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Want

PESTICIDE RESIDUE SURVEY

ON THE RED CEDAR RIVER, SOUTHCENTRAL MICHIGAN

by

Kouame Adou

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Entomology and Pesticide Research Center

1994

ABSTRACT

PESTICIDE RESIDUE SURVEY
ON THE RED CEDAR RIVER, SOUTHCENTRAL MICHIGAN

by

Kouame Adou

Pesticide use has in part resulted in the
contamination of most environments. In Michigan, the Red
Cedar River has been described as contaminated by DDT and
DDT analogues, with the level of pollutants increasing in a
downstream direction (Zabik et al., 1971).

To check the Red Cedar River for pesticide
contamination, seven sampling stations were set out on it.
Duplicate water and sediment samples were then collected
monthly from each station, from May 1992 to October 1992.

Analysis of the collected samples by Gas
Chromatography showed residues of DDT, DDD, DDE, atrazine,
alachlor, 2,4-D, and dicamba in the river. The level of DDT
and its metabolites was approximately 1,000 times less than
in 1971 and was related to the samples organic matter
content. Atrazine and dicamba showed a relationship with
their major period of application, while the concentration
of alachlor was rather related to the volume of surface

run-off.

ACKNOWLEDGMENTS

The author would like to express his sincere gratitude
and thanks to Dr. Matthew J. Zabik, for his valuable
guidance, encouragement, and financial aid throughout the
course of this research. A

Special thanks are also given to the Department of
Entomology and the International Office of Students and
Scholars for their financial support.

Appreciation is also extended to Dr. Frank D’Itri, Dr.
Larry Olsen, and Dr. Robert Hollingworth for participating
in his guidance.

Dr. James Kells, Dr. Karen Renner, and the Michigan
State Cooperative Extension Service are also thanked for
their willingness to help deal with some of the problems
that arose in this study.

The author would finally like to express his
gratefulness to Dr. R. Leavitt and the IR-4 group, as well

as colleagues in Dr. Zabik’s laboratory, for their faithful

help throughout this study.

ii

TABLE OF CONTENTS

LIST OF TABLES O O O O O O O O O O O O O O O O O O O O O O O O ....... O O O O O O O O ..... v
LI ST OF FIGURES O ....... O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Vii i
I- INTRODUCTION 0 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O 1

II- LITERATURE REVIEW............................... ...... 4
A- Pesticide Residues in the Environment.... ....... ...4
-B- Most Commonly used Pesticides in Michigan ......... .10

III- DESCRIPTION OF STUDY AREA ........ ........... ........ 14

IV- MATERIALS AND METHODS ... ..... .....................17
A- Materials..........................................17
1- Equipment.......................................17

2- Reagents........................................17

a- Solvents.....................................17

b- Chemicals.................. ............ ......18

A c- Miscellaneous Items..........................19

d- Glassware....................................19

B- Methods............................................19
1- Sampling Design and Samples Preservation....... 19

2- Glassware Preparation...........................20

3- Residue Survey Scheme...........................21

4

Organophosphate Pesticides and
Chlorinated Hydrocarbons............ ...... ......33

iii

9-

a- Extraction from Water Samples................33
b- Extraction and Cleanup from Sediment

Samples......................................34
c- Sediment Samples Organic Matter Content......35
d- Sediment Samples Moisture Content............36
Triazine Herbicides.................... ...... ...40
a- Gas Chromatography Procedure.................40
b- Enzyme-Linked-ImmunoAssay

(ELISA) Procedure............................40
Chlorinated Herbicides..........................41
Recovery Study................. ....... .. ..... ...43
a- Water Samples..................... ..... ......43
b- Sediment Samples.............................44
Quantification................ ...... ............46
a- Water Samples................................46
b- Sediment Samples.............................46
Mass Spectrometry and Confirmation.. ........ ....47

10- Results and Discusssion................ ..... ...48

a- ReSUItSoooooooooooooooooooooocooooooo ..... .0048
b- Discussion. .......... ........... ...... .......89

11- summarYOOOOOO...0....0.0.000...0.0.00.00000000094

LITEMTURE CITED..........OOOOOOOOOOOOO...0.0.0.000000000096

iv

Table

Table

Table

Table

Table

Table

Table

Table

Table

1.

2.

LIST OF TABLES

Most commonly used Pesticides on
Field Crops in Michigan, 1992a.................11

Most commonly used Pesticides on
Vegetables in Michigan, 1992b............. ..... 12

Most commonly used Pesticides on
Fruits and Nuts in Michigan, 1991..............13

Background of Water and Sediment Samples
in Relation to the Assessed Pesticides.. ...... ,-32

Average percent organic matter of sediment
samples per sampling station..................36

Sediment Samples Percent Moisture....... ....... 38
Percent recoveries from water samples
of alachlor, p,p'-DDE, atrazine,

2,4-D methyl ester, and dicamba................44

Percent recoveries of p,p’eDDE, p,p’-DDD,
and p,p’-DDT from sediment samples.............45

Florisil-celite (5:1)- column recoveries
for DDT complex................................45

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

10.

11:

12.

13.

14.

15.

16.

17.

18.

19.

20.

Results for Duplicates G.C. Analyses of Water
Samples for Atrazine...........................49

Atrazine Concentration (ppb) in relation
to Sampling Month and Station According
to GC dataOOOOOOOOOOOOOOOO......OOOOOOOOOOO....50

Results for Duplicate ELISA Analyses
of Water Samples for Atrazine................. 54

Atrazine Concentration (ppb) in relation
to Sampling Month and Station

Acccording to ELISA Data.................. ..... 55

Results for Duplicate Analyses
of Water Samples for Alachlor........... ....... 58

Alachlor Water Concentration (ppb) in
realtion to Sampling Month and Station ...... ...59

Results for Duplicate Analyses
of Water Samples for p,p'-DDE. ..... . ........... 62

p,p’-DDE Water Concentration (ppt) in
relation to Sampling Month and Station.... ..... 63

Results for Duplicate Analyses .
of Water Samples for 2,4-D ........ .......... ..66

2,4-D Concentration (ppb) in relation
to Sampling Month and Station..................67

Results for Duplicate Analyses
of Water Samples for Dicamba...................70

vi

Table

Table

Table

Table

Table

Table

Table

21. Dicamba Concentration (ppb) in relation
to Sampling Month and Station......... ......... 71

22. Results for Duplicate Analyses of
Sediment Samples for p,p'-DDE... ............... 74

23. p,p'-DDE Sediment Concentration (ppb) in
relation to Sampling Month and Station ......... 75

24. Results for Duplicate Analyses of
Sediment samples for p,p’-DDD. ................. 79

25. p,p’-DDD Sediment Concentration (ppb)
in relation to Sampling Month and Station ...... 80

26. Results for Duplicate Analyses of
Sediment Samples for p,p’-DDT ................... 83

27. p,p'-DDT Sediment Concentration (ppb) in
relation to Sampling Month and Station .......... 84

vii

Figure 1.

Figure 2.

Figure 3.

Figure 4.

Figure 5:

LIST OF FIGURES

Map of the Red Cedar River with
the study sectionOOOOOOOOOOOOOOOO0.... ..... 0.0.16

Chromatograms of two different water
samples and a standard mixture
comprising chlorinated hydrocarbon
compounds and organophosphate
pesticides injected under the same G.C.

conditionSOOO.......OOOOOOOOOOOOCOOO 0000000000 23

Chromatograms of a water sample and a

standard mixture comprising chlorinated

acid herbicides injected under the

same G.C. conditions............. ..... .........26

Chromatograms of two different

water samples and a triazine standard

mixture injected under the same

G.C. conditions....................... ......... 28

Chromatogram of a sediment sample and

a standard mixture comprising

chlorinated hydrocarbon compounds

and organophosphate pesticides

injected under the same G.C. conditions ...... ..30

viii

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

10.

11.

12.

13.

14.

15.

16.

Water Level by Sampling Month .................. 51

Atrazine Concentration (ppb) by
Sampling Month According to G.C. Data ........... 52

Atrazine Concentration (ppb) by
Sampling Station According to
G.C. DataOCOOOOOOOO OOOOOOOOOOOOOOOOOOOOOOOOOOOO S3

Atrazine Concentration (ppb) by
Sampling Month According to G.C.
and ELISA Data.......... ....................... 56

Atrazine Concentration (ppb) by

Sampling Station According to
G.C. and ELISA Data........ ..... . .............. S7

Alachlor Water Concentration (ppb)
by Sampling Month ........... . .................. 60

Alachlor Water Concentration (ppb)
by Sampling Station ............................ 61

p,p’-DDE Water Concentration (ppt) by
Sampling Month.................... ............. 64

p,p’-DDE Water Concentration (ppt) by
Sampling Station.... ...... ....... .............. 65

2,4-D Water Concentration (ppb) by
Sampling Month.................. .............. .68

2,4-D Water Concentration (ppb) by
Sampling Station.. ...... ........... ............ 69

ix

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

17.

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.

Dicamba Water Concentration (ppb)

by Sampling Month..............................72

Dicamba Water Concentration (ppb)
by Sampling Station............................73

Average Percent Organic Matter

by Sampling Station............................76

p,p’-DDE Sediment Concentration (ppb)
by Sampling Month..................... ...... ...77

p,p’-DDE Sediment Concentration (ppb)
by Sampling Station............................78

p,p’-DDD Sediment Concentration

by Sampling Month..............................81
p,p’-DDD Sediment Concentration

by Sampling Station........... ................. 82
p,p'-DDT Sediment Concentration

by Sampling Month ..... ........ ...... .... ....... 85
p,p'-DDT Sediment Concentration

by Sampling Station........... ................. 86
DDT complex Sediment Concentration

by Sampling Month...... ...... ........ ....... ...87

DDT complex sediment concentration
by Sampling Station............................88

I- INTRODUCTION

The use of pesticides has undoubtedly led to many
positive results, enhancing the capability of man to combat
various threats to public health and increase the
productivity in agriculture. Yet, once applied, these
chemicals may undergo several processes resulting in the
contamination of the environment and groundwater as well as
our drinking water and food. In particular, pesticides may
be carried by surface water in a dissolved or bound state to
oceans, lakes streams, rivers, and ponds.

The widespread use of pesticides, along with the
potential for runoff of these compounds, has resulted in the
pollution of most of our aquatic environments (Bedford et
al., 1968). For example, the Red Cedar River (Michigan,~
Ingham County) has been described as contaminated by
pesticides. In research to check whether the freshwater

mussel could be used as a good monitor of pesticide

2

concentrations in surface waters, Bedford et al.(1968) found
residues of methoxychlor, aldrin, and DDT and its
metabolites (DDE and DDD) in the Red Cedar River.
They also found that the content of DDT and its metabolites
increased in a downstream direction. In 1971, Zabik et a1.
not only confirmed the presence of DDT and its metabolites
in the river, but also observed the downstream pollution
pattern indicated by Bedford et al.. Moreover, they reported
the waste_water treatment plants on the study section as the
major source of pollution. Beside these studies, other
research projects have been undertaken to evaluate the water
quality of the river with respect to varied pollutants and
factors. Investigating the river water with regard to the
urbanization of the river watershed, Jensen (1966) observed
that the water quality decreased in a downstream direction
and pointed out the drain effluents as the primary source of
contamination. Similar results were obtained by Talsma in
1972.

Overall, these past works have described the Red Cedar
River as a contaminated river, with the amount of pollutants
coming principally from drain effluents and increasing in a
downstream direction. As a follow-up on the research done by
Zabik et a1. (1971), this study was designed to check for
the presence of pesticide residues in the Red Cedar River.
However, in addition to the chlorinated hydrocarbons studied

in their work, this research was also concerned with other

3
groups of pesticides. Organophosphate insecticides,
chlorinated herbicides, and triazine herbicides were also
part of our compounds of interest because some of them have
been listed among the most commonly used pesticides in
Michigan. For the same reason, alachlor was also included in
this study.

Chlorinated hydrocarbon and organophosphate compounds
were analyzed through water and sediment samples; the
remaining groups through water samples only. Certainly,
analysis of more types of sample including biological
samples could give a better picture of the river's pesticide
contamination. Unfortunately, the shortness of the time
allocated to this research did not allow us to do so.
Nevertheless, the collected samples were representative of
the study area and provide a useful indicator of changes of

water quality in the study section since the 1971 study.

II- LITERATURE REVIEW

A- Pesticide residues in the environment

Earlier we alluded to the environmental effects of
pesticides, discussing the particular case of the Red Cedar
River. Based on the literature, this section is designed to
give a general idea of pesticide residues in the
environment.

Pesticides have been intensively used throughout the
world to control a variety of pests. In the United States
for example, the amount of formulated pesticides applied per
year is roughly estimated at 2.6 billion pounds (Mott and
Snyder, 1987). Yet the properties of these chemicals give
them the potential to contaminate all component parts of our
environment( agricultural soils, atmosphere, ground water,
surface waters, living organisms, foods) in small amounts.
Adsorption to soil particles, volatization,
photodegradation, microbial degradation, chemical
degradation, plant uptake, crop removal, surface runoff, and
leaching are the possible fates of a pesticide in the
environment (Renner and Kells, 1992).

The presence of pesticide residues in cropland soils
primarily results from the process of adsorption which is

the adhesion of the chemical molecules to the surface of

5
soil colloids. The binding of a given compound to soil
particles is a function of a variety of factors including
the chemical properties of the compound itself.
Organochlorine pesticides such as DDT, chlordane, and
lindane may be held by the soil particles for years due to
their low water solubility, hydrophobicity, and resistance
to chemical and microbial degradation. In research to
investigate the persistence of DDT, dieldrin, and lindane in
the soil over a long period, Martijn et al.(1993) reported
that residues of these compounds were still present in soil
21 years after application. Use of DDT, as well as other
organochlorine insecticides (lindane, dieldrin, aldrin,
heptachlor, aldrin,...) has been restricted in most
countries because of their great persistence in the
environment and detrimental effects on living organisms. In
the United States, their use was cancelled in 1972 by the
United States Environmental Protection Agency (Mott and
Snyder, 1987). Despite this cancellation, the soil
environment is still contaminated by pesticides. Bitch and
Day (1992) indicated that high amounts of DDT and its
metabolites where found in some western USA soils in 1980.
In 1992, they also found that some Texas agricultural soils
still had residues of these compounds, with the level of DDT
being even higher than of DDE. Although they have been
classified as the most persistent in the environment,

organochlorine compounds are not the only chemicals which

6
leave residues in soils. Soil pesticide contamination
invalves other groups of compounds as well. A recent study
by Jabber et al.(1993) revealed the presence of
monocrotofos, dimethoate, profenofos, cyhalothrin,
fenvalerate, and cypermethrin in some Pakistan agricultural
soils.

Pesticides may also be present in the atmosphere
through the process of volatization. Gaseous chemicals can
move along with air current in the atmosphere, process known
as vapor drift (Renner and Kells, 1992). Transport by air
currents, either in a gaseous form or in a dust-particle-
adsorbed form, has been described as the major path of DDT
redistribution in the world (Woodwell et al.in Filonow,
1974). Pesticides having a high vapor pressure may be
redistributed through the same process.

Another environmental component contaminated by
pesticides is groundwater. The major process involved in
groundwater contamination is leaching or movement of the
compound through the soil pores as influenced by water flow.
Like adsorption and volatization, leaching is a function of
several factors including the pesticide itself. Highly water
soluble compounds are more likely to leach and reach
groundwater. Several studies have reported examples of
groundwater to be contaminated by pesticides. In Pakistan,
Jabber et al. (1993) studied the possible contamination of

cropland soils and shallow groundwater in the Punjab as

7
related to pesticide use in the area. They detected residues
of monocrotofos, cyhalothrin, and endrin in the shallow_
groundwater of the studied area. The residue level ranged
from traces to 0.2 ppm for cyhalothrin, 0.1 to 0.2 ppb for
endrin, and 40 to 60 ppb for monocrotofos. A similar study
was undertaken by Bushway et al. (1992) to evaluate the
water quality of some wells in Central Maine with respect to
the use of alachlor, atrazine, and carbofuran in the area.
Of the 58 samples analyzed, 18 were atrazine positive, with
2 samples having a residue level greater than the 3.0 ppb
MCLG (Maximum Contaminant Level Goal); 19 samples
contained alachlor above the zero ppb MCLG whereas
carbofuran was only present in 4 samples. Contamination of
groundwater by pesticides is then a reality. Effective ways
to prevent this situation are needed as groundwater is still
a major source of drinking water in the world. In the United
States, 95 percent of the rural population and 50 percent of
the whole population rely on groundwater as source of
drinking water; yet a 1987 EPA report indicated that
residues of more than 20 pesticides have been found in at
least 24 states groundwater (Mott and Snyder, 1987).

Like groundwater, surface waters have also been
victim of pesticide contamination. A study conducted by
Mugachia et al. (1992) in Kenya revealed the presence of
organochlorine pesticides in the Athi River, Kenya. Of the

analyzed fish, 73 percent of the samples contained residues

8

of the following compounds: p,p'-DDE, p,p’-DDT, p,p’-DDD,

o,p’-DDT, o,p’-DDD, HCH, and heptachlor. Similar cases of
surface water pollution have also occured elsewhere in the
world. For example, from March 1988 to April 1989, Fingler
et al. (1992) performed a residue survey on the Kupa River,
in Croatia. They found the river water to be polluted by a
variety of compounds including organochlorine pesticides
such as hexachlorobenzene and DDT and its metabolites. In
1983, the East Central Michigan Planning and Development
Region (ECMPDR) reported the Pine River, East Central
Michigan, to be contaminated by high levels of DDT. In the
United States, several currently used pesticides have also
been detected in surface waters. In the Midwest U.S., the
herbicide alachlor has been detected not only in
groundwater, but also in surface waters (Mott and Snyder,
1987). In the Ohio area, Baker (1987) undertook a study of
surface water contamination on the Lake Erie Basin, in
relation with land use activities. Along with other
findings, he reported that many pesticides are transported
to river waters during runoff events following their
application. Giving a particular attention to atrazine,
alachlor, metolachlor, and cyanazine in the Honey Creek
Watershed at Melmore, in the northwestern Ohio, he observed
that these four herbicides had similar Spring runoff
patterns and were primarily carried to the watershed between

May-and July. Like in the previously named areas of the

9
world , surface waters in Canada are also victim of
pesticide contamination. From 1971 to 1985, Canadian
governmental agencies evaluated the river quality of some
Ontario, Canada rural ponds with regard to pesticide use in
the corresponding areas. The results of this study indicated
that 12 ponds were polluted by the insecticides carbofuran,
chlorpyrifos, diazinon, DDT, endosulfan, parathion; 5 ponds
with the fungicide PCP, and 122 ponds with the herbicides
alachlor, 2,4-D, cyanazine, dicamba, simazine, diquat,
glyphosate, and atrazine (Frank et al., 1990). The same
research observed atrazine as the most frequently detected
herbicide, which is in support of the U.S EPA new rules to
modify the atrazine label with regard to surface water
contamination. Indeed, in order to reduce the potential of
atrazine for surface water contamination, the EPA has
recently required the use of lower rates and the
establishment of buffer zones between-application areas and
surrounding surface waters (Kells et al., 1993).

Hence, pesticides are everywhere; on the ground, in
the air surrounding us, in drinking water, groundwater,
streams, lakes, ditches, rivers, oceans,.... As a result,
all living organisms including man are exposed to them on a
regular basis. Effective ways to monitor these chemicals

are strongly needed.

10

B-Most commonly used pesticides in Michigan

As pesticide regulations change, pesticide use change.
As a result, a given agricultural chemical described as most
frequently used in a given area over a given period of time
may be subject to changes in terms of use. Adapted from
various sources, the following tables show the most
frequently used pesticides in Michigan over the past three

years.

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Table 2: Most commonly used Pesticides on Vegetables in Michigan, 1992

12

 

herbicides

total applied (1,000 Lbs)

 

 

 

 

 

metolachlor 36.2
pendimethelin 24.4
EPTC 24.1
simazine 23.8

1 6.6

 

 

 

 

 

 

 

 

carbaryl 61
disulfoton 16.1
insecticides carbofuran 1 3.6
. cblerpyrifee ‘ . "1 2.7

 

.......................

 

  

 

chlorothelonil

163.5

 

 

mancozeb

 

39.3

 

 

 

Vegetables 1992 Summary. USDA, Washington, D,C..

adapted from: NASS and A88. 1992b. Agricultural Chemical Usage

 

 

Table 33 Most commonly used Pesticides

13

on Fruits in Michigan, 1991

 

herbicides

total applied (1,000 Lbs)

 

 

 

 

 

simazine 20.5
glyphosate 1 1.4
paraquat 10.8
diuron 10.3
2.4-0 5.5

 

 

 

 

 

....
.....

insecticides

 

 

 

 

petroleum distillate 1 ,409.70
azinphosmethyl 147.8
phosmet 131 .5
chlorpyrifos 91 .1
propargite

 

 

 

  

...........................................................

 

fungicides

captan

1,003.20

 

 

sulfur

 

639.2

 

 

1991 Fruits and Nuts Summary. USDA, Washing. D,C..

adapted from: NASS and A88. 1991. Agricultural Chemical Usage

 

 

III- Dascnrpmxou or STUDY AREA

Previous studies have described the Red Cedar River as
a warm-water stream located in southcentral Michigan,
originating from Cedar Lake (Livingston County, Michigan),
and flowing through Livingston and Ingham counties before
joining the Grand River in Lansing, Michigan (Talsma, 1972;
Zabik et al., 1971). Small grain agriculture and pasturage
are the main activities upstream whereas the downstream
region is characterized by an extensive agricultural
development, urbanization, and industrialization (Zabik et
al., 1971). The current usage of the river water is
restricted to agricultural irrigation, recreational
purposes, and treated water disposal.

For the purpose of this study, seven permanent
sampling stations were set out in the vicinity of East
Lansing, from just above the M-52 bridge to below the East
Lansing Wastewater Treatment Plant (Fig. 1). Station 1 is
located just above the M-Sz bridge. The bottom material
primarily consists of sand. The river water is relatively
clean and agriculture is the major activity above this
station (Zabik et al., 1971). Station 2 is located
approximately 4 Km downstream from station 1, at the
Williamston wastewater treatment outlet. The river bottom
comprises sand and stones in the middle, detritus and silt

14

15
on the sides. Station 3 lies approximately 8 Km downstream
station 2, at the M-43 bridge. The bottom at this station
consists of small stones mixed with sand. This area has also
been described as agricultural.
Station 4 is situated just below the Okemos bridge, about 15
Km downstream from station 3. The river bed is primarily
comprised by sand covered by approximately one inch of silt.
The surrounding area is mainly residential. Station 5 lies
above the Hagadorn bridge, about 1 Km from station 4. The
bottom material is made up of sand covered by beds of
sludge, decaying leaves, and silt. Station 6 is located on
the Michigan State University campus, approximately 500 m
downstream from station 5. Here, the riverbed consists of
large stones and coarse gravel in the middle, silt and
detritus along the edges. Station 7 is situated below the
East Lansing Wastewater Treatment Plant, about 2 Km from
station 6. The bottom is covered with 2 to 3 inches of
sludge beds, silt, and detritus.

Station 4, 5, 6, and 7 are located in highly.
residential areas. Consequently, drain effluents and street
run-off might be the main sources of the river water
contamination. Stations 4, 5, and 6 represent high levels of
contamination, stations 2 and 7 areas with water quality

recovery, and stations 1 and 3 relatively clean areas .

     

 

 

 

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IV- MATERIALS AND METHODS
3- Materials

1- Equipment

- Hewlett Packard Gas Chromatography model 5890 Series
II with 43Ni Electron Capture and Nitrogen Phosphorous
Detectors V

- Perkin-Elmer Gas Chromatography model 8500 with 43Ni
Electron Capture Detector

- Gas Chromatograph Mass Spectrometry Nermag RIO-10C

- Zymark TurboVap Evaporator

- Buckler Rotary Evaporator

- Beckman pHmeter

- Mettler P3 Analytical Balance

- Mettler HGT Analytical Balance

- EnviroGard Enzyme ImmunoAssay Kits

2- Reagents

a- Solvents

- Hexane, acetone, methylene chloride, methanol,
Pesticide Quality

- Diethyl ether, reagent grade

17

18

b- Chemicals

- pesticide standards: Aldrin (98.7%), dieldrin
(99.5%), lindane (98.5%), methoxychlor (99.0%), DDT-o,p'
(99.5%), DDT-p,p’ (99.0%), DUE-p,p’ (99.0%), DOD-p,p’
(99.0%), metolachlor (98.7%), endolsulfan I (99.8%),
endosulfan II (97.9%), heptachlor (99.5%), alachlor (98.7%),
chlorpyrifos (99.7%), dyfonate (98.5%), terbufos (99.7%),
methyl parathion (99.9%), phosmet (99.5%), monocrotofos
(99.7%), glyphosate (99.9%), atrazine (99.0%), simazine
(99.6%), metribuzin (99.0%), ametryne (99.0%), prometone
(99.6%), 2,4-D methyl ester, silvex methyl ester, dicamba.

- other chemicals:

* sodium sulfate anhydrous, granular, stored at 130‘k!

* florisil-PR grade, 60-100 mesh; activated at 135 °C

* concentrated sulfuric acid. ACS grade; used as

received

* diazomethane; prepared as described by the EPA

method 8150 (1986)

* potassium hydroxide, ACS grade

SC

ad

19

c- Miscellaneous items

- glass wool, pyrex

- glass rod

- filter papers

d- Glassware

volumetric flasks: 5- 100 mL

- beakers: 100-500mL

separatory funnels: 125-1000 mL

graduated centrifuge tubes: 10-50 mL

Zymark concentrating tubes: 200 mL

chromatographic columns: 50-200 mL

round bottom and reflux flasks: 50-500 mL

8- Methods

1- Sampling design and samples preservation

Seven permanent sampling stations were set out in the
Williamston-Okemos area, in a downstream direction, from
above the M-52 bridge to below the East Lansing Wastewater
Treatment Plant.

Samples collection was made according to a monthly

schedule starting from May, 1992, to October, 1992, with an

additional water sampling in April, 1993. Water samples were-

 

20
collected as 5-liter grab samples. Sediment samples with a
sediment corer. All samples were taken in duplicate, in the
middle of the river or on the river edge during flood
conditions. Water samples were held in a one gallon glass
brown jugs sealed with teflon lined screw caps, preserved
'with sodium sulfate (3ml/gallon), and stored at.4l°C before
analysis. Sediment samples were held in 8.02 widemouth glass
containers with a teflon liner and stored at 4 C. Each
sample was stored for no more than six months before
anlalysis. The storage period was based on past unpublished
research done by the Pesticide Chemistry Laboratory of the

Michigan State University Pesticide Research Center.

2- Glassware preparation

Glassware was thoroughly washed with hot tap water and
detergent, then rinsed with distilled water followed by
acetone and hexane. It was finally stored in a 450 %:
furnace for at least one day before use.

Glassware used to analyze the chlorinated acid
herbicides was rinsed with a 1:1 sulfuric acid solution

followed by a rinse with distilled water.

21

3- Residue survey scheme

The residue survey was performed according to a scheme
comprising three major steps: preliminary analysis or
background checking, actual residue analysis, and
confirmation.

In the preliminary analysis step, a gas
chromatographic procedure was set up for each class of
pesticides. Recovery tests were then conducted to verify the
applicability of the method to the corresponding group of
compounds. According to whether the recoveries were in an
acceptable range (our set range was 68-110%) or not, the
method was validated or modified until acceptable recoveries
were obtained. The recovery study was performed with
pesticide standards belonging to the studied group of
compounds and with three randomly selected samples. The
validated procedure was then used to analyze seven randomly
chosen samples representing the seven sampling stations. The
extracts and selected pesticide standards were injected into
a gas chromatograph under the same conditions. 0n the
Chromatograms, retention time was the parameter of interest;
whenever an unknown peak matched the retention time of a
given pesticide to plus or minus 0.03 min, we assumed this
peak and the pesticide could possibly have the same

identity. The plus or minus 0.03 min- retention time windows

22

was selected based on the EPA method 800 (1986). When
applicable, a further qualitative study was performed using
a different detector. Figures 2, 3, 4, and 5 are an
illustration of this process. The results obtained from this
preliminary analysis are shown in table 4

In step 2, actual residue analyses were undertaken for
the suspected compounds. The extracts were then combined
and concentrated for a gas chromatography/mass spectrometry-

confirmation study in step 3.

Figure 2:

23

Chromatograms of two different water samples
and a standard mixture comprising chlorinated
hydrocarbon compounds and organophosphate
pesticides injected under the same G.C.

conditions:

60 m DB-S column

Electron capture detector
Oven temperature: 215 °C
Inlet A temperature: 250 °C
Inlet 8 temperature: 260 °C
Detector A: 300 °C

Detector B: 250 °C

Zli

Relative Response

v
0
0

~00;

A‘fl‘.

 

 

1
'00..

 

 

wumcno no"

 

‘33.” ‘-—-—-—'—"Lindane

 

Alachlor

 

 

hlorpyrifos

ldrin

 

.p'sDDE
ieldrin

:m\n

 

 

p.v'-DDD

I ‘

 

 

l0

Msflmunm

 

 

90

11

dune Azwaeneev

mnesnnnn nuances nonunuewsw

nzponwsenoe swanonenaoae use

enmesovsoeureno ween»n»aee

 

 

 

 

 

e
3
n
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OI

(sainUIH) Bull
‘ OF:

 

(£6 IIJdV ‘z Ulopesen) atdmes 1°39“ ‘33 alnsii

25

'0098
”004.8

.Relative Response

      
    

nus—V ‘ '
a)" R: "'

l_l.277‘\\
Alachlor

 

p,p'-DDE

 

 

 

wFUhknown

5%
30.647

aamo

Figure 3:

26

Chromatograms of a water sample and a standard
mixture comprising chlorinated acid herbicides
injected under the same G.C. conditions:

60 m DB-S column

Electron capture detector
Oven temperature: 215 °C
Inlet A temperature: 250 °C
Inlet 8 temperature: 260 0C
Detector A: 300 °C

Detector B: 250 °C

27

Relative Response

9
o
o
9

00.00...

0000.L

00001

0000.

 

Manama we.

2.6-D

m$———Dicalba

4““1"‘Silvex

 

Iafll<:

 

 

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1116!
an

1&2

 

ause Azwaeneev

mneaaene luuncne em aspenuaeneo
>npe znncunuaee

Relative Response

4
O
O
O

0000..

0000..

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0000..

Dice-be

 

laug=z

 

 

 

 

 

 

c i ‘

anew Azwacnouv
meaeno we. canon meavwe Azieu. Cece uoo~v

Figure 4:

28

Chromatograms of two different water samples
and a triazine standard mixture injected under
the same G.C. conditions:

30 m DB-S column
Nitrogen-Phosphorus (NP) detector
Oven temperature: 170 °C

Inlet A temperature: 250 °C

Inlet 8 temperature: 240 °C
Detector A: 240 °C

Detector B: 280 °C

 

 

 

 

 

 

 

 

 

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s
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RPAPAUAU

 

 

 

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Atrazine

 

 

 

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A ore-on p. gene a».

Figure 5:

30

Chromatograms of a sediment sample and a
standard mixture comprising chlorinated
hydrocarbon compounds and organophosphate
pesticides injected under the same G.C.

conditions:

60 m DB-S column

Electron capture detector
Oven temperature: 215 °C
Inlet A temperature: 250 °C
Inlet 8 temperature: 260 °C
Detector A: 300 °C

Detector B: 250 °C

31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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o o D D D
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0000. r 0000.
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Hose Azwscneuv mnmcne ma. mmapsmsn meanwn Aoroaom H. e:~< oNv

nuncno we. mnesnena apunzno noavnwmwam aspenusonna
znanonencose can anaesouroevsene
weenpnpaae

32

Table 4: Background of Water and Sediment Samples in
Relation to the Asssessed Pesticides

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

   
 

 

 

   

 

     
 

  
 

Class of Pesticide Compounds Water Sediment“
aldrin nd nd '
dieldrin ' nd nd

5333;223:235 heptachlor nd nd "
metolachlor nd nd
metoxychlor nd nd "
alchlor suspected nd
lindane nd nd "
endosulfan I nd nd
endosulfan II nd nd
DDT-p,p’ nd ' suspected
DDE-p,p suspected suspected
DDD-p,p' suspected suspected
DDT-o,p’ nd nd

ll
chlorpyrifos nd nd 4|
gggggggggsphate terbufos nd nd
dyfonate nd nd
methyl parathion nd nd
phosmet nd nd "
monocrotofos nd nd
atrazine suspected nd

Triazines , ,

Herbicides eima21ne nd nd
prometone nd nd
ametryne nd nd
metribuzin nd nd

i Chlorinated 2,4-D suspected nd
1 Acid herbicides MEEF§E?E_"#“_MM- . suspected nd .

 

 

 

 

33
4- Organophosphate pesticides and chlorinated
hydrocarbons

a- Extraction from water samples

An extraction procedure was set up to co-extract
organophosphate pesticides and chlorinated hydrocarbons.
This procedure was adapted from methods 8080 and 8140 of the
EPA " Test Methods For Evaluating Solid Wastes" (1986), with
some modifications.

A 50 ml volume of methylene chloride was added to a
500 ml of microfiltered water sample placed in a 1000 ml-
separatory funnel. The funnel was then sealed, shaken for 1
to 2 min and left undisturbed for approximately 10 min to
allow the partition of the pesticides from the aqueous
fraction into the solvent. The organic layer was then
collected into a 200 ml-beaker. This extraction procedure
was performed two more times with 50 ml of fresh methylene
chlorine. The three solvent extracts were combined, dried
over a drying column containing 10 cm of activated
anhydrous sodium sulfate, collected into a 200 ml-
concentrating tube, and concentrated almost to dryness on a
Zymark TurboVap evaporator. Hexane (50 ml) was then added to
the tube and concentrated to about 1 ml. Ultimately, the
1 ml extract was adjusted to 2 ml by rinsing the tube with
hexane. This 2 ml extract was analyzed on a Hewlett Packard

gas chromatograph, 5890 Series II, under the following

34

conditions:

60 m DB-S column with a 0.25pm thickness

Electron capture detector
- Detector A temperature: 250 k:

- Detector B temperature: 300 k:

- Inlet A temperature: 250 k:
- Inlet B temperature: 260 W:
- Oven temperature: . 215 k:

The Method Quantification Limit (MQL), defined as the lowest
concentration of a substance that can be measured and
reported, was: I

- Alachlor: 0.036 pg/l

- p,p’-DDE: 0.0016 pg/l

p,p’-DDD: 0.002 pg/l

- p,p’-DDT: 0.0026 “9/1
b- Extraction and cleanup from sediment samples

The two classes of pesticides were co-extracted and
cleaned up from sediment samples according to the procedure
described by Zabik et al. (1971), with some minor
modifications. .

A 100 9 sample of sediment was placed into a 500 ml-
round bottom flask and thoroughly mixed with 200 ml of a
(1:1) hexane-acetone mixture. The slurry was then shaken

for 10 min and allowed to stand for 12-14 hr. After an

35

additional shaking of 10 min, the hexane portion was poured
into a 100 ml-separatory funnel. The extraction procedure
was performed two more times with two 100 ml portions of
fresh hexane. The three hexane extracts were combined and
treated exactly as described by the above authors, with the
following exception. The concentrated 10 ml extract was
eluted with 250 ml of hexane followed by 250 ml of a ( 1:1)
hexane-acetone mixture. The collected eluate was reduced to
100 ml and analyzed on a Hewlett Packard gas chromatograph,
5890 Series II, under the conditions described in 4a. The
MQL was 0.4 pg/Kg, 0.5 pg/Kg, and 0.65 pg/Kg for p,p’-DDE,

p,p’-DDD, and p,p’-DDT respectively.
c— Sediment samples organic matter content

Sediment samples percent organic matter was determined
by the Michigan State University Soil Testing Laboratory
using a Wet Digestion Method.

One gram of sediment was placed into a 50 ml-
Erlenmeyer flask and 10 ml of Na2Cr207 and 10 ml of
concentrated sulfuric acid were added. The flask was then
left undisturbed for 30 min after which the slurry was mixed
with 15 ml distilled water and allowed to stand for at least
3 hr. Five mililiters of supernatant was then diluted in 5
'ml of distilled water and the orange color intensity of the

resulting solution was read on a calorimeter calibrated to

36
give 0 absorbance ( 100% transmittance) at 645 nm with
appropriate blank samples and to read percent organic matter
(or tons per acre) from a standard curve prepared from

sediments of known organic matter contents. Table 5 shows

the results obtained.

Table 5: Average percent organic matter of sediment samples

per sampling station

  

sampling station

 
   
  
  
  
  
  
 

M-52 0.8

Williamston WWTP 2.1
M-43 bridge 0.4
Okemos bridge 0.4
Hagadorn 3.7
M80 campus 0.7
East Lansing WWTP

 
 

 

 

note: WWTP: WasteWater Treatment Plant

d- Sediment samples moisture content

A sediment sample (59) was placed in an aluminum dish
and dried in a vacuum oven for at least 3 hr. The sample was

then cooled in ambient temperature for about 1 hour and.

37
reweighed to determine its dry weigh. The moisture content

was obtained from the following equation:
2
% moisture = ------- * 100

where:
- wl is the sample wet weigh
- w2 is the sample dry weigh

Table 6 is a tabulation of the results.

Table 6: Sediment Samples Percent Moisture

38

 

 

May-92

Jun-92

‘ Jul-92

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

sample 10 w1 (g) w2lgl $6 moisture
M52 I 5 4.8 4
M62 II 5 4.8 4
WP I 6 4.4 12
WWWTP u 5 4.5 ‘ 10
M43 I 5 4.9 2
M43 11 5 4.9 2
OKEMOS I 5 4.9 2
OKEMOS u s ' 4,3 4
HAGADORNI 5 3 4o
HAGADORN u 5 3.1 38
MSU I 5 4.9 2
MSU u S 4.9 2
ELWWTPI 6 4.5 10
...... ELWWTP u .. 5 4.5 10
1.....- 052.
M5211
wwwrPI
wwwrp u
M431
04-43 In
OKEMOSI
OKEMOS u
HAGADORNI
HAcAoonN n
MSU I
MSU u
ELVWVI’PI
amp " . . . “......
M-SZI “ 5' 4.3 14
M52 ll 6 4.3 14
WWWTPI 5 3.5 30
WP u 5 ' 3.4 32
M43I 5 4.8 4
M3 u s 4.7 6
oxwosu 5 4.8 a
OKEMOS u 5 4,3 4
HAGADORN I 5 3.5 30
HAGADORN II 5 3.4 32
MSUI 6 4.8 4
MSU n 5 4.8 4
awwm s 3.5 30
ELWWTP II 5 3.5 30

 

 

39

 

Aug. 92

Sept. 92

Oct. 92

table 5 cont.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

eemple ID W1 (9) w2(9) % moisture
M52 I 5 4.8 4
M52 ll 5 4.7 6
WT? I 5 3.5 30
wwwrP u s 3.3 34
M43 l 5 4.8 4
M43 ll 5 4.9 2
OKEMOS l 5 4.7 6
OKEMOS ll 5 4.6 8
HAGADORN I 5 3.8 24
HAGADORN ll 5 3.7 26
M80 l 5 4.5 10
MSU II 5 4.5 10
ELWWTPI S 3.5 30
ELWWTP ll 5 3.4 32

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

exams: 4.7
exams n 4.8
HAGADORNI 3.4
HAGADORN II 3.6
Msu l 4.2
new I: 4.5
ewwvrp I 3.5
awwrp u 3.5
43m..-~4.m..2
M52! 5 4.8
M52 :1 5 4.7
wwwm s . 3.4
wwwrp u s 3.5
M43 I 5 4.9
M43 4 5 4.9
OKEMOSI 5 4.8
oxmos I 5 4.8
mewonm 5 3
HAG/mom n s 3.2
MSUI s 4.8
MSU u 5 4.7
awwm s 3.5
awwrp u 5 3 .4

 

 

L

ELWWTP-s East Lansing Wastewater Treatment Plant
WWWI’P- Williamston wastewater Treatment Plant

 

 

40
5- Triazine Herbicides

a- Gas chromatographic (G.C.) procedure

Triazine herbicides were extracted using the procedure
described in 84a with the exception that the final 2 ml

extract was analyzed under the following conditions:

30 m DB-S column with a 0.25 pm thickness

NP dectector

Detector A temperature: 240 %:

- Detector 8 temperature: 280 W:

- Inlet A temperature: 240 %:
- Inlet B temperature: 250 %:
- Oven temperature: 170 °C

The MQL was 0.036 pg/L for atrazine.
b- Enzyme-Linked-ImmunoAssay (ELISA) Procedure

Beside the above G.C. method, the triazine herbicides
were also analyzed by ELISA according to the EnviroGard
. Triazine Test Kit.

. Twenty antibody-coated test tubes were placed in a
test tube rack. 160 p1 of negative control was added to tube
1, 160 pl of a 0.1 ppb atrazine calibrator to tube 2, and
160 pl of a 1.0 ppb atrazine calibrator to tube 3; each of
the remaining tubes received 160 pl of the corresponding

sample. This step was immediately followed by an addition of

41

160 pl of atrazine-enzyme conjugate to each tube. The tubes
were then swirled for 2 to 3 sec, left undisturbed for

5 min, emptied, and washed three times with distilled
water. After the washing step, 160 pl of substrate was added
to each tube followed by 160 pl of chromogen. The tubes were
gently mixed for a few sec, then a 40 pl of stop solution
was added to each of them. Finally, the absorbance of each
test tube was read on a spectrophotometer calibrated to

read 0 absorbance for a blank sample at 450 nm.
6-Chlorinated herbicides

A gas chromatographic procedure was adapted from
method 8150 of the 1986 EPA "Test Methods For Evaluating
Solid Waste" to extract chlorinated herbicides from the
water samples. This method comprises four major steps:
extraction, hydrolysis, cleanup, and esterification.

- Extraction: 500 ml of.micro-filtered water (pore
size of filter paper: o.45p ) with a pH adjusted to less
than 2 with sulfuric acid (1:1) was placed in a 1000 m1.
separatory funnel. Diethyl ether (100 ml) was added to the
funnel which was then sealed, shaken for 1 to 2 min, and
left undisturbed for at least 10 min. The organic layer was
collected in a 300 ml-reflux flask containing 2 m1 of 37%
KOH. The extraction was repeated two more times with 50 m1

of fresh diethyl ether and the three extracts combined.

42

- Hydrolysis: Since the compounds of interest may
occur in water as the salt, ester, or acid form of the
herbicide, it was required that the solvent extracts be
hydrolyzed in order to determine the active part of these
compounds. In this procedure, 15 ml of distilled water was
added to the combined extracts and the resulting mixture was
concentrated for 60 min'on a Zymark TurboVap evaporator. The
hydrolyzed ether extracts were let stand for about 10 min
and transfered into a 60 ml-separatory funnel using 10 m1 of
distilled water. The basic solution was then washed twice
with two 20 ml-portions of diethyl ether for 1 min. The
organic layer was discarded and the aqueous layer kept for
subsequent analysis.

- Solvent cleanup: the content of the funnel was
acidified with 2 ml of cold sulfuric acid (1:3), mixed with
20 m1 ethyl ether, and shaken for 2 min. The solvent layer
was then collected into a 150 ml-beaker containing 0.5 g of
acidified Nazsov This extraction process was performed two
more times with 10 ml aliquots of ethyl ether. The extracts
were combined, kept in contact with the Nazso4 for
approximately 2 hr, and then concentrated on a Zymark
TurboVap evaporator to about 0.5 ml. Next, 0.1 ml of
methanol was added to the concentrated extract and the
volume adjusted to 2 ml with diethyl ether.

- Esterification: 2 ml of diazomethane was added to

the tube and the extract was let stand until the yellow

43
color persisted. The colored extract was reduced to less
than 1 ml by vaporization under ambient conditions, adjusted
to 2 ml with hexane, and analyzed on a Hewlett Packard G.C.,
5890 Series II, under the conditions described in B4a, '
except the oven temperature was 190 °C. The method
quantification limit was 0.022 pg/l and 0.0115 pg/l for

dicamba and 2,4-D respectively.

7- Recovery study

a- Water samples

Recovery tests were performed for alachlor, atrazine

p,p’-DDE, 2,4-D methyl ester, and dicamba in the water
samples. Three different samples were randomly selected and
two sub-samples of 500 ml were taken from each sample. One
duplicate was spiked with 1 ml of a 0.5 ppm spike solution
comprising the compounds of interest whereas the other was
left unspiked. The samples were then left undisturbed for
approximately 12 hr and extracted according to the

appropriate procedure. The results are tabulated in Table 7.

44
Table 7: Percent recoveries from water samples of alachlor,

p,p’-DDE, atrazine, 2,4—D methyl ester, and dicamba

 

 

compound recovery average Std Dev (%)
range (8) recovery (%)
alachlor 82.86 - 93.43 88.38 5.30
p,p’-DDE 87.73 -106.28 94.37 10.33
atrazine 90.80 -104.18 97.67 7.00
2,4-D ME 70.87 - 75.51 72.83 2.40.
dicamba 69.27 - 73.44 71.36 2.94

 

 

 

 

 

 

b- Sediment samples
- Sample recovery
The recovery study for sediment samples was similar

to that of the water samples with the following exceptions.
Each of the three samples was divided into two duplicates of
100 9. One duplicate was spiked with 1 ml of a 5 ppm
standard mixture comprised by aldrin, p,p'-DDE, p,p'-DDD,
p,p’-DDT, lindane, heptachlor, dieldrin, chlorpyrifos, and
alachlor; the other duplicate was left non-spiked. The
samples were then kept undisturbed for approximately 24 hr
after which they were extracted according to the procedure
described in IV 4b. Table 8 shows the recoveries of p,p'-

DDE, p,p'-DDD, and p,p’-DDT from the sediment samples.

Table 8: Percent recoveries of p,p'-DDE, p,p'-DDD, and
p,p’-DDT from sediment samples

 

 

 

 

 

compound recovery average Std Dev (%)
range (%) recovery (%)

p,p’-DDE 83.35 -104.29 91.54 11.19

'p,p'-DDD 82.07 - 95.13 88.57 6.53

p,p’-DDT 85.70 -109.22 98.58 11.92

 

 

 

- Column recovery

A recovery test was also conducted to evaluate the

suitability of the cleanup column for the analyzed

compounds. In this perpective, 1 ml of a 5 ppm pesticide

mixture was added to the column, eluted, and concentrated as

described in IV 4b. The recoveries obtained for DDT and its

metabolites are tabulated in Table 9.

Table 9: Florisil-celite (5:1)-column recoveries for DDT

 

 

complex
a
compound recovery average Std Dev (%)
range (%) recovery (%)
p,p-DDE 89.23 -102.12 95.52 6.45
p,p’-DDD 88.55 - 98.41 93.04 4.99
p,p'-DDT 93.78 -110.34 103.25 8.53

 

 

 

 

 

 

46
8- Quantification

a- Water samples

A standard curve was constructed for each pesticide of
interest to determine its concentration in the final extract
based on its peak area. This concentration and the volume of
water extracted were the basis for the pesticide
quantification. The amount computed from these parameters
was then corrected to compensate for the amount lost during
the extraction. The calculations were performed with the
following equation:

c * vf_
amount (ug/ml) = ------------- * 100/R
v
where:

- c is the concentration in ppm of the pesticide
obtained from its standard curve

- vf is the final extract volume in ml

- v is the volume in ml of sample extracted

- R is the percent recovery of the pesticide
b- Sediment samples
The quantification of the compounds extracted from

sediment samples was performed as in the water samples with

the exception that other parameters were taken into account

47
in the calculations. The amount of pesticide extracted was

computed using the following formula:

c * vf
amount (pg/g) = --------- *100/R,* 100/RC
Dw

where:

+ c = concentration in ppm obtained from a standard curve

extract final volume (ml)

- vf
- DW = sample Dry Weigh (9)

- R, and Rc = sample recovery and column recovery .

respectively

9- Mass Spectrometry and confirmation

A confirmation study was performed for the previously
analyzed compounds using a Nermag R10¥10C gas chromatograph-
mass spectrometer system under the following conditions:

- Capillary column-DB-l 30 m with 0.25mm diameter

- Column pressure: 20 psi

- Carrier gas: Helium

- Moderating gas: methane

- Oven temperature program: 180 to 250 °C at 5 °C per min

- Quadrupoles scan range: 60 to 500 u

For each compound of interest, the combined and

concentrated extracts and the corresponding pesticide

standard were injected into the confirmation system, under

48
the same conditions. Confirmation was based on the
comparison and interpretation of the resulting molecular
ions. Overall, each of the seven suspected pesticides
(alachlor, atazine, 2,4-D, dicamba, p,p’-DDE, p,p’—DDD, p,p-

DDT) was cofirmed.

10- Results and Discussion

a-Results

The residues data for alachlor, p,p’-DDT complex,

atrazine, 2,4-D, and dicamba are shown in the following

Tables and Figures:

Table 10: Results for Duplicate G.C. Analyses of Water Samples
for Atrazine -

atrazine concenttation (no/ml)

station ID duplicate 1 duplicate 2 mean

MENDMN

HAGADORN

 

50

amqwm Hp" >nnmNHpm oocnmnnnmnwos Atmvv H: HmHmnHo: no mmavacm Zocd: mod mnmnwoc >nnonnfipm.no.no

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Gene
.503: maniac mason
«<2»?
3m» 2,224... 3mm _ 0.8-sow I>o >0. 3m: 2.5255

25-8 98 98 #8 98 1.8 98 98 9 8
.88 ..8 98 98 9d. 98 9.3 98 98
.....-8 98 92 98 9: 98 98 98 98
>58 98 98 98 98 98 98 93 9.3
98-8 98 9. o 98 98 93 98 98 98
oz- 8 98 98 98 98 98 98 98 98
>28 98 98 98 98 98 98 98 98
m<a3na

 

 

 

 

 

 

 

 

 

 

 

 

ssssssss

3.5

2.5

1.5

0.5

51

Relative Water Height (1 =low, 2=medium, 3=high)

 

 

 

 

May June July Aug Sep_ Oct April
| 92 | 93 |

Sampling Month

Figure 6: Water Level by Sampling Month

 

(L8

0.6

0.4

0.2

52

Average Concentration (ppb)

 

 

 

 

i

May June July Aug Sept 92 Oct April
I 92 l 93 |
Sampling Month

 

 

Figure 7: Atrazine Concentration (ppb) by Sampling Month
According to G.C. Data“

53

Average Concentration (ppb)

 

0.6

 

 

0.5
0.4 V
0.3
0.2

0.1

 

 

 

 

 

 

 

 

If I". .-"-' ..4"; ..-
I/ a", f. a”
,l / ...". ’2', x“.
’z' _. J..- .r /

.r'

o ..I ..I x
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

 

 

Figure 8: Atrazine Concentration (ppb) by Sampling Station
According to G.C. Data

54

Table 12: Results for Duplicate ELISA Analyses of Water Samples
for Atrazine

atrazine eensentratien (no/mil .

nail-n I) duplicate 1 duplicate 2 mean

 

55

amqpm H0" >nHmNMcm oosomcnnmnwos Awpdv H: nmwmnw

o: no mmamwwcm Zosn: mam mnmnpoc >ononuwnm no

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

mer> Umnm
0.30.50 0320:
20:3 e<e3oe
20» g 8m: 29.00 .30)? 30¢ 93

:33» 0.00 0.00 d .00 0.00 ..00 0.00 0.00 0.00
95.3 ..00 ..00 ..NN ..00 ..N0 fnm f: ...0
care» 0.00 ..dm 5.00 3.0 ..00 ..L0 ..00 faq
)8...» 0.00 ..0» ...0 ..00 ...N 30¢ d..0 ..00
0%-.» a .00 d. ._ 0 ...wa ... 0 0.00 0.00 . .00 ..00
03. on 0.0% 0.0. 0.00 0.00 0.0a OLQ 0.5.0 0.3.0
>260 0.0. 0.0. 0.00 0.00 0.00 0.0» 0Q» 0.00
23de 0H0 0.00 d .00 0.0V ..0‘ 0.0» 0.0a

 

 

 

0.8

0.6

0.4

0.2

56

Average Concentration (ppb)

 

x... ' mms-mrmr Mrs-r
:9.93§3§3§3§3999323&+

‘ A. .'-.
#5 mm Wflw

*4

3:-
55;:
-.*:- .
:44
23:

#332292:-
u‘fi'fn'u'u'l

A

a' .‘Nu'
{MN-f ar'n-rnvr wry ("r e r ,(h‘ _
<«-x445~:45:<<<<44<$:~.-.-:...4-2..-..... -.-.~_. .. . .

fimww

If it!
- .. 43 -: 4444-24-3:

. u a . s a'.‘-'-'-V
- s '.‘.‘."’.‘.'s'

 

 

 

IGC data
fiEUSA data

 

 

 

" O'COI. .‘l .I‘° I...’.::a II. C. I. C‘IICI.II.I ll'll ..
’ . .'2- 535513293; .555 3.4”?» I. N' NI.~?$§'I§$$§$£P?$#I‘ r' .-' 55355-9154 ‘ _

 

May June July Aug Sep Oct April

I 92
Sampling Month

|93|

Figure 9: Atrazine Concentration (ppb) by Sampling Month

According to G.C. and ELISA Data

 

 

1.4

1.2

0.8
0.6
0.4

0.2

0.6

0-5
0-4 ..
o-3
O-2

0.1

 

 

57

Average Concentration (ppb)

 

 

IGC. data
ELISA data

 

 

 

-M'l- .-. .. . n‘ ’\ . x .
. 3.x .\ “3;.
’ ‘ ' skir‘cm$$&m: “<E;;$:.;:5.

 

.:. ........
..................
' - 5'. )))))

 

 

. “wt-‘33?”
...-m?“ '

\ “\

 

 

 

 

 

 

 

 

 

 

 

0’...
.x

x”

.1}..- ’.- 3"}
...r .... I: ,r
.r / . ..f
x x x x j/l

 

' M52 WWWTP M

43 OKEMOS HAG. MSU ELWWTP
Sampling Station

Figure 10: Atrazine Concentration (ppb) by Sampling Station

According to G.C. and ELISA Data

1.2

0.8

0.6

0.4

0.2

'58"

Table 14: Results for Duplicate Analyses of Water Samples
for Alachlor

alachlor concentration (no/ml)

station ID duplicate 1 duplicate 2 mean

0.16
0.1

 

59

amUHm G" >HMnEbn Sunny. nonnmsnfimnwos 9005 H5 9.3.03.0: no 0080550 3053.. msa mam—3.0:

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

2633 09.30.30 0820: 3563
:3 <<<<<<.:u 3mm 0.82.00 :35. gm: 8525.0

2.30» 0; 0 0; N 0.00 0.0» 0.3 0.; 0.: 0.00
0:30» 0.00 0.»; 9.5 0.00 0.00 0.: 0.0.» 0.00
cc_.0~ 0.00 0; 0 9.0 0.3 0.00 0.00 0.00 0.:
>50» 0.; 0.~0 0; 0 0.00 0.30 0.00 .000 0.00
08-0w 0.0. 0.0» 0.00 0.00 0.00 0.00 0.00 0.0»
02- 0» 0.00 0.00 0.8 03.0 0.00 0.00 0.0.x 0.8
>800 0.00 4.00 fnm 4.40 3.00 d; 0 0.00 ..mN
23803 0.25 0.30 0.00 0.00 0.00 0.00 0.9.»

 

1 .6
1 .4
1 .2

1
0.8
0.6
0.4
0.2

0

60

Average Concentration (ppb)

 

 

 

I

May June July Aug Sept 92 Oct April
| 92 l 93

Sampling Month

 

 

 

Figure 11: Alachlor Water Concentration by Sampling Month

 

61

Average Concentration (ppb)

 

0.7

 

0.6
°‘5 W /
0.4
0.3

0.2

 

 

 

 

 

 

 

0.1

 

I...
_,.- I. x’ f/ ._
1‘ ,3 _.- .1 If
I

x’ -'
. . I/ x

M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

 

 

I Figure 12: Alachlor Water Concentration (Ppb) by Sampling Station

62

Table 16: Results for Duplicate Water Analyses of Water Samples
for p,p'-DDE

2,4-0 Motion (nolmll

duplicate 2

 

63

Hugh 3" 0.0.l00m tuna... nonomdnnmnwon €03 H5 HmHmnHos no mmavwwnm 3052. won .mnmnHos

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

02.32.30 0320:
2.03: =m<o80o
2m» 2525.. 2m: 2820"... 1.5.5. 2m: 0.22.:v
2.30» A22. A29 fimo A22. A29 #00 NS 0.00
.530» A23 A29 A29 ..um PG A22. A22. 0.00
020» A22. A29 2m A2? A22. A22. A23 . 0.5.
>50» A29 A29 A22. A22. A22. A2? A22. A29 ,
030» A29 ..mm ..8 A23 A29 A29 A29 025
on»- 0» A29 A29 ob» A29 A22. A22. A29 . 0... »
>200 A23 A22. 9.3 A22. ...3 ...8 A2? 0.00
E 0.00 0.»» 0.00 02.0 0M3 0.25 0.00
2.9. n .5232. 03820: :3:

 

 

 

 

 

64

Average Concentration (ppt)

 

 

 

 

 

0.8

0.6

0.4

0.2

0
May June July Aug Sept.92 Oct April
| 92 l 93 1

Sampling Month

Figure 13: p,p'-DDE Water Concentration (ppt) by Sampling Month

 

65

Average Concentration (ppt)

 

0.8

 

0.6

 

 

0.4

 

 

0.2

 

 

 

 

 

 

 

 

 

 

 

0 p. 5“ ,F ,F \fi
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

Figure 14: p,p'—DDE Water Concentration (ppt) by Sampling Station

66

Table 18: Results for Duplicate Analyses of Water Samples
for 2,4-D

2.4-0 concentration inolmll

notion ID duplicate 1 Meet. 2

 

67

HwVHm H0" N170 nonnmnnnmnwon 905

~
H: HmHmnHon no 02:05.50 sonny mam mnunhop

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

203: m<m30m
2S 5225,. 2m: 2820.». 15>? 2.8 0.5251
§m<0N 0.»; 5N0 090 N05. 0.00 0.A# ...Am . 0.00
Lc3-wN 0.00 0.00 Tum 4.0m 0.00 0.00 ._.NN 0.00
0:..0N 0.0V 0.00 N00 NON 0.0m 0.mu 0.00 0.0%
>cn.mN 0.#N 0.05. 00‘ ...N0 ...N0 0.uw 0M0 0.00.
mmu-wN 050 05» 9mm 0.0M 0.5.5. 0.Nu 0.00 03>.
007 mm 0.Nw 00V 0.NN 0.0m 0.5.0 0...“ 0.00 0.00
>200 0.Nw 0.00 0.0m 0.»: 0.00 OLw 0.0V 0.Nw
0.00 0km“ .

 

1.4

1.2

0.8
0.6
0.4
0.2

0

68

Average Concentration (ppb)

I I I l I I7

May June July Aug Sept 92 Oct |Aprill
| 92 93

Sampling Month

 

 

 

 

 

 

 

 

 

 

Figure 15: 2,4—D'Water Concentration (ppb) by Sampling Month

69

Average Concentration (ppb)

 

1.4

 

1.2

. 1 / .
0.9 / /

0.5 /

 

0.4

 

0.2

 

 

 

 

 

 

 

{'1 //I .’2" ’l/ f.-

x .
' x / /' I’
I/ 3". I
’/ x" x/ ’f

0 Ax ‘ _ 4 J
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

 

Figure 16: 2,4-D Water Concentration (Ppb) by Sampling Station

70

Table 20: Results for Duplicate Analyses of Water Samples for Dicamba

Dicamba concentration lnolrnl)

outlon lD dupliooto l dupllooto 2 moon

0

O

 

71

.30...» NH" 0.»0»st 0058530305 305 H5 HmHmnwo5 no 02:0...50 035.”... ~50 032.05

 

 

 

 

 

 

 

 

 

 

 

 

0032.30 08:03
2.033
2.0» <<<<<<.:u 2mm 0.82.00 I>o>0. 30c m..<<<<....u 0330a
2.30» 0.».» 0.0. 0.»0 0.»0 . 0.00 0.»» ...0 0.2.0
.530» 0.0 0.»0 . 0.»0 0.». 0.»0 0.; 0.». 0.»»
«.20» 0..» 0.0 0.»0 0.»0 0.»0 0.0 0.3 0.0.
>80» 0.0 0.»0 0.»0 0.»0 0.0 0.00 0.0 0.0
02.0» 0...» 0..» 0.0 0.... , 0.0 0.0 0.0 0.0
On»- 0» 0..» 0.0 0.3. o... 0.0 0.0 on: 0.0
>200 0... 0.0 0.. . 0.»0 0.»» 0.0 0... . 0.»
.0580.“ 0.0 0.»0 0.». 0.»» 0.0 0.00

 

 

 

 

 

 

 

 

 

 

 

 

0.5

0.4

0.3

0.2

0.1

72

Average Concentration (ppb)

 

 

 

 

 

 

 

 

May June July Aug Sept 92 Oct April

‘| 92 | 93

Sampling Month

Figure 17: Dicamba Water Concentration (ppb) by Sampling Month

73

Average Concentration (ppb)

 

0.35
0.3
0.25
0.2
0.1. 5

0.1

 

 

 

 

 

 

 

0.05

 

... ' .... ' I..'. ’ ,-"‘ If...
/ /// /’/ ’/’ I/
I I" I' I! 3"

0 .2’ ./ _/ 1’ if
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

 

Figure 18: Dicamba Water Concentration (ppb) by Sampling Station

74

Table 22: Results for Duplicate Analyses of Sediment Samples
' for p,p'-DDE -

 

p,p‘-DDE concentration (no/g)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

station ID ‘ duplicate 1 duplicate 2 mean Std
M62 0.48 0.61 0.66 0.09
WWWTP 5.72 3.59 4.66 1.51
May-92 MERIDIAN 2.65 3.02 2.84 0.26
OKEMOS 1.90 2.62 2.21 0.44
HAvoonN 11.02 12.16 11.59 0.81
Msu 2.33 2.11 2.22 0.16
ELWWTP 6.09 6 .71 6.40 0.44
‘ average May
ERR-$3521:izizir-rEIE-Erér$125135:33353522555355? t23533553553;Egs'gEgigégisizjg535353335};53535-15251313335353335355532;£5EgigEgégigigifiigi;353555533353353353233
M52 0.00
wwwrP 18 21
MERIDIAN 1.18
Jun-92 OKEMOS 4.12
HAGADDRN 8.63
Msu . 3.18
EwarP 8.39
average June '
£2332:s:2:3:3:5:a:;:::2=2.2:3:s=z:s:2:2:z:::3:s:szz:5 3:325:3233523225:23223322522:255:52::23:12?sit3:53353533335333353152333333‘s52325253523;5253233523553533523253322:3:5:s:?:3:3:::2:3.’;:3:=-2:::29323255222:
M62 0.00
WP 18 37
MERIDIAN 0.73
Jul-92 OKEMOS 1,41
NAGADORN 7 .49
Msu 6.32
ELWWTP 34 10
average July
M52 0.64
we 26 14
MERIDIAN 0.88
Aug. OKEMOS 2.28
HAGADORN 7.68
M56 6.38
EwarP 23.78

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

MERIDIAN 0.80 0.66 0.73 0.10
Se OKEMOS 2.86 1.93 2.40 0.66
HAoADoaN 7.34 6.35 6.85 0.70
Msu 2.67 3.46 3.07 0.66
ELWWTP 25 91 19.23 22 57 4 72
Sept average 6 89
7 fi’ .srfi"
M62 0 59 1.34 O 97 O 53
we 8 67 10.11 9 39 1 02
MERIDIAN 1 07 0.67 0 87 O 28
Oct-92 - OKEMOS 1.85 2.18 2.02 0.23
HAoADORN 13 46 13 20 13 33 O 18
mm 6.01 7.12 6.57 0.78
am 1634 21.53 1894 367
Oct average 7 44 fl
=3:$33255339225535535333???2523253355553535235_ Iézéfiiisizéisésésésis523355;;§a;3;“:52333232325;§§§2§a§s§a§si5§2§s§§3§2§z§§§s§s§zi3:55:55§s§s§s§2§z§s§sg§z§s§sQ53;is;2;;§s§s§3§333525233:$555335;5253s_I;z;23325353;5?;:§:§z§s§s§z§2§if;53::fs§3§§3§§z§s§sfsgs§{95:3§3§s?§§s§5§;§s§:§zis€352:s§5§:§?§s§:§3§s§s§z§3§§

 

75

96va mm“ yvruum mmnwsmsn nonnmunnmnwo: 98qu MD anmnHos game—wwubm 303...: mum mnmnHon

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

mmSESo 933:

2.03:

=38on

. h
2.3 $2521 :9 0.330.». . :33. am: 22.25...

2.3-8 9mm 93 NE NE ...mc ~..- 9.8 92
L573 98 3.8 ...8 9% V 3 93 3.3 +8
acrwu 0.8 3.: 98 a 8 N8 93 8.8 9.3
>co-m~ 93 ~98 9mm N3 3 am 98 3.8 8.8
m8-w~ 0.?» 3.8 0.3 P8 8 mm 93 3.3 9%
00». S 0.3 98 0.8 ~.o~ 6.8 9.3 8.0.. 6.2
m<maom 0.3 8.3 #8 NS 9; 9% 3.8

 

 

 

76

Average Percent Organic Matter

 

 

 

 

 

 

 

 

. /. /. /,. /
/’ .
/ // // / ./
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

figure 19; Average Percent Organic Matter 63' Sampling Station

 

77

Average Concentration (ppb)

 

12

1O

 

 

 

 

May June July Aug Sept 92 Oct
| 92- |
Sampling Month

Figure 20: p,p'—DDE Sediment Concentration (ppb) by Sampling Month

78

Average Concentration (ppb)

 

 

 

 

 

 

 

 

 

 

 
  

 

 

 

 

20

1 5

1 O

5
// ./fi / -// ///_,..-

 

0 _ ..v’ . .
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

Figure 21: p,p'-DDE Sediment Concentration (ppb) by Sampling Station

Table 24: Results for Duplicate Analyses of Sediment Samples for p,p'-DDD

79

 

p,p'-DDD concentration (no/g)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

I

atation ID duplicate 1 duplicate 2 mean Std
M62 0.16 0.47 0.32 0.22
wwwrr 4.92 4.67 4.90 0.18
MERIDIAN 0.68 0.79 0.74 0.08
oItEMos 0.00 0.00 0.00 0.00
I-IAcAooRN 6.97 7.29 7.13 0.23
M60 4.70 5.01 4.86 0.22
ELWWTP 10.80 8.70 9.75 1.48
MERIDIAN 1.20 1 .30
OKEMOS 0.00 0.00
HAvooRN 5.79 6.84
M30 3.80 2.90
ELWWTP 8.39 8.02
average June '
E7“ 777
M62 0.00 0.00
WWWTP 1.69 2.41
MERIDIAN 1.12 1.46
OKEMOS 0.99 0.75
HAvooRN 6.93 5.90
Msu 4.68 3.51
ELWWTP 16.31 12.29
average July
M62 0.04 0.05
WWWTP 3.12 1.25
MERIDIAN 0.01 0.08
OKEMOS 0.12 0.05
HAvooRN 2.27 3.13
Msu 1.66 3.01
ELWWTP 2.19 2.65
average Aug.
M62 0.00 0.00
wwwrr 2.42 2.54
MERIDIAN 0.65 0.57
OKEMOS 1.53 1.65
HAGADORN 9.22 5.08
Msu 3.67 2.45
EwarP' 8.34 6.53
W Sept. average r
M62 1.34 0.98
wwrr 4.25 5.03
MERIDIAN 0.00 0.00
DItEMos 0.07 0.05
HAOAooRN 6.45 12.13
Msu 3.40 4.21
ELWWI' 9.56 13.89
Oct. average

 

 

 

80

Hmvpm Nmn Furuuudmawamsn nounmunnmnHos.€vg H: anunHo=.no mmsvfigm Kenn: man mnwnwon

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

.503: 9.3250 93.0:
2.3 2225.6 am: 9338 1.5.5. 2......c m..<<<<....u m<2moa
_<_m<-w~ o.w~ Krmo 0.06 AZ? .55 kram 9.3 Pm...
...c:.m~ Agar mhm .78 A39 m.w~ w.~m P». whm
..c..m~ Agar Pom ..Nw Paw 93. 6.5 True 9.2...
>co.m~ Agar P; 0.0m obw P00 P”: New ...5
966» R29. Pam 9m. ..mw 0.; ubm 0.23 ”...;
02. mN ... m 6.? A39. 0.0m whw 9mg 3.0m how
m<o$oo ohm Pun 9mm 9AA m.mo w.mm mbm
ZUru 2.832. 0682.03 :3:

 

 

 

81

Average Concentration (ppb)

 

 

 

 

 

May June July Aug Sept 92 Oct
l 92 I
Sampling Month

Figure 22: p,p'-DDD Sediment Concentration by Sampling Month

 

82

Average Concentration (ppb)

 

1O

 

 

 

 

 

 

 

 

 

 

 

 

 

 

0 ./// //// /// .// ///
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
Sampling Station

Figure 23: p,p'-DDD Sediment Concentration by Sampling Station

83

Table 26: Results for Duplicate Analyses of Sediment Samples for p,p-DDT

p,p'-DDT concentration (ng/gl

station ID duplicate 1 duplicate 2 mean

M62 0.73 0.91 0.82
WWWTP 8.66 10.32 ' 9.49
MERIDIAN 1.22 0.69 0.98
OKEMOS 0.00 0.00

HAGADORN 3.98 5.90

Msu 0.84 0.98
ELWWTP

MERIDIAN
OKEMOS
HAOADORN
MSU
ELWWTP

MERIDIAN
OKEMOS
HAOADORN

MERIDIAN
OKEMOS
HAGADORN

MERIDIAN
OKEMOS
HAGADORN
MSU
ELWWTP

M52
WWTP
MERIDIAN
OKEMOS
HAGADORN

ELWWI
“‘0

 

84

HDUHD Nu" p.v.IUUH mmmwansn oosnmnnnmnwon Appvv H: demnHoD no mvaHHDm Kenn? mum

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

.MnmnHoD
2.03:
9.32:6 maze:

2.8 <53... 2.? 032.9... +396. 26: 32.3 .2286
33%» PmN who 9mm A_<__u_. true ob. 9mm 9mm
53-3 A22. 9mm 2.0.. Agar 96w ..ou 93 PE
cc_-.m~ A2.o.. Pom .26.. 25.. P. N ..m. 5mm Pom
>cn-m~ A39. mbm 26.. A39. mhm P. w 5.8 Pam
”6.8.8 29 NS 22 22. 8.8 8.3 . . .8 an:
02- 8 0... PS 22 Agar 98 mm. 6.8 N...
guano 0.. m m.~m 9.3 A26... . ab. PNO 9mm

 

2.0.." 2.2on 0362.0: :3:

 

 

 

85

Average Concentration (ppb)

 

 

 

 

 

May June July Aug Sept 92 Oct
I 92 l
Sampling Month

Figure 24: p,p'-DDT Sediment Concentration by Sampling Month

 

86

Average Concentration (ppb)

 

 

 

 

 

 

 

 

 

 

 

 

 

1 O
8
6
4
2
i
3 -
’xx’" / 1.x“ /"
// /' ../" ,/ /'/

 

0 . g . . , . '
M52 WWWTP M43 OKEMOS HAG. MSU ELWWTP
' Sampling Station

Figure 25: p,p'-DDT Sediment Concentration by Sampling Station

87

Average Concentration (ppb)

 

 

Ip,p'-DDE Ip,p'-DDD Ip,p'-DDT

 

 

 

10

 

 

   

Aug

 

l ' 92 .
Sampling Month

Figure 26: DDT Complex Sediment Concentration by Sampling Month

88

0. Average Concentration (ppb)

 

 

 

Ip,p’-DDE .p,p'-DDD Ip,p’-DDT

 

 

  
    

 

15

10

 

 

 

 

 

 

 

M52 WWWTP M43 OKEMOS HA . MSU ELWWTP
Sampling Station '

   

Figure 27: DDT Complex Sediment Concentration by Sampling Station

89

b- Discussion

The results for the preliminary.analysis (samples
background checking) are shown in Table 4. Seven of the 26
compounds studied: atrazine, 2,4-D methyl ester, dicamba,
alachlor, P,P’-DDT, p,p’-DDE, and p,p'-DDD were found in the
water and/or sediment samples.

In the water samples, residues of atrazine, 2,4-D
methyl ester, dicamba, alachlor, and DOE-p,p' were found.
The residue levels ranged from 0.039 to 1.36 ppb for
atrazine (based on both G.C. and ELISA data), 0.04 to 2.04
ppb for alachlor, 0.08 to 2.64 ppb for 2,4-D methyl ester,
and 0.08 to 0.44 ppb for dicamba. The residue level was
below the Maximum Contaminant Level (maximum permissible
level of a contaminant in water which is delivered to any
user of a public water system) set by the EPA (1994) for
drinking water. The Maximum Contaminant Level (MCL) being
3.00 ppb, 2.00 ppb, and 70 ppb for atrazine, alachlor, and
2,4-D respectively. ' ‘

Two data sets were obtained for atrazine using two
different analytical techniques: the gas chromatography
technique (G.C.) and the ELISA technique. The Wilcoxon rank-
sum test carried out on the two data sets showed that the
residue levels obtained by ELISA-were higher than those
obtained by G.C. at 99 percent confidence level. The

difference in concentrations could be explained by the

90
difference in specificity between the two techniques. While
the amount of atrazine obtained by G.C. was based on the
detection of only atrazine, the residue level given by the
ELISA kit was actually based on all triazines present in the
samples. Consequently, the concentrations computed by the.
ELISA procedure were higher than those of the G.C. method.
This result is not surprising because as illustrated in
Figure 4b, atrazine was not the only compound detected under
the conditions described in Figure 4. The NP detector (which
is specific to nitrogen and/or phosphorus-containing organic
molecules) indicated the presence of other nitrogen and/or
phosphorus-containing compounds that might belong to the
triazine group. The ELISA procedure seems to be more
suitable for qualitative studies than for quantitative
analyses.

In general, the concentrations of atrazine, 2,4-D
methyl ester, and dicamba decreased over the sampling period
(Figures 7, 15, and 17), May, June, July, and August being
the major period of input. 0n the other hand, the highest
concentrations of alachlor were obtained during flood
conditions, that is, June, September, and April. Hence, the
run-off pattern of alachlor during the sampling period was
different from the other detected herbicides. This finding
is in partial agreement with the study by Baker (1987) who
observed that cyanazine, atrazine, alachlor, and

metolachlor had similar Spring runoff patterns and were

91
primarily carried to the watershed between May and July. Why
did alachlor behave differently in our study? The water
solubility and leaching and run-off potentials of these
compounds are listed in Table 1 (page 11). The sorption
coefficient is 190, 163, and 2 for alachlor, atrazine, and
dicamba respectively (Farm Chemicals Handbook, 1990). A
possible explanation of the difference in pattern between
alachlor and the other three compounds could be based on the
ways these chemicals are applied. Under the assumption that
alachlor has been more incorporated in the soil by farmers
than the other herbicides, higher levels of alachlor could
be expected with stronger surface run-off leading to higher
water levels. On the other hand, atrazine, 2,4-D methyl
ester, and dicamba would not need any strong surface run-off
to reach the water. The first run-off following their
application would do the job. Consequently, their highest
concentrations in the water would correspond to their major
period of application, that is, May to June.

The residue levels over the study section are shown in
Figures 8, 12, 16, and 18 for atrazine, alachlor, 2,4-D'
methyl ester, and dicamba respectively. Generally, the
residue level tends to increase at the M-43 and Hagadorn
bridges for atrazine and alachlor. The concentration of
2,4-D methyl ester increases from the M-52 bridge to Okemos
and decreases from Okemos to the MSU campus before

increasing again. As far as dicamba is concerned, its

92
concentration tends to increase in a downstream direction.
Overall, the downstream pollution pattern indicated by Zabik
et al. (1971) and Talsma (1972) is only observed with
dicamba. The variation of the concentrations could best be
explained based on more complete and accurate information
about the use of these herbicides in the vicinity of the
study area and about the locations of drain effluents.
However, in the absence of such information, one could
attempt to explain the differences in variation pattern.
under the assumption that these four chemicals have not been
equally used at the same locations. That is, while some
might be heavily used at a given location around our study
area, others might rather be used at higher rates at another
location.

p,p’-DDE was detected in 28 percent of the 98 water
samples. The residue level ranged from 0.21 to 2.54 ppt,
which is approximately 1,000 times less than the
concentration of p,p'-DDT metabolites found by Zabik et al.
in 1971 (about 4 to 28 ppb). The variation of p,p’-DDE over
the sampling zone did not show any particular pattern.
Neither did its variation over the sampling period.

In the sediment samples, only p,p’-DDT and its
metabolites (p,p’-DDE and p,p'-DDD) were detected. The
residue level was between 0.48 and 37.79 ppb for p,p,p'-DDE,
0.01 and 16.31 ppb for p,p’-DDD, and 0.69 and 15.02 ppb for

p,p’-DDT. These numbers suggest a quality recovery in the

93
bottom material of the river as far as contamination by DDT
is concerned. Indeed, the residue level found by Zabik et
al. in 1971 ranged approximately from 4 to 65 ppm for DDT
and from 1 to 44 ppm for DDT metabolites. An explanation of .
the levels founds in the present study could be the lack of
further input of DDT since the cancellation of the use of
this compound in the 1970’s. Also, volatization, leaching,
and degradation might have contributed to the disappearance
of DDT-complex from the river water. These facts could
explained why the downstream pollution pattern reported by
the 1971 study was not observed in this research for DDT and
its metabolites.

The amount of p,p'-DDE detected at each sampling
station was generally higher than that of p,p'-DDD which was
in turn greater than that of p,p’-DDT (Figures 26 and 27),
contrary to the 1971 study by Zabik et al. (in 1971, the
amount of DDT was much greater than that of its
metabolites). Figure 19 is a plot of the percent organic
matter by sampling station. The variation of the
concentration over the study section is shown in Figures 21,
23, and 25 for p,p'-DDE, p,p’-DDD, and p,p'-DDT
respectively. The variation of the residue levels over the
sampling period is shown in Figures 20, 22, and 24. In the
whole, the concentrations seem to be more related to the
organic matter content than to any other parameter.

All-these findings suggest that p,p’-DDT has not been '

94
used in the vicinity of East Lansing, Michigan for a long

time.
11- Summary

Analysis of 98 water samples and 74 sediment samples
collected monthly at seven different points led to the '
following results:

- 0f aldrin, methoxychlor, and DDT and its metabolites
previously reported to be present in the Red Cedar river,
only p,p'-DDT, p,p’-DDD and p,p’-DDE were detected in the
river.

- While all three compounds were detected in the
sediment samples, only p,p’-DDE was found in the water
samples.

- Overall, the content of DDT and its metabolites was
approximately 1,000 times less than that found by Zabik et
al. in 1971.

- The concentration of p,p’-DDT and its metabolites in
the bottom material appeared to be more related to the
samples organic matter content than to any other parameter.

- These results indicate a quality recovery of the
river water as far as contamination by DDT and DDT analogues
is concerned. .

- Beside DDT and its metabolites, atrazine, alachlor,

2,4-D methyl ester, and dicamba (which were not studied in

95
1971) were also detected in the river water. The residue
levels ranged from 0.037 to 1.37 ppb for atrazine, 0.04 to
2.04 ppb for alachlor, 0.08 to 2.64 ppb for 2,4-methyl
ester, and 0.08 to 0.44 ppb for dicamba.

- While the concentrations of atrazine, 2,4-D, and
dicamba showed a relation with the major periods of
application (May-June) for these pesticides, the residue
level of alachlor was rather more related to the water
height due to release to the river in run-off.

- Overall, the downstream pollution pattern indicated

in 1971 by Zabik et al. was not observed.

96
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Bushway, R.J., H.L. Hurst, L.B. Perkins, L. Tian, C.G.
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