v>EPA
United States
Environmental Protection
Agency
Municipal Environmental Research EPA-600/2-80-113
Laboratory August 1980
Cincinnati OH 45268
Research and Development
Maximum
Utilization of Water
Resources in a
Planned Community
Contributions of
Refractory
Compounds by a
Developing
Community
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. .Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are: j
1. Environmental Health Effects Research
2, Environmental Protectioifi Technology
3. Ecological Research I
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technica
7. Interagency Energy-Env
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
Assessment Reports (STAR)
ronment Research and Development
This document is available to the [public through the National Technical Informa-
tion Service, Springfield, Virginia^ 22161.
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EPA-6.00/2-80-113
August 1980
MAXIMUM UTILIZATION OF WATER RESOURCES
IN A PLANNED COMMUNITY
Contributions of Refractory Compounds
by a Developing Community
by
F. M. Fisher
Department of Biology
Rice University
Houston, Texas 77001
Grant No. 802433
Project Officers
Richard Field
Anthony N. Tafuri
Storm and Combined Sewer Section
Wastewater Research Division
Municipal Environmental Research Laboratory (Cincinnati)
Edison, New Jersey 08817
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental
Research Laboratory, U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the
contents necessarily reflect;the views and policies of the U.S.
Environmental Protection Agency, nor does mention of trade names
or commercial products constitute endorsement or recommendation
for use.
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FOREWORD
The U.S. Environmental Protection Agency was created because
of increasing public and government concern about the dangers of
pollution to the health and welfare of the American people.
Noxious air, foul water, and spoiled land are tragic testimonies
to the deterioration of our natural environment. The complexity
of that environment and the interplay of its components require
a concentrated and integrated attack on the problem.
Research and development is that necessary first step in
problem solution; it involves defining the problem, measuring its
impact, and searching for solutions. The Municipal Environmental
Research Laboratory develops new and improved technology and sys-
tems to prevent, treat, and manage wastewater and solid and haz-
ardous waste pollutant discharges from municipal and community
sources, to preserve and treat public drinking water supplies,
and to minimize the adverse economic, social, health, and aes-
thetic effects of pollution. This publication is one of the
products of that research and provides a most vital communications
link between the researcher and the user community.
The research reported here describes the role of a develop-
ing community in contributing refractory organochlorine compounds
to the aquatic ecosystem. Water, soil, and biotic components from
a natural drainage system in The Woodlands, Texas, were assayed
over a 38-month period from 1973 to 1976.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
111
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PREFACE
The overall goal of this research was to evaluate the water
resource plan for The Woodlanjds, Texas, and to made recommenda-
tions, as necessary, to maximize its effective utilization
through alterations in design and management. Any recommended
alterations were to be critically evaluated as to their com-
patibility with the natural environment.
Collection and utilization of stormwater runoff for recrea-
tional and aesthetic purposes was a major feature of the water
resources plan at The Woodlands. Control of downstream flooding
was also of great importance and so storage reservoirs, in the
form of recreational lakes and wet weather ponds, were created
by the developers. Water qua;lity was a concern if the impound-
ments were to be aesthetically appealing and/or suitable for
recreation. Therefore, a major sampling and analytical program
was designed to monitor water quality and quantity at different
locations in the developing area. The Storm Water Management
Model (SWMM) provided the focal point for combining the water
quality and quantity data into a predictive tool for design and
management purposes. :
SWIM was originally developed for highly urbanized areas
and, therefore, was calibrated for this project in an urban
watershed (Hunting Bayou). Subsequently, SWMM was modified to
model runoff and water quality from natural drainage areas, such
as The Woodlands. Because of the lag in the construction
schedule at The Woodlands, the dense urban areas were not com-
pleted during the project period. Consequently, Hunting Bayou
and other urban watersheds were sampled to provide a basis for
predicting pollutant loads at The Woodlands in the fully devel-
oped state. :
Water analyses included many traditional physical, chemical,
and biological parameters used in water quality surveys. Patho-
genic bacteria were also enumerated since the role of traditional
bacterial indicators in stormwater runoff was not clear. Algal
bioassay tests on stormwater were conducted to assess the eutro-
phication potential that would exist in the stormwater impound-
ments. The source, transport, and fate of chlorinated hydro-
carbons in stormwater runoff Were also investigated.
Several of the large Woodlands impoundments will receive
reclaimed wastewater as the major input during dry weather.
i
iv
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Besides their use as a source of irrigation water, the lakes will
be used for non-contact recreation—primarily fishing and boat-
ing. Because the reclaimed wastewater must be disinfected, there
was a concern about disinfectant toxicity to the aquatic life in
the lakes. Consequently, comparative fish toxicity tests were
conducted with ozone and chlorine, the two alternatives available
at the water reclamation plant.
Porous pavement was considered by the developers as a method
for reducing excessive runoff due to urbanization and an experi-
mental parking lot was constructed. Hydraulic data were col-
lected and used to develop a model compatible with SWMM, to pre-
dict the effects of using porous pavement in development. Water
quality changes due to infiltration through the paving were also
determined.
Hopefully, the results of this project will contribute in a
positive way to the development of techniques to utilize our
urban water resources in a manner more compatible with our
cherished natural environment.
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ABSTRACT
This project was undertaken to examine the role of a devel-
oping community in contributing refractory organochlorine com-
pounds to the aquatic ecosystem.
i
Water, soil, and biotic 'components from a natural drainage
system in The Woodlands were assayed for halogenated compounds
by gas-liquid chromatography. In addition, components from two
man-made lakes and the recipient stream were evaluated.
Polychlorinated biphenyl (PCB) residues were detected during
each year of the three-year study. The levels of PCBs were
highest during the first year (about 350 ppb in soil and animal
samples) and diminished to 1/10 of those values during the second
and third years of study. The highest residue values were coin-
cident with the period of development when cut and fill opera-
tions, roadbed construction,[and service installation were being
effected. |
The chlorinated camphene, mirex, which is used for fire ant
control was found in soil, water, and organisms from the drainage
area around The Woodlands Golf Course as were residues of chlor-
dane. The presence of these .refractory compounds in the water
and soil was reflected in samples of mosquitofish collected in
the same area.
Although the pesticide levels in fish were highest around
The Woodlands Golf Course, the level never exceeded 5.6 ppb for
mirex and 6.1 ppb for chlordane. Both compounds were apparently
transported into the Conference Center Lakes by stormwater and/or
washed in by returning irrigation water from the golf course.
Pish from Panther Branch, which receives stormwaters from over-
flow of the Conference Center Lakes, contained less than one-
fourth the amount of mirex and chlordane found in golf course
samplings. The data indicated that biotic and abiotic components
of the lakes serve as effective "sumps" for these pesticides.
This report was submitted in partial fulfillment of Grant
No. 802433 by Rice University under the sponsorship of the U.S.
Environmental Protection Agericy. This report covers the period
from September 1, 1973 to December 15, 1976, and work was com-
pleted as of March 15, 1977. !
VI
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CONTENTS
Foreword
Preface iv
Abstract ....... vi
Figures viii
Tables . ix
Abbreviations ...... ....... x
Acknowledgments xi
1. Introduction. . . 1
2. Summary of Results/Conclusions/Recommendations. . 5
3. Results and Discussion. *8
References 24
Appendices
A. Experimental Procedures 27
B. Tables 40
vi i
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iFIGURES
Number Page
1 Map of sampling locations in The Woodlands
waterways \ 9
2 Map of Lakes A & B indicating location of freshwater
marsh and relationship of the lakes and marsh to
Panther Branch . . . ; 12
i
3 Temporal distribution of polychlorinated biphenyls in
The Woodlands. . . . i 13
4 Temporal distribution of polychlorinated biphenyls in
aquatic fauna in TheiWoodlands 16
5 Temporal distribution of mirex in The Woodlands Golf
Course : 19
6 Temporal distribution of mirex in the Conference
Center Lakes (A & B) 21
7 Temporal distribution of chlordane in The Woodlands
Golf Course . 22
Vlll
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TABLES
Number
Paqe
Distribution of Samples by Year and Type of
Material Analyzed. . • <
2 Polychlorinated Biphenyl Residues in Soil Samples.
3 Polychlorinated Biphenyl Residues in Water Samples
4 Polychlorinated Biphenyl Residues in All Animal
Samples •
8
11
14
17
IX
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ABBREVIATIONS
Aldrin — 1,2,3,4,10,10-hexachloro-1,4,4',5,8,8'-hexahydro
1,4-endo, exp 5,8 dimethanophthalene
1,2,4,5,6,7,8,8-octachloro-2,3,3',4,7,7s-hexahydro-
4,7-methanoindene
-2-(0-chlorophenyl)-2-(p-chloro-phenyl)-1,1-
dichloroethane
2,2-bis(p-chlorophenyl)-l,l-dichloroethane
1,l-dichloro-2,2-bis(p-chlorophenyl)ethylene
1,1,1-trichlorp 2,2-bis(p-chlorophenyl)ethane
1,2,3,4,10,10'-hexachloro-6,7-epoxy 1,4,5',5,6,7,8,8'
octahydro-l-4-endo,exo-5,8-dimethano-naphthalene
Heptachlor — 1,4,5,6,7,8,8'-heptachloro-3',4,7,7'-tetrahydro 4,7-
methanoindene
Chlordane
O,P.DDD
p,p-DDD
p,p-DDE —
p,p-DDT
Dieldrin
Heptachlor
epoxide
Lindane
Mirex
PCB
Toxaphene
GLC
ppm
CCM
1,4,5,6,7,8,8•~heptachloro-2,3-epoxy-3l,4,7,7'
tetrahydro-4>7 methanoindene
gamma isomer of 1,2,3,4,5,6-hexachlorocyclohexane
Dodecachlorooctahydro-1,3,4-metheno-2H-cyclobuta(cd)
pentalene
polychlorinated biphenyl
a mixture of chlorinated camphenes
Gas-liquid chromatography
parts per billion
parts per million
Conference Center Marsh
x
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ACKNOWLEDGMENTS
The Woodlands, a developing community north of Houston,
Texas, is gratefully acknowledged for their cooperation and
interest in this project. The research group of the Environ-
mental Science and Engineering Department at Rice University
collected some abiotic samples for this phase of the study.
XI
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SECTION 1
INTRODUCTION
The name chlorinated hydrocarbon has been loosely applied to
a group of synthetic organochlorine compounds which share certain
qualities, the most important of which is an insecticidal action;
or as Moore (1) more accurately described it, a "biocidal"
action. With few exceptions, the chlorinated hydrocarbon in-
secticides also share the properties of a broad spectrum of in-
secticidal action, relatively simple structure (promoting ease of
manufacture), prolonged stability and residual action, and rela-
tively low mammalian toxicity (2). Highly insoluble in water,
most organochlorine insecticides share the property of high lipid
solubility. Though the exact mode of action of these compounds
is not known, it is generally thought that they act on cell mem-.
brane surfaces, a theory which the lipid nature of membranes
would seem to support. Metcalf (2) suggested that DDT disorders
the surface membranes of nerves affecting calcium permeability,
and O'Brien (3) speculated that cyclodiene insecticides acted
similarly by complexing with neural membranes in such a way as to
modify their properties. Since cell membranes are common to all
living organisms, it would appear that organochlorine formula-
tions do possess the potential of being biocidal.
The persistence and biomagnification of chlorinated hydro-
carbons in the environment are the principal factors which have
led to a decline in usage. Available commercially only since
1945, DDT has been detected in remote regions of the globe and
the discovery that marine fish are almost universally contami-
nated with DDT residues are testimony to the problems of persis-
tence and biomagnification. Since lower animals serve as food
for the higher animals, the chlorinated hydrocarbon content in
fatty tissue tends to increase in concentration as one moves up
the food web. The discovery of DDT in human milk (4) suggests
that man is not immune to the process of biomagnification.
The problem of contamination is a unique environmental situ-
ation in that pesticides are deliberately introduced for benefi-
cial and/or monetary purposes. They are not for the most part
waste products as is characteristic of the large majority of en-
vironmental contaminants. Though initially introduced into an
agricultural or urban ecosystem in a controlled manner to elimi-
nate a target species, the action and fate of persistent com-
pounds are neither simple nor controlled, but rather complex and
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uncontrolled. The reasons for this are numerous: first, the
organochlorine compounds are not selective in their action for a
single pest species; instead they demonstrate a broad spectrum of
biocidal action. In order tojreach the target organism, all
other organisms and components of the system are subjected to the
chemical.
One of the first components of an ecosystem to come in con-
tact with an organochlorine formulation is the soil. The behav-
ior of such residues in soils has been the subject of numerous
investigations. The persistence of these refractory compounds is
dependent on such factors as concentration (5), volatility (6),
temperature (7), organic content of soil (8), clay and moisture
content (9), and usage of soil (10).
I
The long life of chlorinated hydrocarbon residues is com-
pounded by extremely slow diffusion of the compounds through
soil. Over 80% of the chlordane and dieldrin residues remain in
the top 10 cm of soil ten years after 'application. Leaching of
such compounds into subsurface waters does not therefore present
a particular problem. What then is the fate of such refractory
compounds in soil? Two major!pathways of dieldrin loss from
soil are volatilization and sediment transport, but the amounts
dissolved in runoff water andj absorption by vegetation may be
significant (11). Though only very slightly soluble in water,
chlorinated hydrocarbon compounds enter waterways dissolved in
minute amounts or in much greater amounts adsorbed onto sus-
pended sediment particles (12) . Certainly, the primary means
whereby toxic residues are transported from one area to another
is water and compounds need not be in solution for such trans-
port. It is this presence of residues in surface waters that
exposes yet another biological community to chlorinated com-
pounds. Numerous non-target Arthropods, molluscs, fish, and
algae are sensitive to these formulations (13). It is a fact
that most populations of organisms in the world have exhibited no
readily visible effects from contact with chlorinated hydrocarbon
compounds, but it does not suffice to assume that there are none.
Certainly, acute effects of some formulations have produced kills
of non-target organisms following ingestion or absorption. How-
ever, the effects most common and difficult to assess are the
sub-lethal effects, i.,e., effects due to any dose of a compound
below that which produces death. Growth retardation may be at-
tributed to chlorinated hydrocarbon exposure ,(12,14,15,16,17,
18). Somewhat more subtle effects of chlorinated hydrocarbons
have been noted on metabolismj and growth at the cellular level
where long-term effects can be classified as carcinogenic, tera-
togenic, or mutagenic. '
I
A basic principle of ecojlogy is that no component of an
ecological system can be altered without affecting the whole sys-
tem. Any factor or factors that affect even so much as a single
organism or component will produce an effect on the system as a
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whole. As Moore (1) pointed out, no plant or animal lives in
isolation. An application of a chlorinated hydrocarbon never
results in a total reaction of the form:
Pesticide -> Pest
All pesticide applications, in fact, consist of the reaction:
Pesticide •> Ecosystem in Which Pest Lives
It has been predicted that stability of an ecosystem is corre-
lated with diversity of organisms and that decreasing diversity
leads to decreased stability (19). This idea is significant in
light of research by Menhinick (20), who observed,reduced diver-
sity in areas of pesticide application.
At present some data exist on the distribution, location,
and impact of pesticides in natural living systems. A hindrance
in obtaining such information has been a lack of understanding of
normal patterns and variations in biotic communities needed to
.serve as baseline for understanding pesticide pollution effects.
Studies of halogenated hydrocarbon residues have been undertaken
in relatively few complete systems. Freshwater marshes (21),
freshwater streams (22),, saltwater marshes (23,24), and brackish
water marshes (25) have been examined.
In 1971 registration cancellation proceedings were initiated
against the manufacturers of DDT, mirex, aldrin, and dieldrin.
The subsequent ban on nearly all uses of DDT, aldrin, and
dieldrin demonstrated the risk of the chlorinated hydrocarbon
formulations to man and the environment. With the decreased
usage of the refractory halogenated compounds, there has been a
concomitant increase in the usage of the less persistent car-
bamate and organophosphorus formulations. Although these latter
classes of pesticides have relatively short half-life in the
environment, they exhibit, in general, greater acute toxicity to
both vertebrates and invertebrates. It is important, therefore,
to understand the routes and velocity of pesticide loss from
treated areas and transport to aquatic environments. Such an
understanding in concert with knowledges of the effects of non-
target species could provide an equitable basis for administra-^
tion and regulation of these alternate chemicals.
Although not considered biocides, another group of chlori-
nated hydrocarbon compounds has been noted in the environment in
recent years. The polychlorinated biphenyls (PCBs) have been
used in industry for forty years. Under the trade name
"Aroclor," these refractory compounds are involved in manufac-
turing as plasticizers, flame retardants, insulating fluids, and
a host of other applications. As 'additives to many products,
the "Aroclors" improve the quality of the product or material.
Such is the case with printers ink, floor tile, electrical
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I
products, synthetic rubber, varnishes, waxes, asphalt, and ad-
hesives. The source of these compounds which consist of chloro-
biphenyls or chloroterphenyls
interest that at one time the
is many or varied and it is of some
addition of PCBs to chlorinated
pesticides was suggested to suppress vaporization, therefore,
extending their half-life. By the methods employed in this
study, the PCBs were analyzed[in a large number of biotic and
abiotic samples. i
There is, however, a paucity of information on chlorinated
hydrocarbon contamination frorh urban ecosystems. This source of
pollution is relevant in view!of recent demographic trends which
suggest that approximately 75% of the population in the United
States will reside in a 100-mile band adjacent to the coastline
by 1980 (26). Water from such centers of population often supply
the freshwater component to important coastal estuarine eco-
systems. One of the-most important estuaries in the Texas
Coastal Zone is the Galveston;Bay Complex which receives major
surface runoff via the San Jacinto and Trinity Rivers. Numerous
small streams and bayous also;contribute freshwater to this
productive bay ecosystem. The Woodlands is located on Spring
Creek which contributes surface water to the San Jacinto River
drainage basin. That river not only supplies Galveston Bay with
its riverine component, but also affords a major water supply to
the City of Houston from a man-made impoundment, Lake Houston.
One could not expect a developing community the size of The
Woodlands to be especially significant in adding refractory com-
pounds to this waterway; however, the location of The Woodlands
in an area with little agricultural history suggests that there
would be little or no background input of pollutants in the
stormwaters. Hence, any measurements would be the result of
urbanization or urban processes.
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SECTION 2
SUMMARY OF RESULTS/CONCLUSIONS/RECOMMENDATIONS
CHLORINATED HYDROCARBON SURVEY
During the two and one-half, year study, some 2,500 biotic
and abiotic samples were collected in The Woodlands and analyzed
for halogenated hydrocarbon compounds. The major emphasis was
directed toward surface water (90,5) and aquatic fauna (899)
samplings; however, 560 soil-sediment and 113 plant samples were
also analyzed.
POLYCHLORINATED BIPHENYLS (PCBs)
1) The major class of chlorinated compounds detected during
the study was the polychlorinated biphenyls (PCBs). These formu-
lations are used in a variety of industrial applications such as
varnishes, paints, inks, waxes, flooring tile, synthetic rubber,
and asphalt; however, the greatest usage is in the electronics
industry in the production of capacitors and transformers. The
PCBs have been produced for over forty years but only recently
have they been observed as a pollutant in the environment.
2) In January 1974, a sudden increase in the PCBs in soils
(up to 341 ppb) was observed, which was followed by a rise in the
concentration in surface waters (maximum of 8.2 ppb) some four
mpnths later. The rates of decline of both of these peak con-
centrations resemble a first order curve. No further increase in
PCBs in water was observed throughout the remainder of the study.
By extracting larger amounts of soil concentrating the compounds
on activated charcoal followed by elution and subsequent analy-
sis, a second minor peak was observed in soil samples during the
spring of 1975. The peak in 1975 was three orders of magnitude
lower than the major peak in 1974. Several plant samples were
found to contain trace amounts of PCBs, but these minute amounts
could have been due to surface contamination since they coincided
with the highest values observed in water and soil samples. The
level of PCBs in aquatic animal samples started rising in late
1973 and reached a peak (30 ppb) in April of 1974, which is
coincident with about 3.0 ppb in the water samples. The concen-
tration in the aquatic organisms is about 10 times that in the
water samples but 1/10 that observed in the soil samples.
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3) The source of the PCfes in The Woodlands is not known.
It is of interest that the peak of PCBs in all components of the
ecosystem appeared during a period of intense cut and fill
operations as well as utility installation. An abandoned land-
fill with disposed capacitors or other electronic materials
could have effected the increase in concentration, as could the
use of road oil contaminated With PCBs. Neither of these
thoughts were verified by observation. The use of PCBs in
synthetic heat resistant oils, including hydraulic oils, may
represent a possible source of this contamination. The highest
level of PCBs was observed during a period where the maximum cut
and fill operations were underway. The utilization of hydraulic
systems or such equipment is well documented.
CHLORINATED HYDROCARBON PESTICIDES
1) Traces of DDE were observed in samples of crayfish,
mosquitofish, and bluegills obtained from The Woodlands aquatic
ecosystem during the first year of study. Following completion
of recreational facilities such as the golf course, mirex and
chlordane were found in soil and water samples associated with
this facility.
2) In the spring of 197J5, mirex was detected in water (to
15 ppb) , soil (to 30 ppb) , an^. some aquatic organisms (to 55 ppb).
The highest values were found; in the mosquitofish (55 ppb) and
the lowest in water samples with the residue in soil being inter-
mediate between the fish and water. If there was any biological
amplification in the fish from this aquatic system, it was
limited to about a four-fold increase over concentrations in the
water. Water from the Conference Center Lakes (A & B) was used
for irrigation of portions of: the golf course. Since these man-
made impoundments were the potential recipients of both irriga-
tion and stormwater runoff, the lake water sediments and mosquito-
fish were examined for mirex.j The highest level of mirex was
observed in mid- to late summer (1975), and thereafter the concen-
tration of all three components of the pond ecosystem diminished
rather rapidly with the soil Residues showing the slowest rate of
decline. The concentration o;f mirex in the lake aquatic system
was at least one order of magnitude lower than that observed on
or adjacent to the golf cours;e. The lower concentration possibly
being due to dilution and runoff.
3) During August of 197*4, chlordane was also detected in
the golf course study. Residues were found in soil, water, and
aquatic organisms. The highest levels of chlordane were found in
the crayfish (43 ppb) from golf course ponds. Somewhat less was
observed in the same organism' from ditches adjacent to the
course. Similar, although noft as pronounced, results were ob-
served in the concentration of chlordane in the waters from the
same areas.
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CARBAMATE COMPOUNDS
Attempts were made to examine the runoff of a carbamate
pesticide from an urban yard. Although the resemblance of a
first order curve was obtained/ it was unfortunate that the in-
terpretation of the data was in error. Extract of runoff waters
was examined by gas-liquid chromatography (GLC) prior to deriva-
tization with trifloroacetic anhydride and the results were
nearly identical with derivatized samples. During concurrent
studies in a ricefield-marshland ecosystem, the same observations
were made. Naturally occurring compounds often effect spurious
peaks in GLC determinations, especially when electron capture
detectors are employed. Solfur or sulfur-containing compounds
are among the more notorious contaminants in producing such arti-
facts. Such contaminants can be removed from samples with bright
copper or treatment with mercury.
MONITORING PROGRAMS
The present study reinforces the notion that monitoring pro-
grams for chlorinated hydrocarbon compounds should be continued.
That such compounds appear and increase in amount with urbaniza-
tion of a heretofore "pristine" area is sufficient argument for
continued monitoring. Specifically, chlorinated hydrocarbon
compounds should be monitored in The Woodlands on at least a bi-
annual basis to follow the distribution of refractory compounds.
Monitoring should be restricted to the Conference Center Lakes
(A & B). These lakes receive runoff waters from the golf course,
which appears to be a major source of.insecticidal compounds at
the present time. Since waters from these lakes are used for
irrigation of the golf course, there is a possibility of reach-
ing toxic levels of mirex and chlordane in lake sediments. If
the lakes are to be used for any form of, recreation, the monitor-
ing schedule should be enhanced. At present, the lakes appear to
be functioning as a "sump" for the above refractory compounds.
All attempts should be instituted to prevent scouring and move-
ment of the halogenated compounds downstream.
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SECTION 3
RESULTS AND DISCUSSION
SAMPLING
During this 38-month study of surface waters in The Wood-
lands, some 2,500 biotic and abiotic samples were analyzed for
halogenated hydrocarbon compounds and/or carbamate formulations.
The major portion of these samples was collected in the drainage
system within The Woodlands development. A resume of the
samples by year and type of material examined is presented in
Table 1. !
TABLE 1. DISTRIBUTION OF SAMPLES BY YEAR
AND TYPE OF MATERIAL ANALYZED
Type of Sample
1973H74
1974-75
1975-76
Total
Water
Soil
Animal
Plant
TOTAL
513
182
376
73
1,144;
1
270
270
438
40
1,018
122
108
85
0
315
905
560
899
113
2,477
1
Considerably more attention was directed toward the analysis
of water (905) and animals (899); however, 560 soil-sediment
(herein referred to as soil) and 113 plant samples were also
analyzed. .The experimental procedures are presented in Appendix
A. The major number of samples were collected from sites along the
the major waterways in or adjacent to the development (Figure 1).
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Initially, four sampling 'locations were selected on Panther
Branch (P-04, P-10, P-20, P-30), one on Bear Branch (B-03), and
one on Spring Creek at Interstate 45 (S-10). Lakes A and B (A,B)
as well as a transient freshwater marsh (M) near the headwaters,
of Lake B were also examined during the first year of study. ...
With the exception of the freshwater marsh (M) and the Bear
Branch station (B-03), all study sites were continued during the
second year of study. During ithis phase of development, The
Woodlands Golf Course was added to the sampling regime. This was
considered necessary since watlers from the Conference Center
Lakes (A & B) were used for irrigation of portions of the golf
course. Excess irrigation water as well as storm runoff from
the golf course re-entered the lake system. The monitoring of
halogenated hydrocarbon compounds during the last six months 6£
the study was confined to the Conference Center Lakes (A & B),
the golf course, and the downstream station on Panther Branch
(P-30). i
POLYCHLORINATED BIPHENYLS (PCBs)
i
The most common halogenated hydrocarbon compounds identified
during this study were the polychlorinated biphenyls (PCBs) sold
under the trade name "Aroclor.-" The resume of the polychlori-
nated biphenyl residues in soil is presented in Table 2 where the
data are arranged according to; sampling sites. The upper por-
tions of the watershed of Panther Branch are of particular in-
terest. The two sampling points near the western and northern
boundary of The Woodlands, B-0|4 on Bear Branch and P-04 on
Panther Branch, display quite idifferent quantities of PCBs in
soil samples. Samples from Bear Branch (B-04) analyzed during
late 1973 and the first half of 1974 did not have any appreciable
PCBs; however, corresponding samples from Panther Branch (P-04)
had residues ranging from trace amounts (less than 0.5 ppb) to
97 ppb during the same collection period. Based on these obser-
vations, B-04 was deleted during the second year of study and
replaced with P-10 downstream from P-04 (Figure 1).
i . .
The first three monthly samples at P-04 (September through
November 1973) did not contain sufficient quantities of PCBs to
obtain quantitative data; however, the samples collected over the
next six months contained residues approaching 100 ppb. It is
also of interest that elevated residue levels were observed at
stations P-20 and P-30 (Table 2) some five and seven miles down-
stream within The Woodlands (Figure 1). It would appear that
this particular incident of PCB introduction came from outside T
of The Woodlands. During this same time period, PCBs also
appeared in soil samples from Lakes A & B (Table 2). It is im-
probable that the residues in Lakes A & B are associated with
the pollution event in the Panther Branch system since the lakes
are located about 0.4 miles upstream from Panther Branch (Figures
2 and 3). The residue analysis of soil samples throughout the
remainder of 1974 failed to disclose any appreciable quantities
1 10
-------
of PCBs (Table 2). During the spring of 1975, there was a minor
occurrence of PCBs in the Panther Branch system and did not in-
volve Lakes A & B (Table 2). Small amounts of PCBs were present
in soil from P-04 for several months and corresponding values
were also recorded at P-10 some three miles downstream from P-04.
The residues were also recorded at P-20, P-30 and S-10, the
station at Spring Creek and 1-45.
TABLE 2. POLYCHLOKENATED BIPHENYL
RESIDUES IN SOIL SAMPLES (ppb)
Y . Collection Site
Month
1973/S
0
N
D
1974/J
,,: ,f
•M
A
M
J
J
A
S
0
"• ' N
' D
1975/J
F
M
A
M
J
J
A
S
0
N
D
Tr =
ND =.'
NS =
B-04 P-04 P-10
Tr
Tr
NS
NS
Tr
Tr
NS
Tr
. Tr
NS
NS
Trace
Tr
Tr
Tr
73.0
80.0
90.2
97.0
83.0
92.0
Tr
NS
1.1
1.8
Tr "
1.5 •"
1.1
1.3
1.1
1.5
1.2
1.0
0.8
1.4
1.0
1.3
1.0
1.0
0.8
2.1
1.7
0.8
P-20
NS
NS
NS
Tr
80.0
130.0
172.0
30.0
NS
NS
2.1
1.7
1.1
0.7
0.9
i.o
Tr
2.0
1.7
0.9
t
P-30
TV
Tr
Tr
51.0
Tr
341.0
200.0
54.0
Tr
Tr
NS
1.0
0.9
0.7
1.0
1.9
1.0
0.8
1.6
1.1
Tr
1.0
1.4
1.7
0.9
1.0
Tr
0.9
S-10
ND
Tr
ND
10.0
Tr
Tr
Tr
4.0
Tr
Tr
NS
2.1
Tr
Tr
Tr
1.0
1.0
1.4
3.1
3.6
2.1
Lake A
Tr
ND
1.0
1.0
Tr
92.0
239.
170.
120.
Tr
NS
0.8
Tr
Tr
1.0
Tr
1.2
Tr
0.7
0.7
1.0
1.1
1.3
0.9
0.9
ND
ND
Tr
Lake B Marsh
Tr ND
Tr ND
Tr 1^
13.0 Tr
Tr 3.1
NS NS
NS 16.0
161.0 ND
173. ND
130.0 ' NS
NS NS
1.1
0.9
0.7
Tr
0.8
1.2
0.7
0.9
0.8
1.2
1.2
1.1
1.0
1.0
Tr
Tr
Tr
Not detected
No sample
11
-------
H
ffi
En
0)
-P
CO
0)
CO
Q)
tr> CU
(0 IH
O O •
T3 &i O
C -H fl
CO M
W (-! CQ
O
U) -H !-l
•P (U
-------
o
] SOIL(PPB)
n w
o
o
C\J
o /
./o
/ o
a
o
o
a
o i
o
i
to
a
o
a
a
o
a
a
~* 10
2 ~
u.
o
O
(O
2
U.
o
to
2
o 22
H31VM (Odd)QOd
1IOS
•H
M
O
iH
XJ
O
>i
iH
ft W
'd
-------
The concentration of PCBs in water never approached that
measured in soil samples (Table 3). The observation of PCBs in
soil samples (early 1974, Tabl|e 2) appears to be reflected in
water samples from Panther Branch at nearly the same sampling
time. The same seems to be true for water samples from Lakes
A & B. To further examine the temporal relationship of PCBs in
the abiotic components, the grand monthly means from Tables 2 and
3 are slotted in Figure 3. It is important to realize that bio-
cide mobility is a function of runoff in an experimental area.
TABLE 3. fiOLYCHLORINATED BIPHENYL
RESIDUES IN WATER SAMPLES (ppb)
Year/Month
B-OU p-04
19737S
0
N
D
197U/J
F
M
A
M
J
J
A
S
0
N
D
1975/J
F
M
A
M
J
J
A
S
0
N
D
Tr «
ND -
NS =
Tr
Tr
Tr
ND
Tr
1.9
Tr
1.2
Tr
ND
NS
Trace
Tr
1.1
1.0
Tr
Tr
1.2
Tr
1.2
Tr
1.0
NS
2.1
1.0
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
P-10
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
!
Collection Sites
I
P-20;
Tr t
Tr 1
ND .
ND
Tr
1.6,
2.r
2.3!
1.4
1-4,
NS
Tr :•
Tr
Tr
Tr
Tr !
Tr ;
Tr i
o.vi
Tr
Tr
i
1
P-30
1.2
1.3
Tr
1.1
1.0
3.6
1.5
'4.8
1.1
3.4
NS
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
0.5
0.6
0.5
Tr
Tr
S-10
Tr
Tr
1.1
1.2
Tr
Tr
1.1
1.2
1.1
Tr
NS
Tr
Tr
Tr
Tr
Tr
Tr •
Tr
Tr
Tr
Tr
Lake A
Tr
ND
1.9
2.0
2.1
Tr
8.2
6.1
1.0
ND
NS
Tr
Tr
Tr
Tr
Tr
Tr
Tr
0.5
0.6
Tr
Tr
Tr
Tr
ND
ND
ND
ND
Lake B
ND
ND
Tr
2.0
Tr
Tr
2.5
2.1
1.1
NS
NS
0.8
0.5
Tr
Tr
Tr
Tr
Tr
Tr
0.7
0.9
ND
Tr
ND
ND
Tr
ND
ND
Marsh
1.0
ND
1.3
1.2
Tr
2.1
Tr
Tr
2.0
1.2
NS
Not detected
No sample
14
-------
In an ecosystem as large and diverse as The Woodlands it is
difficult, if not impossible, to examine this parameter without
time averaging. The areas of application are minute compared with
the magnitude of the watershed and the intensity of rainfall in
concert with the natural slope result in a highly erratic flow in
the waterways. Standing or permanent water is restricted to two
lakes and these are subject to great turnover during modest rain-
fall. These climatic and topographical features are complexed with
the extreme amount of sediment burden in stormwaters and the
natural rates of decomposition of the applied biocides.
In ideal situations following application of a pesticide, a
first order decay curve is commonly observed (13); however, these
results are predicated to a great degree on time averaging of the
runoff system. Inherent in such an ideal system is a standing
water basin, a watershed with little slope, and slow or impeded
runoff. To gain an overall representation of the temporal flux
of PCBs in The Woodlands, the data from all sampling stations in
the watershed are plotted versus time of year. This rationale in '
the treatment of these data is presented in Figure 3. As can be
seen, the peak concentration in the water appears during March and
April of 1974, while the highest value for soil residues appears in
January of 1975. Since PCBs and most clorinated compounds are
strongly adsorbed to sediments, it appears that there is a gradual
release of the compounds to the stream waters. Two ordinal scales
are presented for the soil data. The highest concentration in
PCBs was in late 1973 and early 1974, with a minor peak in 1975
which was three orders of magnitude lower than the 1973-74 peak.
The source of the PCBs in this study remains unknown. The
major use of the "Aroclors" is in the manufacture of capacitors
and transformers. Many paints and varnishes contain PCBs, as do
wax, printers ink, flooring tile, synthetic rubber, and asphalt.
The wide usage and their new ubiquitous occurrence in the environ- .
ment have only recently been known. It is of interest that the
major cut and fill operations for roadway construction were under-
way during the observed peak of PCBs. Utility installation was
also being accomplished at the same time.
PCB residues were not observed in plant sampling in measur-
able quantities; however, several samples were found to have trace
quantities (<0.5 ppb) . These samples coincided with the highest
values recorded in Figure 3. The chemical nature of the halo-
genated hydrocarbon compounds suggests that the few plant samples
were contaminated externally with PCBs.
The PCB levels in aquatic animal samples reached the
highest levels in late 1973 and early 1974 (Table 4). The grand
mean of these values is about 40 ppb. Examination of the temporal
distribution of these compounds (Figure 4) reveals that the
elevated levels in three species of aquatic organisms, mosquito-
fish, bluegill, and crayfish, superimpose with the highest concen-
15
-------
PCB(PPB)
«•» V
10 O 1 llO c
h~ lO ° °OJ ° H
1 i i i •* i
9
i
o
,
•
0
o
o
*
^
0
D ,
O
o
0 •
• o
00 »
D *0
• i
Q rH
2 1*
• W
_ -H
•2 tJ
«t rH
S LI
u. R
^ "H
O W
!1
E^ —
fi J!
•H CO
•H
a o
s -P
(0 -H
m »3
&
u to
•H 0
(0
^
-7
CO
CO
g
(d
^
n3
CJ
JH
CO
M-4
>i
2
0
O
O
^.
&< I ft
03 • CO
O —
O
(add)aod
O i|
0)
^
en
•H
Pn
16
-------
trations in soil and water (Figure 3). The levels of PCBs in
mosquitofish and crayfish samples examined during the second year
of study were much lower than those in year one. The values ob-
tained with the sample size used necessitated concentrating the
sample with activated charcoal and elution of the material from the
absorbent. During this procedure some naturally occurring electron
dense compounds are concentrated and, therefore, interfere with the
quantitative results. The data (Figure 4) during the second half
of 1974 and 1975 were obtained by this technique. Even though
these samples were concentrated, the values are still low compared
with the data obtained in late. 1973 and early 1974. The important
consideration is that the introduction of a refractory material
into the environment results in the passage of that component
through various components of the ecosystem.
TABLE 4. POLYCHLORINATED BIPHENYL
RESIDUES IN ALL ANIMAL SAMPLES
(1/1/73 - 6/30/74)
Location
%Positive
Average & Range (ppm)
B-OM
P-OM
P-20
P-30
S-10
Lake A
Lake B
Marsh (M)
17
61
58
53
39
75
100
81
Tr
121.8 (1.3-250)
7.0 7.0
3.1 (1.1-M.6)
1.3 (1.0-1.7)
20.7 (1.7-62.0)
U2.5 (36-49.1)
110.9 (32-300)
The source of the PCBs in this ecosystem remains obscure, but
it is of interest that the major amount of cut and fill operations
was underway when the peak in concentration was observed. There
was also a great amount of utility installation occurring at this
time. With the heavy usage of PCBs in capacitors for electric
motors, florescent lighting, etc., it is possible that an aban-
doned disposal area was encountered during the cut and fill
operations. PCBs have also been incorporated in road oils and if
such were used to control dust problems, these would contribute
to the :peak in concentration in early 1974. No observations con-
firming these assumptions were made.
CHLORINATED HYDROCARBON PESTICIDES
During the first year of this investigation, trace levels, of
DDE were found in samples of crayfish and mosquitofish from
stations P-04 and P-30 on Panther Branch. Mosquitofish collected
from Lake A and the freshwater marsh (M) also contained trace
17
-------
amounts of DDE. The station oil Spring Creek (S-10) , which re-
ceives the combined runoff from Panther Branch and Lakes A & B,
yielded crayfish which contained DDE residues. With the ex-
ception of the samplings at S-10 and the freshwater marsh, all
stations yielded trace amounts; as early as October 1973. Con-
firmation of the DDE in these samples was effected by utiliza-
tion of two-column analysis, binary solvent extraction, and co-
chromatography with authentic DDE standards.
The cyclodiene pesticide,|dieldrin, which is the epoxide of
aldrin, was recovered in fish and crustacean samples from
stations on Panther Branch. Samples of bluegill from P-04 con-
tained trace amounts of dieldrin, whereas samples of crayfish
and bluegills collected at P-30 contained from trace amounts to
2.1 ppb of that compund. The mosquitofish (Gambusia sp.) was
the only organism from Lake A which contained dieldrin. Values
from trace amounts to 11.3 ppb[were recorded in samples of this
fish.
i
Following completion of The Woodlands Golf Course, the
ephemeral water on the course,jponds, and adjacent ditches were
examined for chlorinated hydrocarbon pesticides. During the
spring of 1975, mirex, a chlorinated camphene, was first oby
served in the water, soil, and!mosquitofish samples. The re-
sults of the study of this portion of The Woodlands watershed
are presented in Figure 5, where the grand means of all samples
from the golf course are plotted against the time of year.
Highest amounts of mirex appeared during the months of July,
August, and September. Water samples contained the smallest
amount, followed by soil samples which contained about two
times as much mirex as the covering water. Of particular
interest is that the residue levels found in the mosquitofish
reached an average level of twice that in the soil samples
(Figure 5) .
Mirex at the time of thisi investigation was used locally in
the Gulf Coast States for the control of the fire ant (Solenopsis),
a troublesome species accidently introduced into the United
States from Argentina. It is Commonly applied on wheat brand
or similair food stuff which the ant consumes. Spring and
summer were the common periodsj of treatment for this pest. It
is suggested from the data presented in Figure 5 that this com-
pound can undergo biological amplification in a rather restricted
environment such as a golf course. At this writing it is, how-
ever, impossible to state how the mosquitofish obtained the com-
pound, i.e., via the food web or by direct absorption from the
water. The latter route has been illucidated by several in-
vestigators (25,30,31). In particular, Murphy (31) stresses
the point that gill absorption! is important in small fish where
the ratio of gill surface to body weight is large. Certainly,
mosquitofish would fall into this category.
18
-------
60
50
CO
CL
2:30
X
LJ
10
O
ASONOJ F M A M J J ASONO
1974 1975
Figure 5. Temporal distribution of mirex in
The Woodlands Golf Course.
•-« mosquitofish (Gambusia sp.);
B-O soil; o-o water.
19
-------
During the drier months of 1975, water from Lakes A & B was
used as irrigation water for -the golf course. During such a
practice, there existed the possibility that return runoff from
irrigation and/or runoff from istorm events would transport mirex
residues into those lakes. W^ter, soil, and mosquitofish samples
were analyzed from the lakes and the results are presented in
Figure 6. The amount of mirex in the water and fish disappeared
rapidly during the late summer and early fall. The residues in
the soil, however, diminished imore slowly. The concentration in
all three components of this ecosystem was at least an order of
magnitude lower than that observed in the golf course system.
The greater volume of water and dilution from surface waters
could contribute to this level of pesticide.
i
Another halogenated hydrocarbon pesticide was also observed
on the golf course during this investigation. During August of
1974, chlordane residues were :detected in samplings of water,
soil, and aquatic organisms from golf course ponds and adjacent
ditches (Figure 7). Of particular interest are the residues de-
tected in crayfish from the ponds and ditches adjacent to the
golf course. The highest amount of chlordane was observed in
the organisms from the ponds with a lesser amount in the same
organisms from the ditches. These findings appear to correlate
with the amount of chlordane observed in the water samples
(Figure 6). These findings suggest that the initial application
may have occurred on the golf >course and runoff water contri-
buted to the residues in the ditches. During the latter part of
1975, mosquitofish and soil samples were obtained from the pond.
No crayfish were present at this time. The levels of chlordane,
although low, were higher thari those observed in the water or
soil samples. Again, it is difficult to state if,this increase
was due to direct adsorption or to accumulation through the food
web (25,30,31).
CARBAMATE PESTICIDES
Utilizing the methodology developed by Wong and Fisher (28)
and Butler and McDonough (29) ,, an attempt was made to examine the
runoff of a carbamate pesticide and its metabolites from an urban
yard. Although the resemblance of a first order decay curve was
observed, it was unfortunate that the first interpretation of the
data was in error. Extracts of runoff waters were examined
without derivatization with trifloroacetic anhydride and com-
parable results were obtained [as with derivatized samples. Dur-
ing concurrent studies in a ricefield-marshland ecosystem, the
same observations were made. [Numerous naturally occurring com-
pounds will effect peaks in GLC determinations, especially where
electron capture is employed as the detection system. Sulfur-
containing compounds are the most notorious in creating such
artifacts. Samples can often[be "cleaned up" by batch process or
columns of bright copper or by exposing the extracted sample to
mercury. The problems encountered in the determination of sevin,
20
-------
40
30
DO
0.
CL
X
LU
a: 20
10
0
--.ft-0—00
ASONDJFMAMJJASOND
1974 1975
Figure 6. Temporal distribution of mirex in the
Conference Center Lakes (A & B).
O-O soils; •-• mosguitofish (Gambusia sp.);
o-o water.
21
-------
ASONDJ FjMAMJJASOND
1974 1975
F
Figure 7. Temporal distribution of chlordane in The
Woodlands Golf Course.
A-A crayfish (Cambarus sp.) from pond;
A-A crayfish (Cambarus sp.) from ditch?
o-o pond water; •-• ditch water; mosquito-
fish (Gambusia sp.) from pond; O-P soil
from pond.
22
-------
captan, and carbofuran are not, however, due to sulfur or sulfur
compounds as treatment with copper did not reduce the peaks in
the underivatized samples. With these observations, we have
routinely incorporated injection of underivatized samples to
preclude such future errors in analysis.
We have also observed great difficulty in determining car-
bamate pesticides in both standing (ricefield) or stormwaters,
especially where the waters are of alkaline pH and/or high in-
organic material. Further encumberances on detection are
observed during periods of elevated temperature and/or intense
solar radiation.
23
-------
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r
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25. Butler, P. A. 1966. Pesticides in the Marine Environment.
J. Appl. Ecol. 3, Suppl 1:253-259.
26. Ketchum, B. H. 1972. ThejWaters Edge: Critical Problems of
the Coastal Zone. The MJI.T. Press, Cambridge, Massachu-
setts, i
27. Bonelli, E. J., and K. Pi Dimick. 1964. Gas Chromatography
and Electron Capture Analysis of Pesticides. In: Lectures
on Gas Chromatography (Mattick and Szymanski, eds.), Plenum
Press, New York.
28. Wong, L., and F. M. Fisher. 1975. Determination of Carbo-
furan and Its Toxic Metabolites in Animal Tissue by Gas
Chromatography of Their N-Trifluoroacetyl Derivatives.
Agri. and Food Chem. 23:315-318.
29. Butler, L. I., and L. M.tMcDonough. 1971. Determination of
Residues of Carbofuran and Its Toxic Metabolites by Electron
Capture Gas Chromatography after Derivative Formation. J.
of AOAC 54:1351-1360. |
30. Chadwick, G. G., and R. W. Brocksen. 1969. Accumulation of
Dieldrin by Fish and Selected Fish-food Organisms. J. Wild-
life Mgmt. 33:693-700. :
31. Murphy, P. G. 1971. The Effect of Size on the Uptake of DDT
From Water by Fish. Bull. Environ. Contam. Toxicol.
6:38-45. !
26
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APPENDIX A
EXPERIMENTAL PROCEDURES
GENERAL PROCEDURES
Sample Collection and Transportations -
Sites for sampling water, sediments, and organisms were
selected at appropriate locations along the major waterway in
The Woodlands and Spring Creek, the receiving body for surface
drainage from this development.
Water samples and corresponding sediment samples, as well as
aquatic organisms and plants, were collected on a monthly sche-
dule or more often during or following periods of rainfall and
subsequent runoff. Biotic samples were not available during the
colder winter months. Water samples were obtained by the grab
method and transported in clean 3.8 1 brown glass bottles with
Teflon-lined caps. Sediment samples (top 7-8 cm) were collected
with an aluminum scoop and wrapped in aluminum foil before en-
closing in plastic bags. Animal samples were obtained with
traps, seines, and nets. Biotic samples were first wrapped in
aluminum foil and the foil package placed in a plastic bag. All
samples, biotic and abiotic, were transported to the research
laboratory in insulated chests at 0°C. Sufficient smaller
organisms were collected to yield a sample of 30-120 grams. Upon
receipt in the laboratory all biotic samples were stored at -20°C
as were the sediment samples. Water samples were extracted 24
hours after arriving in the Houston laboratory. The resultant
extracts were stored at -20°C until time for clean-up and
analysis by gas-liquid chromatography (GLC).
Sample Preperation and Analytical Procedures
Samples were prepared, extracted, and processed through the
preliminary "clean-up" and the GLC Analysis by the procedures
outlined below.
General Comments
Glassware should be washed thoroughly in Alconox detergent
or an equivalent cleaning agent and should be rinsed with tap
water and glass distilled water to removed all soap residue.
27
-------
The glassware should be rinsed| with pesticide grade acetone prior
to use.
Separatory funnels should| be fitted with Teflon stopcocks
and Teflon or plastic caps. With the exception of the chroma-
tographic tubes used in the clean-up procedure, all other glass-
ware should utilize ground-glass joints.
Solvents should be of thel highest purity available to avoid
the interference of electron ctapturing impurities. Mallinckrodt
"Nanograde," Fisher "Pesticide; Grade," or the equivalent purity
of other manufactures should b;e used. Each new lot of solvents
should be examined by gas-liquid chromatography prior to utiliza-
tion in the analytical laboratory.
i
DETERMINATION OF ORGANOCHLORINE COMPOUNDS
General Comments
This procedure is essentially that of Ginn and Fisher (13).
Procedure for Animal Materials;
r
1. A 30 gram or larger s|ample of animal material is admixed
with Na2S04 at a ratio of 1:3 in a blender jar.
2. The sample ground thoroughly to a homogenous mixture.
3. With sample in jar and cutting assembly still affixed,
the jar is placed in a freezer at -20°C for 15 to 30 minutes.
i
4. The sample is reground and refrozen as necessary to
effect a freely flowing, homogenous Na2SO4~tissue powder.
5. If sample is to be stbred for future extraction, wrap
the powder carefully in aluminum foil and affix accession number
before storage in a freezer at -20°C.
6. A plug of glass wool tis used in the Soxhlet to support
the tissue mixture in lieu of paper thimbles.
7. For extraction, a weighed quantity of the tissue-Na2S04
mixture is refluxed for 4 hours with 250 ml petroleum ether at a
temperature sufficient to produce cycling of the solvent every 5
to 10 minutes in the Soxhlet apparatus.
8. Following the 4-hour extraction the volume of the
extract is reduced to approximately 15 ml over steam using a
Snyder three-ball condenser to; prevent evaporative loss.
28
-------
9. The reduced extract is quantitatively transferred to a
separatory funnel and the volume" adjusted to 50 ml with petroleum
ether for partitioning over acetonitrile.
10. The extract is partitioned over a 50 ml volume of
acetonitrile for one minute with vigorous agitation and frequent
venting of the separatory funnel.
11. The acetonitrile is collected in an evaporating dish and
step 10 repeated.^
12. The combined acetonitrile extracts are reduced to near
dryness on a slide warming tray at 40°C. Prolonged drying and
excessive heating are to be avoided because of losses due to
volatilization.
13. The resultant residue is taken up in petroleum ether and
added to a 10-gram column of Florisil (Floridin Co., Berley
Springs, W. Va.) contained in a 400 x 20 mm glass chromatography
column.
14. The column is eluted with 150 ml of a 6% solution of
anhydrous ether in petroleum ether. The eluate being collected
in a flask with ground glass neck.
15. The column is next eluted with 150 ml of a 15% solution
of ethyl ether in petroleum ether. This eluate being collected
in glassware as in step 14.
16. The 6% eluate from step 14 is reduced to approximately
15 ml by evaporation over steam with a Snyder three-ball con-
denser affixed to the flask.
17. The reduced 6% eluate is quantitatively transferred to
a glass-stoppered graduate cylinder and the volume adjusted to
25 ml with petroleum ether. This fraction is suitable for GLC
analysis without further manipulation.
18. The 15% eluate is reduced to approximately 20 ml over
steam and quantitatively transferred to a 400 x 20 mm chromoto-
graphic tube charged with 10 g of a 1:1 (w/w) mixture of
magnesium oxide and "Celite" (Johns Manville Co.).
19. The column is eluted with 100 ml petroleum ether under
a vacuum sufficient to effect a flow of about 35 ml per minute.
20. The eluate is reduced over steam quantitatively trans-
ferred to a glass-stoppered graduate cylinder and the volume
adjusted to a known volume with petroleum ether prior to
analysis by GLC.
29
-------
Procedure for Plant Materials |
1. Plant materials to be extracted are reduced in size by
the use of a food chopper, food cutter, or knife.
2. The reduced material is placed in a Mason jar affixed
with a cutting assembly and ground with 1 ml acetronitrile/gram/
plant material and ground at high speed for 5 minutes.
3. The homogenate is allowed to settle in the grinding jar
and the supernatant acetonitrile decanted into a crystallizing
dish.
4. Fresh acetonitrile (skme ratio) is added and the
material reground for 5 minutes at high speed.
5. The combined extractsiare evaporated to dryness on a
slide warming tray at 40°C.
6. The soil isfc discarded! and the extract evaporated to dry-
ness on a slide warmer at 40°C|.
7. The residue is resuspended in petroleum ether and sub-
jected to preparative -chromatotfraphy in Florisil as above
(step 13).
Procedure for Water and Soil ,
1. A 2000 ml or larger water sample or 100 gram or larger
sample of soil is extracted in^ separatory funnels by agitation
for 5 minutes with 100-150 ml pf hexane. Occasionally two
original field samples are extracted and the extracts combined
(step 4).
2. The phases are allowed to separate and the solvent
collected in an Erlenmeyer flask over anhydrous ^2804.
3. The sample is extracted a second and third time with
equivalent volumes of solvent. |
4. The combined extracts are dehydrated with anhydrous
Na2SO/i and the supernatant poured into clean flask ground glass
neck flask.
5. The Na2S04 is washed with petroleum ether and added to
the extracts. '
6. The volume of the extract is reduced to approximately
15 ml over steam with a Snyderi three-ball condenser affixed to
the flask. i
30
-------
7. The extract is adjusted to a known volume in a glass-
stoppered graduate cylinder and subjected to GLC analysis or
8. The extract is subjected to preparative chromatography
as above.
NOTE: Numerous stormwater and wastewater samples, especi-
ally urban, industrial, or.developing areas, have
many substances which interfere with GLC analysis
utilizing the electron capture method of detection.
Treatment of extracts from step 7 above with bright
copper or mercury often removes the interfering
substances. Passage of 1 ml of the extract over a
2 cm bed of bright copper in a 20 x 1 cm chromato-
graphic column is the most efficient clean-up
procedure.
Analytical Instrumentation
1. Residue analysis is by gas-liquid chromatography on a
Varian Aerograph Model 2100 dual channel chromatograph equipped
with tritium electron detection detectors.
2. Read out is on a Varian Aerograph Model 20 dual Ren
recorder.
3. On-column injection into an all-glass system is incor-
porated to prevent decomposition of certain organochlorine com-
pounds (27) .
4. Columns are 180 cm capillary U-tubes with 2 mm internal
deameter.
5. Packing material consists of 80/100 mesh Gas Chrom Q
(Applied Sci. Lab.) solid phase with silicone oil liquid phases.
6. Liquid phases are 3% DC-200, 5% QP-1, a 2:1 mixture of
5% QF-1 and 5% DC-200 as well as a 3:1 mixture of 3% DC-200 and
10% OV-17.
7. Nitrogen is used as the carrier gas at 65 psi and rate
of flow of 40 ml/m.
8. The column temperature is 190°C.
9. The injection is at 215°C to insure rapid and complete
volatilization.
10. Sufficient sensitivity is achieved without exceeding
the thermal limit for Tritium dectectors (225QC by operating the
detector at 215°C) .
31
-------
11. Maintaining detector temperature above that of the
columns prevents condensation of sample in the detectors and
negates loss of sensitivity and frequent cleaning of the
detector foils.
12. The detectors operate; on a 90 volt DC mode.
13. Though this range of electron capture detectors is
limited, linearity is obtained in the range of pesticide con-
centration assayed (10"11 to 10~9).
i
14. Data are quantitated by comparison of printout of
sample peak height and/or areal with comparable standard mixture
pesticides.
15. Standards are injected following every third experi-
mental sample.
16. Confirmation of analysis is achieved by use of two
liquid phases of differing polarity such as DC-200 and QF-1.
17. Additional confirmation is gained by the use of binary
solvent systems which rely on the solubility ratios of pesti-
cides in immiscible solvents.
DETERMINATION OF CARBAMATE PESTICIDES
General Comments
This procedure is a modification of the procedure presented
by Wong and Fisher (28). J
Procedure for Animal Materials
1. Place 30 grams of animal material in a quart blending
jar, add 200 ml anhydrous methanol, and fit the jar with a cut-
ting assembly. Blend the sample completely.
i
2. Filter the methanolicj extract through a large funnel
containing anhydrous sodium sulfate and collect the cleared ex-
tract in a 850 ml beaker. Rinse the insoluble material on the
sodium sulfate filter with 300! ml methanol. Combine the rinse '
with the initial methanol extract.
3. Place the beaker under a light stream of air on. a steam
table and evaporate the methanol extract to near dryness.
4. Redissolve the residup in 500 ml 0.25 N HC1 and transfer
the aqueous mixture to a 1000 ml round bottom boiling flask. Add
several boiling chips to the flask, connect an Allihn condenser,
and set the flask in an electric heating mantle. Reflux the
mixture for 1 hour.
32
-------
5. Disconnect the Allihn condenser and chill the flask in
an ice bath. Transfer the sample to a 1000 ml separatory
funnel. Rinse the round bottom flask with 50 ml glass distilled
water and transfer the rinse to the separatory funnel.
6. Add 100 ml methylene chloride and extract the aqueous
phase by shaking the separatory funnel vigorously for 1 minute.
Allow the phases to separate, then drain the methylene chloride
phase (lower phase) into a 500 ml evaporating flask through a
funnel containing anhydrous sodium sulfate. Repeat the extrac-
tion of the aqueous phase with two 100 ml volumes of methylene
chloride. Combine the extractions and rinse the sodium sulfate
funnel with 50 ml methylene chloride.
7. Add boiling sand to the flask, connect a Snyder column,
and evaporate the solvent to approximately 50 ml on a steam
table.
8. First Activated Florisil Column Clean-up: Prepare a
400 x 20 mm chromatographic tube with 12.5 cm of activated
Florisil topped with 2.5 cm anhydrous sodium sulfate. (The
Florisil is activated by heating at 135°C for a minimum of 24
hours.) Attach the column to a vacuum flask and add the con-
centrated methylene chloride extract in 1 to 2 ml aliquots, at
intervals, to permit the complete evaporation of solvent and the
collection of residue on the top 2.5 to 5 cm of the Florisil
column. Rinse the flask with three 5 ml volumes of methylene
chloride and add each rinse to the column in small aliquots as
described above.
9. Disconnect the column from the vacuum flask and elute
the column with 300 ml 35% ethyl acetate in hexane (v/v).
Collect the eluate in a '500 ml flask. Add boiling sand to the
flask, fit the flask with a Snyder column, and evaporate the
solvent to approximately 5 ml on a steam table. Add 50 ml of
petroleum ether to the flask and reduce the volume to 5 ml on
the steam table.
10. Clean-up by Solvent Partition: Transfer the petroleum
ether sample to a 250 ml separatory funnel, along with two 10 ml
petroleum ether rinses of the flask. Rinse the flask with two
50 ml volumes of a 9:1 mixture of acetonitrile-water and trans-
fer both rinses to the separatory funnel. Vigorously shake the
separatory funnel for 2 minutes to partition the carbamate
residues into the acetonitrile-water phase.
11. Allow the phases to separate, then drain the lower phase
(acetonitrile-water) into a second 250 ml separatory funnel. Ex-
tract the acetonitrile-water sample with two additional 20 ml
volumes of petroleum ether and discard both petroleum ether
fractions.
33
-------
12. Drain the ace'tonitrilei-water phase into a crystallizing
dish, along with two 10 ml acetbnitrile-water rinses of the
separatory funnel. Place the crystallizing dish on a slide
warming tray (45°C) and allow the complete evaporation of the
solvent.
i
13. Second Activated Florisil Clean-up: Prepare a 400 x 20
cm chromatographic tube with 12>5 cm of activated Florisil and
top the activated.Florisil column with 1.25 cm of anhydrous
sodium sulfate. Prewet the column with approximately 50 ml of
hexane. ' i
14. Redissolve the acetoni'trile-water residue in 1 ml ethyl
acetate or less, and dilute with 5 ml hexane. Transfer the sam-
ple to the column along with three 10 ml 6% ethyl acetate in
hexane rinses of the crystallizing dish. Elute with 300 ml 6%
EA, acetonitrile and hexane and discard.
15. Elute the column with |300 ml of hexane containing 1%
acetonitrile and 15% ethyl acetate (v/v) and collect the eluate
in a 500 ml evaporating flask. > This solvent mixture elutes
carbofuran and 3-k.etocarbofurari from the column.
i
16. Elute the column with 300 ml of 35% ethyl acetate in
hexane to recover 3-hydroxycarbofuran. Collect the eluate in a
second 500 ml evaporating flask;.
i
17. Add boiling sand to ea|ch flask and attach a Snyder
column. Place the flask on a steam table and evaporate the
solvent to approximately 50 ml.: Transfer the sample to a
crystallizing dish, along with |two 10 ml ethylacetate-hexane
rinses of the flask and evaporate the samples to dryness on a
slide warming tray (45°C).
18. Remove the crystallizing dishes from the slide warming
tray when the last of the solvent has evaporated, then redis-
solve the residue in 2.0 ml (or other known volume) ethyl
acetate. Transfer the ethyl acetate sample to 2-dram vials
sealed with Teflon-lined caps. '
i
19. Prepare the N-trifluoroacetyl derivatives of carbo-
furan, 3-hydroxycarbofuran, and 3-ketocarbofuran according to
the procedure described in the 'section on water analysis. The
gas-liquid chromatography of the derivatives is also as
described.
Procedure for Water :
1. Transfer 1500 ml of water (acidified 'to 0.25 N HC1) to
a 200 ml round bottom flask and add several boiling .chips. Con-
nect an Allihn condenser to the flask and set the flask in an
electric heating mantle. Reflux the water for 1 hour.
!34
-------
2. Disconnect the Allihn condenser and chill the flask in
an ice bath. Transfer the water to a 2000 ml separatory funnel
(Teflon stopcock and Teflon or plastic stopper). Rinse the round
bottom flask with 50 ml glass distilled water and transfer the
rinse to the separatory funnel.
3. Add 100 ml of methylene chloride to the separatory fun-
nel and extract the aqueous phase by shaking the separatory fun-
nel vigorously for 1 minute. Allow the two phases to separate
and drain the methylene chloride phase (lower phase) into a
500 ml evaporating flask, through a funnel containing anhydrous
sodium sulfate. Extract the aqueous phase with two additional
100 ml of methylene chloride. Rinse the funnel.-of sodium sulfate
with 50 ml methylene chloride.
4. Add boiling sand to the flask and attach a Snyder
column. Place the flask on a steam table and evaporate the
methylene chloride to approximately 5 ml. Add 50 ml of petro-
leum ,ether to the flask through the column and evaporate the
solvent mixture to approximately 5 ml on the steam table.
5. Prepare a 400 x 20 mm chromatographic tube (Kontes) with
12.5 cm of activated Florisil and top the Florisil bed with 2.5
cm of anhydrous sodium sulfate. (Activate the Florisil by heat-
ing at 135°C for a minimum of 24 hours.) Prewet the column by
adding 50 ml (petroleum ether) hexane. ',- ,
6. Transfer the petroleum ether-water extract to the column
along with two 10 ml hexane:acetonitrile:ethyl acetate (84:1:15)
rinses of the flask. Elute the column with 300 nil, of the, same
hexane:acetonitrile:ethyl acetate mixture and collect the eluate
in a 500 ml evaporating flask. This solvent mixture elutes car-
bofuran and 3-ketocarbofuran selectively from the ^column*
7. Elute the column with 300 ml 35% ethyl acetate in hexane
and collect the eluate in a second 500 ml evaporating flask.
This solvent mixture elutes 3-hydroxycarbofuran.
8. Add boiling sand to each flask and attach a Snyder
column. Evaporate the solvent mixtures to approximately 50 ml
on a steam table. Rinse the Synder column with several ml of
hexane, then disconnect. Transfer the concentrated eluates to
crystallizing dishes and place the crystallizing 'dishes on a
slide warming tray (45°C) to evaporate the remaining solvent.
9. Remove the crystallizing dishes from the slide warming
tray when the last of the solvent has evaporated. Allow the
crystallizing dishes to cool to room temperature,
-------
10. Carbofuran, 3-hydroxycarbofuran, and 3-ketocarbofuran
are prepared for gas-liquid chromatography as N-trifluoroacetyl
derivatives according to the following procedure:
a. Transfer 0.2 ml of the ethyl acetate sample to a
second 2-dram vial.
i
b. Carefully pipet OJ1 ml of trifluoroacetic anhydride
(Aldrich Chemical |Co.) to the vial and seal the
vial tightly with |a Teflon-lined cap.
c. Wrap the vial in aluminum foil to protect from
light and place the vial on a slide warming tray
(45°C) for a minimum of 16 hours for the complete
derivatization.
d. At the completion of the reaction, remove the vial
from the slide warming tray and allow the vial and
its contents to come to room temperature. Open
the vial and add 2 ml hexane and 4 ml of glass
distilled water. Reseal the vial and shake the
vial vigorously to destroy the unreacted tri-
fluoroacetic anhydride. Allow the phases to
separate, then with a Pasteur pipet remove the
aqueous phase (lower phase) and discard this phase.
Wash the hexane please with two additional 4 ml
volumes of glass distilled water.
e. Transfer the hexane phase to a 25 ml graduated
cylinder through a small funnel containing anhy-
drous sodium sulfate. Rinse the vial with three
2 ml volumes of hexane and transfer each rinse to
the graduated cylinder. Rinse the sodium sulfate
with 5 ml hexane.'
f. Record the final volume of the hexane sample and
gas-liquid chromatograph at 5 yl aliquot.
11. Prepare fresh derivatized standards of carbofuran,
3-hydroxycarbofuran, and 3-ketocarbofuran for each group of
samples analyzed. Convenient stock standard solutions are 100
yg/ml carbofuran, 10 lag/ml 3-ketocarbofuran, and 5 yg/ml 3-
hydroxycarbofuran, in ethyl acetate. Derivatize 0.2 ml of each
stock standard as described above with 0.1 ml trifluoroacetic
anhydride in a 2-dram vial sealed with a Teflon-lined cap.
12. Gas-liquid Chromatography: A Varian Aerograph Model
2100 is equipped with two 6-ft!glass columns (2 mm i.d.) and
tritium foil electron capture detectors. Column one is packed
with 3% DC-200 on Gas Chrom Q,:30/100 mesh. The columns are
maintained at 175°C, injected port at 220°C, and detectors at
36
-------
215°Ci Gas flow (Zero grade N2) is 60 ml/min and the recorder
is a dual pen Varian Model 20.
13. Identify carbofuran and its carbamate metabolites by
comparison of peak retention times on the two columns.
14. Calculate residue concentration on the basis of peak
height and/or area.
DETERMINATION OF CARBAMATE PHENOLS
General Comments
This procedure is a modification of a procedure presented by
Wong and Fisher (28). The procedure for the trichloroacetylation
of the phenols is basically that of Butler and McDonough (29).
Procedure for Water
1. Transfer 1500 ml of water (acidified to 0.25 N HC1) to a
2000 ml round bottom flask and add several boiling chips. Con-
nect an Allihn condenser to the flask and set the flask in an
electric heating mantle. Reflux the water for 1 hour.
2. Disconnect the Allihn condenser and chill the flask in
an ice bath. Transfer the water: to a 2000 ml separatory funnel
along with a 50 ml glass distilled water rinse of the round
bottom flask.
3. Add 100 ml of methylene chloride to the separatory fun-
nel and extract the aqueous phase by shaking the separatory fun-
nel vigorously for 1 minute. Allow the two phases to separate
and drain the methylene chloride (lower phase) into a 500 ml
evaporating flask, through a funnel containing anhydrous sodium
sulfate. Extract the aqueous phase with two additional 100 ml
methylene chloride. Rinse the funnel of sodium sulfate with
50 ml methylene chloride.
4. Add boiling sand to the flask and attach a Synder
column. Place the flask on a steam table and evaporate the
methylene chloride to approximately 5 ml. Add 50 ml of petro-
leum ether through the column to the flask and evaporate the
solvent mixture to approximately 5 ml on the steam table.
5. Prepare a400x20mm chromatographic tube (Kontes) with
12.5 cm of activated Florisil and top the Florisil bed with 2.5
cm of;anhydrous sodium sulfate. (Activate the Florisil by heat-
ing at 135°C for a minimum of 24 hours.) Prewet the column by
adding 50 ml (petroleum ether) hexane.
6. Transfer the petroleum ether-water extract to the column
along with two 10 ml 35% ethylacetate in hexane rinses of the
37
-------
flask. Elute the column with ^00 ml of the same solvent mixture
and collect the eluate in a 500 ml evaporating flask.
7. Add boiling sand to the flask and attach a Synder
column. Evaporate the solvent! mixture to approximately 50 ml
on a steam table. Rinse the Synder column with several ml of
hexane, then disconnect. Transfer the sample to a crystallizing
dish on a slide warming tray ({45°C) to evaporate the remaining
solvent. ,
I-
8. Remove the crystallizing dish from the slide warming
tray when the last of the solvent has evaporated. Allow the
crystallizing dish to cool to room temperature then redissolve
the residue in 2.0 ml (or other known volume) ethyl acetate.
Transfer the ethyl acetate sample to a 2-dram vial with a Teflon-
lined cap.
9. Carbofuran phenol, 3-hydroxycarbofuran phenol, and 3-
ketocarbofuran phenol are prepared for gas-liquid chromatography
as N-trichloroacetyl derivatives according to the following pro-
cedure:
a. Transfer 0.2 ml oif the ethyl acetate sample to a
second 2-g-ram vial and under a light stream of N£
evaporate the ethyl acetate solvent.
i
b. Add 1 ml pyridine solution (0.1 ml Florisil eluted
pyridine in 99.9 ml methylene chloride, stored in a
dark bottle) and heat vial on a steam table (90-
100°C) until the methylene chloride is evaporated.
c. Cool the vial to aroom temperature, then add 1 ml
trichloroacetyl chloride solution (0.1 ml tri-
chloroacetyle chloride in 9.9 ml methylene chloride).
Heat the vial on a steam table (90-100°C) until the
methylene chloride is evaporated (3 to 5 minutes).
d. Remove the vial from the steam table and add 2 ml
hexane and 4 ml saturated sodium bicarbonate solu-
tion. Seal the vial with a Teflon-lined cap and
shake vigorously 'to destroy the unreacted tri-
chloroacetyl chloride.
e. Allow the phases |to separate. With a Pasteur pipet
withdraw the aqueous phase (lower phase) and discard.
Wash the hexane phase by extracting twice with 4 ml
volumes of glass distilled water. Discard each wash.
f. Transfer the hexane phase to a 25 ml graduated
cylinder through :a small anhydrous sodium sulfate
funnel. Rinse the vial with two ml volumes of
i
38
-------
hexane.
hexane.
Rinse the sodium sulfate funnel with 5 ml
g. Record the volume of the hexane sample and gas-liquid
chromatograph a 5 yl aliquot.
Quality Control
Routinely blank samples were processed to examine for possi-
ble interfering substances in analytical materials and reagents.
Standard solutions were prepared in appropriate solvents using
analytical grade compounds obtained from the Pesticide Reposi-
tory, Perrine, Florida. Duplicate injections of experimental
samples and standard solutions were routinely examined. Quanti-
tation of data was determined by comparison of printout of sample
extract peak with the peaks from standard solutions. Although
the linear range of electron-capture detectors is limited,
linearity was obtained in the range of concentration examined
(lO-11 to 10~9 g). Peak height and/or area was used to estimate
sample concentration. Samples corresponding to the collected
environmental samples were routinely spiked with relevant com-
pounds to examine recovery efficiency. Chlorinated hydrocarbon
compound recovery was always above 95%.
39
-------
APPENDIX :B - TABLES
Number
Paqe
10
11
12
13
Survey of Polychlorinated Biphenyls in Upper Bear
Branch at B-04 (9/1/73 jto 6/13/74) 42
Survey of Polychlorinated Biphenyls in Upper Panther
Branch at P-04 (9/1/73 ;to 6/30/74) . . 43
Survey of Polychlorinated Biphenyls at Site P-20 on
Panther Branch (9/1/73 ;to 6/30/74) 44
Survey of Polychlorinated Biphenyls at Site P-30 on
Panther Branch (9/1/73 ;to 6/30/74) 45
Survey of Polychlorinated Biphenyls at Site S-10 on
Spring Creek at 1-45 (9/1/73 to 6/30/74) 46
i
Survey of Polychlorinated Biphenyls in Lake A
(9/1/73 to 6/30/74) . .j „ „ . . 47
I
Survey of Polychlorinated Biphenyls in Lake B
(9/1/73 to 6/30/74) . .[ • . . 48
i .
Survey of Polychlorinated Biphenyls in the Conference
Center Marsh (CCM) (9/1/73 to 6/30/74)........ 49
Resume of Distribution of Polychlorinated Biphenyl
Residues in Samples from The Woodlands (9/1/73 to
6/30/74) | 50
Polychlorinated Biphenyl !Distribution in Animals
(9/1/73 to 9/30/74) . .j 51
Species Distribution of Polychlorinated Biphenyls
(9/1/73 to 6/30/74) . .| . . 53
Distribution of Trace Amqunts of DDE in Animals
(9/1/73 to 6/30/74) . .; . . 55
Distribution of Dieldrin in Animals (9/1/73 to
6/30/74) ; 56
40
-------
14
15
16
17
18
19
Temporal Distribution of Polychlorinated Biphenyls
in the Panther Branch Aquatic Ecosystem Soil/Water
(PPB) 7/1/74 to 5/31/75 ,
21
22
23
24
25
Temporal Distribution of Polychlorinated Biphenyls in
the Panther Branch Aquatic Ecosystem Cambarus Sp.
(Crayfish) (PPB) 7/1/74 to 5/31/75 .
Temporal Distribution of Polychlorinated Biphenyls in
the Panther Branch Aquatic Ecosystem Gambusia Sp.
(Mosquitofish) (PPB) 7/1/74 to 5/31/75
Temporal Distribution of Mirex in the Panther Branch
Aquatic Ecosystem Water (PPB) 7/1/74 to 5/31/75 . .
Temporal Distribution of Chlordane in the Panther
Branch Aquatic Ecosystem Water (PPB) 7/1/74 to
5/31/75
Temporal Distribution of Mirex in the Panther Branch
Aquatic Ecosystem Gambusia Sp. (Mosquitofish) (PPB)
7/1/74 to 5/31/75 .
20 Temporal Distribution of Chlordane in the Panther
Branch Aquatic Ecosystem Cambarus Sp. (Crayfish)
(PPB) 7/1/74 to 5/31/75 .
Temporal Distribution of Polychlorinated Biphenyls in
The Woodlands Aquatic Ecosystem Soil/Water (PPB)
6/1/75 to 12/15/75
Temporal Distribution of Polychlorinated Biphenyls in
The Woodlands Aquatic Ecosystem Gambusia Sp.
(Mosquitofish) (PPB) 6/1/75 to 12/15/76
Temporal Distribution of Mirex in The Woodlands
Aquatic Ecosystem Soil/Water (PPB) 6/1/75 to
12/15/76 ,
Temporal Distribution of Chlordane in The Woodlands
Aquatic Ecosystem Soil/Water (PPB) 6/1/75 to
12/15/76 . ,
Temporal Distribution of Mirex/Chlordane in Gambusia
Sp. (Mosquitofish) from The Woodlands Aquatic
Ecosystem (PPB) 6/1/75 to 12/15/76. ........
57
58
59
60
61
62
63
64
65
66
67
68
41
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-------
TABLE 10.POLYCHLORINATED BIPHENYL DISTRIBUTION IN ANIMALS
(9/1/73 to 6/30/74)
Month
S
0
N
D
J :
F
M
A
M
J
Total
(1)
2
5
4
-
-
-
6
2
4
1
24
B-04
(2)
0
1
0
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-
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3
0
0
0
4
(3)
0
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0
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50
0
0
0
17
(1)
10
12
8
2
2
4
10
5
12
3
68
P-04
(2)
1
4
2
2
1
3
10
5
11
3
42
P-20
(3)
10
12
25
100
50
75
100
100
92
100
62
(1)
5
8
12
3
-
2
10
5
' 3
5
45
(2)
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3
0
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9
5
2
3
28
(3)
0
50 .
25
0
-
100
90
100
66
60
62
P-30
(1)
5
6
10
3
2
2
5
8
2
3
37
(2)
0
1
2
1
1
2
4
8
2
3
24
(3)
0
17
20
33
50
100
80
100
100
100
65
(1) Total number analyzed
(2) Total positive, including samples with trace amounts
(3) % positive samples
51
-------
TABLE 10. (Continued)
FOLYCHLORINATED BIFHENYL DISTRIBUTION IN ANIMALS
(9/1/73;to 6/30/74)
S-10
Month
S
0
N
D
J
F
M
A
M
J
Total
U)
5
8
6
5
2
2
10
3
8
8
60
(2)
0
0
1
1
0
1
8
1
4
6
22
(3)
0
0
17
20
0
50
80
33
50
75
37
Lake! A
(1)
6
5
5
2
2
2
1
2
3
-
28
(2)
• 2
2
5
2
2
2
i
?
3
-
21
(3)
33
40
100
100
100
100
100
100
100
-
75
Lake B
Xl) (2)
-
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1 0
- -
1 1
2 2
-
1 1
2 2
-
9 6
(3)
-
0
0
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100
100
-
100
100
-
67
(1)
10
6
13
-
4
2
17
12
22
5
71
CCM
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6
7
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4
2
15
10
18
5
68
(3)
10
100
54
-
100
100
88
83
82
100
"95
i
(1) Total number analyzed
(2) Total positive, including samples with trace amounts
(3) % positive samples
52
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53
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TABLE 11. (Continued) SPECIES DISTRIBUTION OF POLYCHLORINATED BIPHENYLS
(9/1/73 to 6/30/7U)
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TABLE 12. DISTRIBUTION OF TRACE AMOUNTS OF DDE IN ANIMALS
(9/1/73 to 6/30/74)
Month
S
0
N
D
J
F
M
A
M
J
Totals
P-04 Lake A
21
I1 21
I1
I1
21, I2 I1
21
I1 I1
51, I2 91
P-30
I1
21
I1
I2
21, 22
2\12
21
10\.2
S-10 CCM
32
I2 I1
I2 I1
52 21
Mosquitofish (Gambusia sp.)
Crayfish (Cambarus sp.)
55
-------
TABLE 13 DISTRIBUTION OF DIELDRIN IN ANIMALS
(9/1/73 to 6/30/7H)
Month
S
0
N
D
J
F
M
A
M
J
Totals
P-04 |
i
i
f
i
i
i2
[
1
I2
P-30
I3
21
I3 (2.1)
21, 23
Lake A
I1 (11.3)
I1
21
I1 (1.3)
51
Mosquitofish (Gambusia sp.)
*2
Crayfish (Cambarus sp.)
3Bluegill (Leponis sp.)
Uumbers in parentheses indicate dieldrin in ppb. All others are trace
amounts.
56
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-80-113
3. RECIPIENT'S ACCESSION NO,
4. TITLE AND SUBTITLE
MAXIMUM UTILIZATION OF WATER RESOURCES IN A PLANNED
COMMUNITY; Contributions of Refractory Compounds by a
Developing Community
5. REPORf DATE
August 1980 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
P.M. Fisher
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Rice University
P.O. Box 1892
Houston, Texas 77001
10. PROGRAM ELEMENT NO.
35B1C5DU No. B-124. Task 40420
11. CONTRACT/GRANT NO.
802433
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory—Gin.,OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final-9/73-12/76
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES See also EPA-600/2-79-050a ,b ,c,d. ,e ,f and EPA-600/2-80-127
Richard Field (201) 321-6674 - FTS 340-6674
Anthony N. Tafuri (201) 321-6676 - FTS 340-6676
Project Officers:
16. ABSTRACT
Water, soil and biotic components from a natural drainage system in The
Woodlands, a developing community in Texas, were assayed for halogenated compounds.
PCB^s were highest .during year one (about 350 ppb in soil and animal samples) and
diminished to 1/10 of those values during the second and third years of study. The
nlS!« residue values were coincident with the period of development when cut and fil
operations, roadbed construction, and service installation were being effected. Mirex
and chlordane were found in soil, water and organisms from the drainage system around
the golf course. These were also observed compounds in mosquitofish collected from
the same area. Both compounds entered lakes by storm water and/or washed in by re-
turning irrigation water from the golf course. Organisms from a stream which received
storm waters from the lakes contained less insecticide than the golf course sampling.
The data suggest that biotic and abiotic components of the lakes may serve as effective!
sumps for these pesticides.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Urban areas, Runoff, Chlorohydrocarbons,
Chlordane, Fishes, Crayfishes.
Water sampling, Biotic
and abiotic components,
Hydro!ogic data, Pesti-
cides, Stormwater, PCB's,
Mi rex
13B
SUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFTFD
21. NO. OF PAGES
81
2O. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
69
* U.S. GOVERNMENT PRINTING OFFICE: 1980—657-165/0103
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