
tion.
It is recommended that the continuation of this study be reconsidered.
Modifications in time and techniques of sampling should be considered in
order to provide for optimum evaluation of the actual situation. This
would mean more intensive sampling during the seasons when pesticides are
being used with less effort during the non-use seasons. Better timing of
sampling to correspond with heavy rainfall and the subsequent high river
flow and also with periods of low river flow during the growing season
would provide better means for evaluating the movement of pesticide resi-
dues from the point of application to the water way systems. Better
techniques in the procedures for obtaining more representative water
samples from large rivers should also be considered.
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SECTION III
INTRODUCTION
The well known pollution of Lake Erie has caused a decrease in the desir-
able commercial fish and a deterioration in the water quality which grossly
affects the recreation and water usage of the lake. Many sources contribute
to the pollution of this body of water, causing it to be termed by some "a
major cesspool problem" for the United States. Concern has been expressed
at times relative to pesticide contamination associated with the river
drainage systems and the contribution of agriculture to such contamination.
However, the pesticide content of the streams and rivers flowing through
these intensified agricultural areas of Ohio and hence into Lake Erie has
never been determined. Nor have related comparisons been made between agri-
cultural and urban sources of pesticide contamination in these areas. It
thus becomes necessary to determine the sources and extent of pesticide
contamination in order to provide guidelines to control and/or regulate
the flow of pesticide residues via these rivers into Lake Erie. If agricul-
tural lands are contributing significant quantities of these residues,
research should provide a correlation between pesticide residues in the
drainage systems, agricultural practices and soil types. Once the sources
are determined and such relationships established, appropriate action might
be taken to alleviate the problem. This study in Ohio would also correlate
with work being done in Michigan and Wisconsin to not only provide informa-
tion on pollution in Lake Erie, but also provide a picture of the Great
Lakes region.
Considerable investigation has been and is being conducted in the United
States concerning the monitoring of agricultural soils and river drainage
systems for pesticide content. (Health Aspects of Pesticides - Abstract
Bulletin 1968-71 and Pesticide Monitoring Journal 1968-71). In 1957, the
the Public Health Service of the U.S. Department of Health, Education and
Welfare began a surveillance system for chemical, physical, and biological
water quality in relation to pollution. This monitoring program had grown
to 131 sampling sites in the U.S. by 1966. From 1959 through the winter
of 1962-1963, the residue levels of DDT, toxaphene, and BHC were monitored
in the water emanating from an agricultural watershed in northern Alabama;
samples being taken from both the untreated and treated water at a munici-
pal purification plant located at the river confluence (Nicholson, et al ,
1964). The impact of these residues on the nature and distribution of the
zooplankton, bottom fauna, and fish in Flint Creek was studied (Grzenda,
et al, 1964). In 1964, a monitoring system was initiated by the USDA at
five locations on the lower Mississippi River Delta. In 1965, the U.S.
Geological Survey initiated a limited program of pesticide monitoring on
11 streams in the Western United States (Brown & Nishioka, 1967). Also in
1965, a monitoring program for chlorinated hydrocarbon pesticides in soil
and root crops was initiated in the eastern states (Seal, et al, 1967).
In 1966-67, researchers from the Department of Fish and Game in California
(Modin, 1969) monitored selected estuaries from northern to southern Cali-
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fornia to determine chlorinated hydrocarbon pesticide residues in oysters,
mussels, shellfish, and other fish species as related to offshore exposure
and to agricultural and urban areas. As reported in Volume 1, Number 1
issue of the Pesticides Monitoring Journal, June 1967, Federal Departments
of Defense, Interior, Agriculture and HEW are in the process of initiating
and conducting surveys of pesticide content in soil, water, tissues, and of
organisms existing in such medium throughout the United States. Results of
these surveys have been published in subsequent issues of the journal as
the data has become available.
In the water surveys conducted under the direction of the Federal Departments
indicated in the preceding paragraph, sampling sites were selected at the
mouths of major streams throughout the country and in some locations in mid-
dle or upper areas of some streams. This monitoring program, however, did
not include any of the northern Ohio rivers that empty into Lake Erie. The
survey also does not attempt to establish the sources of pesticide pollution.
Agriculture, because of its wide use of pesticides, will in all likelihood
bear the brunt of public disdain as the major cause of pesticide pollution
of the water resources, particularly among those who are not agriculturally
oriented or unknowledgable scientifically with the problem.
Pesticide residue monitoring on some major streams in Ohio has been conducted
by the Ohio Department of Health since 1966. This program has been concerned
basically with water quality and consequently with trace amounts of pesti-
cides in grab samples. No attempt was made to determine source of contamina-
tion. The Plant Protection Division of EPA as a part of the federal monitor-
ing system has selected 312 sampling sites on cropland and non-cropland in
Ohio. Data accumulated during the 4-year study (2 years results now tabu-
lated) will associate residue with watershed as a potential stream pollution
problem.
Our laboratory, The Cooperative Extension Service Pesticide Analytical
Laboratory, has conducted residue analysis for the past 3 years on surface
and tile drainage waters from controlled agricultural plots in a project
designed to determine the role of agriculture in stream contamination.
Such data will supplement that derived from the project reported herein
from the past year's collection and monitoring of water, bottom sediment,
and clam samples from major rivers in the Lake Erie watershed.
Programs which have been or are now underway in several states on the soil
and water monitoring program are concerned principally with DDT and related
chemical residues. In Massachusetts (Lyman et al, 1968) the investigation
was for DDT and its metabolites in fish in all the major watersheds during
1965, 1966 and 1967. In Oregon (Marston et al, 1968) the study centered on
the movement downstream from a watershed sprayed aerially with the herbicide
Amitrole. In Arizona (Ware et al, 1968-1971) the study involved the movement
and persistance of DDT in the soil. Other investigators such as Swoboda
and Thomas, 1968; Nash and Woolson, 1968; and King and McCarty, 1968, have
studied the movement of pesticides in the soil. Bailey and White, 1964;
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Bailey, 1966; and Bailey, 1968 investigated the role of soil chemical and
physical properties, absorption and desorption, and climate on the relation-
ship of pesticides in soils and drainage water. Epstein and Grant, 1968,
studied the chlorinated pesticide content of runoff water in Maine potato
fields as affected by crop rotation. Many other studies too numerous to
cite individually (Journal of Agricultural and Food Chemistry, 1965-1971;
Bulletin of Environmental Contamination and Toxicology, 1966-71; Pesticide
Monitoring Journal, 1968-71; and other journals) have likewise been concerned
with the fate of pesticides in soil, water, and commodities. Although all
these studies have direct relationship to possibilities of pesticides in
the drainage from agricultural land, research is yet needed to determine
the source of stream pesticide pollution in the Lake Erie watershed and
relate it to the agricultural and urban cultural practices or waste disposal
methods, the soil types, topography, etc.
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SECTION IV
SAMPLE COLLECTION
Sites for sampling water and corresponding sediment were selected at
appropriate locations representing agricultural and municipal areas along
the tributaries and the main streams of the Maumee, Portage, Sandusky,
Huron, and Grand Rivers in northern Ohio. (See Appendices I and II) Sites
were preferentially selected to show pesticide residue runoff from intensi-
fied agricultural areas and to contrast that with pesticide levels in the
streams after the influence of drainage systems of large communities or
cities. Sites that would exhibit the influence of heavy industrial manu-
facturing, pesticide formulation, and barrel reclaiming areas were generally
avoided. Sites were also selected at the mouths of the rivers as they flow
into Lake Erie and around the islands near Sandusky Point.
Water samples, bottom sediment samples, and fresh water clams (where
available) were collected from each site on a monthly basis or more often
following periods of heavy rainfall and runoff. (See Appendix III)
Sampling was done as feasible during the inclement cold weather of late
December, January, and February (ice conditions on rivers and the lake
generally make sampling prohibitive during this period). Water samples
were obtained with a model 1200 Ekman Water Sampler and transferred to
clean aluminum foil capped, one-half gallon glass milk bottles for trans-
port to the laboratory. Approximately one gallon of water was collected
at each site. Sediment samples were collected as the water sediment inter-
face from the bottom of the river at appropriate locations across stream
with a six inch model 196 Ekman Dredge. A weighted Model 196 dredge was
used at locations in the river and in the lake where the bottom was deep.
Sediment collections were transferred to plastic bags for transport to the
laboratory and after removal of the water were transferred to large Dixie
cup type covered containers. Clams were collected by hand from the natural
beds located in the bottom of the streams and were transported to the
laboratory in plastic bags. Flexibility in a sampling was maintained be-
tween rivers and sampling sites so that if problem areas arose they could
be adequately evaluated as required and modifications made in the intensity
and frequency of sampling of the particular area.
Water samples were generally extracted as received in the laboratory by the
appropriate procedures outlined in Appendix V. The extracts were then
stored in a -20°Cfreezer until analyzed by gas chromatography for residues
of organochlorine insecticides such as DDT, aldrin, dieldrin, heptachlor,
lindane, methoxychlor, and appropriate metabolites considered of significance
in the ecosystem; for organophosphate insecticides such as parathion, mala-
thion, diazinon and others considered of agricultural importance in the
appropriate areas; and for herbicides common to Ohio agriculture including
the chlorophenoxy acids and triazines. Bottom sediment samples were stored
in the freezer until the time schedule permitted their extractions accord-
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ing to the procedures outlined in Appendix VI. Likewise the extracts were
stored in the freezer until analyzed by gas chromatography. Clam samples
were stored in the freezer upon arriving in the laboratory. They were not,
however, analyzed for pesticides residues in this study because of the
limited number of samples obtained.
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SECTION V
SAMPLE PREPARATION AND ANALYSIS
Samples were prepared, extracted and pesticide residues analyzed by the
procedures outlined in Appendix V and VI. Confirmation of residues was
accomplished by the comparison of gas chromatography on 2 or more columns
and in many cases two or more gas chromatographs, by determination of p
values and in some cases by bromination. The following gas chromatographic
conditions were utilized.
a. Organochlorine pesticide residues: (1) Barber Colman Series
5000 Gas Chromatograph equipped with a Trituim foil Electron
Capture Detector and a 6 ft column of 10.4% DC-200 plus 15.1%
QF-1 (mechanical mixture) on Gas Chrom Q operated at 180-190° C
with detector at 210° C and injection port at 215°. Nitrogen
used as carrier gas. (2) Varian 2100 Gas Chromatograph equipped
with a Ni Electron Capture detector and columns: 6 ft of 3.0%
SE-30 Variport 30 and 4 ft of 5% Dexsil 300 on Gas Chrom Q
operated at column temperatures of 175-190° C, detector temera-
ture 240-245° C and injector temperature of 220° C. Nitrogen
used as carrier gas. (3) Tracor Microtek 220 Gas Chromatograph
equipped with a °%i Electron Capture detector and columns: 6 ft
4.5% DC-200 plus 0.5% Epon 1001 on Anachrom ABS operated at
column temperature 180-190° C, detector temperature 260° C and
injector temperature 225° C. Nitrogen used as carrier gas.
b. Triazine herbicide residues: (1) Varian 2100 GLC equipped
with alkali flame ionization detector with columns: 6 ft SE-30 on
Variport 30 and 4 ft 1.0% OV-17 plus 2% OV-210 on Gas Chrom Q
operated at temperatures indicated for organochlorine pesticide
residue analysis. Hydrogen and Nitrogen flow rates were adjusted
to provide for optimum sensitivity. (2) Barber Colman Series
5000 GLC equipped with detector and column as above for organo-
chlorines. (3) Tracor Microtek 220 equipped with bJNi Electron
Capture detector and 4 ft column of 1.0% OV-17 plus 2.0% OV-210
operated at temperatures indicated for organochlorines.
c. Organophosphates. (1) Varian 2100 equipped with AFID and
columns: 6 ft SE-30 on Variport 30 and 4 ft 1.0% OV-17 plus 2.0%
OV-210 on Gas Chrom Q operated as above for triazines.
d. Chlorophenoxy acid herbicides. Analyzed on all three gas
chromatographs listed previously for analysis of organochlorines
and utilizing all columns thus listed with the exception of the
Dexsil 300.
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SECTION VI
RESULTS AND DISCUSSIONS
The tabulation of analytical data from analysis of water and bottom
sediment is contained in Appendix VII. Results for organochlorine
insecticides, triazine herbicides, chlorophenoxy herbicides, and organo-
phosphate insecticides are found in Table 14 through 17 respectively.
The number of mussel samples collected was too few to be of significance
and consequently such data is not included in the tabulation. The river
flow data, indicating periods of runoff caused generally by drainage from
rainfall or irrigation, as compiled by the Geological Survey for the period
of time spanning the sampling is listed in Appendix IV. Soil character-
istics and cropping practices associated with the general areas of sampl-
ing are shown in Appendix II.
The analytical methods used in this study were capable of measuring organo-
chlorine pesticide concentrations as low as 1.0 part per trillion in
water and 10 parts per trillion in bottom sediment and in the sub-part
per billion range for other pesticides (although the sensitivity levels
were established as indicated below). The gas chromatography instruments
were capable of measuring as little as 15 picograms of aldrin with one-half
scale recorder response. Thus extremely low concentrations of pesticide
residue could be measured with accuracy. At those extremely low levels
of measurement, the background for some samples sometimes became bothersome
and consequently required additional analysis with other chromatographic
systems (columns and instruments as indicated in Section V) in order to
determine the presence or non-presence of pesticide residue. In addition
"p" values were calculated in confirming residues (partitioning coefficient
of the pesticide between equal volumes of hexane and acetonitrile). When-
ever the resolution of the gas chromatographic peak was doubtful or re-
analysis and "p" value calculation still resulted in non-evaluable results,
the entry was left blank for the particular sample and pesticide residue
in question. Astericks in place of numbers in Tables 14-17 indicate that
the representative peaks for the residue involved were observed by two or
more gas chromatographic systems but that the "p" value was slightly out-
side the accepted book value range and the value range determined accord-
ing to our laboratory techniques. Consequently, no residue values were
calculated for those particular samples and it is doubtful that any resi-
dues were present. The letter "N" in Tables 14-17 indicate that no
pesticide residues were determined at the sensitivity level of approximately
1 ppt in water and 10 ppt in bottom sediment for organochlorine insecticides,
and 0.1-1.0 ppb for organophosphate insecticides, 0.5-1.0 ppb for triazine
herbicides, and 0.5 to 1.0 ppb for chlorophenoxy acid herbicides in water
and bottom sediment respectively.
The occurrence of organochlorine pesticide residue in water and bottom
sediment samples is recorded in Table 14. Some .indication of residue was
evident in the initial analysis but confirmatory analysis by the procedures
indicated in the preceding paragraph failed to substantiate such presence.
Five water samples gave indication of residue but could not be satisfactorily
10
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substantiated via the confirmatory process. Several blanks in the table
of data indicate non-availability of analytical data or the uncertainity
of results as indicated in the preceding paragraph.
Seventeen of the bottom sediment samples gave positive residue indication
for dieldrin with 15 more possible (denoted by asterick) but not positively
confirmed; 11 samples contained p,p'-DDD with 7 more possible; 2 samples
contained p p'-DDT; and 4 samples contained p,p'-DDE with 2 more possible.
There was no apparent correlation in the samples for occurrence of the DDT
isomers and metabolites. Concentrations of dieldrin ranged from 1.06
parts per billion to 17.6 ppb with an average for the 17 samples of 5.54 ppb.
Concentration of p,p-DDD in the confirmed samples ranged from 0.7 ppb
to 158.54 ppb with an average of 15.77 ppb. All except 2 samples were
below 8.0 ppb. The two samples containing p,p'-DDT were at 5.1 and 16.44
ppb and the range of the 4 samples containig p,p'-DDE was 2.1 to 34.6 ppb
with 3 of the samples less than 3.2 ppb. Thus the concentration of organo-
chlorine pesticide residue showing positive in this small fraction of the
total sampling was negligible and insignificant.
The occurrence of triazine herbicide residues in water and bottom sediment
samples is shown in Table 15. Ten water samples and eleven bottom sediment
samples gave indication of atrazine (2-Chloro-4 ethylamino-6-isopropylamino-
a-triazine) residues and 4 water samples appeared to contain simazine
(2-Chloro-4,6-bis(ethylamino)- s - triazine). Atrazine residues in such
water samples ranged from 2.73 to 69.44 ppb with an average of 23.82 ppb
and in bottom sediment from 4.47 to 95.19 ppb with an average of 43.27 ppb.
Simazine concentrations in the four samples were 26.40, 29.93, 32.40, and
238.86 ppb. Some correlation of triazine residue was observed between
the water and corresponding bottom sediment samples in that when residues
were determined in water they were also generally found in the bottom
sediment samples from the corresponding or next adjacent sampling site.
The most common occurrence of triazine herbicide residues was associated
with the spring cultivation season and generally with agricultural related
sites. In several cases, residues were determined in the samples from the
same site at each sampling period during May and June. Triazines are used
quite extensively in Ohio for weed control in corn. The occurrence of
minute traces of atrazine following irrigation or rainfall was also noted
by Schwab et al, 1970 and 1971 in studies conducted on drained research
plots at the Castalia Branch of the Ohio Agricultural Research and Develop-
ment Center.
Residues of chlorophenoxy acid type herbicides were practically non-existent
in the water and bottom sediment samples collected during this study (Table
16). The only exceptions were two samples; i.e. a water sample containing
an apparent residue of 7.0 ppb 2,4,5-T and a bottom sediment sample with an
apparent residue of 22.7 ppb dicamba (3,6-Dichloro-o-anisic acid). Initial
investigations had indicated that minute concentrations of 2,4-D and dicamba
might have been present in several samples but additional analysis on
different chromatographic systems did not confirm such occurrence. The
11
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vater sample was associated with an agricultural site on the Portage
River in late June and the bottom sediment sample with a municipal site
on the Huron River in mid-May. The occurrence of the herbicide residue
at each of these respective sites is not explanable in that 2,4,5-T is
no longer registered for agricultural nor home owner use (only for non-
cropland) and dicamta would not generally be associated with municipal
use. The only explanation for the latter would be an industrial spill
or dumping or the disposition of material from agricultural areas of the
river. In view of the fact that no indication of dicamba (or 2,4,5-T)
residues were found at any other locations nor at any other sampling
date casts considerable doubt on the validity of the residues indicated
above.
The analytical data for organophosphate insecticide residues are tabu-
lated in Table 17. The only valid occurrence of residue was in the bottom
sediment at two sites on the Huron River from the May and June 1972 samp-
lings. Two other occurrences, one from the Maumee River sampled in
December and one from the Huron River in December are not explanable
unless some waste was dumped at those times. Concentrations of residues
in the six bottom sediment samples indicating diazinon (0,0-Diethyl
0-(2 isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate) were very low
ranging from 3.6 to 13.6 ppb. One sample from site No. 1 on the Huron
River in June 1972 indicated the possible presence of 3.3 ppb of ethyl
parathion (0,0-Diethyl 0-p-nitrophenyl phosphorothioate).
The results of this monitoring survey corresponds favorably with published
results of similar monitoring by the Ohio Department of Health on major
streams in Ohio (1966-71). One site each on the Maumee and the Sandusky
Rivers were included in their sampling in which no organochlorine nor
organophosphate pesticide residues were reported in 1971. Data for 1972
for comparative purposes is not yet printed.
It is at present impractical to relate any pesticide residue occurrences
to particular areas or particular cultivation and cropping practices. There
are no significant differences between residues attributed to agriculture
versus that attributed to municipalities and industry because basically
no significant occurrence of pesticide residues were found at any locations.
If any relationships were attempted, it would appear that triazine (sima-
zine) in water was associated with the residential and industrial area
of Fremont on the Sandusky River, but atrazine with agricultural areas on
the Huron River systems. Some corn acreage preceded Fremont upstream and
sites 1 to 4 on the Huron River were associated with corn producing areas
(See Appendix II). As indicated before, triazines are used for weed control
in corn. The few occurrences of triazine (atrazine) in mud samples are
associated generally with one particular agricultural area of the Maumee,
Portage, Sandusky, and Huron Rivers and were evident during the planting
and early growing season. The residue value for site 1 on the Sandusky
River in November 1971 cannot be explained. The minimal occurrence of organo-
phosphates pesticide residues reported, appears to be related with one part-
icular section of the Huron River in which agriculture and corn production
is the predominant environmental factor. Diazinon is used for insect con-
trol in corn production.
12
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At present, it is unreaslistic to associate pesticide residue occurrence
in this study with soil and topographical characteristics. Comparison
of the data in Appendix VII with the descriptions of corresponding sites
in Appendices I and II indicates that most sites on the Maumee, Portage,
Sandusky, and Huron Rivers were related to level or nearly level topo-
graphy; the major exceptions being some slightly rolling topography near
some of the stream depressions. Hilly topography was more noticiable in
the Grand River watershed. Correlation of pesticide residue data with
soil structure, drainage, etc., is not attempted at present because the
residue data are not significant and soil descriptions are not available
for all areas of particular interest. Any such attempted correlation
would be meaningless.
The river flow data which would indicate possible periods of rainfall and
consequent drainage runoff is listed in Appendix IV. In accordance with
the discussion of the previous paragraph, any correlation between drain-
age reflected as river flow and pesticide residue is meaningless at
present. The main observation made is that the optimum time for sampling
as far as drainage is concerned may not have been attained, particularly
during the 1972 planting and early growing season. Of course, other
factors such as times of soil preparation, pesticide application, cultiva-
tion, plant growth, etc., are equally as important as is drainage and
runoff in assessing the relationship of pesticide residues in the streams
to the source of contamination. Also, the flow data of Appendix IV raises
the consideration of more practical procedures in sampling water from
large rivers where the volume of water flowing creates great dilution
factors. Because of such phenomenon, drainage waters from residential
and industrial areas near the mouth of a large river may be so diluted
that the analytical procedures and instrumentation used in this study
could be incapable of measuring positive values. Any consequent compari-
son between municipal sources and agricultural sources of pesticide
pollution may be invalid. On the other hand, measurable concentrations
of pesticide residues in the water at the mouths or large areas of the
river multiplied by the flow rate of the river could result in an inter-
pretation of residue content that is astronomically high and thus also
invalid.
It is advisable that this project be reinstituted for the remaining 2
years of the three-year proposal. Some revisions perhaps should be
made in sampling in order to obtain samples at the optimum times and by
improved techniques. Residue data from three years of sampling would
appear to be much more valid than that from only one year and could likely
also be more comprehensively evaluated, if the time of sampling were more
selective in schedule. This would permit more intense sampling during
the cultivation and planting season and during periods of high runoff
following rainfall as well as at periods of low river flow.
13
-------
SECTION VII
ACKNOWLEDGEMENTS
The advise of Dr. David H, Stansbery, Director of the Museum of Zoo-
logy, The Ohio State University, relative to determining the location
and types of mussels and to Dr. Charles E, Herdendorf III, Director of
the Center for Lake Erie Area Research, The Ohio State University, for
providing assistance in sampling in the lake and bay areas by providing
equipment (until ours was finally obtained) and a boat and counsel on
collecting water and bottom mud samples is hereby acknowledged.
Dr. D. Lyle Goleman, Chairman of the Department of Entomology, The Ohio
State University provided administrative counsel during the course of
this research.
Drs. Thomas Curtin and Richard Hill of The Ohio State University Research
Foundation who coordinated the administrative matters in contracting, fin-
ancing, and operating of the project.
Richard D. Myser collected the samples, prepared the extracts for analysis,
and served as Laboratory Technician in the analytical laboratory during
the time that funds remained available for the project. Susan Jackson,
Laboratory Chemist, conducted the majority of the gas chromatographic
analysis. The assistance of these laboratory personnel plus other short-
term or part-time employees during the period of the research is appreciated.
River flow data was supplied by the Water Resources Division, Geological
Survey, USDI, Columbus, Ohio. Soils maps were furnished by the Division
of Lands and Soil, Ohio Department of Natural Resources, Columbus, Ohio.
The work of Mrs. Evelyn Larrimer and Mrs. Betty Russell, secretaries in
this office, in typing quarterly and annual reports and in typing the
final formal report respectively is acknowledged.
The support of the project by the Office of Research and Development,
Environmental Protection Agency and Dr. George W. Bailey, Project Officer,
is hereby acknowledged.
14
-------
SECTION VIII
REFERENCES
1. Bailey, G. W. Entry of Biocides Into Watercourses. Proc Symposium
of Waste Waters, Water Resource Center, U. of Calif., April
1966.
2. Bailey, G. W. Role of Soils and Sediment in Water Pollution Control-
Part I. Reactions of Nitrogenous and Phosphatic Compounds
with Soils and Geologic Strata. U.S. Dept. of Int., Fed.
Water Pollution Control Admin., Southeast Water Lab.,
March 1968.
3. Bailey, G. W. and White, J. L. Soil Pesticide Relationships: Review
of Absorption and Desorption of Organic Pesticides by Soil
Colloids, with Implications Concerning Pesticide Bioactivity.
J. Agr. Food Chem. 12:324-352, 1964.
4. Brown, E. and Nishioka. Pesticides in Selected Western Streams -
A contribution to the National Program. Pesticides Monit.
J.. 1 (2): 38-41, Sept. 1967
5. Bulletin of Environmental Contamination and Toxicology, Vol. 1-6,
Springer-Verlag New York Inc. 1966-71.
6. Epstein, E. and W. J. Grant, Chlorinated Insecticides in Runoff
Water as Affected by Crop Rotation. Soil Sci. Soc. Amer.
Proc. 32(3), 432-426. 1968.
7. Grzenda, A. R., Lauer, G. J., and Nicholson, H. P. Water Pollution
by Insecticides in an Agricultural River Basin. II. The
Zooplankton, Bottom Fauna and Fish. Limnol. Oceanog.
9:318-323. 1964.
8. Journal of Agricultural and Food Chemistry, Vols 13-19. American
Chemical Society, Washington, D. C., 1965-71
9. King, P. H. and P. L. McCarty. A Chromatographic Model for Predicting
Pesticide Migration in Soils. Soil Sci. 106(4). 248-61.
1968
10. Lyman, L. D., W. A. Tompkins, and J. A. McCann. Massachusetts Pesti-
cide Monitoring Study. Pesticides Monit. J. 2, (3): 109-122.
Dec. 1968.
15
-------
11. Marston, R. B., D. W. Schultz, S. Tamotsu, and L. V. Snyder,
Amitrole Concentrations in Creek Waters Downstream from an
Aerially Sprayed Watershed Sub-basin. Pesticides Mpnit,
J._ 2 (3): 123-128. Dec. 1968.
12. Modin, J. C. Chlorinated Hydrocarbon Pesticides in California Bays
and Estuaries. Pesticides Monit. J. 3(1): 1-7.
June, 1969.
13. Monitoring Agricultural Pesticide Residues, "A Preliminary Report
of Studies on Soil, Sediment, and Water in Mississippi River
Delta." ARS 81-13 ARS-USDA Dec, 1966.
14. Monitoring Agricultural Pesticide Residues 1965-1967. A Final Report
on Soil, Crops, Water, Sediment, and Wildlife in Six Study
Areas. ARS 81-32. ARS-USDA July 1969.
15. Nash, R. G. and E. A. WooIsen. . Distribution of Chlorinated Insecticides
in Cultivated Soil. Soil Sci. Soc. Amer. Proc, 32(4);
525-27. 1968.
16. Nicholson, H. P.,Grzenda, A. R.,Lauer, G. J., Cox, W.S,, and Teasley,
J. I. Water Pollution by Insecticides in River and Treated
Municipal Water. Linnol.Qceanog. 9:310-317. 1964.
17. Ohio Department of Health, Pesticide Monitoring Program of Major
Ohio Streams. 1966 through 1971.
18. Pesticides Monitoring Journal, Vol. 1-5 Div. of Pesticide Community
Studies, EPA, Chamblee, Georgia 1967-71.
19. Schwab, G. 0. aid McLean, E. 0. Chemical and Sediment Movement from
Agricultural Land Into Lake Erie. State of Ohio Water Re-
Source Center, Ohio State University. USDI Contract //A-018-
Ohio. Report No. 390X Sept. 1972.
20. Schwab, G. 0., McLean, E. 0., Waldron, A. C., White, R. K., and
Michener, D. W. Quality of Drainage Water from a Heavy
Textured Soil. J. Trans, of Amer. Soc. Agr. Engr. 1973 (In print)
21. Schwab, G. 0., Taylor, G. S., and Waldron, A. C. Measuring Pollutants
in Agricultural Drainage. Ohio Report 55: 87-89. 1970
OARDC, Wooster, Ohio.
22. Seal, W. L., L. H. Dawsey, and G. E. Gavin. Monitoring for Chlorinated
Hydrocarbon Pesticides in Soil and Root Crops in the Eastern
States in 1965. Pesticides Monit.J. 1(3): 22-25. 1967.
16
-------
23. Swoboda, A. R. and G. W. Thomas. Movement of Parathion in Soil
Columns. J. Agr. Food Chem., 16: 923-927. 1968.
24. Ware, G. W., B. J. Estesen, W. P. Cahill. An Ecological Study of
DDT Residues in Arizona Soils and Alfalfa. Pesticides Monit,
J^_ 2(3): 129-132. Dec. 1968.
17
-------
SECTION IX
APPENDICES
No. ?ae' No ,
I Sampling Sites 19
Table 1. Sampling Sites 20
II Soil Characteristics and Cropping at Sampling Sites 22
Table 2. Soil Characteristics and Cropping at 23
Sampling Sites
III Sample Collection 26
Table 3. Sample Collection 27
IV River Flow Data: August 1971-July 1972 30
Table 4. Auglaize River near Fort Jennings 31
Table 5. Auglaize River near Defiance 33
Table 6. Maumee River near Defiance 35
Table 7. Tiffin River near Stryker 37
Table 8. Maumee River at Waterville 39
Table 9. Portage River at Woodville 41
Table 10. Sandusky River near Mexico 43
Table 11 . Sandusky River near Freemont 45
Table 12. Huron River at Milan 47
Table 13. Grand River near Madison 49
V. Procedures for Determination of Pesticide Residues in 51
Water
VI Procedures for Determination of Pesticide Residues in 60
Bottom Mud Sediment
VII Pesticide Residues in River Water and Bottom Sediment 65
Samples
Key to Sample Designation 66
Table 14. Organochlorine Insecticide 67
Residues in River Water and Bottom Sediment
Samples
Table 15. Triazine Type Herbicide Residues in River 79
Water and Bottom Sediment Samples
Table 16. Chlorophenoxy Acid Type Herbicide Residues 84
in River Water, Bottom Sediment and Mussel Samples
Table 17. Organophosphate Insecticide Residues in 89
River Water and Bottom Sediment Samples
18
-------
APPENDIX I
SAMPLING SITES
19
-------
River
Maumee
Portage
Sandusky
Huron
Site
1
2
3
A
5
1
2
3
4
5
6
7
1
2
3
4
5
6
7
1
2
3
4
5
6
Table 1 Sampling Sites
Description
Rt 49 in Antwerp
Auglaize River, Rt 66 Oakwood
Tiffin River, Steven Rd off Rt 18
Rt 109 Bridge between Napoleon and Grand Rapids
Interstate 280 bridge in Toledo. Before sewage
treatment disposal
At buoy #48 Maumee Bay. After sewage treatment
disposal
At buoy #38 Maumee Bay
Rt 199 near Scotch Ridge
Rt 6 near New Rochester
Bradner Rd east of Pimberville
Rt 20 in Woodville
Rt 19 in Oak Harbor. Before sewage treatment
plant
Rt 163 drawbridge in Port Clinton
200 yds into Lake Erie
Rt 602 off Rt 96 N.E. of Bucyrus
Rt 231 1/2 mi north of Wyandot
Rt 103 1/4 mi east of Rt 53 at Tymocktee
1/4 mi east of Rt 53 Fort Seneca
Rt 20 bridge in Fremont
Between buoys #134 #14 at mouth
From bay bridge
Rt 162 between Rts 61 and 99
Rt 61 at Peru
Off Rt 61 on Snyder Rd west of Peru
Fries Landing off Rt 13 north of Milan
Rt 2-6 bridge in Huron
Pier into Lake Erie at mouth
Latitude Longitude
41° 12'
41° 06'
41° 19'
41° 25'
41° 39'
84° 44'
84° 22'
84° 24'
84° 00'
83° 30'
41° 41'
41° 43'
41° 24'
41° 22'
41° 25'
41° 27'
41° 30'
41° 31'
41° 32'
40° 50'
40° 44'
40° 57'
41° 12'
41° 22'
41° 27'
41° 28'
41° 08'
41° 10'
41° 10'
41° 20'
41° 23'
41° 24'
83° 28'
83° 25'
83° 31'
83° 30'
83° 26'
83° 22'
83° 08'
82° 58'
82° 57'
82° 51'
83° 08'
83° 15'
83° 10'
83° 06'
83° 00'
82° 50'
82° 40'
82° 38'
82° 43'
82° 34'
82° 34'
82° 33'
-------
Grand 1 Rt 88 off Rt 534 in Farmington 41° 23' 80° 57'
2 Footville-Richmond Rd west of Rock Creek 41° 40' 80° 53'
3 Sweetzer Rd off Rt 45 41° 42' 80° 52'
4 Sexton Rd off Rt 307 40° 45' 80° 54'
5 Harpfield Rd covered bridge 41° 45' 80° 57'
6 Madison Ave off Rt 84 41° 44' 81° 16'
7 Richmond Rd in Painesville 41° 44' 81° 16'
Lake Erie 1 North and south of Put-in Bay and Stone Laboratory on
South Bass Island
2 Other locations at mouths of rivers, etc. as boat facilities
are available in cooperation with Dr. Herdendorf of O.S.U.
-------
APPENDIX II
SOIL CHARACTERISTICS AND CROPPING
AT SAMPLING SITES
22
-------
River
Maumee
Table 2 Soil Characteristics and Cropping at Sampling Sites
Site No.
NJ
LO
Portage
5
6 & 7
2
3
4
Description of Soil* and Terrain
Characteristics
Major Crops in Area
1971 1972
Paulding-Roselms Assn. Clay, Hoytville- Corn primarily
Nappanee Assn. Clay; Latty-Nappanee
Assn.Clay. Level to nearly level
Paulding-Roselms Assn. Clay. Level to Corn primarily
nearly level
Hoytville-Napanee Assn. Clay. Level to
nearly level
Toledo-Fulton-Lenawel Assn. Clay;
Millgrove-Mermill-Haskins Assn,
Loam; Hoytville-Napanee Assn. Clay;
Colwood-Kibbie Assn Loam; Granby-
Ottokee-Tedrow Assn , sand. Level to
gently sloping
Inside city limits of Toledo-prior to
sewage disposal site
In Maumee Bay
Ottokee-Granby-Seward-Remer-Wauseon
Assn, Sandy loam; Hoytville Assn.
Clay. Level to nearly level
Soil characteristics same as site 1
Soil characteristics same as site 1
Hoytville Assn Clay; Millsdale-
Randolph-Romero Assn. Level to
nearly level
Soil characteristics same as site 4
plus Haskins-Haney-Belmore Assn
Sandy. Level to sloping
Corn, tomatoes
primarily
Corn primarily
Residential and
Industrial
Resdential and
Industrial
Corn, tomatoes
Corn, tomatoes,
grains
Corn, soybeans
grains
Industrial &
residential,
corn primarily
Residential and
Industrial
Corn, soybeans,
wheat
Corn, soybeans,
wheat, oats,
clover, alfalfa
Corn, soybeans,
wheat
Corn, soybeans,
wheat, clover,
sugar beets,
diverted acerage.
Residential and
Industrial
Resdential and
Industrial
Corn, Wheat
Corn, soybeans,
grains
Corn, soybeans
grains
Industrial and resi-
dential, corn,
soybeans, wheat
sugar beets.
Residential and
Industrial
-------
Sandusky
Huron
Grand
6 & 7 Bay and Lake at Port Clinton
1 Soils map not available. Level to
gently sloping and rolling
2 Blount-Peruams Assn, clay loam; Morley
Blount Assn, clay loam. Nearly
level to gently sloping and
rolling
3 Generally same as site 2
4 Haskins-Haney-Belmore Assn. Sandy;
Eel, Shoal-Sloan-Genesee Assn.
Salty. Nearly level to sloping
5 Generally same as site 4. No soils
map available
6 & 7 In bay and lake
1 No soils map available-probably
Blount-Pewamo Assn, clay loam
nearly flat to sloping and
rolling
2 Same as site 1
3 Same as site 1
4 No soils map available
5 & 6 At bay and lake at Huron
1 Fitchville-Mahoning-Lobdell Assn.
Loam. Nearly level
2 Caneadea-Candice Assn; Griggs-
Frenchtown Assn, silty loam and
clay. Level to sloping to steep
sloping
Residential &
Industrial
Corn, soybeans
Corn, soybeans
Corn, soybeans
Wheat, corn
alfalfa
Industrial,
residential
Industrial and
residential
Corn, general
farming
Oats, corn
Corn primarily
Corn
Industrial &
Residential
Some corn
Corn, livestock
Residential &
Industrial
Corn, soybeans
wheat
Wheat, pasture
corn, soybeans
Wheat, corn,
soybeans
Sugar beets, oats
row crops
Industrial, residen-
tial (corn, wheat
sugar beets, row
crops prior to Fremont)
Residential and
Industrial
Wheat, soybeans
corn, alfalfa,
pasture, general
farming
Wheat, corn
Wheat, corn
Corn
Industrial &
Residential
Pasture, some corn
diverted acreage
Corn, livestock,
wheat, oats,
alfalfa
-------
River
Grand
(contd)
Site No.
3
4
Ul
Appendix II (Continued)
Description of Soil* and Terrain
1971
Soil characteristics same as site 2
Griggs-Frenchtown Assn; Caneadea-
Candice Assn; Silty clay and loam.
Level to sloping to steep sloping
Griggs-Frenchtown Assn; Griggs-Pierpont
Assn; silty clay and silty loam. Level
to moderately steep sloping.
Chagrin-Lobdell .Assn; Chila; Mahoning-
Trumbull Assn; Ellsworth-Mahoning Assn
silt loam and clay loam. Sloping to
near level to flood plain.
Chagrin-Lobdell Assn; Caneadea-Paines-
ville Assn. Silt loam and sandy loam.
Flood plains
Major Crops in Area
1972
Corn, livestock
Some Corn
Corn, general
farming, grapes
Grapes, Corn,
; Nursery stock
Industrial and
Residential
Corn, livestock
pasture
Grapes, corn, general
farming
Grapes, corn, nursery
stock
Industrial
Residential
* Soil characteristic maps were not available for all counties involved.
characteristics are assumed to be similar to that of adjacent counties.
In some cases, soil
-------
APPENDIX III
SAMPLE COLLECTION
26
-------
Table 3 - Sample Collection
Date
River
ho
Site
1971
1972
Samples Collected
Water
Maumee
Portage
Sandusky
Huron
1
2
3
/.
H
5
6
7
1
2
3
^
5
6
7
1
2
3
4
5
6
7
1
2
3
4
5
6
9/20-21;10/27;12/3
"
H
II
9/27;
"
"
n ii
*
n n
11/24
11
"
9/16-17;10/26;12/2
"
"
it
"
n
9/27;
10/4;
"
M
1 1
ti
9/27
9/30;
"
ii
"
"
"
n ii
n n
ti ii
n n
12/1
12/2 (too rough)
11/8;12/14
n it
ii n
n n
n ii
11/8
11/8; 12/14
it n
n n
it ii
ii n
"
3/24;4/18;
n n
ii n
M n
5/1
3/24; 4/18;
n ii
ii ii
ti n
n n
3/29;4/19;
4/19
3/20;4/17;
n n
11 n
" "
n H
3/20;4/17;
n n
n n
ii n
n n
n n
5/17;6/15;6/28
n n n
n ii n
n n n
6/8
M
_
5/17;6/15;6/28
n n n
n it n
n n n
6/8 -
n __
4/17;6/14;6/27
n n n
M ii n
n n n
ii M n
5/17;6/14;6/27
ii n n
n ii n
n ii n
n n n
II it t;
XXXXXXXX
XXXXXXXX
xxxxxxxx
xxxxxxxx
XX X
xxxx
XX
xxxxxxxx
xxxxxxxx
xxxxxxxx
xxxx * xxx
xxxxxxxx
xxxxxx
xcxx
xxxxxxxx
xxxxxxxx
xxxxxxxx
xxxxxxxx
xxxxxxxx
X
X
xxxxxxxx
xxxxxxxx
xxxxxxxx
xxxxxxxx
-xxixx
xxxxxxx
xxxii_xx
X X"*' X
xxxxxxxx
xxxxxxxx
XX X
xbxx
XX
xxxxxxxx
xxxxi-xx
xxxxxxxx
-xxx-l-xx
xxxxxxxx
x-xxxx
xc-x
xxxxxxxx
xxxxxxxx
xxxxxxxx
xxxxxxxx
X
xxxxxxxx
xxxx*-xx
xxxxxxxx
xxxxxxxx
xxx^x
xxxxxxx
u.«,u.t[L
x ak
xx k x
x k
xx-d- xx
xx-d-k-x
-------
Grand 1 8/23;9/23-24;ll/4;12/13 3/20;4/27;5/18;6/17;6/30 xxxxxxxxx xxxxxxxxx x e kxx-
2 " " " " " " " " " xxxxxxxxx xxxxxxxxx xxf k
3 " " " " " " " " " x g x g g k
4 " " " " " " " " " xxxx xx - xxf k
5 " " " " " " " " " xxxxxxx -xxxxxxxx xxf k
6 " " " " " " " " " XXXXXXXXX -XX-h XXh k
7 " " " " " " " " " -xxxxxxxx ixxx i
Lake Erie Some samples have been collected from Put-In-Bay and other areas of Lake Erie but are
limited in numbers and presently located in other laboratories. We will have access
to such samples when we can schedule the analyses.
to
00
-------
Notes:
a. Clams not found on 1/27; too cold to get in water on 12/3.
b. Boat not available on date of sampling. Arrangements made
with another department at O.S.U. on boat availability for Lake Erie
and bay areas for cooperative sample collection.
c. Lake Erie too rough for boating although boat available for
sampling.
d. Too cold to get into water to dig clams.
e. No clams found 9/23-24; water too cold to dig clams 11/4
and 12/13.
f. Water too cold to dig clams 11/4 and 12/13.
g. No clams found at site. Site abandoned because of close
proximity to adjacent site.
h. Water too cold to dig clams 11/4 and 12/13; river flow too
great to sample mud and clams 12/13.
i. Industrial site - no mud or clams available.
j. Water flow and height too great to sample mud. Couldn't get
to sites for water sample.
k. Water too high and cold to dig clams in March, April of 1972.
Key: x sample collected on date indicated
- no sample collected for reasons given above in notes or for
other reasons including inaccessibility at time of sample. Blank spaces
with no markings indicate that the particular type sample is not avail-
able at the site selected.
29
-------
APPENDIX IV
RIVER FLOW DATA: AUG 1971 - JULY 1972
30
-------
u>
Table 4
04186500 Auglaize River near Fort Jennings, Ohio
LOCATION.Lat 40°56'55", long 84°15'58", in SE 1/4 sec. 15, T.1S., R5E., Putnam County, on left bank
200 ft upstream from bridge on U.S. Highway 224, 3.5 miles northeast of Fort Jennings, 6 miles up-
stream from Ottawa River, and 7.3 miles downstream from Jennings Creek.
DRAINAGE AREA.332 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun
1
2
3
4
5
6
7
1>
9
10
11
12
13
14
15
16
17
18
19
20
21
54
46
40
37
33
32
30
28
27
27
36
40
42
34
29
25
24
24
23
24
27
23
24
41
45
58
72
259
200
87
49
35
27
25
24
24
24
23
22
22
29
254
51
51
42
38
35
34
34
31
36
43
38
37
35
39
39
45
49
41
38
35
32
27
27
27
24
21
20
21
20
22
24
23
22
24
24
24
25
25
25
25
27
25
70
61
45
46
43
48
493
1,610
1,030
491
463
493
265
244
1,550
2,080
1,200
508
311
238
218
1,320
578
482
350
300
260
230
210
220
854
1,020
543
366
272
210
190
170
160
170
200
220
130
120
110
100
92
84
80
74
70
68
66
64
62
66
84
120
170
180
140
110
94
97
1,330
2,780
2,190
668
380
279
224
185
167
145
136
450
1,290
1,290
752
518
382
274
217
199
228
188
163
168
198
197
1,100
3,370
3,540
1,410
830
534
1,770
4,270
3,860
1,120
1,840
2,180
881
2,220
5,350
193
181
169
150
132
119
107
91
248
1,280
1,270
454
292
271
685
1,290
740
400
277
213
178
432
306
200
155
121
102
94
80
76
77
63
57
108
95
110
143
102
80
64
58
285
-------
22 26 232 35 24 235 231 82 196 5,810 158 534
23
24
25
26
27
28
29
TO
Jw
"}]
J J-
TOTAL
MEAN
MAX
MIN
26
27
25
22
21
21
22
914
29.5
54
21
117
60
43
39
318
371
159
75
/ j
2,781
92.7
371
22
45
58
67
70
56
47
41
1L
JT1
27
£* /
1,303
42.0
70
27
22
24
24
24
27
32
37
SI
j j.
767
25.6
51
20
216
206
194
168
138
144
137
Of)0
jUj
i £60
JL y \J\J\J
14,908
481
2,080
43
325
384
361
325
260
230
200
1 70
J. / U
1 SO
J.-XU
10,961
354
1,320
150
70
62
58
54
52
50
52
2,564
38.4
180
50
204
194
166
148
142
162
276
Tn/i
jU4
9cm
&.yj
16,040
517
2,780
97
5,000
3,110
962
522
377
290
238
o no
zuy
51,935
1,731
5,810
163
137
120
106
94
78
72
68
O~7A
J/U
10,057
324
1,290
68
344
204
154
122
100
82
79
O O /
334
4,761
159
534
57
Cal yr 1971 Total 86,723 Mean 238 Max 3,280 Min 15
Wtr yr 1972 Total 123,677 Mean 338 Max 5,810 Min 20
-------
u>
Table 5
04191500 Auglaize River near Defiance, Ohio
LOCATION. Lat 41°14'15", long 84°23'57", in NE 1/4 sec. 9, T.3N., R.4E., Defiance County on right
bank 125 ft downstream from dam of Toledo Edison Co., 0.2 mile upstream from Jackson ditch, and
3 miles south of Defiance.
DRAINAGE AREA.2,318 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day
Aug
Sep
Oct
Nov
Dec
Jan
Feb
Mar
Apr
May
Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
237
204
160
146
138
123
115
107
104
115
107
123
160
150
137
128
108
96
95
85
80
80
69
124
139
166
203
265
358
686
572
370
240
171
141
121
95
85
83
77
78
117
181
537
300
225
195
2,000
184
21
22
24
24
24
98
176
161
144
137
134
133
130
128
127
123
81
31
42
45
52
74
78
77
70
80
92
74
85
78
88
85
82
84
95
101
95
58
72
161
201
208
186
180
188
330
2,700
5,170
3,390
2,320
1,880
618
284
3,650
7,150
6,570
3,340
2,200
1,590
1.190
350
6,200
3,650
2,340
1,790
1,370
935
825
795
792
2,000
4,570
3,740
2,450
1,610
828
597
528
530
601
823
992
1,050
478
412
385
358
323
312
276
247
223
199
185
177
186
224
373
597
813
853
713
520
418
381
384
5,280
11,100
11,500
6,310
2,600
2,080
1,560
1,090
760
696
641
4,470
10,500
11,400
11,100
8,120
5,350
3,420
1,250
1,340
1,310
1,190
1,010
813
804
1,040
1,300
2,780
11,000
12,000
9,670
4,740
4,610
7,400
11,400
12,700
8,260
7,420
10,300
7,090
6,980
14,600
23,500
1,240
1,150
1,050
932
804
704
576
551
738
4,370
5,840
3,700
3,690
2,460
3,090
3,270
5,080
3,740
2,360
1,560
1,130
994
3,790
2,370
1,430
1,150
1,210
951
746
614
505
660
790
668
517
565
648
689
820
841
673
520
464
1,030
-------
23
24
25
26
27
28
29
30
31
63
73
70
65
58
60
73
71
60
517
366
255
213
196
523
614
425
27
27
28
30
30
30
30
31
31
78
82
86
79
93
83
109
137
29
275
492
497
497
453
456
898
4.^70
1,360
1,780
2,130
1,400
1,150
995
869
699
sss
342
290
267
267
244
240
256
1,280
1,210
1,040
838
722
686
790
949
i i sn
25,800
23,500
14,000
6,240
3,750
2,410
1,700
1,370
TOTAL
MEAN
MAX
MIN
3,391
109
237
58
7,987
266
686
69
4,855
157
2,000
21
2,385
79.5
137
31
51,823
1,672
7,150
29
49,954
1,611
6,200
528
10,559
364
853
177
110,926
3,578
11,500
384
239,377
7,979
25,800
804
834 1,150
682 786
585 577
524 471
467 398
411 345
374 325
474 1,250
2,080
55,460 26,953
1,789 898
5,840 3,790
374 325
Cal Yr 1971 Total 462,730 Mean 1,268 Max 13,500 Min 21
Wtr ₯r 1972 Total 706,163 Mean 1,929 Max 25,800 Min 21
-------
Table 6
04192500 Maumee River near Defiance, Ohio
LOCATION.--Lat 41°17'31", long 84°16'52", in NW 1/4 sec. 22, T.4N.,R.5E, Defiance County, on left bank
40 ft upstream from Independence Dam, 4 miles downstream from Auglaize River, and 4.5 miles east of
Defiance.
DRAINAGE AREA.5,545 sq mi
Day
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Aug
Sep
Oct
Nov
Dec
Jan
Feb
Mar
Apr
May
Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
470
430
380
350
330
300
280
260
240
220
260
308
422
363
324
315
292
252
244
220
217
229
169
276
307
310
439
504
534
840
947
762
583
446
367
344
318
291
275
286
275
374
383
914
1,080
865
750
2,380
1,430
629
326
293
314
291
378
440
401
397
392
391
388
374
360
347
333
369
415
385
330
323
338
339
322
296
311
458
332
285
283
306
286
275
283
284
304
303
255
248
388
476
449
421
437
454
705
3,220
8,850
8,380
7,730
6,940
4,740
3,130
8,540
15,500
15,100
11,200
7,680
5,450
4,360
3,000
12,800
10,100
7,160
5,920
5,270
4,060
3,400
2,610
2,870
4,250
7,790
7,320
5,400
3,910
2,400
1,500
1,260
1,470
1,810
2,260
2,600
3,000
1,400
1,300
1,200
1,100
950
820
740
680
620
580
540
520
500
520
890
1,230
1,560
1,800
1,710
1,420
1,160
1,180
1,060
7,020
13,800
16,900
11,800
7,020
4,980
4,580
3,750
2,730
2,120
1,830
7,380
17,600
21,500
21,200
19,000
16,000
10,000
8,200
7,000
7,000
5,090
4,200
3,480
3,460
4,240
4,560
5,600
16,600
20,000
17,900
13,800
11,400
14,100
20,800
23,000
20,100
22,400
24,400
21,000
18,900
25,300
36,400
5,050
5,530
4,300
3,660
3,550
3,370
2,980
2,640
2,710
6,420
9,560
6,990
6,190
4,940
6,320
8,070
9,480
7,580
5,600
4,400
3,640
3,160
6,540
5,890
4,040
2,810
2,830
2,350
1,860
1,570
1,260
1,350
2,040
1,900
1,290
1,110
1,570
3,780
3,780
2,500
1,740
1,320
1,100
1,490
-------
23
24
25
26
27
28
29
30
31
TOTAL
MEAN
MAX
MIN
214
195
225
324
233
207
213
185
165
8,667
280
470
165
862
603
481
481
493
823
1,780
1,540
17,007
567
1,780
169
318
624
988
1,090
782
607
504
437
444
18,722
604
2,380
291
259
277
273
255
308
283
313
382
9,311
310
458
248
1,860
1,700
1,750
1,660
1,570
1..470
1,460
3,040
9,190
140,850
4,544
15,500
388
4,320
5,400
6,400
5.200
3,800
3,000
2,400
1,990
1,600
133,270
4,299
12,800
1,260
1,110
1,010
775
798
735
695
735
28,278
975
1,800
500
7,200
6,600
5,920
5,120
4,380
3,970
3,590
4,240
5,540
259,030
8,356
21,500
1,060
40,700
39,400
31,000
22,000
15,200
10,600
6,820
4,810
507,260
16,910
40,700
3,460
2,600
2,200
1,790
1,530
1,400
1,250
1,100
1,230
3,160
132,400
4.271
9,560
1,100
1,830
1,450
1,160
986
848
822
834
1,360
63,410
2,114
6,540
822
Cal Yr 1971 Total 1,142,259 Mean 3,129 Max 31,400 Min 165
Wtr Yr 1972 Total 1,628,853 Mean 4,450 Max 40,700 Min 248
-------
Table 7
041850000 Tiffin River at Stryker, Ohio
LOCATION.Lat 41°30'17", long 84°25'49", in SW 1/4 sec. 5, T. 6N., R.4E., Williams County, on right
bank 0.5 mile downstream from bridge on State Highway 191 at west edge of Stryker, 0.6 mile upstream
from Penn Central bridge, and 1.6 miles downstream from Leatherwood Creek.
DRAINAGE AREA.410 sq mi.
Day
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Aug
Sep
Oct
Nov
Dec
Jan
Feb
Mar
Apr
May
Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
21
20
18
19
21
19
16
15
14
13
17
18
16
14
13
12
12
11
11
10
9.3
9.2
10
7.0
10
13
19
18
23
18
18
17
15
13
11
11
11
11
9.8
9.0
8.5
8.0
16
26
27
20
19
16
16
17
16
19
19
23
24
24
25
23
23
24
23
22
21
20
20
21
22
28
37
28
29
30
31
29
28
27
28
28
29
31
30
29
25
24
23
23
24
29
30
33
31
29
42
33
32
33
35
29
58
84
88
96
132
163
143
112
143
205
222
181
133
107
97
87
74
594
601
490
369
275
227
194
195
198
217
244
238
222
202
150
110
94
86
92
130
194
252
410
120
110
100
96
92
86
82
78
74
72
70
72
76
84
96
120
171
181
150
130
120
110
110
155
305
439
428
348
269
214
211
181
152
147
157
338
800
1,090
1,540
1,760
1,730
1,500
1,190
890
842
887
358
332
303
310
364
381
356
318
301
301
295
274
288
354
426
693
1,160
1,360
1,570
1,470
1,320
1,510
1,590
304
406
582
670
609
452
353
318
334
379
395
349
295
269
279
328
361
341
290
240
205
180
160
265
209
180
275
257
182
140
113
97
87
76
68
71
73
155
332
244
151
109
90
89
122
111
-------
24 9.9 16 45 26 79 469 100 989 1,470 142 102
25 9.5 15 51 28 74 475 94 1,000 1,240 127 87
26 9.0 14 53 29 71 402 90 792 941 113 80
27 8.0 16 47 31 70 318 86 567 646 102 99
28 8.0 20 37 33 76 250 88 425 439 92 106
29 8.5 22 34 38 79 206 98 372 349 86 102
30 8.5 21 31 41 176 171 371 302 93 104
31 7.5
oo
16
15
14
16
20
22
463.3
15.4
27
7.0
.04
.04
78,736.
78,279.
45
51
53
47
37
34
01
JX
OQ
£.y
829
26.7
53
16
.07
.08
7 Mean
0 Mean
26
28
29
31
33
38
A1
H-L
874
29.1
41
23
.07
.08
216
214
79
74
71
70
76
79
1 7ft
-L / O
/.ac
H-jj
3,399
110
435
32
.27
.31
Max 2,910
Max 1,760
469
475
402
318
250
206
i AH
_L*+U
8,215
265
601
86
.65
.75
Min 7.0
Min 16
100
94
90
86
88
98
2,956
102
181
70
.25
.27
CFSM
CFSM
989
1,000
792
567
425
372
20,465
660
1,760
147
1.61
1.86
.53 IN
.52 IN
1,470
1,240
941
646
439
349
on?
j\jf.
21,021
701
1,590
274
1.71
1.91
7.14
7.10
142
127
113
102
92
86
oo
-/ J
1 Q£
J.7U
9,050
292
670
86
.71
.82
TOTAL 407.4 463.3 829 874 3,399 8,215 2,956 20,465 21,021 9,050 4,176
MEAN 13.1 15.4 26.7 29.1 110 265 102 660 701 292 139
MAX 21 27 53 41 435 601 181 1,760 1,590 670 332
MIN 7.5 7.0 16 23 32 86 70 147 274 86 68
CFSM .03 .04 .07 .07 .27 .65 .25 1.61 1.71 .71 .34
IN. .04 .04 .08 .08 .31 .75 .27 1.86 1.91 .82 .38
Cal Yr 1971 To
Wtr Yr 1972 To
-------
Table 8
04192400 Maumee River at Waterville, Ohio
LOCATION:~Lat 41°30'00", long 83°42'46", Lucas County, on downstream side of second pier from left end of
bridge on State Highway 64 at Waterville, 3 miles downstream from Tontogany Creek, and 21.1 miles above
the mouth.
DRAINAGE AREA. 6,330 sq mi.
to
Day
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Aug
Sep
Oct
Nov
Dec
Jan
Feb
Mar
Apr
May
Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
560
560
500
420
390
370
330
300
270
240
330
400
520
440
410
380
350
310
280
250
260
270
220
340
360
390
520
580
660
860
1,000
1,200
840
660
540
420
380
360
340
330
380
440
500
600
1,500
1,050
848
884
2,880
1,130
614
306
350
339
328
339
405
443
383
394
394
443
405
394
383
493
405
628
394
317
259
383
443
250
268
455
418
405
317
295
430
350
328
383
558
394
360
214
450
400
500
460
450
520
800
2,230
7,640
10,800
9,280
8,380
6,920
4,260
7,000
16,300
18,200
14,100
9,960
7,080
5,610
4,540
14,300
13,200
9,420
7,440
6,440
5,820
5,220
4,060
3,480
4,670
7,800
9,150
6,760
5,000
3,000
2,300
1,800
1,600
1,900
2,400
3,600
3,690
1,700
1,500
1,400
1,300
1,200
1,100
1,000
900
800
740
660
620
580
640
860
1,500
2,000
2,100
1,800
1,600
1,400
1,300
880
6,360
15,500
19,500
14,800
9,550
5,960
5,150
4,640
3,940
3,040
2,330
5,190
19,200
24,600
24,900
22,500
18,700
15,000
11,700
8,430
8,520
5,680
4,940
4,160
4,190
4,700
5,120
5,120
11,400
20,800
19,700
16,500
11,800
12,500
19,100
24,500
23,000
25,700
26,100
23,400
19,700
23,300
38,400
5,360
6,200
5,400
4,420
4,060
4,000
3,270
3,180
3,570
5,080
9,510
8,520
6,170
5,850
5,780
8,740
9,060
8,520
6,320
5,120
4,320
3,510
5,500
6,840
5,680
4,190
3,570
3,160
2,490
2.050
1,570
1,320
1,660
2,130
1,930
1,500
1,500
3,020
4,800
3,630
2,490
1,850
1,800
1,590
-------
23
24
25
26
27
28
29
30
31
TOTAL
MEAN
MAX
MIN
CFSM
IN.
Cal Yr
Wtr Yr
250
230
300
370
400
300
230
200
170
10,590
342
560
170
.05
.06
1971
1972
1,000
700
560
500 1
600 1
620
1,100
1,900
18,900 21
630
1,900 2
220
.10
.11
Total 1,311,
Total 1,853,
505
443
902
,390
,170
866
642
544
544
,711
700
,800
306
.11
.13
775
731
232
290
320
370
370
350
340
380
10,906
364
628
214
.06
.06
Mean 3
Mean 5
3,020
2,200
2,000
1,900
1,800
1,700
1,700
2,100
7,320
159,620
5,149
18,200
400
.81
.94
,594 Max
,065 Max
5,220
7,000
7,880
6,000
4,500
3,400
2,600
2,200
1,900
163,750
5,282
14,300
1,600
.83
.96
38,900
46,900
1,200
1,100
1,000
900
820
760
800
33,280
1,148
2,100
580
.18
.20
Min
Min
8,290
7,760
6,480
5,820
5,150
4,480
4,290
4,450
5,330
302,440
9,756
24,900
880
1.54
1.78
170 CFSM
214 CFSM
46,900
44,400
36,200
25,500
18,000
12,400
8,250
5,990
547,450
18,250
46,900
4,160
2.88
3.22
.57
.80
3,180
2,570
2,100
1,730
1,520
1,430
1,250
1,280
2,000
143,020
4,614
9,510
1,250
.73
.84
In 7
In 10
2,030
1,950
1,500
1,230
1,070
920
1,050
2,200
76,220
2,541
6,840
920
.40
.45
.71
.89
-------
Table 9
04195500 Portage River at Woodville, Ohio
LOCATION.Lat 41°26'58", long 83021'41", in sec. 28, T.7N., R.13E., Sandusky County, on left bank of
bridge on U.S. Highway 20 in Woodville, 600 ft downstream from unnamed right bank tributary, and
10.3 miles upstream from Sugar Creek.
DRAINAGE AREA.428 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
30
22
16
12
11
11
10
8.6
7.7
6.6
9.3
26
30
18
13
10
7.8
7.1
7.4
8.6
14
25
6.4
7.9
11
15
13
13
14
14
14
13
13
11
12
12
10
8.8
10
11
10
22
51
73
38
28
23
17
16
14
15
17
22
42
43
30
22
19
17
18
18
17
15
15
14
17
24
22
19
19
20
19
16
15
16
16
17
18
20
20
17
17
15
11
12
12
13
14
52
42
39
29
25
32
190
534
373
245
245
195
138
110
582
1,070
594
315
190
152
138
117
930
522
422
333
240
150
160
170
140
910
975
598
419
288
160
140
120
110
110
120
160
230
90
82
82
94
90
86
82
78
74
70
66
64
62
90
120
240
200
160
130
100
90
80
70
1,610
2,860
1,030
490
253
200
160
130
120
120
130
935
3,160
2,720
2,130
1,730
1,080
690
482
408
429
136
127
114
138
267
288
264
250
288
345
359
282
288
397
359
498
1,670
1,140
634
638
1,660
2,370
185
276
294
208
152
125
112
114
785
1,700
765
426
309
297
720
985
586
380
267
208
171
146
422
276
208
321
240
156
120
101
81
70
60
55
55
144
138
115
102
81
60
51
122
127
-------
23
24
25
26
27
28
29
30
31
16
17
11
9.0
8.1
8.6
11
9.1
7.5
40
25
19
17
160
225
100
54
24
30
33
29
28
26
26
25
25
13
11
10
10
14
18
33
46
93
90
84
80
74
70
66
486
1,700
360
400
538
401
320
240
160
130
100
70
60
52
46
44
42
54
482
345
258
228
200
183
165
167
158
3,660
1,850
820
514
366
276
225
195
120
99
85
73
63
55
48
55
140
90
73
61
54
59
54
176
660
TOTAL
MEAN
MAX
MIN
GO
MEAN /
CFSM /
IN /
408.4
13.2
30
6.6
5.26
7.94
.02
.02
1,004.1
33.5
225
6.4
5.98
27.5
.06
.07
723
23.3
43
14
5.37
17.9
.04
»05
527
17.6
46
10
4.71
12.9
.03
.03
8,150
263
1,700
25
4.24
259
.61
.70
10,056
324
975
100
4.78
319
.75
..86
2,598
89.6
240
42
4.82
84.8
.20
.21
23,123
746
3,160
70
4.38
742
1.73
2.00
20,318
677
3,660
114
4.78
672
1.57
1.75
9,949
321
1, 700
48
5.16
316
.74
.85
4,332
144
660
51
4.54
139
.32
.36
-------
-P-
OJ
Table 10
04197000 Sandusky River near Mexico, Ohio
LOCATION.Lat 41°02'39", long 83°11'42", in sec. 13, T.1N., R.14E., Seneca County, on right bank at
downstream side of county road bridge, 4.1 miles upstream from Honey Creek, 4.2 miles north of Mexico,
4.9 miles south of Tiffin, and 8.3 miles downstream from Mile Run.
DRAINAGE AREA. 774 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun
1
2
3
4
5
6
7
8
9
10
11
112
13
14
15
16
17
18
19
20
21
22
52
42
37
35
32
29
26
24
21
20
24
25
22
20
22
20
18
18
18
16
13
13
13
13
13
14
14
14
14
13
15
23
32
25
22
17
15
15
14
13
13
17
21
27
18
17
17
15
14
14
14
14
19
21
21
32
41
34
41
36
29
24
22
21
22
26
26
26
24
24
25
26
29
31
31
30
29
29
29
29
31
31
30
31
34
34
36
36
49
47
50
47
47
53
74
108
145
165
139
108
86
83
122
309
494
443
285
182
139
115
1,460
1,010
567
380
300
260
240
280
296
522
1,340
1,290
803
539
340
260
200
170
150
140
190
220
110
90
120
150
160
140
130
120
120
110
110
100
100
110
180
380
650
911
560
450
320
240
140
1,790
3,790
3,310
2,150
1,200
700
480
400
360
340
310
1,150
4,150
4,480
3,720
3,110
2,520
1,530
957
696
1,100
274
248
232
235
238
224
523
2,100
2,060
1,830
1,280
912
1,790
3,240
2,980
2,590
3,680
3,690
2,820
3,670
6,260
9,290
396
351
314
279
249
221
196
190
1,660
3,650
3,290
2,520
1,170
761
2,530
4,050
3,690
2,730
1,350
756
539
416
341
315
276
223
177
148
129
116
109
105
97
88
108
232
387
394
311
228
184
143
120
108
-------
23
24
25
26
27
28
29
30
^i
12
11
11
12
14
17
15
14
i *
36
32
24
24
25
22
22
20
31
38
32
28
30
31
28
28
9Q
42
40
36
33
33
36
43
43
103
98
91
83
78
75
74
93
624
517
610
500
340
280
240
200
160
130
190
150
130
110
90
82
76
2,380
2,070
1,080
731
571
471
403
360
312
11,200
7,910
4,630
1,810
1,040
742
572
461
335
277
233
199
171
154
139
170
352
102
99
91
88
85
80
165
395
TOTAL
MEAN
MAX
MIN
CFSM
666
21.5
52
11
.03
582
19.4
36
13
.03
787
25.4
41
14
.03
957
31.9
43
24
.04
4,609
149
624
47
.19
13,934
449
1,460
130
.58
6,189
213
911
76
.28
46,761
1,508
4,480
140
1.95
78,531
2,619
11,200
224
3.38
33,338
1,075
4,050
139
1.39
5,444
181
395
80
.23
IN. .03 .03 .04 .05 .22 .67 .30 2.25 3.77 1.60 .26
Cal Yr 1971 Total 163,783 Mean 449 Max 6,610 Min 11 CFSM .58 IN 7,87
Wtr Yr 1972 Total 214,791 Mean 587 Max 11,200 Min 14 CFSM .76 IN 10,32
-------
Table 11
04198000 Sandusky River near Fremont, Ohio
LOCATION.Lat 41°18'28", long 83°09'32", sec.l7,T.4N. , R.15E., Sandusky County, on left bank at down-
stream side of county road bridge, 2.e miles upstream from Ballville diversion dam, 2.5 miles down-
stream from Wolf Creek, and 3.5 miles southwest of Fremont..
DRAINAGE AREA.1,251 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
89
77
65
57
54
52
49
47
45
46
49
51
47
45
43
40
41
40
37
37
40
39
35
33
33
34
40
42
42
38
35
39
55
52
48
44
39
36
35
35
40
55
41
39
37
35
33
31
28
29
35
51
47
37
37
53
55
49
51
49
45
41
37
39
41
41
39
37
33
35
37
37
39
41
39
39
39
41
41
41
41
45
47
45
62
62
57
55
55
62
97
172
187
235
223
177
141
129
267
465
703
715
526
353
248
1,640
1,610
940
630
520
460
500
560
399
808
1,850
2,160
1,450
840
600
440
360
300
270
250
300
180
160
180
240
300
250
230
210
200
190
180
170
170
240
340
500
900
1,500
1.100
700
460
190
2,610
6,380
5,120
3,460
1,900
1,100
740
600
500
540
499
1,880
7,700
7,620
6,190
5,120
4,090
2,760
1,710
1,210
440
392
361
369
384
384
392
1,790
2,590
2,290
1,830
1,320
1,430
3,940
4,020
3,630
5,400
5,300
4,190
4,880
8,660
660
640
553
473
415
369
323
316
3,050
6,430
4,990
3,700
2,160
1,250
3,000
5,740
5,320
4,190
2,460
1,300
886
600
526
473
415
490
384
281
223
187
172
156
,141
482
738
1,200
1,610
969
670
482
369
288
-------
22
23
24
25
26
27
28
29
30
71
136
105
54
41
41
41
40
39
40
*Q
52
49
51
54
53
61
56
50
47
35
37
39
45
47
43
41
41
41
39
45
45
45
49
47
49
53
51
62
193
161
141
137
129
125
113
109
172
499
400
600
1,000
700
500
420
360
300
240
200
360
280
240
200
180
160
150
140
1,380
3,460
3,390
2,020
1,250
940
761
640
562
499
12,300
16,500
12,600
7,400
3,510
1,830
1,260
940
749
670
535
440
369
309
267
235
217
260
482
235
210
193
177
172
182
150
235
726
TOTAL
MEAN
MAX
MIN
CFSM
IN.
1.627
552.5
136
37
.04
.05
1,322
44.0
61
33
.04
.04
1,268
40.9
55
28
.03
.04
1,283
42.8
62
33
.03
.04
6,770
218
715
55
.17
.20
21,607
697
2,160
200
.56
.64
10,110
349
1,500
140
.28
.30
76,821
2,478
7,700
190
1.98
2.28
111,081
3,703
16,500
361
2.96
3.30
52,009
1,678
6,430
217
1.34
1.55
13,136
438
1,610
141
.35
.39
Cal Yr 1971
Wtr Yr 1972
Total 314,072
Total 334,750
Mean S60
Mean 915
Max 19,900
Max 16,500
Min 28
Min 28
CFSM .69
CFSM .73
IN
IN
9.34
9.95
-------
Table 12
04199000 Huron River at Milan, Ohio
LOCATION.Lat 41°18'06", long 82°36'25", in SW 1/4 sec. 4, T.5N, R. 22W., Erie County, on right
bank 500 ft downstream from bridge on U.S. Highway 250, 0.2 mile northwest of Milan and 2 miles
downstream from confluence of East and West Branches.
DRAINAGE AREA.371 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
17
15
13
12
12
11
9.6
9.1
11
12
23
13
12
11
13
12
11
11
12
11
9.6
16
8.6
8.6
7.7
10
13
7.7
8.2
8.2
6.3
6.3
6.0
6.0
12
14
12
12
11
9.1
7.7
24
23
16
9.1
7.7
6.3
7.7
8.2
10
11
9.6
19
19
19
18
18
38
20
17
15
15
15
19
19
19
24
28
19
18
15
15
18
14
16
20
19
19
20
19
19
19
16
17
21
21
23
24
33
29
23
25
27
37
75
114
134
92
75
67
65
66
263
494
245
139
100
89
81
75
328
199
175
165
141
128
110
101
141
1,020
700
402
200
120
95
80
70
65
70
80
95
130
36
32
36
42
50
44
40
36
32
30
28
26
30
40
352
646
450
260
210
190
170
156
181
3,140
2,020
622
378
236
238
220
208
168
158
172
2,110
3,460
1,260
937
1,170
721
493
372
320
1,330
168
156
144
152
144
129
138
172
178
194
188
176
228
455
603
766
1,560
760
450
1,320
1,730
2,840
160
172
148
123
106
96
102
116
1,630
1,220
526
332
250
298
1,240
1,150
658
395
292
230
194
180
125
104
88
229
372
174
111
82
67
58
45
41
1,000
2,050
712
874
452
250
180
142
123
119
-------
23
24
25
26
27
28
29
30
ii
12
12
11
9.1
9.1
8.2
6.8
8.6
Q 1
13
11
10
13
19
15
12
11
19
21
24
19
21
19
19
18
20
21
19
19
24
24
29
42
65
62
52
50
48
48
46
227
78R
170
240
210
130
90
70
70
50
4?
192
129
101
89
90
86
101
1,200
508
388
312
262
228
218
212
186
1,920
751
460
342
270
222
190
168
132
118
102
88
75
78
63
110
148
245
380
300
335
320
222
452
808
TOTAL 363.2 341.4 515.6 622 3,734 5,677 3,724 23,428 16,974 10,521 10,460
MEAN 11.7 11.4
MAX 23 24
MIN 6.8 6.0
CFSM .03 .03
IN. .04 .03
Calendar Yr 64,980.2
.p-
oo
-------
Table 13
04212000 Grand River near Madison, Ohio
LOCATION.Lat 41°44'26", long 81°02'48", Lake County, on downstream and of center pier of abandoned
highway bridge, 800 ft upstream from State Highway 528, 0.8 mile upstream from Griswold Creek and
2.1 miles south of Madison.
DRAINAGE AREA.581 sq mi.
DISCHARGE, IN CUBIC FEET PER SECOND, WATER YEAR AUGUST 1971 TO JUNE 1972
Day Aug Sep Oct Nov Dec Jan Feb Har Apr May Jun
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
9.0
7.5
6.3
5.6
4.8
3.8
3.2
2.8
2.1
2.1
2.1
2.1
1.9
1.5
1.5
1.5
1.5
1.3
1.2
1.2
1.2
.91
37
21
14
13
12
14
11
11
5.9
4.5
3.2
2.8
12
29
24
26
48
43
31
32
31
24
19
35
35
32
22
16
19
19
32
122
186
199
229
177
112
71
45
36
31
22
17
14
73
72
68
92
125
110
125
151
154
145
170
201
168
125
92
73
62
54
50
58
130
400
2,160
1,320
900
682
519
1,040
3,760
5,400
4,000
2,640
2,280
1,920
1,360
872
1,370
2,960
2,340
1,660
1,430
1,170
1,030
907
2,590
1,650
1,540
1,340
984
716
555
453
418
496
734
837
752
630
414
250
280
240
550
1,540
1,240
956
220
210
240
300
315
318
300
270
250
240
250
300
400
500
700
1,000
1,200
1,200
1,100
950
850
800
2,800
9,380
9,000
4,980
3,540
2,450
1,890
3,020
3,040
2,040
1,510
1,470
2,080
4,280
4,230
3,590
4,380
3,690
2,580
1,920
1,220
1,060
397
369
354
381
433
418
381
348
336
339
325
308
622
1,120
1,060
3,660
5,720
3,730
2,490
2,050
2,270
1,860
280
372
555
590
492
411
351
315
773
2,040
1,600
1,090
758
488
366
336
351
422
425
381
325
280
136
205
207
205
203
148
110
87
80
80
76
73
90
126
239
908
1,370
758
378
241
172
140
-------
23
24
25
26
27
28
29
30
31
1.7
.91
.91
1.2
1.9
15
25
81
76
21
34
38
33
29
31
34
22
13
11
9.5
23
74
74
78
92
82
453
360
318
308
369
570
886
1,980
682
546
429
433
710
858
851
1,760
3,860
1,400
1,550
1,690
1,370
740
478
368
292
250
750
700
650
600
550
1,600
1,500
1,730
1,480
1,230
1,020
837
666
519
453
433
2,200
1,800
1,320
977
645
429
348
300
241
211
161
118
100
86
76
74
86
2,690
6,190
7,380
5,230
2,580
1,110
560
461
TOTAL 268.73 691.4 1,946.5 7,942 51,849 27,298 18,263 82,511 36,990 14,154 32,233
MEAN 8.67 23.0
MAX 81 48
MIN .91 2.8
CFSM .01 .04
IN. .02 .04
CALENDAR YR 1971 218,312.23
-------
APPENDIX V
PROCEDURES FOR DETERMINATION OF PESTICIDE RESIDUES
IN WATER
51
-------
Appendix V
Procedures for Determination of Pesticide Residues in Water
Dr. Acie C. Waldron
Extension Specialist, Pesticide Chemicals
Ohio Cooperative Extension Service
Ohio State University
General:
All glassware must be thoroughly cleaned, preferrably with Alconox
or Micro washing compounds, thoroughly rinsed in clean water, and
rinsed with glass distilled acetone before use. Separatory funnels
and chromatography columns should be equipped with Teflon stopcocks
and Teflon or plastic stoppers. Avoid any use of silicone grease or
any other lubricant on any glassware item that comes in contact with
the sample.
All solvents used must be re-distilled in all-glass apparatus or must
be purchased as pesticide quality solvents. The reagents indicated have
been found to work most satisfactory in this laboratory. Reagents ob-
tained from different suppliers sometimes perform differently and thus
must be checked out as to their applicability. Aqueous reagent solu-
tions are to be made in double distilled water.
The laboratory technician should run recovery studies at various con-
centration levels in adapting the methods to his techniques. Because
techniques and equipment varies from lab to lab the methods should be
checked out before using on a routine basis.
Analysis for Organochlorine Insecticide Residues
Procedure 1. (Procedure 2 differs only in eliminating the use of 10%
and using 250 ml of water sample.)
1. Place 500 ml of water in a 1-liter separatory funnel (Teflon
stopcock and Teflon or plastic stopper) and add 100 ml of 10%
Na2S04 solution.
2. Add 200 ml of glass distilled petroleum ether and extract the
aqueous phase by shaking the separatory funnel vigorously for
1 minute.
3. Allow the phases to separate and transfer the aqueous phase to a
second 1-liter separatory funnel. (Remove as much aqueous phase
as possible by permitting time for complete separation of phases.
Swirl separatory funnel to dislodge water droplets on sides of
vessel.)
4. Extract the aqueous phase with an additional 100 ml of g.d.
petroleum ether. Separate the phases as above and discard the
aqueous phase.
52
-------
5. Combine the two petroleum ether phases and backwash by shaking
vigorously with 100 ml of 2% NaHC03 for 1 minute. Again separate
and discard the aqueous phase.
6. Transfer the petroleum ether solution to a 500 ml round bottom
evaporation flask (Generally best to carefully pour the solution
through the mouth of the separatory funnel in order to avoid water
pickup from the funnel stopcock and stem.) and concentrate to
about 20 ml volume with a flash evaporator. The temperature of the
water bath should not exceed 40° C.
7. Prepare a 19 x 300 mm reservoired Teflon stopcock chromatography
column (Kontes) for clean-up purposes by one of the two following
procedures.
A 1. Place a small plug of glass wool in the bottom of the column
followed by 4 inches of Activated Florisil (Kensington Scien
tific Corp., 1399 64th St., Emeryville, California 94608;
60/100 mesh, 650 C activation and pre-tested; stored in an
oven at 140° C before use.) and 1 inch of anhydrous
2. Wash the column with a few mis of glass distilled petroleum
ether, discard wash, and then add the concentrated extract
to the top surface of the column material.
3. When the top miniscus of the extract reaches the surface
of the column material, elute the column with 200 ml of
glass distilled petroleum ether and collect the elute in
a 500 ml round bottom evaporation flask at a rate of appro-
ximately 1-2 drops per second.
4. Replace the collection flask with a second 500 ml round
bottom evaporation flask and elute the column with 250
ml of glass distilled benzene.
(Note: Check the elution chart for separation of organo-
chlorine pesticides. Our experience shows that Aldrin,
heptachlor, p,p'-DDE, o,p-DDT and some p,p'-DDT elutes
in petroleum ether and lindane, heptachlor epoxide, dieldrin,
p,p'-DDD, the remainder of p,p'-DDT, and methoxchlor elutes
in benzene.)
5. Concentrate the eluates to an appropriate volume (10-15 ml)
by flash evaporation and inject aliquots on the gas chroma-
tograph. Additional concentration may be required with a
nitrogen gas jet or cleaned air stream to obtain gas chroma-
tographic response.
B 1. Place a small plug of glass wool in the bottom of the column
followed by 2.5 inches of florisil, 2.5 inches of silica gel
(Davison Grade 923, 100-200 mesh, stored in a 140° oven before
53
-------
use.), and 1 inch of anhydrous
2. Wash the column with petroleum ether, add the concen-
trated extract and elute the column with 250 ml of 5%
benzene in petroleum ether followed by 250 ml of benzene
as in the previous procedure. (The elution sequence
is the same as before except p,p'-DDT seems to elute
only in the 5% benzene-petroleum ether.)
3. Concentrate the eluates and inject aliquots on the gas
chromatograph.)
(Note: Recovery values at all concentration levels were
generally 90 to 110%.
8. Gas chromatographic conditions were: Barber-Colman Series 5000
equipped with 6 ft. all glass column packed with 1:1 mixture of
10.4% DC-200 plus 15.1% QF-1 on Gas Chrom Q 100-120 mesh; oven
temperature 200° C; detector temperature 210° C (Tritium foil
Electron Capture); injector temperature 220° C; carrier gas-
nitrogen.
9. Confirmation of residues was accomplished by concentrating the
eluates to a very small volume and injecting aliquots on an
identical column in the same gas chromatographic oven but
attached to a microcoulometer detector or by chromatographing
on two or more instruments and two or more columns and calcula-
tion of "p" values.
10. Calculation of residue concentration based upon comparison of sam-
ple peak areas with areas of organochlorine pesticide standards
analyzed concurrently each day.
Peak area of sample minus control volume of sample (ml)
Apparent p.p.m. = Peak area per ng standard x volume injected (ul)
wt. (vol) of water sample
The apparent p.p.m. is then corrected for percent recovery to obtain
the actual concentration.
Analysis for Chlorinated Acid Herbicide Residues
(2,4-D; 2,4,5-T; Dicamba, etc.)
Place 250 ml of water in a 1-liter separatory funnel and add 100 ml
of a solution of 2% NaHC03 and 0.125% EDTA disodium salt (Disodium
dihydrogen ethylenediaminetetraacetate dehydrate manufactured by
G. Frederick Smith Chemical Co. The EDTA ties up calcium and heavy
metal salts on glassware which, if in sample, would precipitate the acids.)
Extract the aqueous phase by adding 200 ml of glass distilled benzene
and shaking the contents vigorously for 1 minute. (pH of the aqueous
layer should be approximately pH 8.0 at this time.)
54
-------
3. Separate the phases and discard the benzene phase.
4. Add 100 ml of 0.60N H2S04 to the aqueous solution in the separatory
funnel and shake cautiously venting the funnel periodically to permit
evolved CC>2 to escape. (pH 1.5 - 2.0 should be condition of aqueous
phase at this point.)
5. Add 200 ml of glass distilled benzene and shake vigorously for 1 minute.
Vent funnel as required. Separate the phases transferring the aqueous
solution to a second separatory funnel. Save the benzene phase.
6. Extract the aqueous phase with an additional 100 ml of g.d. benzene.
Separate phases and then combine the benzene phases from the two
extractions in a 500 ml round bottom evaporation flask that has been
previously acid and acetone washed.
(Note: After the herbicide acids have been separated from water,
care must be taken to prevent loss on glassware. All glassware used
from this point on, including the evaporation flasks, must be washed with
approximately 0.05N HC1 solution and then with glass distilled acetone
to remove all traces of HCl. This washing removed calcium and heavy
metal salts probably present as carbonates and also C02 present in
distilled water, etc. that would combine with any cations present.)
7. Evaporate the benzene extract with the flash evaporator to a volume of
approximately 5 ml. Transfer the extract to a 15-20 ml centrifuge tube.
Rinse the evaporation flask with a small volume of benzene and add to
the solution in the centrifuge tube.
8. Prepare a diazomethane methylating apparatus consisting of two 2-hole
rubber stoppered 20 x 125 mm test tubes connected with 1/4 inch bent
glass tubing. The first glass tube should be connected to a nitrogen
source and after bending on a 90° angle placed through the rubber stopper
so as to almost touch the bottom of the test tube. The second glass tube
should be bent in a flat U-shape with a short end inserted through the
second hole of the first rubber stopper (extend 1-2 inches into the test
tube) and the long end through the second rubber stopper so as to almost
touch the bottom of the second test tube. A second U-shaped glass tube
is inserted (short end) in the second hole of the second rubber stopper
and the long end left free to insert into the sample centrifuge tube.
9. Place 10-15 ml of glass distilled diethyl ether in the first test tube.
In the second test tube place 2 ml of 60% KOH, 2 ml of glass distilled
carbitol, and 5 ml of glass distilled diethyl ether. Prepare a new test
tube of this nature for each sample to be methylated.
10. Add approximately 50 mgm of Dizald reagent (yellow-orange powder - the
quality can be quickly approximated on the end of a micro spatula) to
the KOH-carbitol solution, connect the tubes to the nitrogen line, place
the sample under the end of the generator so that the diazomethane-nitro-
gen gas bubbles through the extract.
55
-------
(Note: The first test tube cleans the nitrogen and saturates it
with diethyl ether by bubbling the gas through the ether; the second
test tube generates diazomethane again with the nitrogen gas bubbling
through the solution; and the sample is thus methylated in the centri-
fuge tube. The nitrogen gas flow should be regulated to about 5-7
bubbles per second.)
11. Methylate the samples for 1-2 minutes until a faint but brilliant
yellow color is evident and then let them stand for about 10 minutes.
If the samples are sufficiently clean, aliquots can be injected directly
on the gas chromatograph and analyzed with the electron capture detect-
or. In most cases, however, additional cleanup is required to. remove
extraneous materials.
12. Prepare a chromatography column (19 x 300 mm reservoired) with a
glass wool plug, 4 inches of 2% H20 deactivated florisil, and 1 inch
anhydrous ^2804. (The florisil was deactivated to prevent excessive
tailing in elution of the methyl esters.)
13. Wash the column with petroleum ether and elute the methylated herbi-
cides with 200 ml of 10% glass distilled ethyl acetate in glass distilled
benzene. Concentrate the eluate on a flash evaporator to a suitable
volume.
14. Inject aliquots on the gas chromatograph as discussed in the procedure
for organochlorine insecticides. Confirm by microcoulometry or the
procedures outlined on page 54.
15. Calculate the residue present by comparison to the response of methy-
lated standards.
Analysis for Atrazine in Water
Procedure 1.
1. Place 500 ml of water in a 1-liter separatory funnel and extract
the aqueous layer by shaking vigorously 1-2 minutes with 200 ml
of cleaned chloroform. (The chloroform is cleaned by passing it
through a large column containing 6-8 inches of Davison 923 silica
gel. Discard the silica gel in the column when it becomes trans-
parent in color to chloroform. Refill the column with new silica
gel before further use.
2. Separate the phases and extract the aqueous phase a second time
with 100 ml of cleaned chloroform.
3. Combine the two chloroform extracts and backwash by shaking it
vigorously for 1 minute with 100 ml of 2% NaHC03. Collect the
chloroform phase in a 500 ml round bottom evaporation flask and
evaporate with a flash evaporator to almost dryness.
4. Remove the final chloroform under a clean air or nitrogen gas stream.
56
-------
Dissolve the residue in benzene and inject aliquots on the gas
chromatograph. Both electron capture detection and flame thermionic
detection can be used. Electron capture with a 6%i detector provides
the greater sensitivity but also the greatest interference. A
flame thermionic detector with rubidium chloride salt bead (or
potassium chloride as second choice) is the preferred detection system.
Several different column combinations may be used including the
10.4% DC-200 plus 15.1% QF-1; 2% OV-210 plus 1% OV-17; 2.5%
OV-17; and 1.5% QF-1, all on Gas Chrom Q.
Column temperatures should be 170-180°C; Ni63 Electron Capture de-
tector temperature 240-245° C; flame temperature 220-225° C with
hydrogen and carrier regulated to give adequate response according
to manual but not excessive to cause high temperature and melting
of salt bead.
Procedure 2. (Quickest and simplest method.)
1. Place 500 ml of water in a 1-liter separatory funnel and add 100
ml of 10% Na2S04.
2. Extract the aqueous layer with 200 ml of $.ass distilled benzene by
thorough shaking for 1 minute. Separate the phases and extract
the aqueous phase with an additional 100 ml of g.d. benzene. Separate
the phases and discard the aqueous solution.
3. Combine the benzene layers and backwash by shaking 1 minute with
500 ml of 2% NaHC02- Separate the phases and discard the aqueous
solution.
4. Place the benzene phase in a 500 ml round-bottom evaporation flask
and evaporate to the desired volume with a flash evaporator.
5. Inject aliquots of the concentrated extract on the gas chromatographic
column and detect with a electron capture or flame thermionic (KC1 or
rubidium chloride salt bead) detector as in the previous method.
Determination of Organophosphate (and Organochlorine) Insecticides
Procedure 1
1. Place 500 ml of water in a 1-liter separatory funnel. Add 200 ml
of glass distilled acetone and mix thoroughly. Add 10 grams of
^a2^4 an(^ again mix thoroughly.
2. Extract the insecticide residues with 200 ml of glass distilled
petroleum ether by shaking the funnel thoroughly for 1 minute.
Separate the phases and extract the aqueous phase a second time with
100 ml g.d. petroleum ether. Separate the phases and discard the
aqueous solution.
57
-------
3. Combine the petroleum ether phases and backwash by shaking with
500 ml of 2% Na2SO,. Separate phases, discard the aqueous solution,
and transfer the petroleum ether extract (pour from mouth of funnel)
to a 500 ml round bottom evaporation flask.
4. Concentrate the extract to an appropriate volume and inject on a gas
chromatographic column (oven temperature approximately 180°C; flame
and temperature of detector adjusted for optimum sensitivity) and
detect organophosphate residues with the flame thermionic detector
(KC1 bead). The columns indicated in earlier procedures are generally
satisfactory.
Procedure 2
1. Same procedure as above through step 3.
2. Concentrate the petroleum ether extract to approximately 20 ml with
a flash evaporator (water bath temperature 49° C) and then trans-
fer extract to a prepared chromatography column.
3. The chromatography column (19 x 300 mm reservoired) is prepared by
placing a small glass wool plug in the bottom followed by 2-1/2
inches of deactivated florisil (2% H20 added), 2-1/2 inches of
Silica Gel Davison Grade 923, and 1 inch of anhydrous Na2SO,. Wash
the column with g.d. petroleum ether before adding the sample.
4. Elute the sample on the column with 250 ml of glass distilled benzene
to remove the organochlorine insecticides, change receiving 500 ml
round bottom flasks and elute the column with 200 ml of 10% ethyl
acetate in benzene to remove the organophosphates.
5. Concentrate the above eluates with a flash evaporator to a desired
volume and inject aliquots on the gas chromatograph. Organochlorine
residues can be detected with the electron-capture detector and
organophosphate residues with flame thermionic and electron capture
detectors.
Prodecure 3 (For organophosphates that require oxidation to the oxon or
sulfone for gas chromatographic determination.)
1. Same procedure as above to step 5 of procedure 2. Evaporate the
eluate to just dryness on the flash evaporator.
2. Dissolve the residue in 15 ml of cleaned chloroform and add 5 ml of
10 mg/ml metachloroperbenzoic acid in chloroform. Swirl the flask
and let stand for 15 minutes.
3. Place the chloroform solution in a 125 or 250 ml Teflon stopcocked
separatory funnel and add 25 ml of 10% sodium meta-bisulfite. Shake
the contents in the funnel vigorously for one minute and transfer
the chloroform phase to a second separatory funnel.
58
-------
^« Add 25 ml of saturated sodium bicarbonate to the funnel and shake
with the chloroform phase vigorously for 1 minute. Transfer the
chloroform layer to another 125 ml separatory funnel and wash two
times with 25 ml aliquots of distilled water.
5. Transfer the chloroform phase to a 250 ml round bottom evaporation
flask and evaporate just to dryness on the flash evaporator.
6. Dissolve the residue in a known amount of glass distilled benzene
and inject aliquots on the gas chromatograph equipped with a KC1
flame thermionic detector.
59
-------
APPENDIX VI
PROCEDURES FOR DETERMINATION OF PESTICIDE RESIDUES
IN BOTTOM MUD SEDIMENTS
60
-------
Appendix VI
Procedures for Determining Pesticide Residues in River Bottom Sediment
and Mud
General;
Same general considerations on cleaning of glassware and distillation of
solvents as for previous procedures. Recovery studies are also required to
determine the efficiency of the procedures.
Representative samples of mud and sediment should be dried to determine the
dry weight for calculation. The following procedures, however, utilize the
wet mud or sediment after drainage of the excess water.
Calculations are the same as outlined for water samples after determining
the dry weight of the sediment.
A. The Analysis for Organochlorine and Organophosphate Insecticide Residues.
Procedure 1: Organochlorine insecticide residues
1. Place 50 grams of mud sample in a Waring Blendor and add 300 ml
of glass distilled acetone. Blend the contents at slow speed for
5 minutes at the 30 volt setting on the Variac Voltage Regulator.
2. Filter the blended solution through Whatman No. 1 filter paper in
a large conical funnel. Cover the funnel and collecting vessel to
minimize evaporation. Measure the filtrate collected.
3. Place a 150 ml aliquot of the filtrate in a 1-liter (teflon stopcock
and stopper) separatory funnel and add 500 ml of 2% Na^SO,. Shake
the contents of the funnel to mix thoroughly (venting as Required).
4. Extract the aqueous phase in the separatory funnel with 200 ml of
glass distilled petroleum ether by vigorous shaking for 1-2 minutes
(vent funnel as required). Separate the phases collecting the
petroleum ether in a second 1-liter separatory funnel. Re-extract
the aqueous phase with an additional 100 ml of petroleum ether,
separate and combine the organic solvent phase with the first ex-
traction.
5. Wash the petroleum ether extract by shaking with 100 ml of 2%
NaHCOo and then transfer the extract to a 500 ml round bottom eva-
poration flask. Concentrate the extract to an appropriate volume
with a rotating flash evaporator (water temperature not exceeding
40° C) and then proceed with the florisil or fiordsil-silica gel
clean-up and gas chromatographic analysis indicated for analysis
of water samples.
61
-------
Note: If the background is too great for accurate gas chromatographic
analysis, additional clean-up will be required.
Procedure 2: Organophosphate insecticide residues
1. Place 100 g of soil in the Waring Blendor and 400 ml of glass dis-
tilled acetone. Blend the material and filter as indicated in
Procedure 1 above.
2. Place a 200 ml aliquot of extract in the 1-liter separatory funnel
with 500 ml of 2% Na2SO, and extract with petroleum ether as outlined
above.
3. Wash the combined petroleum ether with 500 ml of 2% Na2SO^, transfer
to a round bottom evaporation flask and after concentrating the
solution to an appropriate volume inject aliquots on the gas chromato-
graph equipped with the thermionic detector.
Procedure 3: Organophosphate insecticide residues (when additional clean-
up is necessary)
1. Follow the same procedure as outlined above to and including the
concentrating of volume by rotary flash evaporation. Then follow
the column clean-up procedure as outlined previously for organophos-
phate residue in water samples using florisil and silica gel.
2. Wash the column with petroleum ether and then elute with 250 ml of
glass distilled benzene (contains organochlorines) followed by 200
ml of 10% ethyl acetate in benzene (contains the organophosphates).
3. Concentrate the separate eluates with the flash evaporator and inject
aliquots of the organochlorine extract on the gas chromatograph
equipped with electron capture detection and the Organophosphate
extract on the gas chromatograph equipped with thermionic detection.
Procedure 3 utilizes the sample extraction, etc. of Procedure 2 above
and is used for simultaneous determination and the procedures outlined
for simultaneous analysis in water samples.
Note: These procedures will not always provide adequate clean-up of
some extremely dirty samples. Additional clean-up may be required, parti-
cularly for organochlorine residue determination. The use of a Sweep
Co-Distillation Apparatus at 180° - 185° C oven temperature, Storherr
columns packed with silanized glass wool and the mini-scrubber column of
anachrom will provide as good if not better clean-up of extracts for
analysis of organophosphates by theriomic detection as will the florisil-
silica gel column clean-up.
62
-------
B. Analysis for Chlorophenoxy Acid Herbicide Residues (2,4-D; 2,4,5-T;
Dicamba; etc.) (See procedure for analysis of water)
1. Fifty grams of sample is blended with 500 ml of 2% NaHC03 + 0.125%
EDTA solution in the Waring Blendor for 5 minutes and the solution
filtered as outlined previously.
2. The volume of solution is measured and recorded and the entire sample
extracted in a 1-liter separatory funnel with 200 ml of glass dis-
tilled benzene.
3. After discarding the benzene add 100 ml of 3.0 N H2SO,(pH of aqueous
phase now - 1.0) and extract with 200 ml of benzene as outlined for
the water analysis.
4. An emulsion forms in the above extraction. After phases separate as
much as possible, separate and discard the aqueous phase and transfer
the emulsion to 250 ml centrifuge bottles. Balance the weight and
centrifuge at 2000 rpm for 20 minutes (If bottles break,the speed
of the centrifugation will need to be reduced appropriately.
5. Separate the organic phase and proceed with the evaporation (HCL
washed glassware), methylation, clean-up and measurement as outlined
previously for water analysis.
C. Analysis for Triazine Herbicides
1. Blend 100 g of sample in a Waring Blendor (slow speed) with 400 ml
of acetone for 3 minutes. Then add 125 ml of distilled water and
blend for another 3 minutes.
2. Filter the solution through Whatman No. 1 filter paper and collect
in a 16 oz. bottle. Take care to avoid excessive evaporation.
3. Transfer 1/2 of the total extract to a 1-liter separatory funnel,
add 500 ml of 2% ^280^ and extract by vigorous shaking with 250 ml
of glass distilled benzene.
4. Backwash the benzene twice with 500 ml aliquots of 2% NaHCOg and
then evaporate the benzene extract to approximately 5 ml volume.
5. Prepare a 20 x 350 mm reservoired column containing from top to
bottom 1 inch anhydrous Na2SO/, 15 gram (Approx. 2-1/2 - 3 inches of
polyethylene coated alumina (Kensington Corp.), and 15 g (2-1/2 -3
inches) of Aluminum Oxide - Woelm Act Grade IV.
6. Place the extract on the column. Wash the material on the column
with 200 ml of petroleum ether. Then elute the triazines from the
column with 250 ml of NH3 saturated benzene.
63
-------
7. Concentrate the eluate to an appropriate volume and inject
aliquots on the gas chromatograph equipped with thermionic
detection. (Note: Too much background due to inadequate
clean-up reduces sensitivity on the capture detector.
8. Follow detection and calculation procedures as outlined for
analysis of water samples.
64
-------
APPENDIX VII
PESTICIDE RESIDUES IN RIVER WATER AND BOTTOM
SEDIMENT SAMPLES
65
-------
APPENDIX VII
a. Explanation of code number in sample identification.
Nine digit sample number
River Number Sampling Site Type of Sample Date of Sampling
Month Day Year
1 1 2 05 16 72
Rivers are identified by number:
1. Maumee
2. Portage
3. Sandusky
4. Huron
5. Grand
6. Lake Erie Islands
Sampling site 1-6 or 7 on each river as indicated in Appendix I
Sample Identification:
1 . Water
2. Bottom Sediment
3. Clams
b. Sensitivity level for residues by analytical methods employed:
Pesticide Typ_e Water Bottom Sediment
Organochlorine Insecticide 1 ppt IQ ppt
Organophosphate Insecticide 0.1 ppb i ppb
Triazine Herbicides 0.5 ppb
Chlorophenoxy Acid Herbicides 0.5 ppb
Blank spaces indicate that analytical results were not conclusive enough
to identify and quantitate data.
An * indicates that representative peaks for the residue involved were
resolved by two or more gas chromatographic systems but the "p" values
did not correspond with book or laboratory experimental values.
"N" indicates no residue detected at the sensitivity level of the method
as specified.
66
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * insecticide Residue ppt
111092071
12M92071
. 13109 20 71
141092071
151092771
161092771
171092771
111102771
121102771
131102771
141102771
151112471
161112471
171112471
111120371
121120371
131120371
141120371
111032472
121032472
131032472
141032472
111041872
121041872
131041872
141041872
161050172
111051772
121051772
131051772
141051772
151060872
161069872
111061572
121061572
131061572
-14,1061 W2
111062372
121062872
131062872
Aldrin M
N
N
N
N
N
N
N
N
N
N
N
N
N
N :
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
£L_
N
N
2
a
H
M
'O
rH
0)
ci
N,
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
H__
N
N
N _
N N ,
N
N
N
N
Heptachlor w
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
,_JL
N
N
N
.. .._N.
N
N
Heptachlor
Epoxide
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
. N
N
N T
5
fl)
rfl
'O
H
J
N
N
N
N
N
N
N
N
N
N
N
N
6
M
0
rH
rC
y
fr
o
4J
£
N
N
N
N
N __
N
N
N
N
^N
N
N
N
N
N
N
- N
N
N
N
N
N
N
N
N-,
N
N N
__N... 1 N
N IN-
"I
N
N
N |
N
N I
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_-JL
N
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N ! N L N L ^L N
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._KL__
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7
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N
N
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N i
N '
N
N
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__N-
N ,
N 1
N
N
N
8
§
a
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a,
N
N
N
N
N
N
N
S.
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
^N
N
N
N
N
N
N
N N
N N
9
Q
§
a,
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N
N
N
J}
N
.N
N
N
N
N
N
N
N
N
N
10
Q
Q
Q
a.
>
a
N
N
N
N
N
N
N
N
N
N_
N
N
N
N
N N
_N_'
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
JS
L N
N
N
N
N
N
N
N
N
N
N
N
N
N
U 1
N
N
N
N
M
N
11
H
§
(X
A
O
N
H
N
N
N
N
N
N
N
N
N
N
N
N
N i
N
N
N
N
N
N
N
N_
N
N
_ JL__J
N J
N
_N_
N
N !
12
H
Q
O
1
a.
VI
p..
i
i
J. ....
__1L
N
a
N
N
N
N
H
__N
1 u
N
i _a
N
N I
N '
M
N j
H 1
N
_H 1
N
N
N 1
N
N
N
H
~ a 4
UL f
N J
N_!
! 1
N
_JL
_.H
N
N N '
N N 1
N N ]
N N i
N i N 1 N
N , N ! N
*See key for identification of samples
page 66.
and sensitivity of detection of residues on
67
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * insecticide Residue ppt
141062872
211091671
221091671
231091671
241091671
251091671
261092771
271092771 .
211102671
221102671
231102671
241102671
251102671
261102671
211120271
221120271
231120271
241120271
251120271
261120171
211032472
221032472
231032472
241032472 1
251032472
261032472
211031872
221041872
231041872
241041872
251041872
261041972
271041972
211051772
221051772
231051772
241051772
251Q5177?
261060872
271060872
I
G
H
O
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
L N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2
pi
H
t-i
O
0)
T-I
Q
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
1 N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N_
N
Heptachlor w
N
NO
N
NO
NO
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N J
N
N
N N
N i N
Heptachlor
Epoxide
N
SAMPLI
SAMPLI
SAMPLI
N
N
N
N
N
*
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Lindane ^
N
I ANAI
ANAI
ANAI
N
N
N
*
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
._ N .
N
N
N 1 N
Methoxychlor ^
N
YZED
YZED
YZED
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N.
N
.N.
N .
N .
7
w
Q
Q
1
O
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N '
N
N
N
N
N
8
w
o
P
cx
*
ex
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
... ...N. ..
N N
N j~N
N
N
9
Q
O
P
P.
O
N
.N
N
N
N
N
N
N
N
N
N
N
N
N
N
N 1
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
. N
N
N
10
P
P
O
CX
ex
N
N
N
N
N
N
N
N
N
N
N
N
N
N
L_N
N
N
N .
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
11
O
cx
o*
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N "i
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N.
N _
JL- .
i. N ... -
12
H
P
P
ex
ex
N
N
N
N
N
N
N i
N
1 N
N
N j.
N !
N
N
N 1
N j
N !
N i
. N J
N I
IN
N 1
N
N
H t
N_ I
N
N !
N :
N ...
N
N
....N-- i
N N _j
N_ IN |N
N j N N _.i_N___.
*See key for identification of samples and sensitivity of detection of residues on
Page 66.
68
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * Insecticide Residue r-nt
211061572
221061572
.231061572
241061572
251061572
211062872
221062872
231062872
241062872
251062872
361092771
311100471
321100471
331100471
J341100471
351100571
311110871
321110871
331110871
341110871
351110871
371110871
311121471
321121471
331121471
341121471
351121471
.311032072
321032072
.331032072
_341032072
351032072
311041772
321041772
331041772
341041772
35104177-2
311051672
321051672
331051672
1
Aldrin M
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2
c
H
VJ
O
iH
0)
H
Q
N
N
N
N
N
N .
N
N
N
N
N
N
N
N
N J
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Heptachlor w
NO S
N
NO S
N
NO S
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N '
N
N
N L N
lleptachlor
Epoxide
MPLE
N
NIPLE
N
tfPLE
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
5
0)
C
n
o
c
H
H-)
ANALY
N
VALYZ
N
ANALY
N
N
N
N .
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N ,
N '
Methoxychlor <"
CD
N
D
N
SD
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
7
M
Q
a
ex
M
O
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N N
8
w
o
a
P.
*
ex
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N 1
N
N
N
N
N
N
N
N
N j N N
N j_ N
N
9
o
a
o
i
P<
A
O
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
10
o
Q
Q
I
a
A
a.
N
N
N
N
N
N
N
N
N
N
N
N
N
1 N
N
N
N
N
N -
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N i
11
H
O
O
a.
*
o
N
N
N
N
N
N
N
N
N
N
N
12
H
Q
O
i
a.
r.
a
N
N
N
N I
' N 1
N i
N I
+
N
N 1
N
N
N N
N t N
N
N i
N
N
N
N
N
N
N
N _[
N
N
N
j
N j
N J
"N" '
N i
N 'I
" N "1
N 1
__N__J
N i
N
__£U .
M 1
N w
N
N
N i
N
N i
43 1
N !
N
w 1
N N i
N N
N N !
N | N N
*See key for identification of samples and sensitivity of detection of residues
page 66.
on
69
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * Insecticide Residue ppt . . .
341051672
351051672
311061472
321061472
331061472
341061472
351061472
311062772
321062772
331062772
341062772
351062772
411093071
421093071
431093071
441093071
451093071
461093071
411110871
421110871
431110871
441110871
451110871
461110871
411121471
421121471
431121471
441121471
451121471
411032072
421032072
431032072
441032072
461032072
411041772
421041772
431041772
441041772
451041772
46io"4'i7^2
I
c
H
M
rH
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
r N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2
H
i-4
H
O
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
*
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Heptachlor w
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
NO
N ! N
_JL_
N
LL.
: N
N
N
1 N
Ileptachlor
Epoxide
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
SAMPL
N
N
N
N
i N j_ N
Lindane ^
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
: ANAI
N
N
N
N
N
Methoxychlor **
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
YZED
N
N
N
N
7
Q
O
CX
o"
N
N
N
N
N
N
N
N
N
N
N
N
8
w
Q
Q
CX
CX
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N N
N
N
1
N
N
N N
1 N ! N
| N N
9
Q
Q
O
CX
o"
N
N
N
N
N
N
N
N
N
N
N
N
N
10
O
Q
Q
1
cx
N
N 1
N
N
N
N
N
N
N
N
N
N
N
N
N
N 1
N
N
N
N
N _,
N
N
N
N
N
N
N
N
N
N
N
N
N
N
11
H
O
a
a.
cT
N
N
N
N
N
N
N
N
N
N
N
N
12
H
Q
O
1
CX
n
cx
N
N
N
N
N
N |
N 1
1 N
N
N
N
N
j
>
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
J
i
N J
N j
N 1
N
N N
N ! N
N N 1
N
N
1 ^
N .....
N j N
N
N
N i N
!
N { N
N
_,__N
N 1 N IN
N N j N
N N i N
*See key for identification of samples and sensitivity of detection of residues on
page 66.
70
-------
Table 14, Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * insecticide Residue ppt
411051672
421051672
431051672
441051672
451051672
461051672
411061472
421061472
431061472
441061472
461061472
411062772
421062772
_4Jil062772
441062772
461062772
511082371
521082371
531082371
541082371
551082371
561082371
511092371
521092371
541092371
551092371
561092371
571092371
511110471
521110471
541110471
561110471
57111047
511121371
521121371
541121371
561121371
571121371
511032072
521032172
Aldrin M
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2
a
H
(J
O
rH
0)
H
Q
N
N
*
*
*
N
N
N
. N ,
N
N
N
N
N
N
N
N
H N
N
N
N
N
N
N
N
.. N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
_IL N L
Heptachlor w
NO
NO
N
NO .
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
. N
Heptachlor
Epoxide
AMPLE
AMPLE
N
AMPLE
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
_.._N
N
N
N
N
N
N
N
5
0)
c
M
o
H
i-J
ANALYZ
ANALYZ
N
ANALYZ
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N N
. N_ I N '
_____
Methoxychlor °^
3D
5D
N
!D
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
7
w
Q
Q
a
M
O
N
N
N
N
N
N
_JJ j
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N.
N
N
N
N
N
8
g
Q
"o.
*
04
N
N
N
N
N
N
N
N
N
N
N
N
N ,
N
N
N
N
N
N
N
N
N j
N
N
N
__N
N
N
N
N
N
N
_JN , N N
Jl . J . N 1 N
1
9
n
«
o
P.
*
o
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
,N
10
n
§
"ex
*
Cw
N
N
N
N
N
N
N
i N
' N
N
N
N
^ N
N
N ,
N
N
N
N
N
N
N
N
N
N I
N
N
N
N
N
N
N
11
I
PU
*.
O
N
N
N
N
N
N
N
N
N
12
H
Q
Q
CX
(X
1
N
N
N
N
N
1 N }
N
N
N
N N
N N
N
N
N J
N
N
N
N
N
N
N
N
N
N
N i
N
N
N j
N
N
N
N i N !
N N
N j N
N
N
N
N
N 1
N 1
N
N i
N N I
N
N
JL_ |
N
N j
N J
"N
N !
3 J
*See key for identification of samples and sensitivity of detection of residues on
page 66.
71
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * Insecticide ResidueJLEt-Wat
551032172
561032172
571032172
511042772
521042772
551042772
561042772
571042772
511051872
521051872
551051872
561051872
571051872
511061772
521061772
551061772
561061772
571061872
511063072
521063072
551063072
561063072
571063072
112092071
122092071
132092071
142092071
152092771
162092771
172092771
112102771
122102771
132102771
142102771
152112471
162112471
172112471
112120371
122120371
132120371
1
C
H
VH
a
.H
<
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
! N
N
N
N
N
N
N
N
N
N
N
N
N
N
Dieldrin M
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
8.11
7.10
N
N
N
N
3.5^
Heptachlor w
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
NO
N
N
N
N
NO
N
N
N
N
4
>-i
o
t-<
&
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * Insecticide Residue D-Db
_U212U3ZL_
-H20324J.2
122032472
132032472
142032472
112041872
122041872
132041872
142041872
162050172
112051772
122051772
132051772
142051772
152060872
162060872
112061572
122061572
132061572
142061572
162061372
112062872
122062872
132062872
142062872
212091671
222091671
232091671
242091671
.252091671
262092771
272092771
212102671
222102671
232102671
.142102671
252102671
-26210267-1
212120271
222120271
1
Aldrin M
__JL.
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N ...
N
N
N
N
N
_JSL
N
N
2
e
H
S-J
T3
r-{
CJ
H
R
N
N
N
N
N
N
N
7.55j
N
N
N
N
N
N
N
N ^
_JL_j
*
1.40
__u
N
N
N
N
;-
Heptachlor w
N
NO
N
N
N
NO
NO
BT
N
N
NO
NO
N
N
N
N
NO !
NO |
lieptachlor
Epoxide
N
SAMPLE
N
N
N
.AMPLE
AMPLE
N
N
N
IAMPLE
AMPLE
N
N
N
N
N
lAMPLE
Lindane ^
N
OBTAtt
N
N
N
OBTAIN
OBTAD
N
N
N
OBTAIN
OBTAIN
N _j
N
N .
N
N
OBTAIN
SAMPLE ANALY2
N ! N
_N_j
N
N i N
N
N N
_.»_!
N
N
N
NO
..._.NQ J
Ji 1
N
N
N
N
N [ N
*
N
. N
NO ^
NO J
N
N j_ N
N
N
N
N
AMPLE
AMPT.K
_N
N
N
N
N
N
. N
AMPLE (
AMPLE (
N '
N
N
N
N
N
N
ANALYq
Methoxychlor °*
N
3D
N
N
N
ED
2D
N
N
N
ED
ED
N
N
r N
N
N
ED
ED
N
N
N
N
N
N
N
N
ED
OBTAINED.... _
N N
N
N
N
N
N
N
DETAINS
iSIALNE
N
. N_ . N j.
N 1
N '
N
N
N
H
,D
Jl
7
w
a
Q
(X
s
O
N
i N
N
N
N
N
N
1 N
N
N
N
N
N
N
jTj
N~j
N
N
,_
N
N
N
N
N ,
N _T
N "I
__N 1 N_ J
N_J_N.._
8
w
Q
«
fx
t
0.
N
N
N
N
N
N
N
N
N
L N
N
N
N
N
N j
N
N
N
9
n
Q
Q
P.
^
O
N
N
N
N
N
N
N
N
N
N
10
Q
Q
O
a
a.
N
N
N
N
N
N
N j
2.26
N
4.94
N
N
N
N
N
N
N N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
K
N ,
N
N
N
N
N
N
0.90
7.93 i
N
N
N
N i
11
H
O
P
cx
o
N
N
N
N
N
N
N
N
N
N
I
12
H
a
T
Ci
r.
(X
N
N
N H
N j
' N~l
N
N
"~ 1
N" j
N
N
N | N
1
)
N
N
N
N
N
N
N
__
N
N i
N |
N !
__4
N
N
N
j
i
N _[ w i
N
N I
N __
N i
N ! N 1
N 1
N
N i
_JL
N
_IL j
1 .
i
N i N N i
,*L i. N ! N,. 1
*See key for identification of samples and sensitivity of detection of residues
on page 66.
73
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * J.nsecticide Residue ppt>
23.212027:1
242120271
252120271
262120171
212032472
222032472
232023472
242032472
252032472
262032472
212041872
222041872 ,
232041872
242041872 ^
252041872
262041972
272041972
212051772
222051772
232051772
242051772
252051772
262060872
_272068072
.212061572
222061572
232061572
242061572
252061572
212062872
222062872
232062872
242062872
252062872
362092771
312100471
322100471
332100471
342100471
352100571
Aldrin M
. N ....
N
N
N
N
N
N
N J
N
N
N
N
N
N
N
N
N
N
N
N
N
N
.N
N
N
N
N
2
a
H
Ll
b
rH
0)
H
0
N
N
N
N
*
N
N
N
*
N
N
*
10.99
N
N
N
*
*
*
N
N
*
N
1.06
2.34
N
*
i
t
Heptachlor
N _,
N
N
N
N
NO
NO
N
N
N
N
NO
N
NO
NO
N
NO
N
NO
N
NO
N
N
N
N
No £
N
NO
N
N
N
NO
N
N
N
N 1
NO
N
N
NO
lleptachlor
Epoxide
N
N
N
N
N _j
SAMPLE
SAMPLE!
N
N
N
N
SAMPLE
N
SAMPLE
SAMPLE
N
SAMPLE
N
SAMPLE
N
SAMPLE
N
N
N
N
AMPLE
N
SAMPLE
N
N
N
SAMPLE
N
N
N
N
SAMPLE
N
N '
SAMPLE
Lindane w
N
N
N
N
N
ANAL
ANAL
N
N
N
N
OBTA
N
OBTA
ANAL
N
OBTA
N
OBTA
N
OBTA
N
N
N
N
ANALY
N
ANAL
N
N
N
ANAL
*
N
N
N
ANAL
N
N
OBTAj
6
M
0
t-l
x:
u
5?
o
.c
4-1
3
N
N
N
N
N
yZED
pED
N
N
N
N
LNED
N
INED
fZED
N
CNED
N
[NED
N
[NED
N
N
N
N
^ED
N
FZED
N
N
N
irzEDi
N
N
N
N
?ZED
N
N
7
u
o
Q
(X
M
O
N
N
N
N
N .
N
N
N
N
N
8
H
Q
Q
1
"p.
»
D.
N
N
N
N
N
N
N
N
*
N
i
N
N
N
N
N
N
N
N
N 1 N
N i
N
N
N
N
N
N
N '
N
N .
N
N
N
*
N
N
N
N
N
N
N N
N N
([NED j
9
o
§
a.
*
o
N
N
N
tr
N
N
N
N
N
N
N
L N
N 1
N
N
N
N
N
N
N
N
*
N
N
N
N
N
10
o
«
Q
a.
«
a
N
N
N
N"
*
N
N
N
*
N
N
*
h:i4
14. 4Q
N
N
*
N
*
N
N
*
N
3.24
N
N
11
H
O
P
P.
»,
O
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
I N
1
12
H
a
o
(X
Cu
N
N
N
N
N
i
I_J? i
N "1
N !
N I
J
N 1
N ~~|
N
N
N
N |
N
N
N
I
N !
LJL_ ,
N
[
N
N
N
N
N
[_N
N
N
N
1
-i ,
N
* i N N
- - - i .~4
*See key for identification of samples and sensitivity of detection of residues
on page 66
74
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * Jjasecticide Residue ppb
312110871
322110871
332110871
342110871
352110871
372110871
312121471
322121471
332121471
342121471
352121471
312032072
. 322032072
332032072
342032072
352032072
312041772
322041772
332041772
342041772
352041772
312051672
322051672
332051672
342051672
..352051672
312061472
322061472
332061472
342061472
352061472
312062772
322062772
332062772
342062772
352062772
412093071
422093071
432093071
.442093071
I
a
w
na
rH
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2
a
H
a
t-1
0)
tH
Q
N
*
N
N
N
N
N
N
N
N
N
N
N
N
N
....
3.63
N
N
N
N
N
N
N
3
o
r-i
f,
o
w
4J
ex
ai
N
N
NO
N
NO
NO
N
N
N
N
NO
N
N
N
N
NO
NO
N
N
N
NO
N
N
N
N
NO
N
N
N
N
NO
N
N
N
! NO
N
N
.N .! N
NO
NO
N
N
N
Heptachlor
Epoxide
N
N
SAMPL
N
SAMPL
SAMPL
N
N
N
N
SAMPL
N
N
N
SAMPL:
SAMPLl
N
0.30
N
SAMPL]
N
0.40
N
N
SAMPL:
N
N
N
N
SAMPL]
N
N
N
SAMPL]
SAMPL:
SAMPL:
N
N
JS.
5
M
H
,-J
N
N
; ANAI
N
; OBT/
: OBTV
N
N
N
N
; OBT/
N
N
N
: OBT^
: ANAI
N
N
L N
OB'O
N
N
N
N
OBTV
N
N
N
N
OBT^
N
N
N
ANAI
OB.T/
u ANAI
N
N
Methoxychlor **
N
N
YZED
N
INED
INED
N
N
N
N
INED
N
N
N
INED
YZED
N
N
N
INED
N
N
N
N
INED
N
N
N
N
INED
N
N
N
YZED
INED
YZED
N
7
s
Q
CX
N
N
N
N
N
N
N
N
N
N
N_J
N
N
N
N
N
N
N
N
N
N
N
N
.N
N
. N
N N
N, N i ,N
8
w
o
n
a.
N
N
N
N
N
N
"N
N
N
N
34.60
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
3.10
9
o
o
o
ex
ft
o
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
10
Q
a
Q
i
a.
ex
N
N
3.00
N
N
N
N
N
N
N
N
0.90
N
N
N
N
N
N
N
N
N
N
N
N
N
11
g
n
ex
o
N
N
N
N
N
N
N
N
N
N
N
12
H
Q
a
i
ex
ex
N
N
N
i
N
N
N
N "
N !
N
N 1
^ N
1 "
N N
N N j
N | N j
N
N
N "
N
N
N
N
N _j
N
N
N
N_J
N
N
!
N
N__4
N
j
N
N
N N
j j
N N
N i N
N N
N
N
*See key for identification of samples and sensitivity of detection of residues on
page 66.
75
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * insecticide Residue nnh
452093071
462093071
412110871
422110871
432110871
442110871
452110871
462110871
412121471
422121471
432121471
442121471
452121471
412032072
422032072
432032072
442032072
462032072
412041772
422041772
432041772
442041772
452041772
462041772
412051672
422051672
432051672
442051672
452051672
462051672
412061472
422061472
432061472
442061472
462061472
412062772
422062772
432062772
442062772
462062772
Aldrin H
N
N
N
N
N
N
N
N
N
N
N
N.,,
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2
p:
rl
M
"O
rH
ft)
H
O
2.88
N
*
N
2.76
N
3.27
N
N
N
17.6
N
N
N
N
N
N
N
N
N
3
t-i
o
t-H
O
«
4J
o.
£
N
N
N
N
N
N
N
.N
N
N
N ,
N
N
N
N
N
N
N
NO
NO
N
N
N j N
N
N
5.39
*
N
3.43
*
5.89
7.40
N
N
N
N
N
N
NO
N
N
N
NO
N
N
N
N
NO
N
N
N
Heptachlor
Ep oxide
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
SAMPL1
SAMPL1
L N
| N 1
N
N
N
SAMPL1
N
N
N
SAMPL1
N
N
N
N
SAMP LI
0.5
N
N
Lindane *"
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
6
P
o
H
,e
o
>*
X
o
,c
4-1
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * Insecticide Residue pp.b
512082371
522082371
532082371
542082371
552082371
562082371
512092371
522092371
542092371
552092371
562092371
572092371
512110471
522110471
542110471
562110471
572110471
_512121371 ._
522121371
542121371
-5521212Z1 _
.362121371
.372121371
512032072
522032172
-352032172
562032172
^572032172
512042772
522042772
552042772
562042772
572042772
512051872
522051872
_552051872
562051872
572051872
512061772
522061772
Aldrin M
i
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
JL_
N
N
N
N
2
a
H
V4
a
i-i
a)
H
O
N
N
*
N
N
N
N
N
N
i N
N
N
N
N
N
N
N
N
N
N
N
N
Heptachlor w
NO
NO
NO
NO
NO
NO
N
N
N
N
N
NO
N
N
NO
N
, NOj
N
N
N
N
N
NO
N
N
N
NO
NO
N
N
N
NO
NO
N
N
N
NO
N
Heptachlor
Epoxide
SAMPL
SAMPL
SAMPL
SAMPL
SAMPL
SAMPL
N
N
N
N
N
SAMPL
N
N
SAMPL
N
SAMPL:
N
N
N
N
N
SAMPL1
N
N
N
SAMPL
SAMPL:
N
N
N
SAMPL:
SAMPL:
N
N
SAMPLl
N
5
ft)
(3
-a
c
H
>J
E" OBT/
; OBTY
; OBT/
E OBT/
: OBT/
; OBT/
N
N
N
N
N
; OBT^
N
N
: OBT^
N
! OB'LV
N
N
N
N
N
; OBTAI
N
N
N
OBTV
OB1V
N
N
N
OB17
OBT^
N
N__
OBT/
N
N N N
N | N N
6
w
0
t-t
.c
0
&
o
u
IS
INED
INED
INED
INED
INED
INED
N
N
N
N
N
itfED
N
N
INED
N
INED
N
N
. . N
NED
N
N
N
INED
INED
N
N
N
INED
INED
N
. JJ
INED
N
7
w
Q
Q
&
M
O
N
N
N
N
N
N
N
N
N
N
N,
N
N
N
N
N
N
N *
N
N
N
N N
S
H
O
Q
"o.
*
0.
J
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N { N 1 N
9
o
Q
P
0.
V
0
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
10
Q
g
"p.
a
N
N
N
5.83
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
11
1
ex
«*
o
N
N
N
N
N
L^ N
N
N
N
N
N
N
N
N
N j
N
N
N
N
N
N
N
N j N
12
H
Q
Q
CL.
r>
a
N
N
N
tf
N
N
N
|_ N
N
N
N
J
N
N 1
N
N
N I
-N1 !
N
N
N 1
N
N J
N
*See key for identification of samples and sensitivity of detection of residues on
page 66.
77
-------
Table 14. Organochlorine Insecticide Residues in River Water and Bottom
Sediment Samples
Sample No. * insecticide Residue \mb
552061772
562061872
572061872
512063072
522063072
552063072
562063072
572063072
I
a
H
i-H
N
N
N
N
N
N
2
c
o
-------
Tnblo 15, friazine Type Herbicide Residues in River Water and Bottom Sediment Samples.
Sample
No. *
111092071
121 nq ?071
;nrnq?,o.7]L
^_4ioq207i
151Q9.2771
161092271
171092771
111102771
12.1102771
.-13.1102771
141102771
151112471
161112471
171112471 J
111120371
121120371
131120371
141120371
111032472
121032472
131032472
[ 141032472
111041872
Herbicide Residue ppb
Atrazine Simazine
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
No Samji
N
N
N
N
121041872 | N
131041872
151041872
161040172
111051772
121051772 _,
131051772
141051772
151060872
161060872
111061572
N
N
N 1
N
11.86
N
N
N
N
121061572 i N
131061572 j N
141061572
111062872
'121062872
131062872
J.41062872
_il!091671
221091671
_231091671.
241091671
251091671
261091671
N
N
N 1
N '
N
N
N
N ,
N
N__
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
le analyzed
N
N
N
Bladex
N
,N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
... N.
N
N
N 1
N
N
N
N
N
H
N
N
N
N
N
N
N
N
N
N
N
N
N
N
, N . .
N
_ i
Sample
Ko.*
-211Q32ZZ1
?iiin?.fi7i
221102671
.231102671
?4nn?fi7i
251102671
-2J6J-1Q2A71
211120271
221120271 .
231120271
241120271
,251120271
261120171
1211032472 "
221032472
^31032472
241032472
251032472
261032972
211041872~1
221041872 _j
1231041872
1 241041872
j_251041872
|J61041972
271041972
211051772
221051772
1231051772
[241051772
.251051772 ,
261060872
1271060872
1211061572
221061572
231061572
241061572
251061572
211062872
221062872
23162872
I 241062872
2510J62&72 .
361092771
311100471 ~
321100471
331100471
Herbi<
Atrazine
N
-N ,
N
N
..N
_.H . .
N
N
N
N
N
N
N ^
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
r N
N
N
N
N
r-2 _
56.00
N
N
N
N
N
N
N
N
N
N
N
ja
:ide Resiriv,
Simazine
N
N
.. N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
"N
N
N
N
N
N
N
N
P" N
N
N
L_N
N
N
N
.. -
N
N
- N
N
N
N
N
N
N
N
_ _N .^
2 ppb i
Bladex !
"fl " '
N i
_J3 '
P BL. "1
N " "1
^N f
N i
N [
N " 1
N J
N i
"N i
IN I
N 1
N i
1 N i
h- N i
N i
N j
' N ' -]
u_N !
N !
N !
_N ... ...
" N " "',
N i
N i
PN "j
N !
N j
N !
N
N ~!
N i
N i
N ;
~₯ '~\
N j
N i
N :
N
N :
N
N ;
N
N i
__K :
-See key foi- identification of samples and sensitivity of detection of residues on
page 66.
79
-------
Table 15. Triazine Type Herbicide Residues in River Water and Bottom Sediment Samples.
Sample
No. *
341100471
.,.3,51100571
311110871
321110871
331110871
Karbic.ide Residue ppb
Atrazine j Simazine Bladex
N . N - ... 1 .N
N 4
N
N | N
N i N
N
341110871 j N |
351110871 T N
371110871 N
311121471 [_ N
321121471
331121471
341121471
351121471
311032072
321032072
331032072
341032072
j 351032072
311041772
321041772
N
N
N
N
N
N
._ N
N
N
N
N
331041772 j N
341041772 j
351041772
311051672
321051672
33105 16 72_...
341051672
351051672
311061472
321061472
| 3310~61472~~i
i 341061472
3510614~72
N j
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N .
N
N
N
N
N
N
N
N
N
N 1 N
N j N
N T N
N ! N
27.62
N
N 1
I 3H062772 i N
! 321062772
331062772"1
341062772
351062772
411093071
! 421093071
431093071
441093071
451093071
__461093071
411110871
421110871
1 431110871
N
N
N
N _j
N
N
N
N
N
N
N
N
32.40
N
N
N
N
"29.93
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
. , J1
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N N N
N N j N
N N I N
j
'
Sample
No . *
441110871
451110871
461110871
4lll21471j
I42112147L
431121471
441121471
451121471
4UQ32072
421032072
431032072
[1441032072
461032072
r_411041772
421041772
4310417*72""
441041772
451041772
1 461041772
_ 411051672
421051672
Herbicide Residue ppb i
Atrazine t Simazine Bladex 1
N
N IN!
N N N ;
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
16.17
14.72
4310516721 22.65
44105167 2 J 14.08
U.-45AQ51672
__461Q51672
L_~41106147~2
421061472
431061472
441061472
_4&lQfil.4J2,
411062772
_-A2106.2ZZ2_
. 43JH6-2JZ2-
461062772
__5-21Q&237_L
.551082371
N
N
N
N
N
Z.73
2.95
N
N 1
N |N|
N N \
: "" - I 1
N 1 N i
N
N
N j
N
N
N
N J
N * 1
N -
" N _J
N ~!
N
N j N 1
N i N !
N I N j
N N \
N i N i
N j N |
N IN i
N N
N N
N N i
, N N
N r N
N
N
238.86
N
N
N
N i
N~ "1
N N
N N i
N 26.40 ! N
N
N
69.44
N
N
N !
N J N i
N N
N
N
N
N
N
5Jil0.82_371 N
_ .5.11 097371
5JtlH9237J_
__5ilQ223J'JL.
571092371
N
N
N
N
N
N
N
N
N
N
N
N
N :
N i
N
N
N
N i
N ;
N
N ;
N IN i
N IN (
N N N '
) N 1 N N !
"'See key for identification of samples and sensitivity of detection of residues on
page 66.
»
80
-------
Table 15. Triazine Type Herbicide Residues in River Water and Bottom Sediment Samples,
Sample
No. *
511110471
521110471
541110471
561110371
571110471
511121371
521121371
541121371
561121371
-571121371
511032072
521032172
551032172
561032172
571032172
511042772
521042772
551042772
561042772
571042772
511051872
521051872
551051872
561051872
5_7joua7jj,.,_.
_J511Q61ZZ2_
I 521061772
551061772
561061872
,571061872
_511Q63072
521063072
551063072
561063072
571063072
Bottom Sedi
112092071
122092071
132092071
142092071
152092771
162092771
172092771
112102771 |
132102771
142102771
Ksrbicide Residue ppb
Atrazine
N
N
N
N
N
N
N _
No Sam
N
N
N
N
N
N
N
N
N
N
N
N
N
N
""N
N
No Sam]
N
N
N
N
N
N
N
. N
/N
N
nent
N
N
N
N
N
N
. No Jiamj
No Sami
N
N
Simazine
N
N
N
N
N
N
N
>le analyze
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
, . N
ile analyzed
N
N
N
N
N
N
N
N
N
N
N
N_ ...
N
N
N
N
IP
le analyzed1
N I
T I"
Bladex
N
N
N
N
N
N
N
d
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Sample
No.*
152112471
172112471
112120371
132120371
142120371
122032472
132032472
142032472
132041872
142041872
162050172
132051772
142051772
152060872
162060872
112061572
132061572
142061572J
112062872
122062872
132062872*
Herbicide Residue pr,b
Atrazine ! Simazine
N
N
N
N
No San
N
N
N
N
N
N
24.98
N
N
N
N
N
N
N
N
_ 26.31
I 142062872 N j
212091671 j N
222091671
232091671
252Q9.16J1 i
2££Q92.7_71_
_272Q22J_Z1_
212102671
1 222102671
232102671j
242102671
1 252102671]
1 212120271
22212027T1
232120271
242120271
252120271
262120171
N
N
N
N 1
N
N
N
N
N
No San
N
No San
N
N
No San
N
T12CT3T472 "~ N~"
232032472 N
2420124.72 N
252TL3.247? N
_26203297_2
N
N
_JL32QA1872 N 1
N
N
N
Bladex I
N
N ~*
N
N N
iple analyzed
N N 1
N N
N
N
N N
N j N
N
N
N
N
N
N
N
N
N
N ~
N "
N
N
N
N IN
N j N
N j N
N
N
N j
N
L _N I N_
N i N
N N
N N
N N
N N
N N
N [ N
N N
N ~f N
pie
N
pie analyze
N
N
d
N
N N
pie analyze
N 1
d
N
N 1 N
N |
N
N
N
N 1 N
N
N
N N
N 1 N
_2520418_72 ' N IN N
*See key for identification of samples and sensitivity of detection of residues on
page 66.
81
-------
Table 15. Triazine Type Herbicide Residues in River Water and Bottom Sediment Samples.
Sample
No. *
262041972
212051772
232051772
252051772
262060872
272060872
212061-572
222061572
232061572
242061572
252061572
212062872
222062872
232062872
232062872
^52062872
362092771
312100471
322100471
332100471
342100471
312110871
322110871
, 332110871
342110871
372110871
312121471
322121471
332121471
__342121471
312032072
322032072
332032072
342032072
312041772
322041772
332041772
342041772
312051672
322051672
332051672
^342651672
312061472
322061471
332061472
342061472
312062772
Harbicide Residue ppb
Atrazine
N
47.33
N
No Sam]
N
N
N.
No S.am]
22.73
N
N
No Sam
N
N
N
No Sam
No Sam
.N. ...
N
N
. _._N_
55.12
^N
N
N
No Sam
N
N
N
N
_ N
,-- N
.. N
N_..
No Sam
N 1
N
N
No Sam
N
N 1
N
N
N
N ._
4.47
N
Simazine
N
N
N
ile analyzec
N
N
N
ile
N
N
N
ile analyzed
N
N
N
Die
>le
N _
- - N
N
N
N
.N
N
N
ile
N
N
N
N
N
N
N_ ,
N
?le
N
N
N
ale analyzet
N
N
N
N
"'N
N _
N
N
Bladex
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
- , N . ,
N
N
N
N
N
N
N
N t
N
N i
" N
N
N
N
N '
N
N
N
H
N
N
Sample
No.*
322062772
332062772
342062772
412093071
422093071
432093071
442093071
452093071
462093071
412110871
422110871
432110871
442110871
452110871
462110871
412121471
422121471
432121471
442121471
452121471
412032072
["422032072
f 432032072
442032012
462032072
A12041772
432041772
4420417J72
Herbicide Residue ppb
Atrazine i Simazine Bladex I
N
52.16
N
N
N
N
N
N
N
._ . N
N
N
N
N
N
No Sai
N
N
N
N
N
N i N 1
N N 1
N N
N 1 N
N N
N
N
N
.. N
N
N
N
N
N
N
iple analyze
N
N
N
N
N
No Saijiple analyze
N
N
N
N
N
N
452041772 ! N
462041772 |
1 412651672
j.. 432JL5JJL72 j
44255167.2
4s?nsi 67?
46,20 51.6.7JL.
412061472
422061472
432061472
442061472
462061472
412062772
422062772
412M21Z2
_ 442062772
462062772
5120&2371
522082371
N
N
No Sai
46 . 20
N
N
N
76.33
95.19
N
N
N
l~25.16
, No Sap
No San
N
No San
No San
N
r N 1
N
N
N
.. .-u 1
N
N
_N
N
N
N
:d
h- N
N
N
N
N
d
N
N N
N
N
N
N
N
N
N
N
N
N
N j N
N
iple
N
N
N
N
N
N
N
N
N
N
iple analyze
.rile analyze
N
N
N
N
N
N
N
N
N
1 N
N
N
d
d
N
iple
iple
*See key for identification of samples and sensitivity of detection of residues on
page 66.
82
-------
Table 15. Triazine Type Herbicide Residues in River Water and Bottom Sediment Samples.
Sample
No. *
532082371
542082371
512092371
522092371
542092371
552092371
562092371
512110471
322110471
552110471
562110471
512121371
522121371
552121371
512032072
5J22m?17?
552032172
512042772
522042772
552042772
512051872
522051872
552051872
572051872
512061772
522061772
552061772
572061872
512063072
522063072
552063072
_S72nfiin?9
Herbicide Residue ppb
Atrazine
No Sam
No Sam
N
N
N
N
No._SaTn
N
N
N
No Sam
N
N
N
N
- -- N
No Sam
N
N
N
N
N
Nn Sf)m
- N._._
N.
N
N
N I
N
N
N
N
Simazine
)le
>le
N
N
N
N
lie analyze
.. N_
N
N
>le
N
N
N
- N"
N
)le analyze
N
N
__. N:
,_ N
N
} 1 P ^T^fl 1 V7Pf
.... N
N.
N
N
N
N
N
N
N
1
Blades
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
U
N
N
N
N
N
N
N
N
N
N
...
Sample
No.*
Herbicide Residue jpr,b
Atrazine Simazine i Bladex !
1
T"
*See key for identification of samples and sensitivityof detection of residues on
page 66.
83
-------
Table 16. Chlorophenoxy Aciu Type Herbicide Residues in River Water, Bottom
Sediment and Mussel Samples
Sample
No. *
111092071
,.131092071 .
' 131092071
141092071
151092771
161092771
171092771
111102771
_mJJ12ZLL_
.JJLLU12ZZL
..141102771
j.151112471
161112471
171112471
111120371
121120371
-iimom.
.1.4111.Q17JL_.
UUQ3.2472
! l?,im?47?
..111032472
-141012472
JJ.1041872
1210.41872
131041872
141041872
161050172
111051772
Herbicide Residue ppb
Dicamba
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
No San
N
JsL
N .
N
IS
N
N
N
N
N
N
N
121051772 N
131051772 J N
141051772 1 N
JL51060872 N
161060872 j N
111061572 i
,-121061572
131061572
141061572
111062872
121062872
pL31062872
p.41062872
-211091(371
~2210JL1671_...
.2310J1671
, 241091671
251091671
261091671
. N..
N '
- - JL ,
N
N i
N
No Sai
N
N _
2,4-D
N
N
N
N
N
|_ N
1 N
N
N
N
N
f N
N
N
N
pie analyze
~- - JL____
N
N .
.... N
.... N
N
N
N
. N.
N
N
N
N i
N
N
N
N
N
N_ J
_ JJ
N
N
_ N_
2r4,5-I
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
r ;
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
JL
-N
. _N_
N
N
#le analyzed
N
N
N j N
No Saijiple analyze
N
. , N , ,
N
N
N N
N
N
N
d
N
N
N
!
(Sample.
Ko.*
271092771
-2111Q2621_
-221.1Q26.71
231102671
241102671
251102671
261102671
211120271
221120271
231120271
241120271
251120271
.261120171
211032472
P221032472
j Herbicide Residue nob i
Dicamba ! 2.4-D
N
u
N
N
N
N
N
N
L N
N
P N
N
N
N
N
231032472^ N
-241fl324Z2_
25im?4.7;5
-2filQ32SZ2_
211041872 i
1 N
N
N -
N
221Q41872 N
-231oiiazi_
2410A1S.72
251041872
261041972
-N
N "^
r. .
N
2710419721 N
211051772
22105l"772 "
r N
N
231051772_j N
.1410.51772...
251051772
261Q60872
2710608'72^
Jilfifil5Z2_
221061572,
,231061572
241061572
251061572
N
N
N
N
N
N
N
N
211062872 T N
-221£6.ZSI2L_
231Q628/2 ,
-241062822...
-2JlQi2SI2-
-261022221^
311100471
32110n471
.331100421
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N j
N
N
N
N
N
N
N
N
N
N
N 1
^ N
2.4.5-T i
L_i_j 1
N 1
N 1
1 B 1
N 1
d 1
N '
N 1
41 4
N !
N !
N ~ 1
N i
N i
N" '" 1
N " 1
N "]
N '" 1
_.~JL_ J
N 1
N ~1
N' 1
N i
N !
N i
N I
N N i
N 1 N- 1
N
N
N i
... _.j
N I N i
N ! N i
N IN!
N ! N 1
N N 1
N
i_ ~ t
rN^ i
- N.... j
N
N j
-N i
_JL_. I
_N _|
^ N N i
N 7.0*
N N 1
N j N j
N N !
, N
N ^
" N j
N !
N N !
N J' N i
N IN]
*See key for identification of samples and ssnsltinitjof detection of residues on
page 66
84
-------
Table 16. Chlorophenoxy Acid Type Herbicide Residues in River Water, Bottom
Sediment and Mussel Samples
Sample
No. *
341100471
351100571
311110871
321110871
331110871
341110871
351110871
f_37lil0871
311121471
321121471
331121471
341121471
351121471
311032072
321032072
jyin32n72
341032072
351032072
311041772
321041772
331041772
341041772
-15JLQ41ZZ2_
311051672
_32iQ5Jj67_2_.
331051672
341051672
351051672
311061472
321061472
331061472
141 nfii 47,2
TiinfiiAJ?
31infi2772
321062772
-23-Ln6.2.7_Z2_,
-141062772
351062772
411093071
,421093071
_431093071
_4A1093071
r451093071
461093071
411110871
421110871
431110871r
Herbicide Residue ;gpb
Dicamba
N
- . N._
N
N
N
N
N
N
N
N
N
N
Na Sa
N
N
N
N
N_
N
N
N
N
JJ
N
N
N
N
N
N
N
N
N
N
No Sa
N
N
L N
N
No Sa;
N
N
N
No Sa;
N
N
N
N
2.4-D
N
N
N
N
N
N
N
N
N
N
N
N
nple analvz<
N
N
. . N _.
__ N
N _
N
... N
N
_N
2.4,5-T
N
N
N
N
N
N
N
N
N
N
N
N
id
N
N
N
N
N
...N
N
N
- JJ , , .
N
... N N
N
N
N
N
N
N
N
N
N
nple analyzi
N
N
N
N
nple analyzi
N
N
N
nple analyzi
N
N
N
N
N
N
N
N
N
N
N
N
N
:d
N
N
N
N
d
N
N
N
d
N
N
N
N
Sample
No . *
441110871
451110871
461110871
41 1 1 21471
_4211 21471
411191471
441 1 91471
/i5119l/l71
^1103°072
421032072
4^1 03?07?
44irn2ny2
-M1Q32QJ2.
4iir>4i772
4^,1041772
4310417,12,
441 H41722..
4.510.417.12-.
461041772
411051672
._42105_lf>Z.2_
._4JUQ5J£Z2_..
_A410Jil6_7_2_1
451051.6.72.
461051672
411061472
421061472
431061472
441061472
461061472
411062772
421062772
431062772
| 441062772
461062772
511082371
521082371
531082371
541082371 1
551082371
561082371
511092371
521092371
^41092.374
sjsinq2^7i
_5£in
-------
Table 16. Chlorophenoxy Acid Type Herbicide Residues in River Water, Bottom
Sediment and Mussel Samples
Sample
No. *
511110471
521110471
541110471
561110421
571110471
511121371
52H21371
541121371
561121371
,.571121371
511032072
521032172
5S103?!??
561032172
571032172
511fU9779
521042772
551042772
561042772
571042772
511051872
521051872
551051872
561051872
571051872
511061772
521061772
551061772
561061872
571061872
511063072
521063072
1551063072
561063072
571063072
Bottom Sedin
112092071
122092071
132092071
142092071
152092771
162092771
172092771
112102771
132102771
142102771
Herbicide Residue ft
Dicamha
N ...
N
N
N
No San
N
N .
. N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2,4-D "
N
N
N
N
pie analvze
N
-. S_
N
N
N
N
N
N
N
N
[ N
N
N
N
N
N
N
N 1 N
N
N
N
N
N
N
N
N
N
N
ent
N
N
N
N
N
No Sam
No Sam
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
jle analyze
ale
N
N
N
Rfi_
2,4, 5-T
N
N
N
N
1
N
N
N
N
N
N
N
N
N
N
N
N
JSL
N
N
N
N
N
N
N
N
N
_N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Sample
No . *
152112471
172112471
.112120171
-112120271
.142120371
1220324721.
132032472
142032472
132041872
142041872
162050172
132051772
142051772
152060872
161060372"
J.12M15JJL
13206 15Z2_
.142061512
JL12.Q62812-.
-laifl&^Z^
132062872
.-142Qfi2aZ2_
Herbicide Residue nob i
Dicamba 2,4-D
N
. ..N.
N
i No Sam
N
N
N
N
N
N
No Sam
N
N
N
N
N
N
N
No Sam
No Sam
No Sam
No Sam
-212Q31fiZlJ_ N
2220.91621
.232091671
-25.2Q21671-,
-242092 7_7J
272092771
N "
1 N
L N
No Sam
... N
212102671 1 N
222102671
232102671
242102671
252102671
212120271
222120271
232120271
242120271
252120171 .
262120171
212032472
232032472
252032472
262032972
.212041872
232041872 ,
252041872 1
262041972
N
N
N
No Sam
N
N
No Samj
N
N
N
No Sami
No Samj
N
N
N
N
N
N
N
N
N
ale analyze
N
N
N
N
N
N
lie analyze
N
N
N
N
N
N
__.N
)le analyze
)le analyze
)le analyze
)le analyze
N
N
N
N
le analyze^
N |
N 1
N
N
N
le
N
N
le analyzei
N
N
12,4,5-Tl
~ N -
r__E i
N
i
N 1
N
N
N
N
N
a i
N
N
r N 1
- N i
N ~J
N ~1
_JL_ 1
a
a
a
i
N 1
N t
N
N i
. ^
N i
N
N -1
N
N ]
N "3
N J
1 1
N J
N
N i N i
le analyzec
le analyze!
N I
N
N
N
N
1
N
N
N
N j
N
N i N
*See key for identification of samples and sensitivity of detection of residues on
page 66
86
-------
Table 16. Ch.lorophenoxy Acid Type Herbicide Residues in River Water, Bottom
Sediment and Mussel Samples
Sample
Ho. *
212051772
232051772
252051772
262060872
272060872
212061572
222061572
232061572
242051572
252061572
212062872
1222062872
! 232062872
242062872
252062872
i 312100471
322100471
i 332100471
i 342100471
1 362092771
! 312110871
322110871
332110871
342110871
372110871
312121471
322121471
332121471 ,
342121471
312032072
1322032072
332032072
342032072
312041772
322041772
332041772
342041772
312051672
,322051672
332051672
342051672
312061472
322061472
332061472
342061472
312062772
322062772
Herbicide Residua ppb
Dicamba
N
N
N
N
N
N
N
N
N
N
N
N
No Sat
No San
No Sai
N
N
N
N
N
N
N
..N
N
No San
N
N
N
N
N
N
N
N
No San
N
N
N
N
No Saffl
No San
No San
_N
N
N
N
N
N
2 4-D
N
N
N
N
N
N
N
N
N
N
N
N
pie analyze
pie analyze
pie
N
N
N
N
N
N
N
N
N
pip
N
N
N
N
N
N
N
N
pie
KL
N
.. N
N
pie analvze
pie ai^alvze
pie analvze
N
-J*
N
N
N
N
_2^4J_5-T
N
N
N
N
N
N
N
N
N
N
N
Id
d
N
N
N
N
N
N
JL
- N
N
N
N
N
N
N
N
N
N
N
N
N_
N
d
d
d
N
.N...
N
N
N
N
Sample I
No . *
332062772
342062772
412093071
422093071
432093071
442093071
452093071
L462093071
[412110871
422110871
432110871
442110871
452110871_j
462110871
4L2121471
422121471
432121471
442121471
452121471
412032072
422032072
432032072
442032072
462032072
412041772
432041772
442041772
452041772
462041772
412051672
1432051672
T42051672
452051672
| 462051672
412061472
422061472
432061472
442061472
462061472
412062772
422062772
432062772
A420.6.2772.
467067777
522082371
532082371
Herbicide Residue ppb
Dicamba 2. 4-D
N
N
N
N
No San
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N n
N
N
N
N
N
N
N
N
N
N
No Sam
No Sam
No Sam
22.7
N
N
N
N
N
No Sam
No Sam
N
N
, N
No Sam
No Sam
No Sam
N
N
N
N
pie analvze
N
N
N
N
N
N
N
N
N
N
N
N
N
N
. . N
N -
N
N
N
N
N
N
N
N
N
>le analyze
)le analyze
>le analyze
N
N
N
-N ,
N
N
>le analvze
>le analvze
N
N
H
ile
»le
2T4.5rT
N
N
N
N
d
N
N
N
N
N I
N -i
Li.1? 1
tr« 4
N 1
N j
N
^ I
N _j
N I
" N 1
__JJ I
N I
"~~N~~ 1
N "'"1
N S
N! 71
N 1
1 N j
N j
a !
1 !
1 i
N j
JJ
N
N !
N !
. N
1
1 i
N I
N 1
}
,le
*See key for identification of samples and sensitivity of detection of residues on
page 66
o/
-------
Table 16. Chlorophenoxy Acid Type Herbicide Residues in River Water, Bottom
Sediment and Mussel Samples
Sample
No. *
542082371
_5J 2092371
-iZ2O22121___
54_2f)9?371
552092371
562092371
J1211QAZ1_J
.522110471
,55.2UQ471._ .
-542110471 _
512121371
522121371
552121371
512032072
522032172
552032172
512042772
522042772
552042772
512051872 .
522051872
552051872
572051872
^512061772
522061772
552061772
512063072
522063072
552063072
572063072
Mussels
113093071
223091671
253091671
223102671
223062872
333100471
343100471
333110871
343110871
333061472
333062772
343063772
513082371
523082371
543082371
Herbicide Residue ppb
Dicamba
No San
N
N
N
No San
N
N
No San
N
No San
N
N
N
N
N
N
N
N
N
No Sai
N
- js . . . _
N !
N
- N_
No Sai
No Sar
No Sai
N
S.amples
M
M
If
tl
II
II
II
M
II
II
It
II
II
M
II
2, 4-D
pie
N
N
N
pie analyze
N
N
pie analyze
N
igle analyze
N
N
N
N
L N
1 N
N
N
N
ipl£_analy_£e.
N
N
N
N
N
N
pie analyze
pie analyze
pie analyze
N
not analvz
?i M
n M
»! II
n M
it ti
it it
rt ii
it it
ti tt
il ll
n n
it ti
ti n
tt ti
" "
.iii'JL-J
N
N
N
d
N
N
d
N
d
N
N
N
N
1 N
N
N
N
d
N
JS
N
N
N
N
d
d
Id
N
£d__
Sample
___Hgrb_i_cidG Residue
DicamFa i 2 4-D
Samplejs noT analy z^d
ppb
-5A3D.22321J
-JH2Q223Z
*See key for identification of samples and sensitivity of detection of residues on
page 66
-------
T:!l:3c. 17. Organophosphate Insecticide Residues in River Water and
Bo 11 cm S e.d ime n t Samples.
Sample No.*
111032472
.121032472
131032472
1^1032472
111041872
121041872
131041872
141041872
161050172
111051772
121051772
131051772
131051772 H
151060872
l6To60872
111061572 |
121061572
131061572
141061572 ^
.111062872
121062872
131062872
JAlM2aZ2_. .
.Z5XX2Q17X
211032472
-22Xm2AZ2_
Insecticide- Rp^irh,^ pr,h
Diazinon
N
_. _ . N
N
_ U , ,,...
N
N
N
N
N
JS- - 1
N
N
N
N
N
N
N
JS
JL~_ .. I
N
N
Methyl
Parathion
. _ :. . N
N
N
N
JS
N
N
N
_._ N
N
._H ^
N
N
N
N
N
N
- N
I Ethyl
Parathion
N
N
N
._ N
N
. _ N
N
N
N
_N
, 1L-
N
r~-,. JL __j
N n
N
N
N
N
!4_
JL j jg
N_ _ i N
N . _L N 1_ N
N
JS
N
N
N
U_ _...
JS_
N
, .N
N
. N 1 H
Kalathion
N
N
N
N
N
N
N
N
N
K| i
N
N
N
N
N
N
N.
N
N *
N 1
N
Thiciat
"NT
N
N
N
N
M
N
N
w
JN_
JL
N
N
N
N
_ U.
M
N I M
H
N
H_ .. L
N
M.
-23T03P.4J2-
261032972
"1
211041872
221041872
_231041872_
241041872
i - -N~-
- -* _^
L -jj i:
N
N
N
. __ .N_.. ._..
251041872_
261041872
271041972
_JL
N
211051772
N
N
N
N
i__
] BL
N_
N
*Sc
key for identification of samples and sensitivity of detection of residues
on page 66
89
-------
Table 17. Organophosphate Insecticide Residues in River Water and
Bottom Sediment Samples.
Sample No.*
231061572
^241061572
251061572
221062872
231062872
241062872
^51062872
311032072
321032072
331032072
341032072
351032072
311041772
321041772
331041772
341041772
311051672
321051672
331051672
341051672
351051672
311061472
321061472
331061472
341061472
351061472
311062772
321062772
331062772
341062772
351062772
411041772
421041772
431041772
441041772
451041772
461041772
411051672
421051672
431051672
441051672
451051672
461051672
411061472
421061472
431061472
Diazinon
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N . .
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N ^
Insectic
Methyl
Parathion
N
N
N
N
N
N
_ N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
:ide Residue
Ethyl
Parathion
N
N._.
N
N
N
N _,
N j
N
N
N
N
N
N
N
N
N
N
N
N
N
N J
N
__ N !
N
N ___
N
._ N
N_
N
N
N
N
N
N
N
N
N_
N
. N_
N
N
N
N
N
N
N
ipb
Malathion
N
N
N
N
N
N
N
N
N
N
N
N '
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Thimet
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N ....,
N
N
.,N-
N
N
N
1 N
N
N
N
N
N
r N
N
r N
N
N
N
N
N
) N
i N
*See key for identification of samples and sensitivity of detection of residues
on page 66
90
-------
Table 17. Organopbosphate Insecticide Residues in River Water and
Bottom Sediment Samples.
Sample No.*
441061472
461061472
411062772
421062772
431062772
441062772
461062772
511032172
521032172
551032172
561032172
571032172
511042772
521042772
551042772
561042772
571042772
511051872
521051862
551051872
561051872
571051872
511061772
521061772
551061772
561061872
571061872
521063072
511063072
551063072
561063072
571063072
Rotfnm Sprlimpnt-
112092071
122092071
132092071
142092071
152092771
162092771
172092771
112102771
Insecticide Residue ur-b
Diaziiion
N
N
N
. . N.
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
It
N
N
N
N
N
N
. N
NO SAMPtI
N 1
Methyl
Parathion
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Ethyl
Parathion
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N j N
N N
N { N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N_
N
N
N
N
N_
OBTAINED
N
Malathion
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Thirnet
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
H
N
N
N i N
N N
N ! N
i
N .
122102771 j ! 1
132102771 N
142102771 , N
N i
N T
N N
152112471 IN IN IN
162112471 _ [_____ m}. sj^T^j QBTAINEEL i
_JJ 1 ^1~"~
N N
N I N
N i N
*See key for identification oi
on page 66
samples and sensitivity of detection of residues
91
-------
Table 17. Organophosphate Insecticide Residues in River Water and
Bottom Sediment Samples.
Sample No.*
172112471
112120371
122120371
132120371
142120371
112032472
122032472
132032472
142032472
112041872
122041872
132041872
142041872
162050172
112051772
122051772
132051772
142051772
152060872
162060872
112061572
122061572
132061572
142061572
162061372
112062872
122062872
132062872
142062872
212091671
222091671
232091671
242091671
252091671
262092771
272092771
212102671
222102671
232102671
242102671
252102671
262102671
212120261
222120271
Insecticide Residue ppb
Diazinon
N
N
NO SAMPL3
4.15
N
NO SAMPL1
N {
N__ ......
N
_HO SAMPT.l
NO SAMPL1
N
N
N
_NO SAMPLI
NO SAMPLI
N
N
N
NO SAMPL!
N
NO SAMPLE
N
N
N
N
N
NO SAMPLI
N
N
N
N
NO SAMPLE
N
N
N
N
N
N
N
NO SAMPLE
NO SAMPLE
N
Methyl
Parathion
N
N
Ethyl
Parathicn
N
N_
. .ANALYZED
N [_ N ,
N N
c_ DETAINED
N
N
N
, nRTATNEP
flRTATNF.n
N
N .
N
OBTAINED
OBTAINED
N
N
N
ANALYZED
N
OBTAINED
N
N
N
N
N
ANALYZED
N
N
N
N
OBTAINED
N
N
N
N
N
N
N
N
-N- - --
N
N
N. ...
_. .H__ r-
N
N_ ..
_ N___ .
1 N
....
- N _|
N
N
..... N.
N
N
N
N
N
L N_
N
N
Kalathion
N
N
N
N _|
N
N
_N . .. . .
N ^
Thine c
N
JJ
N
N
N
._.N _
JL ..
N .....
N - ! $
U. i IL
1
T
...,, , N _ _N
N N . ...
N
N
n N
N
N
N
N
N
N
N
N , ....
N
N. ... ..
N
N
N
JS
N
N
N_ .
N
N
, JL_. . .
. N
I N N
N N i N
(_ N
JL
N ..H .
N
N . | N
-J~ -
OBTAJN.EU ._ J_ . - __ 1
QKLMMBL.'--*-.. . _i - .
N i N
u ..-^ N N
?3919n?71 ! N
242120271 1 _JJ
N - - ! M
. N . .-.. -N_ -
N i N
N i N
N . L_._N
N N
*See key for identification of samples and sensitivity of detection of residues
on page 66
92
-------
Table 17. Organophosphate Insecticide Residues in River Water and
Bottom Sediment Samples.
Sample No.*
252120271
262120171
212032472
222032472
232032472
242032472
252032472
262032472
212041872
222041872
232041872
242041872
252041872
262041972
212041972
212051772
222051772
232051772
242051 77?
25205177?
262Q60872
27206Q872
212061572
222061572
232061572
242061572
_25206157?
.212062872
.222062872
232062872
242062872
252062872
362092771
312100471
322100471
Insecticide Residue ppb
Diazinon
B
N
N
N
N
N
N
N
N
JJO SAMPH
N
NO SAMPLE
N
N
N
NO SAMPLI
N
NO SAMPLI
N . .
N
N
N
NO SAMPLI
N
N 1
N
N
Methyl
Parathion
N
N
N
N
N
. N ,
N
N
N
OBTAINED
N
OBTAINED
N
N
N
OBTAINED
N
OBTAINED
N
Ethyl
Parathion
N
N
N
N
N
._.._ N
N
__ __ N
N
N
... . . . . .
N
N
N
N.
N
N I N J
N J N
N
ANALYZED
N
N
N
N
N j N j__
N
N
N
N
N
N ~1
N IN IN
N j N N
N N i N
N N i N
N N j
NO SAMPLE; ANALYZED
Malathion
N
N
N
N
N
N
N
N
N
Thirnet
N
N
N
N
N
N
N
N
N ._. N.
|
N ! N
N i N
- ... ,-N,,-,, _
N
N
N
N
N
N
N
N
N
N
N
N
N
M .... N, ,. . -,.
' .. .. . _
332100471 r N S N j N i N
342100471 N IN |N
352100571 NO SAMPLE
312110871 N
322110871 j N
332110871 j NO SAMPLE
OBTAINED .
N i N
N
N 1
...ANALYZED . . _ . .
342110871 ( N -N IN
352110871 NO SAMPLED OBTAINED
372110871 ^ NO SAMPLE OBTAINED
312121471 N j N ! N ...
322121471 N - I N N
N
N
N
N
N . <
N
N
|_ . _.N .._
N .
_ N
N -. . .
N
N
N
N
N
N
N
N
N _ . . ..
.. ___KL__ . .
N
N
N
N
N
*See key for identification of samples and sensitivity of detection of residues
on page 66
93
-------
Table 17. Organcphosphate Insecticide Residues in River Water and
Bottom Sediment Samples.
Sample No.*
332121471
342121471
352121471
312032072
322032072
332032072
342032072
352032072
312041772
322041772
332041772
342041772
352041772"
312051672
322051672
332051672
342051672 ,
352051672 "^
"312061472
322061472
332061472
342061472 j
352061472
312062772
322062772
332062772
342062772
352062772
412093071
422093071
T32B53071
442093071
452093071
462093071
462102071
412110871
422110871
432110871
4T2riO'8'71
452110871
"4"6'2T1'0'871
4JXL2.T47T
422121471
432121471
442121471
Insecticide Fes^'due ppb
Diazinon
N
N
NO SAMPL1
N
N
N
N
NO SAMPLI
NO SAMPLI
JJ
N
N
NO SAMPLI
N
N
N
N ""
NO SAMPLI
N
N
N
N
NO SAMPLI
N
N ...
NO SAMPLI
NO SAMPLI
NO SAMPLI
N.
N
N
N
N
N
N
N
N
N
N
N
N
Methyl
Parathion
N
N
OBTAINED
N
N
N
N
OBTAINED
ANALYZED
N
N
N
OBTAINED
N . . .
N
N
N
OBTAINED
N
Ethyl
Para Chi on
N
N_
N
N
N
N
N
N
~ N
N
, -N
JL
N
N
N f N
N IN.
N _j
OBTAINED
N
N
ANALYZED
ANALYZED
OBTAINED
N
N
N
Malathion
..JJ
.N
N
N
N
N
N
N
N
Thinict
N
N . _ ...
N
N
N
N
N
N
N
N 1 KL _ .
i_ _H { N
N IN.
1
N i N_
N
N
N
1
.. ........
- N - -1
N ._
., - -N .
N
N I N
N 1 N
N
N
N
N
N
N
N
N
N
3.62 1 N
N
I N
N
N
N
N
N
N
N
-. _ _N
N. N j M-
|_ N N i . .N
N i N . N
452121471 ! N N N
N
N
N. ..
U
N
__N_
jj_
1
N .
N
N
N
N
N
N
N
N
N
N
L_ N
N
N
N
N
N
N N
N .. | _._._N_. . ...
N 1 N
N
! N ..... _
N
N. .__
j N
._K_. .... _.
44
jj
N i JS_ .
N N
*See key for identification of samples and sensitivity of detection of residues
on page 66
94
-------
Table 17. Organophosphate Insecticide Residues in River Water and
Bottom Sediment Samples.
Sample No.*
412032072
_422032072
432032072
442032072
462032072
412Q41772
422041772
432041772
442041772
452041772
462041772
412051672
422051672
432051672
442051672
452051672
462051672
412061472
422061472
432Q61472
442061472
462061472
412062772
422062772
432062772
442062772
.462062772
.512082371
522082371
532082371
54J2082371
552082371
562082371
512092371 '
522092371
542092371
552092371
562092371
572092371
512110471
522110471
542110471
562110471 j
Insecticide Residue DDK
Diazinon
N
N
N
N
N
N
N
N
N
-X
N
N
NO SAMPL1
13.58-
N
10.31
.N
6.15
N
NO SAMPLI
7.26
N
N
_ N
N
NO SAMPLI
NO SAMPLE
j Methyl
Parathion
N
N
N
N
N
N
N
N
N
N
N
N
: ANALYZED
N
N
N
N
N
.. N
Ethyl
Farathion
N
N
N
N
N
N
N
N
, .._ N
N
N,
N
N
N
_ N.
N ._.
V_?7
N
N j N
N
OBTAINED
N
N
N
N
N
OBTAINED
OBTAINED
NO SAMPL! OBTAINED
NO SAMPLE OBTAINED
NO SAMPL^ DBTATNF.T)
NO SAMPLjJ
N
N
N
N
N
NO SAMPLE
. N
N 1
.NO SAMPLE
N
OBTATNKTl
N
N
N
N
N
OBTAINED
N
N
N._.
N r-
. . . N
JL
N
jg
___._N_
N
N
N_
N
, N
JS
OBTAINED
N
572110471 NO SAMPLES OBTAINED
512121371
522121371
N
N - I N , N ,
.... N ! N N
Mala th ion
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Thimet
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
\T
N ' w
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
£j
N
N
N
N N
N N
1
N
N
N
N
N | N
N ' N
N N
*See key for identification of samples and sensitivity of detection of residues
on page 66
95
-------
Table 17. Organophoppbate Insecticide Residue
Bottom Sediment Samples.
in River Water and
Sample No.*
542121371
552121371
562121371
572121371
512032072
522032172
552032172
562032172
572032172
512042772
522042772
552042772
562042772
57^042772
512051872
522051872
542052772
552051872
562051872
572051872
512061772
522061772
552061772
562061772
572061872
512063072
..522063072 .... ,
-552Q63072
.562063072
572063072
Insecticide Residue oc.b
Diazinon
NO SAMPLI
N
NO SAMPLI
NO SAMPLI
u N
N
N
NO SAMPLI
NO SAMPLIj
N j
N
N
NO SAMPLI
NO SAMPLS
NO SAMPLI
N
N
JJ
NO SAMPLE
N ^ ^
N
N J
N
NO SAMPLI
N
N
N
N
NO SAMPLI
N
-
Methyl Ethyl
Parathicn Parathion
; ANALYZED
N
: ANALYZED
OBTAINED
N
N
N
OBTAINED
OBTAINED
N
N
N
OBTAINED
OBTAINED
ANALYZED
N
N
N
OBTAINED
N
N
N
N
N
N
N
N
N
N
N
N ._.
_ - -N. _ . . ._ N ._.
N i _ N
N
OBTAINED
N
, N
N
N
OBTAINED
N
N
N
N
N
N
N
i !
i !
Malathion
N
N
N
N
N
N
N
N
In liner
N
N
N
N
N
N
N
N
N j N
N
N
N | N
N
N. ..
N
N
N
N
N
N
_N_
. _JS
K
N
N
N
N
N
1
)
i
*See key for identification of samples and sensitivity of detection of residues
on page 66
4U.S. GOVERNMENT PRINTING OFFICE:1974 546-319/395 1-3
96
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
4. Title
PESTICIDE MOVEMENT FROM CROPLAND INTO LAKE ERIE
WALDRON, ACIE C.
10. Project No.
13020 EBL
Organization
DEPARTMENT OF ENTOMOLOGY
THE OHIO STATE UNIVERSITY
COLUMBUS, OHIO 43210
Contract I trr
------- |