PB-293 167
Design and Evaluation of a Terrestrial Model Ecosystem for Evaluation of

Substitute Pesticide Chemicals
Illinois Univ  at Urbana-Champaign
Prepared for



Corvallis Environmental Research  Lab, OR






January 1979
                  U.S.  DEPARTMENT OF COMMERCE
               National  Technical Information Service

                                  NTBS

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United State*
Environmental Protection
Agency
Environmental Research
Laboratory
Corvallts OR 97330
EPA 600/3 79 004
January 1979
   and Development
Design and
Evaluation of a
Terrestrial Model
Ecosystem for
Evaluation of
Substitute
Pesticide Chemicals

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                RESEARCH REPORTING SERIES  .

Research reports of the Office of Research and Development U S Environmental
Protection Agency have been grouped into nine series These nine broad cate
gories were established to facilitate further development and application of en-
vironmental technology  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are

      1   Environmental Health  Effects Research
      2   Environmental Protection Technology
      3   Ecological Research
      4   Environmental Monitoring
      5   Socioeconormc Environmental Studies
      6   Scientific and Technical Assessment Reports (STAR)
      7   Interagency Energy Environment Research and Development
      8    Special Reports
      9   Miscellaneous Reports

This report has been assigned to the ECOLOGICAL RESEARCH series This series
describes research on the effects of pollution on humans plant and animal spe
cies  and materials Problems are assessed for their long  and short term influ-
ences Investigations include formation transport and pathway studies to deter-
mine the fate of pollutants and their effects This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic  terrestrial and atmospheric environments
This document is available to the public through the National Technical Informa
tion Service Springfield  Virginia  22161

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                 NOTICE





THIS DQCUM.ENT HAS  BEEN  REPRODUCED



FROM THE BEST COPY  FURNISHED US  BY



THE SPONSORING AGENCY.  ALTHOUGH  IT



IS RECOGNIZED THAT CERTAIN PORTIONS



ARE ILL3GI9LE,. IT IS  BEING  RELEASED



IN THE INTEREST  OF MAKING  AVAILABLE



AS  MUCH INFORMATION AS  POSSIBLE.

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                                  TECHNICAL REPORT DATA
                           (Please read Instructions on the reverse before completing)
1 REPOflT NO.

   EPA-600/3-79-004
3 RECIPIEN.
5 REPORT DATE

   January 1979
                                                                       CESSION
4 TITLE AND SUBTITLE
  Design  and  Evaluation of a Terrestrial Model Ecosystem
  for Evaluation of Substitute Pesticide Chemicals
                                                                           issuing date
                                                          6 PERFORMING ORGANIZATION CODE
7 AUTMOR(S)
  Robert  L.  Metealf, Larry K. Cole, Susanne 6. Wood,
  Douglas J.  Mandel  and Mary L. Mil brath
                                                          8. PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
   Institute for Environmental Studies
 University of Illinois
         and
 Illinois  State Natural History Survey, Urbana,  II. 6180
                                                           10 PROGRAM ELEMENT NO

                                                            1EA7H
                                                           11 CONTRACT/GRANT NO
                                                            R-80-3249
12/SPONSORING AGENCY NAME AND ADDRESS
 Corvallis  Environmental  Research Laboratory
 Office  of  Research and Development
 U.S.  Environmental Protection Agency
 Con/all is,  Oregon 97330
                                                           13 TYPE OF REPORT AND PERIOD COVERED
                                                             final   7-74 - 9-77
                                                           14 SPONSORING AGENCY CODE
                                                             EPA/600/02
15 SUPPLEMENTARY NOTfiS
 Project  Officer:  Jay D. Gil«, Con/all is Environmental  Research Laboratory, 503-757-464?
16 ABSTRACT
 This grant was  established to design a terrestrial model  ecosystem that was simple,
 inexpensive,  and suitable for examining the  total environmental  fate of radiolabeled
 pesticides in a soil  crop model e.g. soil-corn or soil-soybean.   This was accomplished
 with the practical  development of a system in which  corn  or soybeans are grown on 3 kg
 of  typical Illinois soil types contained in  a 19 1 wide-mouth glass carboy fitted with
 airtight lid  and impingers to sample pesticide content in aspirated air, and a bottom
 petcock  to sample leachate water.- The units are housed in an environmental growth
 chamber  under 12 hours simulated daylight, at 26CTC.   Emphasis was placed on tracing the
 fate of  the pesticide chemical and its degradation products in soil, air, water, phyto-
 plankton and  in the major food chain organisms of the model ecosystems, e.g. Zea mays,
 Glycine  max,  Lurabricus terrestris, Limax maximus, Armadillidium vulgare, Estigmene
 acrea, and Microtus pchregastef-in the soil-plant phase;  and Daphnia magna, Culex
 pipi ens  quinquefasciatus, Physa spp., and Gambusia affinis in the leachate water.
 The "*C-labeled pesticides examined included DDT, methoxychlor,  aldrin, dieldrin,
 fonofos, phorate, parathion, methyl parathion, simazine,  trifluralin, 2,4,5-T isooctyl
 ester, hexachlorobenzene, pentachlorophenol, pentachloronitrobenzene, and captan.
 Detailed summaries  of their fate and degradation, based on more than 20,000 analyses,
 are presented.
17
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                             b IDENTIFIERS/OPEN ENDED TERMS
                                                                        c  COS ATI Field/Group
 Microcosm design
 Pesticides
 Toxicology
                                                                           6T
13 DISTRIBUTION STATEMENT


 Release  to  Public


            <• .  '- 7
                                              19 SECURITY CLASS fThis Report)
                                             2O ^'COMITY CLASS This page/
                                                unclassified
                                             T

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                                               EPA-600/3-79-004
                                               January 1979
DESIGN AMD EVALUATION OF A TERRESTRIAL MODEL ECOSYSTEM

                          FOR

      EVALUATION OF SUBSTITUTE PESTICIDE CHEMICALS


   Robert L. Metcalf, Larry K. Cole, Susanne 6. Wood,

        Douglas J. Mandel, and Mary L. Milbrath
          Institute for Environmental Studies
                 University of Illinois

                          and

         Illinois State Natural History Survey
             163 Natural Resources Building
                    Urbana, II. 61801
                FINAL REPORT R-80-3249

                   Project Officer:

                     Jay D. Gile
              Terrestrial Ecology Branch
      Corvallis Environmental Research Laboratory
                Corvallis, Oregon 97330

      CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY
      ,  '  OFFICE OF RESEARCH AND DEVELOPMENT
          U.S. ENVIRONMENTAL PROTECTION AGENCY
                CORVALLIS, OREGON 97330
                              /-*

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                                DISCLAIMER



     This report has been reviewed by the Corvallis Environmental Research


Laboratory, U.S. Environmental Protection Agency,  and approved for publication.


Approval does not signify that the contents necessarily reflect the views

                                                                   i
and policies of the U.S. Environmental Protection Agency, nor does mention


of trade names or commercial products constitute endorsement or recommen-


dation for use.
                                    ii

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                                FOREWORD

     Effective regulatory and enforcement actions by the Environmental

Protection Agency would be virtually impossible without sound scientific

data on pollutants and their impact on environmental stability and human

health.  Responsibility for building this data base has been assigned to

EPA's Office of Research and Development and its 15 major field installa-

tions, one of which is the Corvallis Environmental Research Laboratory

(CERL)1.

     The primary mission of the Corvallis Laboratory is research on the

effects of environmental pollutants on terrestrial, freshwater, and marine

ecosystems; the behavior, effects and control of pollutants in lake

systems; and the development of predictive models on the movement of

pollutants in the biosphere.

    , This report provides a description of a new method for the evaluation

of chemicals in the environment.  In addition the results of tests on

selected pesticide chemicals are reported.
                                                 James C. McCarty
                                                 Acting Director, CERL
                                     iii

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                                ABSTRACT



     This grant was established to design a terrestrial model ecosystem



that was simple, inexpensive, and suitable for examining the total environ-



mental fate of radiolabeled pesticides in a soil crop model, e.g. soil-corn



or soil-soybean.  This was accomplished with the practical development



of a system in which corn or soybeans are grown on 3 kg of typical Illinois



soil types contained in a 19 1. wide-mouth glass carboy fitted with air-



tight lid and impingers to sample pesticide content in aspirated air,



and a bottom petcock to sample leachate water.  The units are housed in an



environmental plant growth chamber under 12 hours simulated daylight, at 26°C.



     Emphasis was placed on tracing the fate of the pesticide chemical and



its degradation products in soil, air, water, phytoplankton and in the major



food chain organisms of the model ecosystems, e.g. Zea mays, Glycine max,



Lumbricus terrestris, Limax maximus, Armadillidium vulgare» Estigmene acrea,



and Microtus ochregaster in the soil-plant phase; and Daphnia magna, Culex



pipiens quinquefasciatus, Physa spp., and Gambusja affinis in the lechate



water.


         14
     The   C-labeled pesticides examined included DDT, methoxychlor, aldrin,



dieldrin, fonofos, phorate, parathion, methyl parathion, simazine, trifluralin,



2,4,5-T isooctyl ester, hexachlorobenzene, pentachlorophenol, pentachloro-



nitrobenzene, and captan.  Detailed summaries of their fate and degradation,



based on more than 20.000 analyses, are presented.



     This report was submitted in fulfillment of EPA Grant No. R-80-3249 by



the University of Illinois under the sponsorship of the U.S. Environmental



Protection Agency.  This report covers a period from July 1974 to September



1977 and work was completed as of July 1978.
                                   iv

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                               CONTENTS
Introduction                                                         1
Abbreviated Materials and Methods                                    3
Results and Discussion                                               7
Conclusions                                                         20
References dited                                                    20
Appendix:  Detailed Fates of Individual Pesticides
  Methoxychlor '                                                    37
  DDT                                                               44
  Fonofos                                                           51
  Dieldrin (vermiculite) ^                                          58
  Aldrin (mean of systems A and B; vermiculite)                     70
  Aldrin (system A; vennicu-ldte)                                    72
  Aldrin (system B; vermiculite)                                    79
  Aldrin (mean of systems A and B; soil)                            86
  Aldrin (system A; soil)   ,   -    .                                 88
  Aldrin (system B; 'soil)                                           95
  Dieldrin (soil)                                                  102
  Pentachloronitrobenzene  •/                                       113
  Pentachlorophenol,,                                               123
  Captan -                           . .. •                          133
  Parathion                '              '                         143
  Methyl Parathion"                                                154
  Hexachlorobenzene (soybean system) ^                            165
  Hexachlorobenzene (corn system) s                                176
  Phorate (Drummer..silty clay  loam-system)                         187
  Phorate (Bloomfield loamy sand system)                           198
  Simazine        . -                                                209
  Trifluralin                                                      220
  2,4,5-T isooctyl ester                                           231
Statistical Comparisons of Aldrin-Treated Systems                  242
Summary Tables and Figures .                                        247
Detailed Materials and Methods                                     270
Cost Analysis of Materials and Methods                             292

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                             ACKNOWLEDGMENT




     Three Project Officers of EPA have been most helpful in carrying




out this project.  We gratefully acknowledge thanks for support by






                          Dr. Alan Lefohn




                          Dr. James W. Gillett




                          Mr. Jay Gile




of the Corvallis Environmental Research Laboratory, U.S. Environmental




Protection Agency.




     In this Contract, Robert L. Metcalf was Principal Investigator and




Larry K.  Cole was Project Coordinator.
                                    vi

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                               INTRODUCTION

      Pesticides  are  used  as  purposeful environmental contaminants and the
 user  generally appears  confident  that  the  benefit/risk ratio is tilted
 decidedly  toward the benefit side.   This is,  however,  not always the case
 and the  unbridled use of  pesticides  has come  more and  more into question
 as one of  the most important deterrents to environmental quality.  Certain
 widely used, persistent organochlorine pesticides have been judged as
 presenting an unacceptable environmental risk and the  use of DDT, aldrin,
 dieldrin,  heptachlor, and chlordane  has been  or  is in  the process of being
 banned by  the Environmental  Protection Agency.   A number of other pesticides
 are under  Rubuttable Presumption  Against Reregistration (RPAR).  Never-
 theless, modern  U.S.  agriculture  is  almost inextricably linked  to the
 widespread use of insecticides, herbicides, fungicides and nematocides.
 During the past  30 years, the U.S. usage of these materials has increased
 from  about 100 million  to 1,300 million Ib. annually and the number of active
 ingredients from less than 100 to more than 1000.

      The exponentially  increasing use  of pesticides in U.S. agriculture
 at a  growth rate of  6.5%  per year (Pesticide  Review 1976) and the rapid
 introduction  of new pesticide products presents a continuing demand for
 evaluation and surveillance  of the effects of pesticides upon environ-
 mental quality.   The ecological effects of many  widely used pesticides
 are not  well understood and  a recent survey (Von Rumker and Horay 1973)
 concluded  that for 20 of  the 35 most widely used pesticides, there was
 inadequate information  about the  nature of the environmental degradation
 products and their effects on environmental quality.   This problem be-
 comes increasingly acute  as  more  suitable  substitute pesticides are sought
 to replace the broad spectrum persistent pesticides that society has
 judged and found unacceptable.

      Our laboratory  at  the University  of Illinois has  pioneered in the
 development of model ecosystem technology  to  evaluate  the environmental
 effects  of radiolabeled pesticides under controlled laboratory  conditions.
 Our terrestrial-aquatic model ecosystem has been used   to evaluate a variety
'of problems arising  from  pesticide development and use (Metcalf 1977) and
 50 pesticides have been screened  under uniform conditions to develop a
 cohesive picture of  their environmental properties (Metcalf and Sanborn 1975).

      The present research project is an effort to develop a comparable
 laboratory model ecosystem to evaluate the suitability of pesticides as
 used  to  protect  row  crops in the  agroecosystem.   We believe that manu-
 facturers,  regulatory agencies, and  research  workers all require reliable
 and economical methods  for predictively screening the  environmental effects
 and fate of candidate pesticidal  compounds in the terrestrial agricultural
 environment.


   ,   Some  of the critical objectives of this  study have been to (1) develop
 a dynamic  living interacting physical  indoor  system In which to study radio-
 labeled  pesticides thoroughly and safely,  (2) compare  the environmental
 behaviors  of various pesticides under  homologous and reproducible agricul-
 tural conditions, (3) obtain reliable  quantitative and qualitative data

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economically and quickly, (4) ascertain the comprehensive environmental
fates of pesticides coherently in soil, air, waters crops, invertebrate
and vertebrate terrestrial animals, and aquatic organisms, (5) work year
round regardless of the outdoor weather, (6) produce indoor results that
are indicative of the outdoor environmental behaviors of the compounds,
(7) determine the effects of different types of soils, (8) test both
preemergent and postemergent pesticide applications, (9) assess the short-
term environmentally toxic effects of normal doses of pesticides, and (10)
predict the chronic behaviors and effects of the compounds investigated.

     Emphasis is placed on the evaluation of the pesticide in regard to
toxicity, degradation, accumulation, and distribution.  It is important
to note that these are interdependent parameters and not independent
processes.  The above parameters are examined in the following components
of the model ecosystem: representative Air, Soil, Plants, Insecta,
Crustacea, Annelida, Mollusca, Mammalia, Surface Waters, Sediments,
Leachates, Phytoplankton, Zooplankton, Aquatic Mollusca, Aquatic Insects,
and Osteichthyes.  The entire model ecosystem is maintained for less than
30 days.  By definition, one cannot directly determine the chronic adverse
biological effects of a given compound in a short period of time.  However,
such a compound's potential chronic hazard can be estimated by comparing
its environmental fate (degradation, distribution, etc.), under homologous
conditions, with the fates of those compounds which have been studied
intensely for long periods of tiae =  Compounds which have similar fates
and similar acute toxicities will likely have similar chronic toxicities.
To further complete the estimate of the chronic toxicity of the given
compound, the acute toxicities of all of its degradation products should
be determined if they have a tendency to accumulate in vital components
of the enviroaaent| a chemical change in the parent compound does not
necessarily bring about detoxification.  One of the strongest advantages
of using a radiolabeled parent compound is that it enables one to
quantitatively keep track of all degradation products even though their
chemical identities and toxicities may not yet be known.

DATA PRESENTATION AND USEFUL REFERENCE POINTS

     Frequently an outdoor "pesticide residue" as determined by gas
chromatography (GC) is the result of an analysis of either the extractable
parent compound only, or a combination of the extractable parent compound
plus selected "major extractable metabolites".  The results are then adjusted
(concentrations increased) based upon an estimate of the extraction effi-
ciency of the parent  compound.  The quantitative values in the present
report were determined by liquid scintillation analyses, not GC, and the
entire residue was positively quantified; an individual "total l^C-pesti-
cidal residue" is the combination of "extractable parent compound"  (EP),
"all extractable l^C-asetabolites" (j^) derived from the parent compound, and
the "unextractable ^C~products"(UN) remaining in the processed sample,  The
entire extractable fraction (parent plus metabolites) was quantified before
it underwent any clean-up procedure and before an aliquot (or all)  of it was
chromatographically separated into its various components that were
identified and quantified.  The chemical nature of the unextractable  (or
bound) radioactive material is unknown since it was quantified by either
thermal destructive oxidation or by chemical disintegrations however, it is
often assumed to represent conjugated or chelated derivatives of  the parent
compound or metabolites.  All absolute quantities of parent compounds are

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                                                     14
 presented invg, and the absolute quantities of all   C-derivatives are
 presented as Vg of parent compound equivalents.  All ppta concentrations
 are yg chemical/g fresh (wet) weight of material.  Concentration in air
 is given as mg/m*, which is the same as a ppm (w/w) assuming one liter of
 air weighs one gram.

      The initial pesticide concentration in the most massive component of
 the model ecosystem, the terrestrial substrate, is a useful reference point
 when comparing the degree of pesticide accumulation in the various compo-
 nents of the model ecosystem.  A given system contained either vermiculite
 or soil (described below) which differ in density, and the simulated acre
 depth of all systems was ca. 3 inches (7.5 cm).  (Outdoor studies fre-
 quently assume an acre depth of 6 inches weighing two million pounds.)
 All Individual systems were treated with 5000 ug of a single pesticide (neat),
 which simulated a realistic application rate of one lb. active ingredient
 (AI) per acre (or 1.12 kg/ha).  For preemergent applications to systems
 containing soil, this tate resulted in an initial pesticide concentration
 in'substrate of 1.25 ppm; the initial pesticide concentration in vermiculite
 was 2.08 ppm.

                             MATERIALS AND METHODS

      Toe basic ecosystem unit (Figure 1) was a 19-liter wide-mouth glass
 carboy 46 cm high with a base diameter of 26 cm.  The metal lid, which was
 on the carboy only when air was being trapped, was equipped with inlet
 and outlet stainless steel tubing to periodically monitor pesticide
 vapors in lair.'  Each carboy contained either 400 g of vermiculite " '
 (Terra-Lite, W.  R. Grace and Co., Cambridge, Mass.) or 3000 g of Drummer
 silty clay loam soU. (particle diameter 2.4 - 4.8 mm).  The general soil
 characteristics were: 9.5% sand, 60.2% silt, 30.3% clay, and 7.1% organic
 matter.  Fifty corn seeds (Zea mays, Pioneer Hi-Bred 3334A, St. Joseph,
.111.) were uniformly planted in each carboy at a depth of one cm.  For
 preemergent application of a pesticide (Figure 2), a total of 5 mg of
.radiolabeled compound in one ml of acetone was injected (20 Vl per injection)
 at a depth of one cm beside each of the seeds.  For postemergent appli-
 cation, the same amount of compound in one ml of acetone was applied to
 each plant (20 yl per plant) ten days after planting the system.  This
 rate simulated a one pound active ingredient per acre application, which
 is the commonly used treatment  rate in the field.  Vermiculite ecosystems
 were sprinkled with two liters, and soil ecosystems with one liter,  of
 Freeman's standard reference water (Freeman, 1953).  Each system was
 weighed after planting and watering, and again 7 and 14 days later at which
 times enough distilled water was added with a sprinkler to restore the
 initial wet weight-, • thus simulating two rains and compensating for the
 evaporation of water.

      The following invertebrate animals were added to the system on Day 10:
'Eatigmene aaaeea (Drury), the saltmarsh caterpillar; Limaac maxima L., a
 garden slug; Lumbrieue terreatri-8 L., an earthworm; and Axmadlllid-iwn vul-
 gccre (Latreille), a pillbug.  Samples of each invertebrate species were ana-
 lyzed for pesticide residue on Day 15, at which time the prairie vole,
•Microtua ockpogoster  (Wagner), was added to the system.  It was supplied with
 a cup of fresh water daily, and removed for analysis on Day 20.  Any readily

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visible plant debris and invertebrate animals remaining in the terrestrial
phase were removed on Day 20 and disgarded; the substrate was then mixed
well and sampled for analysis.  After substrate sampling on Day 20, the eco-
system Has flooded with 7 liters of standard reference water, and snails
(Fhysa sp.), mosquito larvae (Culex pipiens quinquefas&iccbus) and water fleas
(Paphnia magna) were added.  Three fish (Gcaribusia af finis) were- added' on Day
24, and all aquatic organisms, were removed for analysis on Day 27.  The water
was decanted at this time.  The wet sediment was left in the container for 1
or 5 days and then mixed well and sampled for analysis.  The ecosystem units  '
were housed in a 244 x 132 x'198-cm walk-in environmental plant growth cham-
ber (PGW 36, Controlled Environments, Pemhina, N. Dak.) which was operated
at the following parameters: light/dark phase, 12:12 hours; continuous air
circulation; day air temperature, 26°C; night air temperatures, 19°C; day
substrate temperature, 24-26°C; night substrate temperature, 20-21°C; rela-
tive humidity, 50%; light intensity at* substrate surface, 1000 foot-candles.

     Air was routinely monitored for a three-hour daylight period at a flow
rate of 10 ml/sec on the days designated in Figure 2 .  The inlet tube of the
ecosystem carboy was connected by aseans of silicons rubber tubing, fitted
with a needle valve, to a Silent Giant & aquarium pump (Aquarium Pump Supply,
Inc., Prescott, Ariz.) providing & slight positive pressure within the carboy,
which "pushed" the air froa the carboy to the gas traps which were connected
in series and terminated with a flow steter.  The gas traps consisted of two
125=>ffll gas washing bottles connected in series with glass tubing to a flow
meters, shown in Figure 1.  The first trap (closest to the ecosystem carboy)
contained 75 ml of acetonitril®, and the second trap contained 75 ml of a
solution of ethanolamine and 2-sseehoxyethanol (Is 2 by volume).  The volatile
radioactive products trapped in these solutions were quantified by direct
scintillation counting using the scintillation fluid, AquasolR  (Hew England
Nuclear);, and a Packard Tri-Carb Model 3320 scintillation counter.

    The detailed work-up for the determination of the radioactive content
of the biological samples is presented in the Appendix (p. 277)°  It will
only be summarized here.  The biological samples were homogenized with cold
acetone and the total radioactivity determined in the supernatant.  The
aeetone-unextractable radioactivity in the pellet after centrifugation was
determined by dissolving the pellet in Protosol& for 48h at 50°.  Soil was
homogenized in acetone, filtered,, rehomogenized in aethanol and the radio-
activity in the acetone and aethaaol filtrates determined and summed.  The
unextrac table radioactivity was determined by combustion to 1^C02.  Hater
samples were counted directly in Aquasol^,  The separation, identification,
and quantification of degradative products and metabolites from living
organisms and soil was carried out by thin-layer chromatography on silica
gel followed by autoradiography and determination of the total  amount of the
radioactive TLC spots by scraping the appropriate areas of silica gel into
scintillation vials for counting.

                   14
     The following   C labeled pesticides were ring-labeled, except for captan
           phorate   (lCHa), and fonofos (O^Hs) .  Their specific activity
and source of supply  (mCi per a mol) is shown in the Appendix  (p .     ) .
The final adjusted specific activity is shown in parenthesis.   Fifty
microcuries were added to each individual model ecosystem.

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                       PREDICTIVE
          ENVIMNMEinRL TOXICOLOGY
                            BY A
            SINGli UNIT SIMULATED ECOSYSICM
              TOR:
                LANO.A1R
                WATER
                MICRO* AMD
                NIACROBIOTA
               PLUS:
                LANDFILLS
                FARMS
                WATERS
Figure 1.  Physical model ecosystem:  (top) arrangement for periodically moni-
toring volatile components and for evaluating leaching and run-off;  (bottom)
terrestrial and aquatic  sequential phases.
          Plant
          com
                          Add
                        invertebrate*
 Sample
v*rt»brat«
 add vol.
                                         Analyze vole
                                          remov«
                                          plane*
                                         and aniuls
          \naiyza lit
          snail* algae
          matt uap mia
       fiAA  sanpl*  Samp L«
       fis  l**c i«c« s«dlncR
          \>  1 - i - J - u - 5 - o 7  »  •> 10-U 11-13 14 » 16-1? 1ft 19 'T 21 22-23 24 ^5 26 27 28	32
                      j
                     Add
                     vacer
Add
water
 Flood
«co«y*t*n
                                        •wsqulto larvae
                                         and d*piinia
                                              \quacic Pha«*
Figure 2.  Time sequence for the model ecosystem when using a preemergent sub-
strate pesticide application; postemergent foliar applications are made at
day 10, the air-monitoring is shifted to days 10, 11, 12,  15 and 19, and the
corn is sampled on days 12 and 14.

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Methoxychlor  (1.61): l,l,l-trichloro-2,2-bis  (pj-methoxyphenyl) ethane
DDT (3.54): 1.1,l-trlchloro-2.2-bis(p-chlorophenyl)ethane
Fonofcs (2.70): J>-ethyl j>-phenyl ethylphosphonodithioate
Aldrin (3.10): 1,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-endo,
               exo-5,8-dimethanonaphthalene
Dieldrin (3.68): l,2,3,4,10,10-hexachloro-exo-6,7-epoxy-l,4,4a,5,6,7,8,8a-
                 octahydro-1,4-endo, exo-5,8-dimethanonaphthalene
Phorate (8.45): £,^0-diethyl-^-(ethylthio)methyl phosphorodithioate
HCB (5.33): hexachlorobenzene
PCNB or quintozene  (4.32): pentachloronltrobenzene
PCP (2.55): pentachloroplienol
Captan (2.99): II-(trichloroinethylthio)-4-cyclohexene-l,2-dicarboximide
Simazine (4.00): 2-chloro-4,6-bis(etbylamino)-s-trlazine
Trifluralin (7.05): o,a,a-trifluoro-2,6-dinitro-N,N-dipropyl-2.-toluidfne
2,4,5-T (isooctyl ester)  (6.95): 2,4,5-trichlorophenoxyacetic acid, isooctyl
                                 esters  (mixed)
Parathion (4.16): ^,0-diethyl JD-p_-nitrophenyl phosphorothioate
Methyl parathion (5.60) :_0_j_0-dimethyl Jpj-p_-nitrophenyl phosphorothioate

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                         RESULTS AJID DISCUSSION

     This investigation was made to develop a simple, practical terrestrial
model ecosystem for study of the total fate of pesticides in the typical
corn-soil and soybean-soil agroecosysterns that comprise about 100 million A
of farmland in the "corn belt" of the Mid West.  Much of this farmland has
been treated with highly persistent organochlorine pesticides during the
past 25 years and the use of insecticides, herbicides, and fungicides as
pre-and post-emergent applications has increased from about 39.5 million Ib.
in 1964 to 62.3 million Ib. in 1966, and to 96.5 million Ib. in 1971 (HAS 1975)
There is little overall or comparative information about the fate of the
various active ingredients applied, in the soil, air, water or biota and
the rate of introduction of new pesticides is far beyond the capacity of
any environmental •monitoring program for surveillance.

     The laboratory terrestrial model ecosystem methodology, comprehensively
described, has been validated by-studies with 15 radiolabeled pesticides.
The unequalled analytical capability of the l^C labeled compounds has
produced more thatr 20,000 individual measurements about the qualitative
and quantitative fate of these pesticides in the organisms of the model
ecosystem and in the air, water, and soil (detailed in  the 170 Tables and 100
Figures of this report). This wealth of information has scarcely been
tapped as a resource about the ecology of pesticides, and remains as a
major resource for evaluation of the comparative fate of pesticides in
a variety of living organisms, e.g. corn, soybean, earthworm, slugs,
caterpillar ,t and vole.t , Equally interesting comparisons can be made
of the distribution*and'fate of the 15 radiolabeled pesticides in the
soil, air, and water environment.  This larger body of information serves
to demonstrate the value of the laboratory model ecosystem.

     In order to facilitate comparisons of the basic data, the three
"grand summaries" Tables 1, 2, and 3, will be most useful.  These show the
total distribution of 14c pesticide residues for the 15 compounds studied.
These are based on the highly detailed Tables presented under each material.
Many additional calculations can be made easily from these Summary Tables -
but with caution.  For example, in Table 3, if you average the values in
the row across from the heading "vole", you find that the average percent
of. extractable parent compound detected in the total l^C-pesticidal
residues examined .in the vole was 19%.  However, for dieldrin, 89% of
the residues in the vole was parent compound.'  In contrast, 'for fonofos
and 2,4,5-T ester there was no'parent compound  found in the vole.  The
other pesticides fell in the range between these values.  It is clear,
therefore, that 'this set of values gives a precise clue to bioaccumulation
and.food chain transfer.  It is, therefore, a good idea to glance across
the entire row of values in Tables 1-3 to note the extremes and trends
(medians) for the pesticide residues in the various substrates.  In calcu-
lating an average value across the row, the mode of pesticide application,
the.time.of application, and the type of terrestrial substrate are essentially

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 Table  1.—Grand summary no.  li   total   C peatlcidal  residues, ppra,  in terrestrial modular model ecosystems
Ecosystem
component and
postplanting age
at analysis
(days)
Substrate (20)*/
Air (5 or 15)5/
Corn/soybeans (14)-^
Earthworm (15)
Slug (IS)
Pillbug (15)
Caterpillar (IS)
Vole (20)
Water (27)
Sediment (28 or 32^
Snail (27)
Fish (27)
Daphnia (27)
Vermicullte substrate
Postemergent
application
Soil (silty clay
loam) substrate8'
Preemergent application
Meth- Fono- Diel Diel
oxy DDT fog drin Aldrin Aldrin drlnb/
chlor
1.44 1.73
0.002 O.OOO4
13.6 12.6
2.06 2.24
2.09 S.81
4.22 5.53
6.29 85.9
0.469 11.9

a/



0.212 1.41 0.882
0.004 0.006 0.029
1.10 5.66 8.05
3.62 4.13
0.404 0.771 2.58
8.87 3.22
1.04 1.34 3.38
0.270 3.67 1.31
0.022
0.894
70.3
62.6
8.81
1.26 0.828
0.003 0.002
0.7J1
1.26 0.698
0.391 0.184
0.870 0.475
0.502 0.275
0.471 0.947
0.004
0.762
8.70
7.61

Pho- Pho-
rate rate
(loam) (sand)
0.852 0.518
0.027 0.041
1.59 6.48
0.457 1.91
0.376 2.03
0.864 1.40
0.459 2.01
0.128 0.335
0.047 0.083
0.546 0.281
0.226 0.821
0.527 0.772

HCB
(soy
beans)
1.06
0.008
1.15
4.46
0.195
1.53
0.656
0.695
0.0012
0.829
O.B01
2.38

(c^n, «•
0.949 0.858
0.014 0.017
2.64 9.25
0.584 1.39
0.228 0.441
4.09 1.77
0.347 2.44
2.88 0.677
0.0017 0.009
0.818
0.546 1.60
1.13 1.72

PCP
0.634
0.078
6.30
0.5S1
0.212
0.618
1.45
0.530
0.008
...
2.52
1.76

Cap Sima
tan zine
0.165 1.44
Postemergont
application
Tri 2,4, 5-T para Me.
fluralin (es thion P8ra
(s'beans) 'ter)S/ thion
1.13
0.094 0.0003 0.004
0.396 1.39
0.181 4.90
0.069
0.470 2.01
0.299 0.444
0.119 0.077
0.003 0.059
0.888
0.825 0.133
0.378 0.207

1.56
4.29
0.472
0.587
0.326
0.224
0.009
0.882
0.571
0.059
0.146
1.07
0.005
1.09
1.81
...
2.69
0.163
0.036
0.067
0.795
0.193
0.149
0.231
0.577 0.398
0.017 0.276
42.9 24.5
1.29 3.07
2.31 0.955
9.71 6.66
13.5 2.36
0.304 0.532
0.007 0.007
0.630 0.4SS
1.35 1.19
0.223 0.236

a/  One Phorate ecosystem contained Blocmfield loany sand soili  all other ecosystems contained Drummer silty clay loam soil.
b/  Ho corn plants were present in this ecosystem.
c/  2,4,5-V (isooctyl ester).
d/  For Hethoxychlor, DDT, Fonofoa, Dieldrin and Aldrin, value represents extractable 14C onlyi  for Aldrin, 100* of 14C pesticide
e/  Air was analyzed on Day 5 for preemergent application ecosystems and Day 15 for postemergent application ecosystems.
tj  Soybeans were grown in one HCB and the Trifluralin ecosystemsi  corn was grown in all other ecosystems.
g/  Sediment from HCB, Phorate, Simazine, 2,4,5 T and Trifluralin ecosystems was analyzed on Day 28i  all others on Day 32.
was extractable.

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Table 2 •—Grand summary no. 2:  extractable parent 14C pesticidal compounds, ppm, in terrestrial-nodular model ecosystems
Ecosystem
component and
postplantlng age
at analysis
(days)
Substrate (20)-',
Air (5 or IS)2/
Corn/soybeans (14)-^
Earthworm (IS)
Slug (15)
Pillbug (IS)
Caterpillar (15)
Vole (20)
Water (27)
Sediment (28 or 32)d/
Snail (27)
Fish (27)
Daphnia (27)
Vermiculite substrate
Postemergent
appl ication



Soil (silty clay
loam)
substrate^/
Preemergent application
Meth" Fono- Diet Diel
oxy DDT fos fr^ Aldrin Aldrin drtnb/
chlor
0 886 1 12
0.002 Q.0004
11.4 9.57
0.316 1.18
0.700 3 87
1.10 3.48
2.83 2.98
0.041 1.37
*
a/



0.016 1.21 0.125
0.004 0.006 0 029
0.175 3.80 1.55
0 255 0 223
0.012' 0.554 0.182
7.59 0.247
0.0 1.26 0 180
0.0 3.29 0.150
0 009
0.745
62.9
58.1
8.05
0.840 0.722
0.003 0.002
O.115
0.070 0.011
0.012 0.137
0.095 0.138
0.032 0.257
0.008 0.843
FhO
-rate
(loan)
0.010
0.027
0.038
0.003
0 0
0,0
0 049
0.002
e 0.002 <0 0001
0.678
8.02
7.25

0.022
0.004
0.063

Pho
rate
(sand)
0.007
0.041
0.028
0.014
0.0
0.0
0.172
0.004
0.0001
0.011
0.019
0.075

HCB HCB

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 Table  3 .—Grand summary no.  3: resistance  to degradation, expressed as the percent of extractable parent compound present in the total   C pesticidal residue
Ecosystem
component and
postplanting age
at analysis
(days)
Substrate (20)^
Air (5 or IS)2/
Corn/soybeans (14)^
Earthworm (15)
Slug (15)
Pillbug (15)
Caterpillar (15)
Vole (20)
Hater (27)
Sediment (28 or 32)4'
Snail (27)
Fish (27)
Daphnia (27)
Vermiculite substrate
Postemergent
application
Soil (silty clay loam) substrate^/
... Posteraergent
Preemergent application application
Meth Pho-
chlor os n (loam)
61.53 64.74

83.82 75.95
15.34 52.68
33 49 66.61
26.07 62.93
44.99 3 47
8.74 11.51

3/



7.55 85.82 14.17

15.91 67.14 19.25
7.O4 5.40
2.97 71.85 7.05
85.57 7 67
0.0 94.03 5.33
0.0 89.65 11.45
40.85
83.33
89.47
92.81
91.37
66.67 87.20 1.17

15.95 "• 2.38
5.56 1.58 0.66
3.07 74.46 0.0
10.92 29.05 0.0
6.37 93.45 10.68
1.90 89.02 1.56
40.26 0.11
88.98 4.03
92.18 1.77
95.27 11.95

Pho HCB .„ .. Tri 2,4,5-T Me.
rate (soy , IICB . PCHB PCP Cap S}»a fluralin (es . P"a para
(sand) beans) (corn) tan zine (s beans) ter)^ thion thion
1.35 96.23 95.26 43.01 18.77 1.09 70.14 78.58 3.74 18.02 3.77

0.43 69.04 51.52 11.68 16.03 1.01 32.23 38.33 1.74 25.41 2.43
0 73 91.93 90.75 10 SO 8. 35 0 0 66.12 54 78 0 39 43.10 3.00
0.0 78.97 68.42 9.52 16.51 40.58 •" 54.45 "' 63.64 5.55
0.0 97.39 94.13 28.87 3.56 11.28 10.60 31 01 0.0 20.29 2.25
8.56 85.98 82.42 39 88 37.31 6.35 65.77 64,11 21 47 23.63 9 49
1.19 69.64 78.82 7.53 6.98 1.68 20.78 27.23 0.0 4.28 0.94
0.12 41.67 47.06 1.71 8.14 0.10 79.66 0.0 0.0 3.91 1.35
3.91 90.35 85.70 	 59.23 12.02 3.27 4.67 0.29
2.31 57.18 58.42 21.88 1.83 5.82 77.44 29.77 4.66 2.22 0.0
9.72 57.14 37.17 9.94 44.26 5.56 46.38 11.86 4.70 3. 59 16.10
8 22 6.06
a/  One Phorate ecosystem contained Bloomfield loamy sand sollt  all other ecosystems contained Drummer silty clay loam soil.
b/  Mo corn plants were present in this ecosystem.
c/  2.4,5 T (isooctyl ester).
d/  For Methoxychlor, DDT, Fonofos, Dieldrin and Aldrin, value represents extractable   C only;  for Aldrin, 100% of   C pesticide was extractable.
e/  Air was analyzed on Day 5 for preemergent application ecosystems and Day 15 for postemergent application ecosystems.
I/  Soybeans were grown in one HCB and the Trifluralin ecosystemsi  corn was grown in all other ecosystems.
g/  Sediment from HCB, Phorate, Slmazine, 2,4,5 T and Trifluralin ecosystems was analyzed on Day 281  all others on Day 32.

-------
ignored* but each of these characteristics substantially effects
environmental behavior of the pesticide, aa will be discussed  later.
The major subdivisions (extractable parent compound, extractable metabolites,
and unextractable products) of each of the total l^C-pesticides residue
values summarized in Table 1, can be located by referring  to Figures
3-8 and to the detailed Tables of metabolism of each compound  by the major
organisms of the model ecosystem.

INTERESTING COMPARISONS

     The choice of test variations and pesticides employed allow us to
make a number of interesting comparisons about the fate of pesticides
in these soil-crop ecosystems.  A brief survey of these will demonstrate
the great value of the model ecosystem approach and its applicability to
problem solving.

SOIL DEGRADATION

     The more stable compounds were no more readily degraded in soil than
in animals.  Aldr-in and dieldrin were tested in both vermiculite and soil
(Tables 1-3); there was no indication that either of these compounds was
more readily degraded in soil containing a rich microflora than in
vermiculite.  If anything, it appeared that aldrin "was more readily
degraded in vermiculite than in soil; the ratio of parent  compound to total
residue was certainly less in vermiculite than in soil.  But we really
do not know whether these final ratios in .substrate were due primarily -to
degradation that occurred within the substrate itself, or  to degradation
that occurred principally elsewhere within the ecosystem.  Since the
substrate is the most massive component of the model ecosystem, it probably
is a reflection of the degradation that occurred in the substrate.  But
we also have to keep in mind that the final ratio of parent compound to
total residue in substrate was not solely the result of degradation.
Differences in the evaporation rates of parent compound and metabolites
could also have easily altered the ratio of parent compound to total residue
in the substrate.  This was quite possible in the case of  aldrin applied to
vermiculite, because it was estimated that 53% of the total residue was lost
to the atmosphere after 20 days.  But in the vermiculite-contalning system
treated with dieldrin, only 27% of the total residue was lost  to the air after
the same period of time*  The vapor pressure of aldrin (6  x lO'^mm) is about
33x that of dieldrin (1.8 x lO'^mm), and the average concentration of aldrin
in the air of the- model ecosystem was about 6x that of dieldrin (Table 1).
Thus, in the system containing vermiculite and treated with aldrin, the small
ratio of parent compound to total residue may have resulted because aldrin
more readily evaporated from the substrate than did its major metabolite,
dieldrin.-  This is an excellent example of the interdependence of the para-
meters, degradation and environmental distribution; these  measurements are
the results of a combination of processes working together simultaneously.
But the meaningful point is that the final outcome (parent compound/total
residue in substrate) of interacting processes was readily detected and
quantified using a model ecosystem.
                                    11

-------
     In another model ecosystem treated with aldrin - the system containing
soil - it is very improbable that transportation to the atmosphere was the
cause of the change in the ratio of parent compound to total residue in the
substrate, because no significant quantity, of the residue evaporated.  In the
aldrin-soil system, the change was truly caused"principally by degradation;
in the aldrin-vefmiculite system, it is very probable that the major portion
of the change was caused by evaporation.  Thus, although a given table, such
as Table 3, may have a single parameter as its heading - such as "degradation" -
that does not mean that multiple processes did not affect that measurement
or parameter.  It is important to note that the relative degrees of
degradation (transformation) and distribution (transportation) are not
always easy to measure independently in open systems.  Fundamental phenomena
are often the results of very interdependent processes in any living
organism or complex system.  Degradation, accumulation, and distribution, are
fundamentals in the attempts to decipher the environmental fates of toxicants.

EFFECTS OF SOIL TYPES

     Phorate was compared as a pre-emergent application in the soil-corn
model ecosystem incorporating two typical Illinois soil types:  Drummer   A
silty clay loam with 7.1% organic matter and 33.5 cation exchange capacity ,
and Bloomfield loamy sand with 2.1% organic matter-and 2.3 cation exchange
capacity (Figures 64, 67, Tables 1-3).  These two soils had markedly
different effects on the distribution of the phorate and its oxidation
and degradation products.  The Drummer soil with its higher sorption
capacity retained 49.2% of the total 1*C compared to 21.2% retained in
the Bloomfield soil.  Correspondingly, less phorate and degradation products
were released to the leachate water from the Drummer soil (6.6% total l^C)
than in the Bloomfield soil (11.6% total ^C).  The aspirated air contained 0.041
ppm total l^c from the Bloomfield system vs 0.027 ppm from the Drummer system.

     The organisms in the Bloomfield soil system accumulated substantially
higher amounts of both total l^C (Table 1) and phorate (Table 2) than Drummer
indicating the strong sorbtive capacity of the latter:

                                     Bloomfield        Drummer

                 corn                  6.48 ppm         1.59 ppm
                 vole                  0.335            0.128
                 caterpillar           2.01             0.459
                 earthworm             1.91             0.457'
                 slug                  2.03             0.367
                 pillbug               1.40             0.864

     The individual tabulations for the various organisms show the ready
oxidation of phorate to sulfoxide (SO) and sulfone (S02) and to the corres-
ponding oxons.  Detailed comparisons of the fate of these in soils (Tables 109,
117), corn (Tables 110, 118), vole (Tables 113, 121), invertebrates  (Tables
112, 120), air Tables 111, 119), and water (Tables 115, 123), and aquatic organ-
isms (Tables 116, 124), show in general the greater availability of phorate from

* milliequivalent per 100 g


                                     12

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the Bloomfield soil and the consequently more rapid rate of biotransfonnations
into the active oxidation products.  These detailed studies illustrate the
great amount of detailed information to be secured from model ecosystem
studies with radiolabeled pesticides in regard to the qualitative and
quantitative ecosystem fate of individual compounds.

ENVIRONMENTAL DISTRIBUTION

     To ascertain if a toxic substance is likely to be harmful, it is
necessary to know where it is likely to be, and to what extent.  The
distinctly different distributions of the various pesticides and their
derivatives among the major environmental compartments of the model
ecosystems at the end of the 20-day terrestrial phase are summarized
in Figure 9.  The detailed explanation as to how a given pesticide's
distribution was calculated is shown in Figures 19, 21, 23, 25, 28, 30,
32, 34, 40, 43, 46, 49, 52, 55, 58, 61, 64, 67, 70, 73, and 76.

     The major relocation site of all pesticides was either the soil or
the atmosphere.  For those compounds which were applied directly to
Drummer silty clay loam soil containing corn, the ma-y-imum amount of any
pesticide plus its derivatives detected in the total complement of
terrestrial animals was 3.5% of the applied dose (HCB): the minimum amount
was 0.22% (captan) and the average amount was 1.5%.  Parathion and methyl
parathion were carefully and directly applied to corn grown in soil ten
days after planting; the respective amounts of their total residues in
the total terrestrial animal masses were 3.6% and 3.1% of their applied
doses.  Thusrit appeared that the compounds which were carefully applied
(not sprayed) to corn foliage could produce twice as much contamination
of the total animal complement after a short period of time than those
compounds which were applied to soil.  But at this time, we do not know
whether the apparent differences in results were primarily due to differ-
ences In application techniques, or to differences in pesticides.  In
comparing parathion (applied to corn) with aldrin (applied to soil) and
taking into consideration that they are normally applied as simulated, we
would conclude that the long-term, or chronic, potential hazard of parathion
to the terrestrial animals in the agricultural environment would be much
less than that of aldrin, because 52% of the parathion application was lost
to the atmosphere after 10 days, whereas virtually none of the aldrin was
lost to the atmosphere after 20 days.  As indicated in Figure 9, methyl
parathion would be potentially less hazardous than parathion since less
of it was transferred to the animals and less remained in the soil.  This
point is discussed subsequently.

     Figure 9 clearly indicates that the chronic potential hazard of the
four fungicides would be in order HCB-»-PCNB-*PCP*captan.  Their respective
transfers to the total terrestrial animal complements were 3.5%, 2%, 1%,
and 0.2% of their applied soses.  Their respective persistences in soil
after-20 days were 67%, 64%, 48%, and 13% of their applied doses (see
later discussion).
                                       13

-------
     A change in the type of terrestrial substrate drastically altered the
environmental distribution of a given pesticide as is evident by comparing
the distributions'of aldrin applied to vermiculite with that applied to
Drummer silty clay loam soil (organic matter content ?2)» as shown in
Figure 9.  The values shown are the averages of duplicate systems containing
vermiculite and duplicate systems containing soil.  When applied to vermi-
culite, the resulting major site of pesticide contamination was the at-
mosphere; when applied to soil, the vast majority of the total aldrin
residue remained within the soil.  Evidently, aldrin was less tightly bound
to vermiculite than to soil.  Each species of terrestrial animal in the
aldrin-vermiculite system accumulated a greater concentration of total
aldrin residue than did its counterpart in the aldrin-soil system, and the
same relative relationship was even more pronounced in the corn from the
two systems (Table 1).

     For the model ecosystems containing vermiculite, the aldrin-treated
system is directly comparable to the dieldrin-treated system because they
were homologous in all detail except for the type of pesticide (Figure 9).
In comparing these two systems, it will be noted that aldrin was more
volatile than dieldrin.  However, in those systems containing soil, more
dieldrin was lost to the atmosphere than aldrin; the probable cause of this
was the absence of a growing crop in the dieldrin-soil system.  This latter
system was accidentally drenched with the proper amount of water (instead
of it being slowly sprinkled) which compacted the soil and prevented the
seeds from germinating.  He do  not believe that the complete lack of germina-
tion was due to the pesticide, because an aliquot of the same batch of seeds
did germinate in the vermiculite-containing system treated with the same
compound at the same rate.  Soybean (Glycine max) and Swiss chard (Beta.
vulgarls dola) leaves were added to the dieldrin-soil system to serve as
food for the animals (corn leaves were not available).  If a crop had grown
in the dieldrin-soil system, we would have expected the retention of
dieldrin in soil to be comparable to, or greater than, that of aldrin in
soil.  The root system of growing plants in essence contributes a tremendous
quantity of organic matter to the soil environment; furthermore, it greatly
aids in holding the soil together, thus preventing the formation of deep
cracks or fissures which create abundant surface-to-air interfaces which
enhance volatilization.  It would seem strongly advantageous to have at
least a growing crop present in those studies concerned with the fate of
agricultural chemicals in agricultural soils.  Although the volatilization
of dieldrin from vermiculite and from soil-without-a-crop were very similar,
the accumulation of dieldrin residues by each animal species was much greater
in the system with a growing crop.  This implies that the volatilization,
as such, was not nearly as significant a factor contributing to pesticide
accumulation by animals as was the presence of a growing crop.

PESTICIDE TRANSPORT TO SURFACE WATER AND AQUATIC ORGANISMS

     At the termination of the terrestrial phase  (Day 20), many of the
systems were each slowly flooded with seven liters of water, the mass of
which was 1.75 times greater than that of the moist soil (Figure 10 and Tables
154 and 155).  This was certainly a harsh treatment of a land mass with water.
Seven days after flooding the systems that contained Drummer soil, the

-------
                                14
 following total percentages of   C pesticidal residues applied to the
 terrestrial phase, were detected in water and in aquatic organisms:

                                 % in water      % in aquatic organisms

      PCNB                           1.2                 0.04
      PCP                            1.2                 0.05
      HCB                            0.2                 0.06
      parathion                      1.0                 0.02
      methyl parathion               0.9                 0.02
      phorate                        6.6                 0.04
      dieldrin                       0.5                 0.30
      captan                         0.4                 0.01
      simazine                       8.2                 0.02
      trifluralin                    1.3                 0.10
      2,4,5-Tester                   9.4                 0.04

 For the system containing vermiculite and treated with dieldrin, 3.1%
 of the applied dosage was transported to water and 2.3% to the aquatic
 organisms.   Clearly, more total dieldrin residue was transported to the
 same volume of water from vermiculite than from soil.  As noted earlier, the
 total mass  of vermiculite differed from the total mass of soil; thus the
 concentrations of pesticides in the two substrates are not directly
 comparable.  The 1.41 ppm dieldrin residue in vermiculite at the time of
 flooding represents an absolute amount of 3,384 vg; the comparable concentra-
 tion and absolute amount in soil at the time of flooding were, respectively,
 0.828 ppm and 3,312 ig.  %Thus, the absolute amounts of total dieldrin
 residues in vermiculite and soil were almost equal; yet approximately six
 times more  pesticide residue was transported to the water in the vermiculite
 system than to the water in the soil system, indicating that the dieldrin
 residue was about six times more strongly bound to soil than to vermiculite
 under these conditions.

      The amounts of pesticides transported from soil to surface water were
 quilfe small compared to the amounts, transported from soli 'to -air (Figure 9,
•Table 155).""For the eleven pesticides (indicated above) that were studied
 in both the terrestrial and aquatic phases* the average 14c-pesticide res-
.idue •(in-eluding metabolites) transferred to water from Drummer silty clay
 loam soil at the end of the seven-day period of flooding was 2.8% of that
 which was originally applied to the system, with a maximum of 9.4% (2,4,5-
 T) and a minimum of 0.24% (HCB).  The residues in water for 8 of the 11
 compounds were equal to or less than 1.3%.  In contrast, and for these
 same compounds, the average ^C-pesticide residue transferred to air during
 the 20-day  terrestrial phase preceeding the flooding was 40% of the applied
 dose, with  a maximum of 85% (captan) and a minimum of approximately 0%
 (simazine).  For captan, only 0.4% of its applied dose reached water,
 whereas 87% was earlier lost to air, and the reverse of such a distribution
 was shown by simazine which lost virtually no residue to air and subse-
 quently had one of the largest residues in water,  8.2%.  Thus, it was
 apparent that the amount of pesticide likely to reach water was dependent
 upon the pesticide's past history on land, especially its volatilization
 from land.   However, it was noted that pesticides could lose about equal
 fractions to air (2,4,5-T, 25% and HCB, 29%) and yet have distinctly
                                     15

-------
different proportions end up in water (2,4,5-T, 9.4% and HCB, 0.24%).  This
indicated that the eventual amount of pesticide to be found in water was
also a function of a given pesticide's relative mobility from soil to water
(desorption and solubility).  The four pesticides that were most abundantly
transferred to water (2,4,5-T, simazine, phorate and trifluralin) were the
only compounds that killed the fish (Table 154).

     As shown in Figure 11, an aquatic organism accumulated a tremendous
quantity of pesticide from its surrounding aquatic environment, especially
when compared to the general levels accumulated by terrestrial animals from
their surrounding environment (Figure 13).  For example, the concentration
of total dieldrin residue in fish was 1,951 times greater than that found
in the surrounding water, whereas the concentration in the vole was approxi-
mately the same as that detected in the surrounding soil (Table 1).  For total
PCP residues (Table 1), the following pesticide concentration ratlo^ were
noted:  fish/water « 208, snail/water = 297, vole/soil «= 0.836, and
caterpillar/soil = 2.29.  Recall the following exposure periods: 3 days for
fish, 5 days for terrestrial animals, and 7 days for aquatic snails.
Since the exposure period of the terrestrial animals was bracketed by those
of the aquatic animals., there was no indication that the difference in
exposure periods was responsible for the large difference in pesticide
accumulations by aquatic and terrestrial animals.  Clearly, the terrestrial
environment is divided into many micro-compartments, it is not a fluid,
and the accessibility of the total quantity of terrestrial pesticide to
any given individual terrestrial organism is extremely limited.

PESTICIDE EFFICIENCY

     The model ecosystem experiments provide some interesting answers to
the common speculation regarding the percentage of total pesticide applica-
tion reaching the target organism.  For the post-emergent insecticide
applications the total insecticide residue within the salt marsh caterpillars
was <1% of the total dosage applied, except for DDT.  The amounts recovered
were: methyl parathion 0.35% (10% parent compound), parathion 0.6% (25%
parent), methoxychlor 0.99% (45% parent), DDT 14.1% (3% parent, 92% DDE).
(Figures 19, 21, 52, 55, Tables 6, 11, 80, 88).  Parathion killed 88% of
the caterpillars, none were killed by the other insecticides.

     The four pre-emergent insecticide applications of aldrin, dieldrin,
phorate and fonofos would not normally be used to control the- salt marsh
caterpillar.  However, the maximum amount of any of these insecticides
detected as a total residue in the caterpillars was 0.09% of the applied
dose (phorate).

     For the pre-emergent herbicides, the recovery in the plants of the total
amount applied was of similar magnitude: simazine 2.8% (32% parent) in corn,
trifluralin 0.3% (39% parent) in soybean, 2,4,5^ ester 2.7% in corn  (1.7%
parent), shown by the detailed data (Figures 70, 73, 76, Tables 126, 134, 142),

     For the fungicides the comparison as to target site efficiency is
less meaningful.  However, the percentages in corn were: captan 0.7%
(1% parent), HCB 4% (52% parent) PCNB 18% (11.7% parent), and PCP 16%
(16% parent).   (Figures 43, 46, 47, 61, Tables 57, 64, 71, 102).  In soybean
HCB was present to 0.6% of applied dosage (69% parent) (Figure 58, Table 94).
Thus these data strongly support the often quoted statement that only about
1% of the total application of pesticide reaches the target organism.


                                    16

-------
 HARD VS SOFT PESTICIDES

      A major factor in banning the uses of the "hard" insecticides DDT,
 aldrin, and dieldrin was to prevent widespread environmental contamination
 with persistent pesticides and bioaccumulation through food chains.  EPA
 has claimed that suitable biodegradable or "soft" pesticides can be employed
 as substitutes with consequent improvement in environmental quality.  This
 point was investigated in the terrestrial model ecosystem comparing two
 pairs of insecticides in pre- and post-emergent applications (Cole et al  1976a,
 1976b).

      Comparisons were made of aldrin vs fonofos and phorate, substitute
 Insecticides now widely used in corn rootworm control, and DDT vs its
 biodegradable substitue methoxychlor.  The results are shown in Tables 1-3.

 AIDRIN VS FONOFOS

      At the conclusion of the experiments the soil (vermiculite) contained
 0.463 ppm aldirn vs 0.016 ppm fonofos*  the corn plants 0.762 ppm aldrin  vs
 0.175 ppm fonofos and the vole 0.08 ppm aldrin plus 3.48 ppm dieldrin vs
 0.0% fonofos plus 0.27 ppm other breakdown products.  (Tables 14,  15, 17,
 28, 29, 31).  These results clearly demonstrate the hazardous environmental
 conversion of aldrin to the very persistent dieldrin and its bioaccumulation
 and the biodegradability of fonofos. They agree with the "real world"
 experience where the use of aldrin has  resulted in widespread accumulation
 of persistent dieldrin residues and where the use of millions of pounds  of
 fonofos has not resulted in any observed bioaccumulation on food chain
 transfer.

 DDT VS METHOXYCHLOR

      At the conclusion of these post-emergent experiments, the soil
 (vermiculite) contained 1.12 ppm DDT vs 0.886 ppm methoxychlor, the corn
 plant 9.75 ppm DDT vs 11.4 ppm methoxychlor, and the vole 1.37 ppm DDT
 plus 8.20 ppm DDE, vs 0.041 ppm methoxychlor.  (Tables 4, 5, 7, 9, 10, 12).
 These data clearly show the food chain  tranfer and storage of DDT plus DDE
 and. the biodegradability and lack of food chain transfer of methoxychlor.
 The results are completely in accord with a large amount of "real world"
 data showing the bioaccumulation and fat storage of DDT as compared with
 the biodegradability of methoxychlor.

 PARATHION AND METHYL PARATHION

      This comparison is particularly meaningful because of the very large
.amounts of these highly toxic pesticides used.  Methyl parathion (°- rat  oral
 LDsO 24 mg per kg) is somewhat safer than parathion (°- rat oral LDso 3.6 mg
 per kg) and is generally thought to be  environmentally less persistent.  The
 comparative model ecosystem data clearly show this to be the case (Tables
 1-3).  In the Drummer soil of .the model ecosystem the methyl parathion
 concentration at the end of the experiment was 0.015 ppm vs parathion
 0.104 ppm,  (Tables 2, 77, 85).  In the flood waters, the residues were
 methyl parathion 0.0001 ppm vs parathion 0.0003 ppm.  (Tables 2, 83, 91).
                                     17

-------
The greater volatility of methyl parathion and its derivatives is reflected
by the average air samples showing 0.276 ppm for methyl parathion vs
Oo017 ppm for parathion (Table 1).

     In the corn plants, the parent compound residues were methyl parathion
0.59 ppm vs parathion 10.8 ppm (Tables 78, 86).  In the vole at the top of
the food chain, the total body parent residues were methyl parathioni0.005
ppm vs parathion 0.013 ppm (Tables 81, 89) although the voles from both
systems contained 0.2% of the total l^C applied to the. model systems (Tables
2, 3, Figures 529 55).  In the salt marsh caterpillar, the concentration of
methyl parathion was 0.22 ppm vs parathion 3.19 ppm (Tables 2, 80, 88).

HCB, PCNB, AND PGP

     The comparison of these aromatic organochlorine fungicides (Table 165)
is interesting because of the appreciable changes in water solubility and
octanol/water partition values between CgCl5 (H20 solubility 0.006 ppm,
partition 13,560) CgClsNOa (H20 solubility 0.001 ppm, partition 16,059)
and CgClsOH (I^O solubility 14  ppm, partition 6,405).  These differences
uroduce substantially different model ecosystem effects as shown in Table
165.  In the Drummer soil substrate, the concentrations of parent compounds
at the end of the experiments were: HCB 0.90, PCKB 0.37, and PCP 0.12 ppm.
(Tables 2, 56, 63, 101)=  In the flood water the parent residues were HCB
0.0008, PCNB 0.0002, and PCP 0.001 ppm (Tables 29 61, 68, 107).  The total
1*C residues in the air, HCB 0.014, PCNB Q.017, and PCP 0.078 ppm reflect
the relative volatilities of the three fungicides plus their derivatives
(Table 1).

     In the corn plants, the parent residues were HCB 1.36, PCNB 1.08, and
PCP 1.0 ppm (Tables 2, 57, 64, 102).

     In the vole at the top of the food chain, the total body parent
compound residues weres  HCB 2.270 PCNB 0.051, and PCP 0.037 ppm  (Tables 2,
5-, 66, 105).  In the earthworms, the parent residues were: HCB 0.53, PCNB
0.15, and PCP 0.046 ppm, and in the pillbugs HCB 3.85, PCNB 0.51, and PCP
0.022 ppm (Tables 2, 58, 65, 104).  The total residues in the snail were
HCB 0.55, PCNB 1.60, and PCP 2.52, and in the fish HCB  1.13, PCNB 1.72,
and PCP 1.76 ppm (Tables 2, 62, 69, 108) are clearly associated with
increasing availability in the flood water leachates because of relative
water solubility.

PESTICIDE ACCUMULATION AND DEGRADATION IN TERRESTRIAL BIOTA

     There are important differences in the effects of the pesticides in the
various animals used for evaluation.  To take an overview of these, the
pesticide accumulations have been averaged in the 5 common experimental animals
used in this study, e.g. earthworaB pillbug, slug, salt-marsh caterpillar, and
vole (Figure 13) and the pesticide degradations have been average for these 5
species (Figure 14). These comparisons have been restricted to data obtained
from model ecosystem studies where substrates, application patterns and crops
were identical and we have compared tha data from the Drummer silty clay loam
with the synthetic vermiculite substrate  (Figure 13).  The information shows
that DDT and dieldrin are the most accumulative and persistent of the 15
pesticides in the bodies of the food chain animals.  This is, of  course,
common knowledge from the real world situation where their use has been banned
by EPA.  Figure 13 also shows that parathion is substantially sore accumulative

                                    18

-------
than methyl parathion, and Figure 14 demonstrates that methyl  parathion is much
more rapidly degraded in animal bodies than parathion.  A comparable  situation
is also shown by Figures 13 and 14 between DDT and methoxychlor.  Thus it is
clear that both accumulation and degradation should be viewed  together to gain
a composite picture of pesticide hazard to the total environment.

     A similar type of comparison has been made in Figures 15  and 16  for a
single animal species, the vole that is at the top of the food chain  under
evaluation.  This comparison can be extended to include hexachlorobenzene
(Table 105), phorate (Table 113), simazine (Table 130), trifluralin  (Table 137),
and 2,4,5-T ester (Table 146).  These figures demonstrate that there  is no
sharp differentiation between "biodegradable" compounds such as captan, fonofos,
methyl parathion, parathion, and methoxychlor; and "non-biodegradable" compounds
such as aldrin, dieldrin, and DDT.  Thus  the property of  biodegradability is
relative and is expressed over a wide spectrum.  Figure 16 also shows very
clearly the importance of the in vivo formation of persistent  degradative
products, i.e. DDE from DDT and dieldrin  from aldrin.

    ' These data suggest the importance of comparisons of  the environmental
effects of pesticides not only over a range of species but also within species,
and even within the organs of a single species, e.g. the  carcass or liver of the
vole as shown in Figure 12.  Thus from Figure 15, it might appear that FCP and
PCNB are likely to be as hazardous to the vole as aldrin.   However, as shown in
Figure. 12, 68%, 66%, and 10% of the total  body content of  FCNB, PCP, and aldrin
were found, respectively, in the gastrointestinal tracts  of the test  voles.
Therefore, the corrected somatic concentration of aldrin  is roughly two-fold
greater than that of either FCNB or PCP.  (Experimentally this comparison was
done in the reverse order by determining  the total body concentration by
summation of the parts, i.e. Tables 41*, 59*. 66). Furthermore, as shown in
Figure 8, 34% and 51% of the PCNB and PCP applications were lost by volatilization
while virtually none of the aldrin was lost; and Table 3  shows clearly that
PCNB and PCP are more degradable than dieldrin.  Thus, it can  be concluded that
PCNB and PCP are potentially less hazardous environmentally than aldrin and  dieldrin

     The accumulation (or in examples where the pesticide was  applied directly
•to* the corn, the persistence) and degradation of the various pesticides in
corn are shown in Figures.17'and 18.  Figure 17 shows the concentration in the
total plant and the_proportions in shoot  and root.are indicated at the bottom
of each bar.  Figure 18 shows the relative degradability  of these compounds In
the corn plant.  These data can be extended to include hexachlorobenzene
(Table 104), phorate (Table 110), simazine (Table 126), and 2,4,5-T ester (Table
142).  Plants grown in vermiculite treated with aldrin accumulated more total
aldrin residue than plants 'grown in Drummer soil treated  with  aldrin  (Figure
17).  As shown in Figures 64 and 67, and,Tables 110 and 118, corn grown in
Drummer soil, contained much less total    C residue (2.4%  of total) than corn
grown in Bloomfleld soil (10.5% of total).  Thus it is apparent that  soil
type definitely affects the quantity of pesticide accumulated  by the  plant.

-------
                                  CONCLUSIONS

     We have analysed above BOSS of the more obvious conclusions from the wealth
of more than 20,000 precise model ecosystem measurements as recorded in the body
of this report.  These analyses were based largely on questions that interested
us as environmental toxicologists.  Other problems for in depth study include the
relationship of vapor pressure of the pesticide to loss from soil and transfer
to air, the correlation of run-off and leaching with water solubility, relation-
ship of octanol/H20 partition with in vivo storage in invertebrates, fish, and
in various tissues of the vole, and the intricate questions of the model ecosystem
behavior of key pesticide degradation products.  We plan to analyze some of these
at our leisure.

In our evaluation we have included 15 important pesticides.  This represents
about 1% of all of the pesticide active ingredients presently used in U.S.
agriculture.  All of those ought to be studied by model ecosystem technology
for better understanding and evaluation of their environmental effects.  The
results obtained in the present studies  are closely linked with the "real
world" by reason of our investigations of such widely used pesticides as DDT,
aldrin, dieldrin, 2,495~T ester, simazine, trifluralin, captan, hexachlorobenzene,
etc.  We have shown that the model ecosystem results agree very closely with
observations made in nature about such important subjects as biomagnification
and food-chain transferB leachiag sad run-off, soil persistence, and degradation
pathways.  Thus we say examine sad predict with confidence the ecosystem effects
of both proposed new pesticides and those old oneSs> such as RPAR'd products,
about which there is considerable concern.

The terrestrial model ecosystem technology as developed under this grant is
now workable, practical, and relatively inexpensive (see p. 292)«  The results
are reproducible and the systems can be operated in any reasonably well equipped
biological laboratory.  We think it important that this type of investigation
become a continuing part of the environmental evaluation of proposed new
pesticides.
                                REFERENCES

Cole, L. K., R. L. Metcalf, and J. IU Sanborn (1976a).  Environmental fate of
     insecticides in terrestrial model ecosystem.  Intern. J^ Environmental
     Studies. 10, 7-14.
Cole, L. K., J. R. Sanborn, and R. L. Metcalf (1976b).  Inhibition of corn growth
     by aldrin and the Insecticide's fate in the soil, air, and wildlife of a
     terrestrial model ecosystem.  Environ. Entomol.  5, 583-89.
Freeman, L.  (1953).  A standardised method for determining the toxicity of pure
     compounds to fish.  Sewage and Industrial Wastas 28, 845-48.

Metcalf, R.L. (1977).  Model ecosystem approach to insecticide degradation -
     a critique.  Ann. Rev. Entoaol. 22B 241-62.
Metcalf, R. L. and J. R. Sanborn (1975).  Pesticides and environmental quality in
     Illinois.  Bull. Illinois Natural History Sisrvey 31  (9), 381-436.
National Academy of Sciences (1975).  Pest Control: an Assessment of Present and
     Alternative Technologiess Vol II Corn/Soybeans Pest Control, Washington, D.C.

U.S. Department of Agriculture (1976).  Pesticide Review, Washington, D.C.
Von Rumker, R. and F. Horay (1973).  Pesticide Manual, Agency for International
     Development.  AID/cs/ 3296.

                                        20

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           Figure 8.  Summary of the fates of [  C] hexachlorobenzene ,  (soybean system), {  C] trlfluralin (soybean
           system),  [C] slraazine  (corn system, and {C} 2,4,5-trlchlorophenoxyacetic acid, Isooctyl ester (corn
           system);  In the terrestrial phases of soil-terrestrial model ecosystems.  The total !*C residues are
           expressed as parent compound equivalents, ppm  (w/w), and their subdivisions are EP^extractable parent
           compound, EM=extractable metabolites of the parent compound, and UN=ttnextractable products remaining in
           the processed sample.  On day zero, the seeds were planted and the soil was treated at onelb. Al/acre.
           The invertebrates and the vole were added to each system 10 and 15 days later respectively.

-------
SIHAZIfiE

ALDRIN
CAFTAN
TRIFLIJRALIN

HCB (soybeans)
DIELDRI'l   (no crop)
PARATHIO
I1ETHYL PARATHiOT
DDT»
fCTHOXYCHLOR*-
PIELDRH
AUKIM
FONOFOS
PHORATE
S*od
 7  -
 S  - filty clay lota *oll
Sand- looiy aaad;
      ( - 1
         |
                                     Anlffl«l«;
Air;  *Po«cemcrgent  I'   4
       application    IOZ
    9 .—Enviromoacal distribution* of cba total   C-p««tlcldal ce»idu«« (Z of
         Ch» app-llad dose) at the termination ot the t«rr»ttrial phaae of warloua
         modal «co»yst«ffls dosed with a given peitlelde.  Tha plaaci, having b«ea
         consumed and/or demolished by tba anlnala, arc not pricant a« an entity
         •e tba caiBlaatlon of tba tytten.  (Calculation* and mote detailed dla-
         trlbution* »r« presented in the text.)

-------
                                  0.070
                   2.4.5-T
               (isooctyl ester
               Methyl parathion

                       Dieldrin "I °-010
                               •
                         Captan
                      26
27
                                     23        24
                                  Days postplanting

Fig.10 .-Translocations of total **C-pesticidal residues from soil (silty clay
         loam) to water.  All systems were treated initially with the same
         absolute quantity of a given pesticide which in soil - 1.25 ppm.  The
         two parathions were applied Initially to crop foliage, instead of
         soil.  No crop grew in the dieldrin system.
28

-------
vO
               0.009
              0.008
               0.007
               0.006
               0.005
            a
            o
            •H
               0.004

-------
DDT


DIELDRIN  w


DIELDRIN  
-------
        e
        o
        g
s
g
               ANIMALS  FROM
               SYSTEMS  CONTAINING
               SILTY CLAY  LOAM SOIL
                *Postemergent  application
                                                        23
                                          §
                                          f*
                                          4J
                                          a
                                          a
                                          a.
                                                        22
                      -~*

                      §
                      44
                      CO
                      >,
                      CO

                      a
                      •H
                                    a
                                    >4
                                    
-------
DIELDRIN


DDT
PARATHION
METHOXYCHLOR
PENTACHLORONITROBENZEHE
PENTACHLOROPHENOL
CAPTAN


ALDRIN


METHYL PARATHION
FONOFOS
           Extractable parent
           compound;
Extractable
metabolites;
Unext!rac table
products
10%
   14 .—Mean proportions '(2) of extractable parent compound, extractable
         metabolites, and unextractable products detected in the total  ^C-
         pesticidal  residues in terrestrial animals as averaged over 5  species
         (earthworms, slugs, pillbugs,  caterpillars, and voles) from terrestrial
         model ecosystems; only the dieldrin residue was predominately  parent
         compound.   (Degradation within each species and the nature of  the
         metabolites is described in the text.)
                                    32

-------
      I
      p.
      §
      o
         1.0
         0,9
         0.8
         0.7
         0.6
         0.5
         0,4
         0.3
         0.2
         0.1
 VOLES FROM
 SYSTEMS CONTAINING
-SILTY CLAY LOAM SOIL
              *Postemergent application
11.9
                                                         3.6
                                            3.2
                                                         2.8
                                            2.4
                                            2.0
                                                         1.6
                                            1.2
                                            0.8
                                            0.4
VOLES FROM
SYSTEMS
CONTAINING
VERMICULITE
                                                                                     B
                                                                           "O
                                                                           i-H
                                                                           <
Fig. l^ .—Accumulations of total   C-pestlcidal residues (black bars) and parent compounds
          (white bars) in voles (entire body) from model ecosystems containing either a
          vermiculite substrate or a silty clay loam soil.  The voles were analyzed after
          a 5-day exposure within a given model ecosystem.  Each system was dosed with a
          single pesticide at a rate simulating one Ib Al/acre; the mode of application
          was either preemergent to substrate or postemergent to foliage, as indicated.
          No corn germinated in the soil system treated with dieldrin; the system was
          drenched with water instead of normal sprinkling.
                                          33

-------
DIELDRIN


DDT


METHOXYCHLOR


PENTACHLORONITROBENZENE


PENTACHLOROPHENOL


ALDRIN


PARATHION


CAPTAN


METHYL PARATHION


FONOFOS
             Extractable parent
             compound;
                                                *•*.•»•*••••••••••
                                    Extractable
                                    metabolites;
    Unextractable
_»J  products
Fig. 16 .— Proportions (S)  of extractable parent compound, extractable metabolites,
         and unextractable products detected in the total 1/*C-pesticidal residues
         in the entire vole body.  (Degradation within individual vole organs and
         the nature of the Qetabolites is  described in the text.)
                                      34

-------
                                  «
                                  o
44
40
24
20
12
CORN IN
SYSTEMS CONTAINING
SILTY CLAY LOAM
SOIL
                                        24
                                        20
                                              16
                                        12
CORN IN
SYSTEMS CONTAINING
VERMICIILITE
                                                    * Postemergent application
                                                      to foliage
                                                         94   90
                            14
17 .-rConcentrations of total   C-pesticidal residues  (black bars)  and
    parent compounds (white bars) in entire corn plants  14 days
    postplanting, and the proportions  (Z) of the residues  (yg, not
    concentration) located in shoots and roots.  Postemergent applica-
    tions directly to corn foliage were made 10 days postplanting,  and
    preenergent applications to soil were conducted at the time of
    planting.  Each system was dosed with a single pesticide at a rate
    simulating one lb Al/acre.
                                 35

-------
 METHOXYCHLOR1
 DDT1
 PARATHION'
                    M.
 METHYL PARATH.ON'
 DIELDRIN


 ALDRIN


 FONOFOS
ALDR IN
PENTACHLOROPHENOL
PENTACHLORON I TROBENZENE

CAPTAN
                                                                               i R
       lExtractable parent
       |compou".r';
Extractable
metabolites;
                                 10%

.•.lUnextractable  *Postemergent foliage
>*»1produets:       application
    Sh « corn shoots; R « corn roots;  V » vermiculite; S - silty clay loam soil.

Fig. 18 . — Proportions (%) of extractable parent compound, extractable metabolites,
          and unextractable products detected in the total ^C-pesticidal residues
          from corn shoots and roots.   Plants dosed by posteoergent application
         were analyzed 4 days after dosing, and plants from systems treated with
          a preemergent soil application were analyzed 14 days after dosing.
                                      36

-------
      APPENDIX
  Detailed Fates of
Individual Pesticides

-------
                                                       METHOXYCHLOR


                                                       TOTAL RESIDUE
                         Coxa
                          Calculation of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Corn—
Vermiculite (II)
Air
ToCflJC ^flyfTOflP TOtfll.
rlfi&Q
m*88' 8: concentration, «•"»•. W
(Mo.
(10)
(10)
(20)
(10)
( 1)

(44)
) X mass
2.78
3.46
0.0915
0.785
26.2

2.95
( 1)2122


- total w*/8
f •f •* •f **
- 27.8 2.06
• 34.6 2.09
1,83 4.22
7.85 6.29
* 26.2 0.469
98.3
- 130 13.6
- 2122 1.44
[5000 wg-(I+H
(mass) (cone.)
57.3
72.3
7.72
49.4
12.3
109
1768
3056
:)] » 1745
Total residue as
a Z of applied
dose (5000 ug)
l.i
1.4
0.2
1.0
0.2
3.9
35.4
61.1
34.9
a/  Proportion at 14 days postplanting;  the corn,- -having been consumed and/or demol-

~   ished by the animals, is not present aa an entity at the  termination of  the system.
                                                r!4 i
     19. -Terminal environmental distribution of [  Cjmethoxychlar plus metabolites in a

         vermiculite-terrestrial model ecosystem.
                                             37

-------
oo
20

19
18
!l7.
I
I "
9
u
Ef 14
«M
O
" 13-


12


11

10
1,'
/


















^{EMMX 0,'
k 4
MBTHOXYC1ILOR

CO,



2,
>
fEP 84X
13.6{ram 0.00215
i IUH 4x L
\ fEP 80X 1
30,0 {EM 7X 0,00116
i (UN lax i
1 fEP 87X '
90.9
-------
Table  A .—Concentrations of methoxychlor and  degradation
           products in the vermiculite substrate  ("soil")
           of a terrestrial ecosystem 10 days  after care-
           fully applying the methoxychlor to  the  corn
           foliage
Compound
I2/
M-DDE
M*/
M-DDD
II
III
mono-OH
IV
di-KJH
V
RfV
.95
.80
.71
.63
.27
.23
.18
.14
.05
.00
Methoxychlor
Acetone
extract

0.050
0.878
0.010
0.022
0.022
0.121
0.041
0.143
0.101
equivalents, ppm
MethanolS/
extract
<0.001
0.001
0.008

0.001
0.002
0.009

0.013
0.017
Total 14C?
  1.388
  0.051
Biosanple wt (g)
100.00
100.00
a/  Silica gel GF-254, petroleum ether : ether, 17:3 by volume.
b/  The methanol extract is from the sample previously ex-
    tracted with acetone.
c/  Roman numerals = unknown compounds.

d/  Methoxychlor.
                             39

-------
Table 5.—Concentrations of raethoxychlor and degradation products in corn grown in a  terrestrial model ecosystem.
                                          Hethoxychlor equivalents,  ppm.  at indicated postplanting age
                                11 Days
Compound
               R*'
                £
                Entire
 Root    Shoot  plant
                                                         12 Days
               Entire
 Root   Shoot  plant
                                                          13 Days
               Entire
 Root   Shoot  plant
                                                         14 Days
               Entire
 Root   Shoot  plant
  H-DDE



  M-DDD

  II

  mono-OH

  dt-OH

  III
               .97

               .80

               .71

               .63

               .39

               .18

               .05

               .00
            14
Extrectable   C
Unextractable
              14..
Grand Total   C
0.212            0.081

         3.930   2.452

0.055   75.536  47.153

         0.532   0.332

         0.215   0.134

0.011    0.668,   0.421

         0.136   0.085

0.014    0.725   0.458
0.416           0.230

0.024  13.731   6.982

1.006 155.039  79.247

0.218   1.095   0.676

        0.758   0.385

0.021   0.884   0.461

0.009   0.421   0.218

0.067   2.148   1.128
0.008           0.003

        2.320   1.267

0.161  43.868  24.012

        0.178   0.097

                0.061

0.006   0.112   0.171

0.018   0.309   0.069

0.022   0.112   0.454
0.216   0.192   0.204

        1.055   0.504

0.246  23.612  11.418

0.048   0.192   0.117

        0.064   0.031

0.018   0.408   0.204

0.015   0.140   0.075

0.089   1.107   0.576
                        0.292   81.742  51.116    1.761 174.076  89.327    0.215   0.814   26.134    0.632  26.770  13.129

                        0.019    4.366   2.594    0.069   3.219   1.544    0.036   6.822    3.824    0.032   0.978   0.499

                        0.311   86.108  53.710    1.830 177.295  90.871    0.251   7.636   29.958    0.664  27.748  13.628
Biosaople wgt. (g)    " 0.73773  1.07000 1.80773  0.97911 0.82165 1.80076  1.18650 1.42100 2.60750  1.35233  1.30851 2.6*   .


a/  Silica Gel CF-254, Petroleum Ether:  Ether, 17:3 by volume.

b/  Roman numerals • unknown compounds.

£/  Methoxychlor.

-------
 Table 6.—Concentration* of metboxychlor and degradation products in invertebrates
           after a 5-day exposure in a terrestrial model ecosystem
Methoxychlor
Compound
lS>
II
III
H-DDE
IV
V&
M-DDD
mono-OH
V
di-OH
VI
14
Extractable C
14
Unextraotabla C
Total 14C
Average biosample
"fy
1-.77
.94
.91
.80
.77-. 49
.71
.63
.18
.13 „
.05
.00



wt (g)
latribriaua
(worm)
0.031


0.055
0.209
0.316


, -0.121
0.126
0.534
1.392
0.665
2.057
2.78104
Lvoox
(slug.)


0.019
0.050

0.700
0.099
,0.209

0.115
0.701
1.893
0.192
2.085
3.45632
equivalents, ppi
Amodillidium
(pillbug)



0.055

1.102
0.208
0.130
_
0.186
1.781
3.462
0.755
4.217
0.09154
n*-'
Estigmene
(caterpillar)

0.089

0.526

2.829
0.038
0.155
•*
0.425
1.358
5.420
0.866
' 6.286
0.78475
 a/  Average of triplicate determinations.
,b/  Silica Gel CT-254, Petroleum Bcher: Ether, 17:3 by volume.
 £/  Roman numerals * unknown compounds.
 4/  Methoxychlor.            *      ...      "    *
                                         41

-------
                             Table 7.—Concentrations of methoxychlor and degradation products in the prairie vole after a 3-day exposure
                                       in a terrestrial model ecosystem.
*-
K>
Methoxychlor equivalents, ppm
Compound
1^'
II
III
IV
M-DOE
V
M*'
VI
VII
VIII
IX
mono-Oil
X
dl-OH
XI
XII
Extiactable ~^C
unextraetable 14C
Total C
Bios ample wt (g)
R a/
.97
.95
.94
.93-. 80
.80
.80-. 68
.71
.63-. 39
.24
.22
.39-. 05
.18
.12
.05
.00-. 05
.00



Stomach





0.087


0.015

0.019
0.014
0.080

0.541
0.756
1.011
1.767
1.48535
Large
intestine





0.009

0.004
0.002

0.006

0.009

0.127
0.157
0.876
1.033
3.91635
Skin
0.106
0.101


0.035
0.212




0.021

0.054

0.020
0.549
0.205
0.754
3.42487
Small
intestine
0.001
0.002



0.015




0.007
0.006
0.023

0.041
0.095
0,373
0.468
1.57405
carcass
0.009
0.010


0.005
0.013




0.010



0.025
0.072
0.082
0.154
12.65070
Internal-
organs
0.009
0.006
0.004
0.007

0.011
0.014


0.009



0.004

•, 0.064
0.078
0.142
2.67095
Body*'
totals
0.019
0.019

0.001
0.007
0.001
0.041
0.001
0.001
0.001
0.001
0.010
0.001
0.014

0.067
0.184
0.285
0*469

                             a/  Silica Gel CT-254, Petroleum Ether: Ether, 17!3 by volume.
                             b/  Internal organs include heart, parotid gland, lungs, kidneys And adrenals, uterus, tongue, maanary gland,
                                 liver and brain;  extracts of these organs were combined and chromatographed as a single sample.
                             £/  Body totals were calculated using the live wet weight, 26.220 g.
                             A/  Roman numerals " unknown compounds.
                             e_/  Methoxychlor.

-------
Table  8.-«e1atIve affinities of 14 body-parts of the prairie vole^-  for

          [  CJmethoxychlor plus Its metabolites, and comparisons with the

          relative masses of the body-parts.
Body-parts
(organs and tissues)
Large Intestine + contents
Stomach + contents
Skin
Carcass^-'
Small Intestine + contents
Liver
Heart
Tongue
Kidneys + adrenals
Uterus
Mammary glands
Lungs
Parotid glands
Brain

Residue wt in body-part
as a % of total residue
wt In entire body
32.86
21.3*
21.02
15.70
5.98
1,23
0.43
0.35
0.32
0.20
O.T7
0.16
0.15
0.09
100.00
Body-part wt as a %
of entire body wt
15.22
5.77
13. 3T
1»9.18
6.12
4.51
0.63
0.37
1.08
0.18
0.25
0.80
0.56
2.01
99.99
a/  Vole from a vermlculIte-terrestrial model ecosystem treated with
~"   [™C]methOxychlor.

b/  Carcass a the eviscerated body (the removed organs and tissues are listed
**   above);  It consists predominately of muscle and bone.
                                         43

-------
                                                                DDT


                                                          TOTAL RESIDUE
                        (33%)
                         Corn
                                                        Airltnalc
                          Calculation of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Corn*'
Vermiculite (II)
Air
To t&JL "F^ltTi!"™ To tuil.
Mfidn
Ba88' 8! concentration, "*ldue. "8:
(Mo.
(10)
(10)
(20)
(10)
( 1)

(44)
) 3J mass
3.21
2.23
0.0584
0.818
25.32

2.95
( 1)2160


- total P8/8
- 32.1 2.24
- 22.3 5.81
1.17 5.53
8.18 85.9
• 25.32 11.9
89.1
- 130 12.6
- 2160 1.73
[5000 vg-(I+ll
(mass) (cone.)
71.9
130
6.5
703
302
1213
1638
3737
[)] - 50
Total residue as
a Z of applied
dose (5000 wg)
1.4
2.6
0.1
14.1
6.0
24.2
32.8
74.7
1.0
a/  Proportion at 14 days postplanting;  the corn, having been consumed and/or demol-

    ished by the animals, is not present as an entity at the termination of the, system.




                                                r!4 i
Fig. 21.-Terminal environmental distribution of [  CJDDT plus metabolites in a

         vermiculite-terrestrial model ecosystem.
                                             44

-------
Ul
20-
19-

IB •
p.
w
| U-
1
. 15
§
1,,
o
* 13
12

,

11

10
1,-
4














., X ~
3 \EM 3«
1
'
DDT
>O-EO-. ^.ga
y

SEP 531 [& 67X (EP 63X fBP 31
W35X 5.81
-------
Table  9 .-Concentrations of DOT and degradation products  In the
          vermlculite substrate ("soli") of a terrestrial model
          ecosystem  10 days after carefully applying the  DDT to
          the corn foliage.
DDT equivalents,- ppm
Compound
DDE
DDMU
DDT
DDNS
DDD
&
11
III
IV
V
DDA
VI
Total }kC
Btosample wgt. (g)
Rf~
.90
.8A
.80
.70
.63
.*5
.42
.17
.13
.10
.02
.00


Acetone
extract
0.167
0.026
1.1T5
0.042
0.080
0.011
0.055
0.007
0.007

0.019
0.179
1.708
100.000
Methanol-/
extract
0.001

0.002


0.002



0.001
0.004
0.011
0.021
100.000
a/  Silica Gel GF-25A, Hexane:  Diethyl ether, 2
-------
table 10.-Concentrations of DOT and degradation products in corn grown in a terrestrial model ecoayatea.
DDT equivalents, ppn,
Compound
ODE ,
DOT
DDMS
ODD
I-7
II
III
IV
V
VI
DDA
VII
R b/
Rf-
0.90
0.80
0.70
0.63
0.45
0.34
0.28
0.16
0.10
0.05
0.02
0.0
Extractable 14C
Unextractable
UC
Grand Total 14C

Blosample wgt

. 

Root
0.018
0.362
0.213
0.020


0.053

0.043

0.029
0.043
0.781
0.014
0.795

0.40609
11 Days
Entire
Shoot plant
0.950 0.661
52.839 36.625
2.035 1.458
0.371 0.262


0.013

0.010
0.221 0.153
0.329 0.234
1.264 0.884
58.009 40.300
2.335 1.674
60.344 41.974

1.1498 i.5559
, at Indicated postplantlng age
12 Days
Root
0.006
0.043

0.083
0.803
0.008
0.084
0.031
0.004

0.013
^
0.275
0.009
0.284
*
Shoot
3.644
63.542
2.889
1.698





0.462
0.302
0.995
73.532
3.379
76.911

0.74740 1.1599
Entire
plant
1.956
34.077
1.548
0.944
0.001
0.003
0.034
0.013
0.002
0.248
0.166
0.533
39.525
1.856
41.381

1.9073
Root
0.01?
0.072

0.064
0.004
0.007
0.053
0.019

0.008
0.025

0.269
0.017
0.286

13 Days
Shoot
0.387
10,361
0.368
0,258





0.025
0.075
0.284
11.758
1.095
12.853

0.53034 1.4701
Entire
plant
0.298
7.881
0.279
0.211
0.001
0.002
0.013
0.005

0.021
0.063
0.216
8.990
0.828
9.818

2.0004
14 Daya
Hoot Shoot
0.038 1.255
0.297 13.803
0.271
0.170 0.347
0.009
0.018



0.013
0.003 0.109
0.083
0.548 15.868
0.023 2.089
0.571 17.957

0.79407 1.7336
Entire
plant
0.874
9.573
0.186
0.294
0.003
0.006



0.004
0.076
0.057
11.073
1.482
12.555

2.5277
£/ Roman numerals • unknown compounds; both dichlorobenzophenone and Kelthane  cochromatographed at




b/ Silica  Get  GF 25(1,  Hexane:   ether,  2li:1 by  volume.
Spot I (R, - 0.45)

-------
Table 11.-Concentrations of DDT and degradation products in invertebrates after
          a 5-day exposure in a terrestrial model ecosystem.
DDT equivalents, potu^
Compound
DDE
DDMC
DDT
DDKS
DDD
I^7
II
III
IV
V
VI
DDA
VII
Extractable 14C
Unextractable 14C
Total UC
Average biosample vt
* e/
V-
.90
.84
.80
.70
.63
.45
.42
.33
.26
.17
.10
.02
.00



w
Lumbriaus
(worn)
0.287

1.180
0.184
0.165
0.037





0.047
0.076
1.976
0.268
2.244
3.2106
Limax
(slug)
0.300

3.873
0.034
0.766
0.034


0.017
0.010
0.021
0.043
0.366
5.464
0.346
5.810
2.2272
Axmaaillidivm
(pillbug)
1.455

3.476
0.069
0.138





*
0.069
0.104
5.311
0.218
5.S29
0.0584
Eatigmene
(caterpillar)
78.812
1.657
2.984
0.659
0.184
0.157
0.107
0.078



0.104
0.363
85.105
0.769
85.874
0.81801
£/  Average of triplicate determinations.
b/  Roman numerals " unknown coapounds; both dichlorobenxophenone and Kelthane
    cochromatograpbed at Spot I  (Rf * 0.43).

c/  StUca Gel GF-254, Hexane:  ether, 24:1 by volume.

-------
                                     T*M*l2fCMK«iitncl«t« «f GOT *n4 «**»4MlM fnduct* U tlM yralrU *«!•'' ftoi • Urrutrtal aoM *co^>tw.
ID

C^»4
DOt
tan '
DOT
Dm*
DM
£'
II
lit
IV
V
VI
VII
mi
BOA
IX
UOMIHCtttU UC
Cc«n4 Toc«lUC
tlOIMpl* • ( ((>

U .'
V
190
•a4
tie
-.70
,.63
.4)
.32
.23
.14
.U
tW
.0?
,0)
.02
.00


.
Kite.?*
A4x*n*l* ttamtck
19.181 16.844
^ 1.223
'l.WJ 3.87)
0.204
1.85) 0 )M
0.13* 0.20*
< '*
0.019
0.017 0.094
,
0.090
1
' . 0.0*2
0.129 0.121
0.166 0.67*
21.039 ' 24.12)
3.116 0.6»2
28.2)5 2).007
0.3)3*4 0.77900

**.
17.6*9

3.004

0.554
0.182
0.017
0.034


0.101

0.293
0.50}
*
22.401
0.74?
23.14*
0.0*520

Hurt
14.477

2.316

0.)6)
O.i4)
0.01*
0.39)
0.064



0.0)7
0.191
0.58*
18.850
0.694
0.171)2
W>
Llvtr
9.942

0.41?
.'
1.402
0.042
0.076

r

'
O.OM
0.09*
0.37?
12.49*
2.26)
14.763
1.31106
r Motv.i.
|l*ad
11.242

1.600

0.3)9
0.143
0.011
0.01*



0.131
0.16.9
0.237
13.930
0.669
14.599
0.1127)
«t« PPB
tntut.
i.134
0.094
0.214
O.OM
0.40*
0.060
0.049
0.176
0.217
O.OM
O.1O4
0.14)
0.071
0.1*3
1.547
13.14)
l.«60)8

CtrcM*
8.426

1.511
0.016
0.243
0.011
0.014
0.009
0.016


0.02*
0.016
0.106
0.0)4
10.680
0.700
11.3*0
15.0)200

1-,
6.39)

0.1*7

0.092
0.093

0 027
0 01)
0,040

0.160
O.IM
0.363
7.126
3.733
11.2)9
0.2494)

Into *M*
7.631 ).631

!.«** 1.154

0.14* 0.116
0.10* 0.02?
0.011
0.042 0.04)
0.034
0.019


0.2)4 0.1)3
0.23* 0.267
10.407 7.M7
0.121 1.419
10.528 9.314
0.535*0 2.61)29

ttunx
1.646

0.949

0.1)6
0.062
0.011
0.021



0.070
0.132
0.277
7.126
1.547
*.«91
0.1169)

lull
incut.
.742
.074
.411
.0)3
.M?
.OH
.034
0.014
O.OM

0.074

0.02*
0.066
0.313
6.40)
1.49)
7.900
2.0)?))

££
«.201
O.OM
1.373
0.022
0.3)4
0.043
0.01*
0.027
0.03)
0.010
0.019
0.027
0.027
0.127
0.264
10. M?
1.2))
11 *)2

la th« h«>oo« w>4 blch«M cochraM(o|t«pha4 *t «pol t (R( « 0.4)).
                                      j/  Th« voU 41*4 «(t*r
                                      b/  hNua auMrali • inkaoun
                                      {/  Sil(tit fi»\ rt 2)4, ll«lumi  Diaclyl cclMr, 24 I l>y valuna
                                      4f Body totals  were calculated using  live  body  weight, 25.45289 g

-------
Table  13.-fte1atlve affinities of 13 body-parts of the prairie vole*7 for
          [  c]DDT plus Its metabolites, and comparisons with the relative
          masses of the body-parts.
Body-parts
(organs and tissues)
Carcass^7
Skin
Large Intestine + contents
Liver
Stomach + contents
Small Intestine + contents
Kidneys + adrenals
Brain
Heart
Lungs
Tongue
Mammary glands
Uterus

Residue wt in body-part
as a % of total residue
wt In entire body
56.77
8.14
8.11
6.42
6.41
5.39
3.31
1.87
1.11
0.33
0.65
0.54
0.35
100.00
Body-part" wt as a $
of entire body wt
59.45
10.41
7.35
5.18
3.05
8.13
1.40
2.12
0.68
0.98
0.34
0.45
0.47
100.01
a/  Vole from a vermiculIte-terrestrial model ecosystem treated with [  CJDDT.
b/  Carcass a the eviscerated body  (the removed organs and tissues are listed
*~   above);  it consists predominately of muscle and bone.
                                         50

-------
                                                           FONOFOS
                                                         TOTAL RESIDUE
                         Corn
                                                        Animals
                          Calculation of the above estimates:

Ecosystem
component
Earthworms3-
Slugs ,
Pillbugs*'
Pupae
Vole
T


f^f\ft»^
«™UJ. v^.^w Mean • ">-•»-•.
mass, g: . residue, ug:
0 concentration., °
(No.
"(10)'
(10)
(20)
( 5)
( 1)
) X mass - total
3.18 -''31.8'
2.63
0.080
0.643
26.3
1.60
3.22
29.98 29.98
Vg/g

0.404

1.04
0.270
(mass) (cone.)
i (7)
10.6
(7)
3.35
8.09

Total residue as
a 2 of applied
dose (5000 ug)
' (0.14) *
0.21
(0.14)
0.07
0.16
Animal total (I)
                                   92.9
                (44)    2.93
Vermiculite (II) ( 1) 2260
Air
                                  130
                                 2260
      1.10
      0.212
[5000 yg-(I+II)]
 (36)

 143
 479
4485
(0.72)

 2.9
 9.6
89.7
a/  Earthworms and pillbugs were not analyzed in this system.  Since  the mass of earth-
    worms plus pillbugs was approximately equal to- Chat of slugs plus pupae, it was
    assumed that their residues were also approximately equal.
b_/  Proportion at 14 days postplanting;  the corn-, having been consumed and/or demol-
    ished by the animals, is not present as an entity at the termination of the system.


Fig* 23.-Terminal environmental distribution of [  CJfonofos plus metabolites in a
         vermiculite'-cerrastrial model ecosystem.
                                              51

-------
K)
20
1
15
days poacplaat
S
*
8
u
>>
•g 5
0
o.:
t




2.:
212{«92Z 0,'
0,00892 \
i
(EP i6X
IJO^EM 43Z
* IUN 4ix
9.
8.1
11 0.
fEP 62X 0,0
51
-------
Table 14.-Concentrations of  fonofos  and degradation products  In
          th« vermicullte substrate  ("soil") of a terrestrial
          model ecosystem 20 days after applying the insecticide
          to the vermicultte.
Compound
Fonofos
.1'
Oyfoxon
II
III
IV
V t ,
VI
VII
VIM
^
.80
.59
.53
.36
.25
.19
r.15 - :>
.05
.03
.00
Fonofos
Acetone
extract
0.013
0.032
0.005
0.013
0.003
0.002
t - -
0.005
0.003
0.096
equivalents, ppm
Methanol-/
extract
0.003




' .
0.005
v

0.032
Total
      1*.
  0.172
  0.040
Btosample wt.   (g)
100.00
100.00
a/  ill lea Gel Gf-254, CCl^:  Eth Ac. 1;T by volume.
b/  The methanol extract is from the sample previously extracted
~   with acetone.
C/  Roman numerals equal unknown compounds.
                                   53

-------
Table 15.-Concentrations of fonofos  and degradation products In the corn from a terrestrial model ecosystem.
Fonofos equivalents, ppra. at Indicated postplantinn age
Compound
Fonofos
I-'
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
Extraetable C
tfnextractable 14C
Total WC '
Bloaample wt. (g)
•/
.69
.29
.22
.20
.19
.14
.13
.09
.06
.05
.04
.02
.00


6 Days
Root Shoot
4.040 0.791
0.064
0.067

•0.288

0.081
0.404
0.869
0.032


2.130 1.052
7.443 2.375
1.202 1.266
8.645 3.641
0.9145 0.2585

Entire
plant
3.600
0.012
0.012

P. 052

0.015
0.346
0.744
0.006


2.013
6.800
1.224
8.024
1.1730*

Root
10.485


0.035

0.059

0.666
0.886

0.060
0.101
1.448
13.740
1.782
15.522
1.1640
10 Days
Shoot
0.219
0.037
0.090

0.072

0.056


0.150


0.291
0.915
1.142
2.057
0.8970

Entire
plant
5.910
0.016
0.040
0.019
0.032 '
0.033
0.025
0.369
0.491
0.067
0.033
0.056
0.932
8.023
1.484
9.507
2.0610

Root
0.302


0.009



0.048


0.020

0.525
0.904
0.434
1.338
1.3520
14 Days
Shoot
0.042
0.053
0.015

0.016

0.020


0.040


0.196
0.382
0.502
0.884
1.2365

Entire
plant
0.175
0.025
0.007
0.004
0.008

0.010
0.025

0.019
0.010

0.363
0.646
0.437
1.103
2.5885
al  Silica Gel GF-254, chloroform) hexane, 20t80 by volume.



b/  Roman numerals " unknown compounds.

-------
Table 16.-Concentrations of fonofos  and degradation products



          in invertebrates after a 10-20-day exposure in a



          terrestrial model ecosystem.
Compound
Fonofos
Dyfoxon
1
II
Ml
IV
v-,- - _
Extractable C
14
Unextractable C
Total 14C
Biosample wt. (g)
Rf~
.80
.53
.36
.25
.15
.05
.00



'
Fonofos
Lunax—
(slug)
0.012
0.025
0.072
0.017
0.007
0.017
0;022 '
0.172
0.232
0.404
1.7724
equivalents , ppm
c/
Estzgmene—
(moth pupa)


0.365



-0.069
0.434
0.609
1.043
0.64345
aj  Silica Gel GF-254, CC1,: Eth Ac, 1:1 by volume.



b/  Average-of six determinations.



c/  Average of two determinations.
                            55

-------
Table  17.-Concentrations of fonofos  and degradation products In the prairie vole after a 5-day exposure in a terrestrial
          model ecosystem.
Compound
Fonofos
1
Dyfoxon
II
III
IV
V
VI
Extractable
tlnextraetable
Total 14C
Blosample wt
Rf
.80
.62
.53
.48
.42
.20
.02
.00
C
"c

(K)

Large
intestine


0.020
0.053
0.043


0.162
0.278
0.518
0.796
1.1907
Fonofos equivalents, ppm
Kidneys
. . + Small
Stomach— Carcass adrenals Heart Tongue Intestine

0.057
0.090
0.015

0.001
0.002
0.006 0.020
0.251 0.156 0.034 0.033 0.022 0.035
0.191 0.132 0.123 0.120 0.088 0.054
0.442 0.288 0.157 0.153 0.110 0.089
1.1997 21.600 0.5021 0.2168 0.1696 1.2374

Seminal Body-
Liver vesicles Fat Brain totals

0.041
0.066
0.003
0.002
<0.001
0.001
0.011
0.011 0.023 0.016 0.006 0.136
0.059 0.030 0.008 0.011 0.134
0.070 0.053 0.024 0.017 0.270
1.6453 0.8771 0.4098 0.5787
£/  Silica Gel GF-254, CCl^s Eth Ac. 1:1 by volume.
Jfc/  The concentrations of individual degradation products In the following organs were of insufficient magnitude to be
    quantitated:  stomach, kidneys plus adrenals, heart, tongue, liver, seminal vesicles, fat, brain.

cj  The body totals were calculated using live wet weight (29.984 g).

-------
Table 18.-fteletlve affinities of 11 body-parts of the prairie vole^  for
           [  c]fonofos  (Dyfonate*0 plus  Its metabolites, and comparisons with
           the relative masses of the body-parts.
Body-parts as*!***^
(organs and tissues) .
Carcass (Including skin)—
Large intestine * contents
Stomach + contents
liver
Small Intestine
Kidneys •+• adrenals
Seminal vesicles
H«'t
Tongue L . . <, •
Brain
Abdominal fat

a/ Vole from a vermicul Ite-terrestrlal
~ [14Cjfonofos.
*t In b
f total
ent I re
76.53
11.72
6.55
1.42
1.36
0.98
0.57
0.41
, 0.23,
0.11
0.11
99.99
model
i body*1"* of «ntire body wt
72.91
4.02
4.05
5.55
4.18
1.69
2.96
0.73
-,, - 0.57 '
1-95
t.38
99.99
ecosystem treated with
b/  Carcass «the eviscerated body (the removed organs and tissues are listed
~*   above);  It Consists predominately of muscle, skin and bone.
                                         57

-------
                                                         DIELDRIN

                                                       TOTAL RESIDUE
                                                   (VEBKICOLITE SYSTEM)
                                                        Aquatic
                          Corn
              Vermiculite sediment
                             Calculation of the above estimates?
                          Total
Ecosystem
component
                       (Mo.) X maes • total
      «:             ****
      _ _ _ _   concentration,
                     wg/g
                                           Total
                                Ug:
                                       (mass)(cone.)
                                                       Total residue as
                                                        a 2 of applied
                                                        doae (5000 ug)
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
( 8)
( 8)
(13)
( 8)
( 1)
3.48
4.55
0.0768
0.668
22.81
27.8
36.4
0.998
5.34
22.81
3.62
0.771
8.87
1.34
3.67
101
28.1
8.85
7.16
83.8
2.0
0.6
0.2
0.1
1.7
Terrestrial
   animals/total (I)
Corn*'
Daphnia
Snails
Fish
(44)
(600)
(50)
( 3)
3.41   -
0.00344-
0.017  -
0.160  •
 93.3
150
  2.06
  0.850
  0.480
 5.66
 8.81
70.3
62.6
Aquatic
   animal total (II)
Surface water (III)   ( 1)7000
Vermic. sediment6.' (IV) ( 1)2400
Air
                   3.38
              - 7000         0.022
              • 2400         0.894
                [5000 pg-(X+XZ+UX+ZV)]
 229
 849
  18.1
  59.8
  30.0


 108
 154
2146
2363
 4.6
17.0
 0.5
 1.2
 0.6
                                                      2.3
                                                      3.1
                                                     42.9
                                                     47.3
W  The terrestrial animals (and their residues) were reaovcd from the system at the ter-
    mination of the terrestrial phase.
b_/  Proportion at 14 days postplantlng;  the corn, having been consumed and/or demolished by
    the animals, is not present as an entity at the termination of the terrestrial phase, and
    Its residue is distributed among animals, air, and vermiculite.
£/  The direct Interaction of corn, air, and terrestrial animals with the vermiculite
    occurred prior to flooding the system.

Fig.  25.-Terminal environmental distribution of [  CJdieldrin plus metabolites in a
         vermiculite-terrestrial model ecosystem.
                                          58

-------
Ul
VO
fco BAT fEP 90Z
20 1
.
•
IS-
•
9 •
ft
J 10 •
y
I .
fft
1 •
*
ct
I'
•8
«
0
Ifii /*•* vw* 7 C7xou **
.MlW iz» • 3.6/SEM 4Z














2,(
0,00358 f lus *x
I
0.01
f fEP 67Z
5.66SEM 25Z



'561 , fEp n fEP 72Z fEP 861 fEF 95Z
3.62
-------
32 1


3
u
9
!"•
& 26-
•«
g 25-
U
• 24-
o
« 23.
22 .

21.
20-




0,
0,
0,

0.


0.

0,
0,


D1ELDIUN
^OT-

[EP 4ix [EP 92X [EP 89Z
0220
-------
Table  19.-Concentration* of p*c]dieldrin and degradation products in the



          vemiculite of a node! ecosystea 20 days after application of



          [14c]dieldrin to the veroiculita
Compound
x£/
zx
Dieldrin
XXX
W
V
VX
vxx
VXIX
»
X
XX
XXX
xxxx
•* • " **"
Sxtraetable 14C
Sa^I* «« (?)

BfV
.93
.90
.85
.79
.69
.6«
.49
.41
.34
.25
.17
.06
.03
.00


Dieldrin
equivalents, ppn
Acvton* extract Methanol extract^/
0.0085
0.0412
1.1441
0.0067
0.0034
0.0274
0.0020
0.0046
0.0526
0.0072
0.0028

0.0082
0.0228
1,3315
100.000
0.0005
0.0038
0.0686
0.0004

0.0017
0.0001
0.0002
0.0031
0.0004
0.0002
0.0002
0.0002
0.0004
0.0798
100.000
*/  Silica gel GE-.254* £-Junaae i diethyl ether,  3r2 by volon.



b/  Methanol extract i» txtm the -staple previonsly extracted with acetone.



vf  Raeum aumeral* « unknown
                               61

-------
                               Table  20.-Concentrations of  [14c]
-------
 Table  21.-Concentrations of  [  c]dieldrin and  degradation products in the

           from a vermiculite nodal ecosystem
Compound
*
11
Dieldrin
III
IV
^ '
.92
.89
.86
.67
.00
Dieldrin equivalents,
Trap l^/
0.00002
0.00039
0.00513
O.OOOO3
0.00004
ppm
Trap 2^





 Total 14C

 Sum 14C, Traps 1 s 2
0.00561
0.00050
              0.00611
 Air sample- wt
            108.0
 a/  Air vaa trapped for, a 3-hour daylight period at a flow rate of 10 ml/sec
     5 days after application" of •-[14c] dieldrih to the vermiculite'.

 b/  Silica gel GF-254, n_-hexane : diethyl ether, 3:2 by volune.

 c/  Trap 1 was connected directly to the ecosystem container and contained
     75 ml of acetonitrile as the trapping solvent;  the trapping solvent was
     chromatographed.

• d/  Trap 2 was .connected in series to trap 1 and -contained 75 ml of trapping
     solvent (ethanolamine : 2-methoxyethanol, 1:2 by volume);  the trap 2
     solvent was- not chromatographed.

 «/  Roman numerals » unknown compounds.

 f/  One liter of air was assumed to weigh 1 g.

-------
Table 22.— Concentrations of [cl^ieldrin and degradation products in inverte-
           brates after a 5-day exposure in a vermiculite model ecosystem.
Dieldrin equivalents, ppm—
Compound
Dieldrin
1-S/
II
III
IV
V
VI
VII
14
Extractable C
14
Unextractable C
Total 1AC
Average
biosample wt. (g)
Rf~
.80
.71
.59
.31
.24
.20
.03
.00




Armadillidiun
(pillbug)
7.594


0.014
0.208

0.028
0.041
7.885
0.986
8.871
0.077
Eetigmene
(caterpillar)
1.263


0.032
0.006


0.005
1.306
0.030
1.336
0.668
Limes:
(slug)
0.554

0.057
0.033
0.023
0.009
0.022
0,017
0.715
0.056
0.771
4.554
LunibricuB
(worm) i
0.255
3.062
0.028
0.037
0.008 f

0.018
0.010
3.418
0.202
3.620 '
3.475
a/  Average of triplicate determinations.
jb/  Silica gel GF-254, n-hexane : diethyl ether, 3:2 by volume.
c/  Roman numerals • unknown compounds.
                                          64

-------

                                 Ta»l* 23.-Coat«n«ratt O.MS
Haeeury
(land* Uterua

40.614 11. Ml

0.12S 0.160

0.1}7 O.UM



O.M5
40.»74 21.206
O.OS1 0.0*4
41.027 21.170
O.OM O.MS
* Kidney*
1 and
Skin adrenal*
i.
S.126 4.104

e.ois ~ o.eit
' J.
0.024 0.020
r


0:014 0.0*1
1.401 " 4.4S4
1.080 0.074
6.441 4.512
2.12S 0.171
Stonach
0.112
1.105
0.020
0.099

O.O4S
0.019
0.044
0.102
0.147
1.411
oim
4.02}
1.1B1
Carcaa*

1.4)2

O.Olt

0.010



0.027
1.141
0.101
1.644
11.741
Liver Too§tM Bearc

2. 414 2.241 2.241

0.02S 0.017

0.01*
0.014

0.111
0.1M 0.014 0.014
1.741 1.1*4 1.2U
0.114 0.010 0.041
2.47* 1.144 1.121
1.111 0.0*5 0.111
Iot..t<»e
0.012
O.*ll

O.OM



fl.lH

0.114
1.144
0.111
1.411
1.1S*
•odr
loot* 4r*te total*
0.012
0.7*0 0.171 1.141
0.001
0.011
O.OM «0.091
0.011
0.001
0.011
0.011
0.022 0.002 0.0)1
0.412 O.S41 M17
0.04* 0.011 0.111
0.441 O.SM 1.471
0.144 0.540 II.OIO*'
                                     (lite* «
-------
Table 24.-«elatlve affinities of 13 body-parts of the prairie vole*-' for

           [  cjdleldrln plus Its metabolites, and comparisons with the

           relative.masses of the body-parts.     s
Body-parts
(organs and tissues)
Carcass
Skin
Intestines + contents
Stomach + contents
Pectoral fat
Liver
Mammary glands
Kidneys + adrenals
Uterus
Heart
Brain
Tongue
Lungs
Residue wt In body-part
as a % of total residue
wt in entire body
51.30
17.99
6.26
6.16
4.90
M7
3.88
2.02
1.81
0.62
0.41
0.27
0,19
100,00
Body-pert wt as a %
of entire body wt
54.66
10.78
15-12
5.94
0.44
5.63,
0.37
1.73
0.30
1.03
2.69
0.44
0,87
a/  Vole from a vermlculIte-terrestHsl model ecosystem treated with
    [™c]d!eldrin.

b/  Carcass* the eviscerated body (the removed organs and tissues are
*~   listed above); It consists predominately of muscle and bone.
                                       66

-------
er.
                              Table 25. -Concentrations of
                                        7 days after flooding
 [  c]dieldrin and degradation product
 ing the ecosystem with water*/
                .• in the water of a veniculite aodel ecosyctM
                              Compound
                                                                                       Dieldrin equivalent*, ppm
                                                                       Surface water
                                                                                                                     Leachate^/
Ether-extract able
before hydrolysis
Ether-extractable
after hydrolysis^/
Ether-extractable
before hydrolysis
Ether-ex tractable
after hydrolysis
IS/ .93
Dieldrin .88
II .80
III .76
IV .72
V ' .65
VI .56 .
VII .S3
VIII .49
ix ".46 ;
X .39
XI .34
XII .30
XIII .20
XIV .It
XV .12
XVI .09
XVII .05
XVIII .03
XIX .00
Extractable 14C
Unextractable 14C
Total extractable 14C

0.00899
0.00019

0.00017

0.00010
0.00009
0.00045
0.00097
0.00115



0.00017


0.00008
0.00007
0.00063
0.01306

0.01612
-
0.00018


0.00002





0,00002

0.00009


0.00007
0.00019
0.00038
0.00171
0.00040
0.00306
0.00209

Unextractable 14C after hydrolysis 0.00209
14C loss during hydrolysis
Initial 14C in water
Sample volume (1)
0.00380
0.02201
1.000
a/ Ecosystem was flooded with water 20 days after
b/ One liter of water was



application of
0.00053
0.03013
0.00043
0.00007
0,00025
0.00054
0.00017
0.00029
O.O0124
0.00167
0.00174



0.00053



0.00072
0.00165
0.03996

0.04726
0.00436
O.O1080
0.06242
1.000
[14c]dieldrin to the vermiculite

0.00126
o.ooooe







O.OOOO4
0.00007
0.00008
0.00010
0.00045
0.00083

0.00175
0.00217
0.00047
0.00730
0.00436





»
withdrawn through the tap at the jar bottom over a period of 25 min.
c/ Silica gel GF-254, n-hexane > diethyl ether, 3:
d/ The "unextractable" of
the preceding column was
2 by volume.
adjusted to 0

T
.012 N HC1 and maintained at 55-56°C for 18-24 hr
e/ Roman numerals « unknown compounds.

-------
Table  26.-Concentrations of  [14c]dieldrin and degradation products in aquatic

          organisms of a vermiculite model ecosystem flooded with water*/
Dieldrin equivalents, ppm=
1 r
Compound
IS/
XI
Dieldrin
III
IV
V
VI
VII
VIII
attractable 14C
Dnextractable 14C
Total 14C
Average bio-
sample wt (g)
*?
.92
.89
.83
.66
.38
.31
.26
.03
.00





GambnsiaS/
(fish)
0.101
1.612
58.066
0.276

1.190
0.143

0.147
61.535
1.055
62.590

0.160
(snail)
0.267
2.270
62.942
0.626
0.224
2.063
0.418
0.095
0.073
68.978
1.368S/
70.346

0.017
Daphnia*/
(water flea)

0.228
8.048
0.113

0.279
0.017

0.014
8.699
0.106
8.805

1.032
a/  Ecosystem was flooded with water 20 days after application of  [14c] dieldrin
    to the vermiculite.

b/  Average of triplicate determinations for fish;  average of duplicate deter-
    minations for snails;  single determination for water fleas.

c/  Silica gel 6F-2S4, iv-hexane  : diethyl ether, 3:2 by volume.

d/  Fish were added 4 days after flooding the ecosystem, removed 3 days later,
    and processed^individually.

e/  Snails were added on the day of flooding, removed 7 days later, and processed
    in 2 batches of 15 snails each;  average batch weight • 0.252 g.

{/  Daphnia were added on the day of flooding, removed 7 days later, and
    processed as a batch;  many organisms constituted the biosample.

g/  Roman numerals - unknown compounds.

h/  Part of concentrated extract was added to residue pellet during processing.
                                        68

-------
Table  27.-Concentrations of [I4c]dieldrin and degradation products in the

          vennjculite sedioent of a nodal ecosystem 12 days after flooding

          the ecosystem with water8/
Compound
&
IX
Dieldrin
III
-IV.
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
Extractable 14C
Sample wt (g)


Dieldrin
equivalents , ppm
«Sr Acetone extract Methanol extractS/
.93
.90
.85
.79
.66
.49
.43
.41
.34
.31
.25 , -
.22
.17
.03
' .00



0.0055
0.0503
0.6925
0.0039
0.0154
0.0071
0.0028
0.0026
0.0216
0.0034
« 0.0069
0.0013
0.0043
0.0044
0.0070
0.8290
100.000

0.0006
0.0073
O.OS20
0.0006
0.0013
0.0004
O.O001
O.OO02
0.0010
0.0001
0.0004

O.OO02
0.0002
0.0004
0.0648
100.000
1
a/  Ecosystem was flooded with water 20 days after application of  [14cjdieldrin
    to the vermiculite.

h/  Silica gel GP-2S4. jv-haxane .t.diethyl a the*,' 3:2 by volume.

c/  Methanol extract is from the sample previously extracted with  acetone.

d/  RoBan nu&erals • unknown
                                      69

-------
                                                           ALDRIN
                                                         TOTAL RESIDUE
                                                      (MEAN OF VERMICULITE
                                                        SYSTEMS A AND B)
                                                       Animals
                          Calculation of the above  estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Com
Vermiculite (II)
Air
Total ffiff Total
»— ' 8: concenlration. resldue» "*:
(Mo
( 8)
( 8)
(13)
( 8)
( 1)

(44)
.) X mass •
3.98
2.52
0.0335
0.744
34.0

3.41 -
( 1)2400


total
31.8
20.2
0.436
5.95
34.0
- 92.4
150
2400
[5000
Vg/g
4.13
2.58
3.22
3.38
1.31

8.05
0.882
wg-(I+I]
(mass) (cone.)
131
52.1
1.40
20.1
44.5
249
1208
2117
0] - 2634
Total residue as
a Z of applied
dose (5000 pg)
2.6
1.0
<0.1
0.4
0.9
4.9
24.2
42.3
52.6
a/  Proportion at 14 days postplanting;   the corn, having been consumed and/or demol-
    ished by the animals, is not present as an entity at the  termination of the system.


                                                     r!4
Fig. 28.-Mean terminal environmental distribution of  [ Cjaldrln plus metabolites in
         vermiculite-terrestrial model ecosystems A and B.
                                             70

-------
20 i
15 •
it
«
§ 10 -
a
a
41
5 •
*
0 -
0,
i




2,1
JQ., /EP 142
>e* 1EM 862
0,0
8i(
5,;
9,(

)3 0,(
(EP 19%
EM 742
UN 72
fEP 252 0-0
'9 SEM 692
[UN 62
(EP 492
11 
-------
                                                             ALDRIN
                                                          TOTAL RESIDUE
                                                      (VERMICULITE  SYSTEM A)
                         Corn
Animals
                          Calculation of the above  estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Corn*7
Vermiculite (II)
Air
Total maximum „ Total
xiean
"aM» g: concentration, residue' »8:
(No.
( 8)
( 8)
(13)
( 8)
( 1)

(44)
) X mass »
3.98
2.52
0.0335
0.744
26.1

3.41 -
( 1)2400


total
31.8
20.2
ug/g
31.2
2.06
0.436 3.62
5.95
26.1
84.5
150
2400

4.32
2.14

7.77
0.954
[5000 vg~(I+I]
(mass) (cone.)
99.2
41.6
1.58
25.7
55.9
224
1166
2290
:)] - 2486
Total residue as
a Z of applied
dose (5000 vg)
2.0
0.8
<0.1
0.5
1.1
4.4
23.3
45.8
49.7
a/  Proportion at 14 days postplanting;  the corn,  having been consumed and/or demol-
    ished by the animals, is not present as an entity at  the termination of the system.

                                                rlA 1
Fig. 30.-Terminal environmental distribution of [   CJaldrin plus metabolites in
         vermiculite-terrestrial model ecosystem A.
                                              72

-------
                                                19Z
OJ
id •

'8 postplaating
i—
Ul >
8 10
1
o
V
5


t





•

0,00631
j
7,3
4
-
'
Q | \


. /EP i9X
7
-------
Table 28/Concentrations of [  cj Aldrin and degradation

         products in the vermiculite substrate ("soil")

         of the terrestrial model ecosystem A,20 days

         after applying the [  CJAldrin to the substrate.
Aldrin equivalents, ppm
Compounds
Aldrin
Dieldrin
1^
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
Total 14C
Sample
wt. (g)
IU*/
.97
.90
.82
.73
.69
.36
.46
.39
.35
.31
.27
.17
.09
.04
.00

Acetone
extract
0.175
0.459
0,047
0.011
0.003
0.003
0.024
0.005


0.018
0.009
0.008
0.021
0.125
0.908
100.00
Methanol-^
extract
0.011
0.015
0.002



0.001



0.001
0.001

0.002
0.013.
0.046
100.00
a/  Silica Gel GF-254, n-hexane : diethyl ether,
    3 : 2 by volume.
b_/  The methanol extract is from the sample previously
    extracted with acetone.
cj  Roman numerals * unknown compounds.
                         74

-------
Table 29.-Concentrations of £  CJAldrln and degradation products Irr corn grown  In the
          varmteulIte-terrestrlal model ecosystem A.
Aldrln equivalents,
Compound
Aldrln
Oleldrln
£'
II
III
IV
V
VI
VII
VIII
IX
X
Extrae table
Unextractable
Total '*C
Blosample wt.
*'
.97
.87
.74
.58
.48
.42
.38
.18
.11
.06
.04
.00
c
l*c

(g)

Root
4.473
3.891
0.306


0.125


0.265
0,086
0.358
0.593
10.097
0.406
10.503
1.225
6 Days
Shoot
0.848
0.664
0.665






0.126
0.094
0.224
2.621
0.051
2.672
0.340

EntOe
plant
3.683
3.188
0.384


0.098


0.207
0.095
0.300
0.512
8.467
0.329
8.796
1.565

ppm, at Indicated

Root
3.
6.
0.


0.


0.
0.
0.
0.
11.
0.
11.
0.
221
019
475


399


086
049
205
573
027
513
540
748
10 Days
Shoot
0.069
0.068
0.154
0.317
0.290

0.113
0.020

„

0.208
1.239
0.061
1.300
0.852

Ent i re
plant
1.460
2.693
0.296
0.178
0.162
0.176
0.063
0.011
0.038
0.022
0.090
0.369
5.558
0.262
5.820
1.600
postplanting age

Root
3.058
7.396
1.206


0.660


0.107
0.061
0.300
0.987
13.775
0.977
14.752
0.785
14 Days
Shoot
0.081
0.080
0.181
0.372
0.340

0.133
0.024



0.244
1.455
0.087
1.542
0.860

Entire
plant
1.486
3.533
0.664
0.196
0.179
0.311
0.070
0.012
0.050
0.029
0.142
0.594
7.266
0.504
7.770
1.645
a/  Silica Gel GF-254, n^-hexane:  dlethyl ether, 60:40 by volume.
b/  Roman numerals » unknown compounds.
                                          75

-------
Table  30.-concentrations of  [14c]aldrin and degradation products in inverte-

          brates after a 5-day exposure in the vermiculite-terrestrial model

          ecosystem A
Aldrin equivalents, ppmSr
Compound •„.
Aldrin
Oieldrin
l£/

II
III
IV
V
VI
VII
VIII
Extractable 14C
Onextractable 14C
Total 14C
Average bio-
sample wt (g)
*f
.98
.90
.80

.73
.41
.36
.27
.08
.04
.00




Lumbricus
(worm)
0.165
0.235
2.345



0.053

0.015
0.045
0.040
2.898
0.226
3.124
4.51656
Umax
(slug)
0.207
1.640
0.068
_
0.007
0.009

0.018

0.010
0.022
1.981
0.075
2.056
1.35427
Armadillidium
(pillbug)
0.290
2.029

3
0.065
0.137
0.167
0.026


0.030
2.744
0.878
3.622
0.02628
Estigmene
(caterpillar)
0.220
3.627
0.327



0.051



0.034
4.259
0.064
4.323
0.84410
a/  Average of triplicate determinations for pillbugs and caterpillars;  average
    of duplicate determinations for slugs; single determination for worm.

b/  Silica gel GF-254, n-hexane : diethyl ether, 3:2 by volume.

c/  Roman numerals •* unknown compounds.
                                   76

-------
Table 3l.-Concentrationa of [  CJAldrin and degradation products in the prairie vole after a 5-day exposure in the


vermicullte-terrestrial model ecosystem A.
Aldrln equivalents, ppn
Compound
Aldrin
Dleldrin
I*/
II
III
IV
V
VI
VII
VIII
IX
X
Extractable l4
Unextractable
Total C
Blosaople wt
»«/
f
.97
.94
.84
.48
.42
.34
.28
.23
,15
.10
.05
.00
C
"c

(8)
Kidneys
and
Adrenals

7.405
0.009

0.027

0.024




0.006
7.471
0.036
7.507
0.50313
Liver
5.577

0.027
0.043


0.060
0.011
0.012
0.017
0.101
5.848
0.264
6.112
1.21509
Uterus Heart Brain
0.038
2.413 2.027 1.742
0.008
0.030
0.016
0.015 0.011
"•
0.003 0.016

0.031
0.106
0.027 0.012 0.043
2.443 2.070 2.025
0.073 0.076 0.111
2.516 2.146 2.136
O.Q8726 0.33518 0.52473
Carcass
0.026
1.924
0.016

0.009




0.013
0.010
1.998
0,106
2.104
12.71500
Intest.
0.033
1.339
0.030
0.011
0.008


0.001

0.005
0.015
0.013
1.455
0.192
1.647
2.88175
Stomach
0.029
1.193
0.026
0.010
0.007


0.001

0.005
0.014
0.011
1.296
0.328
1.624
0.48150
Skin
0.050
0.482
0.011


0.005
0.002
0.001
0.002

0.002
0.002
0.557
0.818
1.375
6.90475
Body
Lungs Bladder Parotids Totals
0.
0.
0.
0.
0.




0.
0.
0.
1.233 0.
0.083 0.
1.316 0.
0.32015 0.
Oil
451
010
004
003




002
005
004
490 0.045
345 0.003
835 0.048
09848 0.09918
0.290
1.445
0.007
0.011
0.004
0.006
0.001
0.003
0.001
0.002
0.012
0.013
1.821-'
0.314
2.135
26.16620
a/  Silica Gel GF-254, n-hexane : diethyl ether, 3:2 by volume.


b/  Roman numerals • unknown compounds.

~"                                           14
c/  This value represents total extractable   C in all organs; two organ extracts were not subjected to TLC separation.

-------
Table 32.-Re1atIve affinities of 12 body-parts of the prairie vole  for

          [  CJaldrfn plus  Its metabolites, and comparisons with the'

          relative masses of the body-parts; the vole Is from

          vermlcul-Mte-terrestrial model ecosystem A.
Body-parts
(organs and tissues^).
Carcass-
Skin
Liver
Intestines + contents
Kidneys + adrenals
Brain
Stomach + contents
Heart
Lungs
Parotid glands
Uterus + ovaries
Bladder + contents
Residue wt In body-part
as a % of total residue
wt In entire body
47.90
16.98
13.29
8.49
6.76
2.01
1.40
1.29
0.76
0.59
0.39
0.15
100.01
Body-part wt as a %
of enti re body wt
48.59
26.39
4.64
11.01
1.92
2.01
1.84
1.28
1.22
6.38
0.33
0.38
'99.99
a/  Carcass »the eviscerated body  (the removed organs and tissues  are
    listed above); it consists predominately of muscle and bone.
                                     78

-------
                                                            ALDRIN
                                                          TOTAL RESIDUE
                                                      (VERMICULITE  SYSTEM B)
                     f  C25Z)  }
                         Corn
Animals
                          Calculation of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Corn5''
Vermiculite (II)
Air
Total ma-rttmm u
mass, g: ****
' * concentration
(No.) X mass
( 8) ' 3.98
( 8) 2.52
(13) 0.0335
( 8) 0.744
( 1) 41.8
(44) 3*41
( 1)2400
• total
, 31.8 "
20.2
0.436
5.95
41.8
100
- 150
- 2400
[5000
»g/g
5.1'4
3.10
2.81
2.43
0.478
8.33
0.809
jig-(i+r
Total
residue, vg:
• ^ lm ^
(mass) (cone.)
~ ' 164"
62.5
1.22
14.5
20.0
262
1250
1942
O] - 2796
Total residue as
a Z of applied
dose (5000 ug)
3.3
1.2
ois
0.4
5.2
25.0
38.8
55.9
a/  Proportion at 14 days postplanting.;.. the corn,- having been consumed and/or demol-
    ished by the animals, is not present as an entity at the termination of( the system.


Fig. 32.-Terminal environmental distribution of'[  CJaldrin plus metabolites in
        • vermiculite-terrestrial model ecosystem B.
                                               79

-------
                             »
ng
plan
                          I
M
Vfl
                             10
00
o
                          I
0.809 {*
, g
                                                                 0,00872
                                                     (E
                                                     
-------
                             r!4  i
Table 33.-Concentrations of  [  CjAldrln and degradation

          products in the vermiculite substrate  ("soil")

          of the terrestrial model ecosystem B, 20 days
                              r!4 T
          after applying the  I  CjAldrin to the  substrate.

Aldrin equivalents, ppm
Compounds
Aldrin
Dieldrin
I±'
II
III
IV
V
VI
VII
VIII
IX
X
XI
Total. 14C -
Sample
wt (g)
R a/
.97
.90
.82
.73
.69
.56
.46
.39
.27
.17
.09
.04
,00


Acetone
extract
0.053
0.346
0.040
0.017
0.010
0.005
0.025
0.008
0.036
0.009
0.006
0.022
0.179
- 0.756
100.00
Methanol-''
extract
0.010
0.018
0.002



0.001
0.001
0.001
0.001
0.001
0.001
0.017
0.053
100.00
a/  Silica Gel GF-254, n-hexane : diethyl ether,
    3 : 2 by volume.
b/  The'methanol extract is 'from the sample previously
    extracted with acetone.
c/  Roman numerals * unknown compounds.
                         81

-------
Table 34.-Concentrations of  [ CJAldrln and degradation products  In corn grown  In the



          vermlculite-terrestrta) model ecosystem B.
Aldrin eauivalents, ppm, at indicated
Compound
Aldrin
Dleldrin
£7
II
III
IV
V
VI
VII
VIM
IX
X
XI
XII
Extractable 'V
Unextractable '*C
Total C
Biosample wt (g)
Rf
.97
.87
.74
.68
.58
.48
.42
.38
.18
.16
.11
.06
.04
.00






Root
6
3
0



0


0
0
0
0
0
11
0
11
1
.706
.707
.207



.108


.044
.049
.082
.157
.232
.292
.484
.776
.071
6 Davs
Shoot
0.670
0.344
0.377








0.043
0.045
0.067
1.546
0.035
1.581
0.3^2
postplanting afe
10 Days
Entire
plant
5.191
2.863
0.249



0.081


0.033
0.037
0.072
0.129
0.190
8.845
0,371
9.216
1.433
Root
2.130
3.532
0.377



0.248



0.026
0.013
0.139
0.340
6.805
0.439
7.244
0.954
Shoot
0.078
0.077
0.173

0.356
0.325

0.1i7
0.023




0.233
1.392
0.056
1.U8
0.683
Entire
plant
1.255
2.060
0.288

0.147
0.134
0.143
0.052
0.009

0.015
0.007
0.080
0.291
4.481
0.277
4.758
1.637
Root
3.356
8.556
0.939
0.219


0.702



0.103
0.132
0.250
0.731
14.988
1.021)
16.012
0.861
.14 Days
Shoot
0.082
0.081
0.182

0.374
0.341

0.133
0.024




0.245
1.462
0.063
1.525
0.989
Entire
plant
1.619
4.061
0.538
0.103
0.199
0.182
0.330
0.071
0.013

0.048
0.062
0.117
0.474
' 7.817
0.515
8.332
"1.850
a/  Silica Gel GF-254, n^hexane:  diethyl ether, 60:40 by volume.



b_/  Roman numerals • unknown compounds.
                                                 82

-------
Table 35.-Concentration* of  [  CJAldrin and degradation products In

          Invertebrates after a 3-day exposure In the verniculite-

          terreatrial model  ecosystem B.
Compound
Aldrln
Dieldrin
1&
II
III
IV
V
VI

VII
viii
14
Extractable C
14
Unextractable c
Total UC
Average bio-
sample wt (g)
Aldrin equivalents. ppa~
, . Uaabricm Limax Annadillidiua Estigmene
Rf-' (worm) (slug) (pillbug) (caterpillar)
.98
.90
.80
.63
.41
.36
.27
.08

.04
'.00




0.281
0.402
4.009


0.091

0.025

0.077 ^
0.069^
4.954
0.185
5.139
0.63275
0,156
2.678
0.053
0.026
0.030

0.011


0.034
0.039
3.027
0.071
3.098
0.93990
0.204
1.389
0.052

0.159
0.093
0.007

t ,>

0 .045
1.94»
0.863
2.812
0.02050
0.139
1.958
0.244


0.031



_
o.oia
2.390
0.037
2.427
0.82119
£/  Average of triplicate determinations for caterpillars; average of duplicate
    determinations for pillbugs-; single determination for worm  (dead at sampling)
    and slug.            .      .                  \        •.           *
b/  Silica Gel 3F-234, g-hexane  : diethyi ether> 3 : 2 by volume.
c/  Roman numerals z unknown compounds«•
                                   83

-------
                                  Table  36.-Concentration* of [  CJAldrln end degradation product!  in the prattle *»!• efter a )-day eiiposare In tin veralcullte-terrettrjal eodtl ecmyafenl
00
Udtln equivalent!, ppa
Coaipound »[-
Aldrln .97
Dleldrln .9*
£' 44
It .*•
Ill .»2
I* .3*
V .19
n .2)
VII .13
Vllt .10
IX .01
X .00
Intractable
»*e
Unextreet*
eble l C
Total l*C
Bleaaaple
»t (*\
Cent re 1
neck Uterine Pectoral
gland fat fat Uterae Stoueh Tongue Careaae
0.012 0.007
1.693 0.771 O.tM O.381
0.011 O.OM
0.00*
0.003


0.001

0,002
0.00)
0.009 0.009 0.00) 0.001
2.601 2.1*9 1.702 0.782 0.521 0.696 0.**)
O.OM. 0.011 0.00* 0.020 0.0*9 0.101 0.0)7
2.«1), 2.160 1.706 0.802 0.57J 0.797 0.481
0.1S88) Oi711« 0.444M 0.10)121.11592 0 AM)) 20,10254
Llvnr Lunge Parotid!

0.1M

0.002
0.00)


O.OU4
o.oni
0.001
0.001
0.00?
0.401 0.450 0.17$
O.OS6 0.008 0.044
0.4C7 0.»6* \>.«H
1.919810.20)11 0.12110
Int«itln*
0.00)
0.196
0.00*
0.002
0.001




0.001
0.002
0.001
0.212
0.179
0.391
2.8506*
rtaaoary
Heart Skin Gland!
O.Olt
0.3*0 0.02) 0.170
0.00)

0.00)
0.00) 0,00)
0.001

0.001

0.001
0.002 0.001 0.001
O.M8 0.061 0.172
0.010 0.280 0.011
0.168 0.141 0.201
0.19100 11.0)5)* 0.94*18
Kldneyi
and
•rein Afeenala
0.001
0.072 0.00*
•
0.001



0.001
1
0.001
0.00*
0.002
0.08) 0.00*
0.071 0,01)
0.154 0.01*
Body
TMile
0.011
O.J67
0.029
«o.oot
<0 001
0.001
«O.OOI
"0.031
•0.001
•0.001
0.001
0.002
o.»»*>
O.llt
0.*78
0480060.7285*41.7781
                                  V
Silica Cal Cf-25*. n-bexene i  dlethyl ether,  ) t  2 by volme.
lonaa emerala - unknown eoKpounde.
Ttale value represents total extrseteble  1*C in ell organa) ftv« organ estrnte were not eubjeeted to TLC eeparatton.

-------
Tabt« 37. -Relative affinities of 16 body-parts of the prafrle vole for
                      plus Its metabolites, and comparisons with the relative

          masses of the body-parts; the vole Is from vermicullte-terrestrial

          model ecosystem B.
Body-parts
(organs and 1 1 saves)
Carcass-7
Skin
Uterine fat
Intestines * contents
Pectoral fat
Liver
Stomach + contents
Ventral central neck gland
. Mammary glands
Heart
Lungs
Brain
Uterus * ovaries
Tongue
Parottd glands
Kidneys + adrenals

Residue wt In body-part
as a % of total residue
wt In entire body
49.04
18.97
8.15
5.58
A. 65
4.48
3.19
2.4?
0.98
0.55
0.47
0,45
0.42
0.28
0.25
0.07
100.00
Body-part wt as a %
of entire body wt
48.60
26.42
1.80
6.82
1.30
4.60
2.67
0.45
2.31
0.70
0.49
1.39
0.25
0.16
0.29
1.74
99-99
a/  Carcass »the eviscerated body (the removed organs and tissues are listed
~   above);  It consists predominately of muscle and bone.
                                          85

-------
                                                         ALBRIN
                                                      TOTAL RESIDUE
                                                      (MEAN OF SOIL
                                                     SYSTEMS A AHD B)
                                                       Animals
                          Calculation of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Corn*7
Soil (II)
Air
Total max:
mass, |
(No.) X mass
( 8) 3.98
( 8) 2.52
(13) 0.0335
( 8) 0.744
( 1) 44.3

(44) 3.41
( 1)4000

• «... lin
Lnp7*p
j:
" total
31.
20.
0.
5.
44.
103
- 150
m 4000

Mean
concentration,
Wg/g
8 1.26
2 0.391
436 0.870
95 0.502
3 0.421

0.721
1.26
[5000 vg-U+II)]
Total
residue, tig:
(mass) (cone.)
40.1
7.90
0.379
2.59
18.7
70.1
108
5040
- -40
Total residue as
a 2 of applied
dose (5000 ug)
0.8
0.2
<0.1
0.1
0.4
1.5
2.2
101
MI.O
&l  Proportion at 14 days postplanting;  the corn,  having been consumed and/or demol-
~   ished by the animals, is not present as an entity at the termination of the system.


Fig. 34.-Mean terminal environmental distribution of [  CJaldrin plus metabolites  in
         soil-terrestrial model ecosystems A and B.
                                               86

-------
00
20 •
•
IS -
i. '
m
•3
1 -
5 •
0 -
ifft S5 o.«iS«






1,5
0,01
fEp i6z
0,721
-------
                                                           ALDRIN

                                                        TOTAL RESIDUE
                                                        (SOIL SYSTEM A)
                         Com
Animals
                          Calculation of Che  above estimates:
Ecosystem
component
Earthworks
Slugs
Pillbuge
Caterpillars
Vole
Animal total (I)
Corn*7
Soil (II)
Air
Total maximum
mass, g:
(No.
( 6)
( 8)
(13)
( 8)
( 1)

(44)
) X
3.
2.
0.
0.
33.

3.
mass
98
52
0335
744
7

41
( 1)4000



- tota
31
20
0
5
33
92
- 150
. 4000

Mean
concentration,
1 Vg/g
.8
.2
.436
.95
.7
.1


[5000
1
0
1
0
0

0
1
V
.26
.513
.29
.523
.633

.698
.24

Total
residue, yg:
(mass) (cone . )
40.
10.
0.
3.
21.
75.
105
4960
)J - -35.
1
4
562
11
3
5


5
Total residue as
a 2 of applied
dose (5000 ug)
0
0
<0
0
0
1
2
99
"*
.8
.2
.1
.1
.4
.5
.1
.2
.0
ej  Proportion at 14 days postplanting;   the corn,  having been  consumed  and/or demol-
    ished by the animals, is not present as  an entity at the  termination of  the system.



Fig. 36.-Terminal environmental distribution of [  cjaldrin plus  metabolites in soil-
         terrestrial model ecosystem A.
                                             88

-------
                             20
                             20
                          •4  1S
                             10
CO
                                                                 0,00378
                                                                                           fEP  2X
                                                                                      ,633
-------
                            r!4 i
Table 38.-Concentrations of [  CjAldrin and degradation

         products in the soil substrate of the terrestrial

         model ecosystem A, 20 days after applying the

          [  CJAldrin to the substrate.

ft
Compounds
Aldrin
Dieldrin
&
II
III
IV
V
y.i
VII
VIII
IX
X
Total 1AC
Sample
wt. (g)
Aldrin
Rfi/
.97
.90 -
.82
.73
.56
.46
.39
.27
.17
.09
.04
.00


equivalents, ppm
Acetone Methanol—
extract extract
0.830 0.002
0.293 OiOll
0.021
•
0.003
0.007

0.012

0.010
0.007 0.002
0.038 0.004
1.221 0,019
100.00 100.00
a/  Silica Gel G£-254, n-hexane :  diethyl ether,
    3 : 2 by volume.
b/  The methanol extract is from the sample previously
    extracted with acetone.
c/  Roman numerals * unknown compounds.
                         90

-------
Table  ^.-Concentrations «f  [ CJAldrln and  degradation products  In  corn  grown  In  the
           soil-terrestrial model ecosystem A.
Aldrln equivalents, pom, at indicated
Compound
Aldrln
OleldrJn
£'
II
III
IV
V
VI
VII
VIII
j
IX
X
XI
',*•'
.97
.87
.74
.65
.54
.42
.38
.18
.11
, - -°6
.04
.03
.00
6 Days
Root
1.193
0.896
0.106


0.027


0.014
£.015,,
0.035

0.083
Shoot
0.097
0.064
0.056






0.009
0.020
0.011
0.028
Cntire
plant
0.707
0.527
0.084


0.015


0.008
.,-0.013
0.029
0.005
0.059
Root
0.661
0.784
0.143





0.018
0.038
0.054

0.127
po» tpl ant ing age
10 Days
Shoot
0.
0.
0.
0.
0.

0.
0.

«


0.
015
023
040
066
066

047
007




056
Entire
plant
0.291
0.348
0.085
0.039
0.039

0.028
0.004
0.008
0.016
0.023

0.088
Root
0.315
0.987
0.155


0.034


0.020
0.010
0.055

0.180
14 Days
Shoot
0.012
0.018
0.031
0.051
0.051

0.037
0.006

'


0.044
Entire
plant
0.092
0.275
0.063
0.037
0.037
0.009
0.026
0.004
0.005
0.003
0.015

0.079
Extractable   C
Unextractabl*   C
Total 14C
Btosampl» wt.  (g)
2.36"$  0.285   1.447  1.825  0.320   0.969  1.756  0.250   0.645
0.103  0.016   0.064  0.108  0.015   0.053  0.146  0.019   0.053
2.472  0.301   1.511  1.933  0.335   1.022  1.902  0.269   0.698
0.627  0.500   1.127  0.561  0.869   1.430  0.426* 1.048   1.474
£7  Silica C«T GP-254, nj-hexane:    die thy 1 ether, 60:40 by volume.
b/  Roman numera-ls- • uifknown compounds.
                                          91

-------
Table 40.-Concentrations



          brates after a



          system A
of ["c]nldrin and degradation product* in inverte-



5-day exposure in the soil-terrestrial node! ecc—
Compound Rx~"*
Aldrin .98
Dieldrin .90
l£/ ,80
II .73
III .45
IV .27
V .08
VI .04
VII .00
Extractable 14C
Unextractable 14C
Total 14C
Average
biosample wt (g)

Lumbricus
(worm)
0.470
0,053
1.048 '
0.003

0.010
0.007
0.005
0.011
1.207
0.054
1.261
3.59419
Aldrin equivalents, ,ppm£i
tiaax Armadillidium
(slug) (pillbug)
0.015 ' 0.147
0.422 0.723
0.012





0.033
0.482 0.870
0.031 0.420
0.513 1.290
3.08918 0.03095
/
Estigmene
(caterpillar)
0.038
0.344
0.111

O.002
0.001


0.005
0.501
0.022
0.523
0.58810
a/  Average of triplicate determinations.



b/  Silica gel (7-254, n-hexane t dietbyl  ether, 3s2 by volume.



£/  Roman numerals «= unknown compounds.
                                      92

-------
Table 41.-Concentration* of [  c]*ldrln and degradation product* tn the prairie vole after a J-day espoaure In the aoll-terreatrlal Model ocoayatea A.

                	Aldrtn  equivalent*. yf»

                                 Ventral
                                 Central                   Kldneya
                .Uterine Pectoral  neck   HamMry            and                                      ,                                              Body
Compound    R(-   (at     (at    gland   glande  Uterua  Adcenala Parotida Stoawch Llyer  Carcaae   Heart   Skin    Inteatlo* Brain  Tongue  Lunge   locale

Aldrlo      .97 0 496                                    0.173                            0,013                                                     0.011

Dleldrln    .94 3.294   4.291    3.233   3.077   2.303   1.010   1.212     0  976   0.622    0.37O    0.318   0.301   0.217    0.022   0.243   0.124   0.338

I-'         .84                                                    *              O.003                                      0.268                   0.003

II          .72                                          0.043                                                                                      0,001

III         .340.066                    0.024           0.016    '                                                          0.001                   0.001

IV          .23 O.419                                    0.029                                                                                      0.002

V           .13                                                                  0.004                                                             <0,OOI

VI          .10 0.384                                    0.022                   0.003                                      0.00*                   0.002

VII         .03                                          0.023     •             0.006                                                              0.001

VIII        .00 0.948   0.003    0.391   0.010   0.192   0.039   0.147     0.117   0.008    0.002    0.018   0.007   0.024    0.011   0.029   0.013   0.016
bt [actable
                3.619   4,296    3.644   3.116   2.497   1.379   1.3*9    1.093   0.648    O.S83    0.3S6   0.308   0.243    0.313   0.272   0.11*   0.373
BMxtraet'-
  able l*C      0.038   0.032    0.008   0.010   0.007   0.033   0.022    0.0311   0.048    0.066    0.020  0.034   0.039    0.003   0.037   0.033   0.038

local 14C       3.637   4.148    3.632   3.126   2.504   1.414   1.391    1.131   0.696    0.631    0.376  0.362   0.328    0.316   0.309   0.192   0.633

Bioaavpl*
  wt  (g)       0.083830.09200  0.127100.324320.073490.387620.19180  0971681.6324217.18918  0.189338.008613.60730 0.38913 0.08491 OJ7119 33.74423


*'  Slllta Gel Cf 234. o ht.ooe - dlctllyl other. 3 I 2 by voluw.

£•  toaan nuMiala - Unknown cooDounda.

-------
Table «2.-ftelatlve affinities of Ifi body-parts of the prairie vole for

          -1i .
          [ .jCJaldrln plus Its metabolites, and comparisons with the  relative


          masses of the body-parts; the vole Is from soil-terrestrial model
ecosystem A.
Body-parts
(organs and tissues)
Carcass-
Skin
Liver
Stomach + contents
Intestines + contents
Mammary glands
Kidneys + adrenals
Uterine fat
Ventral central neck gland
Pectoral fat
Parotid glands
Uterus + ovaries
Brain
Heart
Lungs
Tongue

Residue wt in body-part
as a % of total residue
wt In entire body
52.53
13.59
5.39
5.1*
5.10
4. 75
3.90
2.22
2.18
1.88
1.25
0.86
0.58
0.33
0.15
0.12
99.99
Body-part wt as a %
of ent! re body wt
50. 9»i
, 23-73
A. 90
2.88
10.69
0.96
1.7*
0.25
0.38
0.27
0.57
0.22
1.15
0.56
0,51
0.25
100.00
a/  Carcass* the eviscerated body  (the removed organs and  tissues are  listed
*~   above);  It consists predominately of muscle and bone.
                                           94

-------
                                                          ALDRIN
                                                        TOTAL RESIDUE
                                                        (SOIL SYSTEM B)
                         (2Z)
                         Cora"
Ani
                          Calculation of the above estimates:
Ecosystem
component
Earthworms - -
Slugs
Pillbugs
Caterpillars
Vole
Animal total (I)
Corn*/
Soil (II)
Air
Total maximum „
nean
****» 8* concentration.
(No.
( 8)
( 8)
(13)
( 8)
( 1)

(44)
) X mass
' 3.98
2.52
0.0335
0.7-44
54.8

3.4-1
( 104000


• total
-31.8" "
20.2
0.436
5.95
54.8
113
» .150 ...
A 4000
[5000
M/g ,
(r.26)^
0.269
0,450
0.480
0.208

'0,744
1.28
vg-d+n
Total
residue, ug:
(mass) (cor.c.)
' '• (40. 1)-''
5.42
0.196
2.86
11.4
(60.0)
112-
5120
)] - -180
Total residue as
a % of applied
dose (5000 ug)
" (0.8)-^ '
0.1
<0.1
0.1
0.2
(1.2)
2.2
102
•vO.O
a/  Extrapolated from replicate aldrin-soil system.
b/  Proportion at 14 days postplanting;  the corn, having been consumed and^or demol-
    ished' by the animals, is not present as an entity at the termination of the system.

                                                rl4 T
Fig. 38.-Terminal environmental distribution of [  Cjaldrln plus metabolites in soil-
         terrestrial model ecosystem B,
                                              95

-------
?n 1 9R» «•
IEP 22
0.208 00209



0



ALDRIN
i
i^^T"r~l^ira
i r« p
"""^IM— ' ""-^ ^-"
o J 1.25 0,00
Cl
Soil Corn Air Slug, ' ' Plllbug Caterpillar Vole
                                                         PPM


Fig* 39.—Summary of the fate of [ .c] aldrln in the soil-terrestrial model-ecosystem B.   The total   C-realdues are
          expressed as aldrln equivalents, ppra (w/w), and their subdivisions are:   EP,r  extractable parent compound,
          EM - extractable metabolites of the parent compound, and UN - unextractable products remaining in the'
          processed sample.  On day zero,the corn seeds were planted and the soil  was treated with aldrln at one
          Ib Al/acre; the Invertebrates and vole were added to the system 10 and 15 days later,  respectively.   The
          vole died 3% days after placing It In the system.

-------
Table  43.-Concentrations  of  [  CJAldrin and degradation

         products  in  the  soil substrate of the terrestrial

         model  ecosystem  B,20 days after applying the

          [  CJAldrin  to the  substrate.
Aid r in equivalents, ppm
Compounds
Aldrin
Dieldrin
1^
II
III
IV
V
VI
VII
VIM. -
Total UC
Sample
vt. (g)
Ra/
.97
.90
.82
.73
.36
.46
.27
.09
.04
• • .-oo


Acetone Methanol—
extract extract
0.846 0.003
0.329 O.Q01
0.022
0.001
0.001
0.004
0.009
0.007
0.012 0.004
0,031 0.007
1.261 0.016
100.00 100.00
a/  Silica Gel GF«=254, n-hexane  : diethyl ether,
    3 : 2 by volume.
b_/  The methanol extract is from the sample previously
    extracted with acetone.
c/  -Roman numerals s unknown compounds.
                        97

-------
Table ^.-Concentrations of  [  cjAldrln and degradation products in corn grown In the



          soil-terrestrial model ecosystem B.
Aldrin equivalents, ppm
Compound
Aldrin
Dietdrin
\y
II
III
IV
V
VI
VII
VIII
IX
X
XI
*r7
.97
.87
.74
.65
.54
.42
.38
.18
.11
.06
.04
.03
.00
6 Days
Root Shoot
0.784 0.091
0.528 0.061
0.090 0.053


0.008


0.011
0.010 0.006
0.018
0.010
0.042 0.011
, at indicated
oostplantintj aqe
• 10 Days
Entire
plant Root
0.490 0.186
0.330 0.419
0.074 0.079


0.004


0.006 0.009
0.008 0.007
0.010 0.026
0.004
0.029 0.050
Shoot
0.007
0.011
0.018
0.030
0.030

0.022
0.003




0.026
Entire
plant
0.094
0.209
0.048
0.016
0.016

0.012
0.002
0.004
0.003
0.013

0.038
Root
0.471
0.958
0.237


0.026


0,027
0.020
0.022

0.180
14 Days
Shoot
0.009
0.013
0.023
0.037
0.037

0.026
0.004




0.032
Ent i re
plant
0.138
0.277
0.082
0.027
0.027
0,007
0.019
0.003
0.008
0.006
0.006

0.073
Extractable 1Z*C



Unextractable 1
-------
Table 45--Concentrations of  [  C]Aldrin and degradation products in

          invertebrates after a 5-day exposure in the soil-terrestrial

          model ecosystem B.
Aldrin equivalents, ppm—
Compound *f~~
Aldrin .98
Oleldrln .90
I-' .80
II .45
III .27
I? .00
14
Retractable C
14
Unextxactable C
Total 14C
Average bio-
sample wt (g)
Limax
(slug)
0.010
0.215
0.008


0.008
0.241
0.028
0.269
3.25515
Armadillidium
(pillbug)
0.042
0.205



-
0.247
0.203
0.450
0.06U5
Estigmene
(caterpillar)
0.025
0.335
0.093
0.001
0.002
0.005
0.461
0.019
0.480
0.71533
a/  Average of triplicate determinations for slugs and caterpillars; average
    of duplicate determinations for pillbugs.
b/  Silica Gel GF-254, Q-hexane » diethyl ether, 3 :  2 by volume.
cj  Roman numerals " unknown compounds.
                                       99

-------
                                  Table  <6.  Ceneentrattons of  [  t JAldrln Mid degradation products In the prairie vole after * S-day enpoaure la th«  soil terrestrial angel ecoeyVtwTB1,
O
o
Aldrln equivalents, ppei
Ventral
Central
. Pectoral Nanoary Uterine neck
Compound »f- fat glands Parotids fat (land Stonach Skin
Aldrln .97 0.032
Oleldrln .94 0.225 0.577 0.154 0.214 0.2B1 0.257 0.076
1^' .84 0 094
II .72
III .34 0.005 0.004
IV .25 0.028
V .11
VI .10 0.025
VII .05
Vllt .00 0.315 0.002 0.041 0.062 0.014 0.011 0.002
Cxtractable
»*C 0.6H 0.584 0.197 0.165 0.317 0.288 0.078
Oftextraet
able **C 0.000 0.002 0.031 0.007 0.007 0.021 0.215
Total1(C 0.634 0.586 0.430 0.171 0.124 0.111 O.»l
BiosMple
wt (*) 0.72571 0.271300.57989 1,696020.771411.7313510.71948
Kidneys
aid
Adrenals Carcass Uterus tongue Intestine
0.016
0.095

0.004
0.001
o.eoi

0.002
0.002
0.006
0.129
0.051
0.182
0.63*59
0.005
0.118 0.109 0.097 0.081
0.027


0.001

0.001
0.001
0.001 0.009 0.012 0.010
0.154 0.118 0.109 0.093
0.014 0.024 0.025 0.022
0.1«8 0.142 0.114 0.115
29.43900 0.15276 0.10755 4.079O4
Body
Liver Lungs Heart Brain Total*
0.004
0.077 0.047 0.014 0.001 0.118
0.016 0.016
'O.OOI
•0.001
0.002
o.ooi «».ooi
. 0.001 0.001 0.002
0.001 . 0.001
0.001 0.006 0.004 0.001 0.010
0.080 0.051 0.018 0.019 0.151
0.022 0.041 0.024 O.OQ1 0.055
0.102 0.094 0.06) 0.02} 0.208
. 2.25017 0.58104 0.456000*1419 54.81771
                                     Silica Gel CF-2M. a-hcunc I  dlathyl ttbtr. 1 « 2 by voluM.

                                 '   Return mewrat* - unknown eonpounds.

-------
Table 47.-Relative affinities of 16 body-parts of the prairie vole for

           [  c]aldrin plus Its metabolites, and comparisons with the  relative

          masses of the body-parts; the vole Is from soil-terrestrial model

          ecosystem 8.
Body-parts aTa^f'tota^res'ldu'l Body-part wt as a %
(organs and tissues) " a *, ., fft*'au8 of entire body wt
wt in entire oooy
Carcass-
Skin
Uterine fat
Stomach + contents
intestines + contents
Pectoral fat
Parotid glands
Ventral central neck gland
Llyer „
Mammary glands
Kidneys + adrenals
Lungs
Heart
Uterus + ovaries
Tongue
Brain

43.81
27.68
5.55
4.76
4.13
4.05
2.20
2.20
' 2',03 , , "
1.41
1.01
0.48
0.25
0.19
0.12
0.11
99.98
53.68
19.58
3.09
3.16
7.44
1.32
1.06
1.41
- - 4.10
0.50
1.16
1.06
0.83
0.28
0.20
1.12
99-99
a/  Carcass - the eviscerated body (the removed organs and tissues are listed
~   above);  it consists predominately of muscle and bone.
                                         101

-------
                             X
                 Terrestrial animals
trial animals   V   Water

 ,—^       ^*y-x
                      // no  \(
                        »..,-
                        Corn
                                                        DIELDRIN
                                                      TOTAL RESIDUE
                                                      (SOIL SYSTEM)
                                                     Aquatic organisms
               Soil sediment
                           Calculation of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Total maadjnuffl „ Total
M8S- *! concentration, residue' "*:
(No.
( 8)
( 8)
(13)
( 8)
( 1)
) X
3.
4.
0.
0.
38.
mass • total
85
40
060
931
17
30.8
35.2
0.78
7.45
38.17
v* 8 (mass) (cone.)
0.
0.
0.
0.
0.
698
184
475
275
947
21
6
0
2
36
1
.5
.48
.371
.05
.1
Total residue as
a Z of applied
dose (5000 ug)
0
0
<0
<0
0
.4
.1
.1
.1
.7

Terrestrial
   animalf/total (I)
Cornk/
              112
66.5
1.2
Algae
Snails
Fish

(3.5)
(50)
( 3)
0.
0.
0.
241
014
113
Aquatic
organism total (II)
Surface water (III) ( 1)7000
Soil sediment0.' (IV) ( 1)4000
Air
0.844 6.19
0.700 8.70
• 0.339 7.61
1.88
- 7000 0.0039
• 4000 0.762
[5000 ug-d+m-m+iv)] -.
5
6
2
13
27
3048
1844
.22
.09
.58
.9
.3
0.
0.
0.
0.
0.
61.
36.
1
1
1
3
5
9
_a/  The terrestrial animals  (and their residues) were removed from the system at the ter-
    mination of the terrestrial phase.
b/  No corn germinated  in  this model ecosystem;  untreated chard and soybean plants were
    supplied for food.
£/  The direct interaction of air and terrestrial  animals vith the soil occurred prior to
    flooding the system.
Fig. 40.-Terminal environmental distribution of
         terrestrial model ecosystem.
                        [  CJdieldrin plus metabolites in a soil-
                                        102

-------
                                             '"1
o
OJ
. *"'
I IS-
u
I .'
A
B
1 .'
S*
10
0
o
*
5





0
t






•









»»\F"» „ f»«
!> . 0,00070 0.947<« 4x
t t
I fEP IX fEP 74Z fEP 2« fEP 94Z
0.00146 0.698 f. the fate of [   cjdieldrln In,the terrestrial phase of a soil-terrestrial model ecosystem.  The
                                       total *4Oresldues are expressed as dieldrln equivalents, ppm (w/w), and their subdivisions are:  EP •
                                       extractable parent compound, EM - extractable metabolites of the parent compound, and UN • unextractable
                                       products remaining in the processed sample.  On day  zero, the corn seeds were planted and the soil was
                                       treated with dieldrin at one Ib Al/acre.   The system was drenched with water, Instead of the usual
                                       sprinkling,  and none of  the corn seeds germinated; extraneous foliage was added later.  The invertebrates
                                       and vole were added to the system 11 and  IS days later, respectively.

-------
32.





M
5
|
O.
w 27 •
41
a
S. 26-
•3
I 25
w
M
1 a*.
})I IcuT cci
^CH" NccT


fEP 40Z
0,00390<™ i« 6.]
A IUN 44Z i
*p >
0.00372


0,00320


0.00306



O.OC
O.OC



1301
1277
1
0.00132 O.C
fEP 72Z
[9
-------
Table 48.-Concentrations of [14c]dieldrin and degradation products in the



          of a model ecosystem 20 days after application of  [14c]dieldrin to



          the soil
Compound
&
II
Dieldrin
III
IV
V
VI
VII
VIII
IX
X
XI
Extractable WC
Sample wt (g)

Dieldrin
equivalents, ppm
JtfSr Acetone extract Methanol extract—'
.93
.90
.85
.79
.66
.49
.41
.34
.25
.17
.03
.00


0.0064
0.0256
0.6068
0.0105
0.0112
0.0015
0.0017
0.0240
0.0035
0.0009
0.0020
0.0043
0.6984
100. OOO
0.0006
0.0051
0.1151
"
0.0022
0.0003
0.0004
0.0038
0.0006
0.0002
0.0004
0.0009
0.1296
100.000
a/  No corn germinated in this ecosystem.



b/  Silica gel GF-254r n-hexane : diethyl ether, 3:2 by volume.



c/  Methanol extract is from the sample previously extracted with acetone.



d/  Roman numerals = unknown compounds.
                                      105

-------
Table  ^.-Concentrations of  [  c]dieldrin and degradation products in the air—/

          from a soil— model ecosystem
'
Compound
Dieldrin
I^/

Rf£/
.86
.00
Dieldrin equivalents, ppm
Trap 1= Trap 2— /
0.00049
0.00001
Total 14C

Sum 14C, Traps 162


Air sample wt  (g) 3/
0.00050                     0.00168

              0.00218


            108.0
a/  Air was trapped for a 3-hour daylight per
    5 days after application of [14c]dieldrin
      period at a flow rate of 10 ml/sec
          to the soil.
b/  No corn germinated in this ecosystem.

£/  Silica gel GF-254, n-hexane : diethyl ether, 3:2 by volume.

d/  Trap 1 was connected directly to the ecosystem container and contained 75 ml
    of acetonitrile as the trapping solvent;  the trapping solvent was chromato-
    graphed.

e/  Trap 2 was connected in series to trap 1 and contained 75 ml of trapping
    solvent (ethanolamine : 2-methoxyethanol, 1:2 by volume);  the trap 2
    solvent was not chromatographed.

f/  Roman numerals = unknown compounds.

g/  One liter of air was assumed to weigh 1 g.
                                        106

-------
 Table 50.—Concentrations of [14C]dieldrin and degradation products in inverte-
            brates after a 5-day exposure in a soil3/ model ecosystem
Dieldrin equivalents, ppn£/
Armadillidium Eatigmene
Compound 'M.Sf (pillbug) (caterpillar)
Dieldrin .80 0.138 0.257
& .71
II .59
III .36
IV .31
V .24 0.142
VI ,09
VII .03
VIII • .00 0.004 0.003
Extractable 14C 0.284 0.260
Onextractable 14C 0.191 0.015
Total 14C 0.475 0.275
Average
biosample wt (g) 0.060 0.931
Limax
(slug)
0.137
0.009

0.005
<0.001
<0.001
<0.001

0.004
0.157
0.027
0.184
4.397
Lurabricus
(worm)
0.011
0.625
0.004

0.004
0.001

0.004
0.002
0.651
0.047
0.698
3.850
 a/  No corn germinated in this ecosystem;   untreated soybean plants and chard
     were supplied for food.
'b/  Average of triplicate determinations for caterpillar and slugs   single deter-
     mination for pillbug and worm.
 c/  Silica gel GF-254, n-hexane : diethy1 ether,  3:2 by volume.
 d/  Roman numerals•= unknown compounds.
                                            107

-------
                                TabU  31*>Ci»
Ventral Kidney*
_ b_/ Uterine Abdoatnal ttonaiary central Pectoral and
Compound t~ fit fnt (loniH Muck p.l ud fnrxlJn fit 5K(n adtcnala Carcaaa Utftrna Liver
Oleldrln .81 3.6«2 3.479 3.467
l*f .37
11 .30 0.060 0.077 0.053
111 .20 0.039 0,049 0.047
IV .09
f .03
11 .00 0.002 0.013 0.003
Intractable 3.763 3,*20 3.370
1 C
tfneatract-
oble 1*C 0.01) 0,030 0.025
Total U6 3.778 3.630 3.593
•loaaepla vt
(() 0.547 0.746 0.539
3.033 2.934 2.726 1.476 0.760 0.704 0.724 0.416

0.047 0.062 0.034 0.023 0.014 0,011
O.Q42 0.061 0.039 0.013 0.010 0.032
0.033

0.010 0.001 0.016 fO.OOl 0.004 0.035
3.122 3,067 2.819 1.317 0.776 0.729 0.728 0.327
0.022 0.049 0.012 0.2*6 0.023 0.039 0.024 0.063
3.144 3 116 2.831 1.783 0.8O1 0.768 0.732 0.392
0.313 0.294 0.498 3.273 0.438 13.380 0.142 1.972
Heart Tongue Slowich
0.337 0.307 0.233

0.006


0.003
0*003 0.009
0.337 0.312 0.233
0.022 0.033 0.028
0.379 0.34$ 0.261
0.148 0.081 1.743
tnttttlite U>n|*
0.183 0.131
O.O08
0.003


0.004
0.003 0.003
0.201 0.138
f
0.047 0.028
0.248 0.164
6.616 0.227
lody
Irata tetala
0.086 0.843
0.001
0.013
0.012
0.002
0.001
0.001 0.004
0.087 0.878
0.006 0.069
0.093 0.947
O.S43 38. 17flt!
                                *l  So corn geminated In thla systw; untreated aoybean plante and chard vet* auppllad for food.


                                fc/  Silica «el Cf 254. n hexane I dlethyl ether. 3(2 by volv—e.


                                el  Keaan atnerala • anknoun compound!.


                                d/  Live bodf oelght.

-------
Table 52.-Relative affinities of 17 body-parts of the pralrte vole^-  for


           [14 i
             Cjdleldrln plus Its metabolites, and comparisons with the



          relative masses of the body-parts.
Body-ixirts "••'*!• ?'" J^VM" Body-part wt as a *
«,„.„, «* „„„, "^.r^^v""' •'-«"*«»«
Carcass— •
Skin
Abdominal fat
Uterine fat
Mammary glands
Intestines * contents
Ventral central neck gland
Pectoral fat
Liver
Parotid glands
Stomach^* contents?
Kidneys 4- adrenals
Heart
Uterus
Brain
Lungs
Tongue

33.13
26.04
7.53
5.72
5.56
4.55
4.46
3.90
3-23
2.53
1.35, 	
0.37
0.40
0.30
0.14
0.10
0.08
99.99
43-25
14.64
2.07
1.52
t.55
T8.37
1.42
1.38
5.47
0.82
4.84 '
1.22
0.69
0.39
1.51
0.63
0.22
99.99
                                                              r14 i
a/  Vole from a so-Il-terrestrial model ecosystem treated with [_  Cjdieldrin.



b/  Carcass**the eviscerated body (the removed organs and tissues are listed

    above); It consists predominately of muscle and bone.
                                          109

-------
Table  53.-Concentrations of  [14cjdieldrin and degradation products in the water of a soil8/ model ecosystem
          7 days after flooding the ecosystem with waterS/
Compound
                                                         Dleldrin equivalents, ppm
                                          Surface water
                                                             L.eachateS/
Ether extractable
before hydrolysis
Ether-extractable
after hydrolysis^/
Ether-eXtractable
before hydrolysis
Ether-extractable
after hydrolysis
ll/
Dleldrin
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
Extractable
.93
.68
.72
.56
.49
.46
.39
.34
.30
.20
.12
.09
.07
.05
.03
.00
14C
0.00005
0.00157
0.00002

0.00002
0.00015
0.00008
0.00012




0.00004

0.00004
0.00008
0.00217
Unextractable 14C

O.OOO01







0.00001


0.00002
0.00005
0.00025
0.00042
0.00076
0.00047

0.00087

0.00002

0.00004


0.00024
0.00007
0.00007



0.00003
0.00012
0.00146
0.00192

0.00008









0.00004
O.OO006
0.00031
0.00032
0.00022
0.00103
0.00066
Total extractable 14C
Unextractable 14C after hydrolysis
14C loss during hydrolysis
Initial 14G in water
Sample volume (1)
                0.00293
                0.00047
                0.00050
                0.00390

                1.000
                                      0.00249
                                      0.00066
                                      0.00042
                                      0.00357

                                      1.000
a/  No corn germinated in this ecosystem.
b/  Ecosystem was flooded with water 20 days after application of [  CJdleldrin to the soil.
c/  One liter of water was withdrawn through the tap at the Jar bottom over a period of about 24 hours.
d/  Silica gel GF-254, n-hexane t diethyl ether, 3:2 by volume.
e/  The "Unextractable" of the preceding column was adjusted to 0.012 N HC1 and maintained at 55-56°C for 18-24 hr.
t/  Roman numerals * unknown compounds.

-------
Table 54.-Concentrations of  p^CJdieldrin and degradation products in aquatic

          organisms of a soil*' model ecosystem flooded with waters/
Oieldrin equivalents,
Compound
&
IX
Dieldrin
?«
XV
V
Exttactable 14C
Onextxactable 14C
Total 14C
Average bio-
sample wt (9)
at GanbusiaS/
"^ (fish)
.92
.89
.83 7.253
.79
.31 0.212
.00 0.027
7.492
0.118
7.610
0.113
Physa*/
(snail)

0.349
8.018

0.182
0.016
8.565
0.130
8.695
0.014
ppm£/
Algae2/
0.068

4.426
0.632
0.147
0.036
5.309
0.880
6.189
0.241
a/  Ho com germinated in this system.
                                                                                  A -*
b/  Ecosystem was flooded with water 20 days after application of  [  CJdieldrin
    to the soil. .

c/  Average of triplicate determinations for fish;  average of duplicate deter-
    minations for snarls;  single determination for algae.

d/  Silica gel -G?-254, in-hexane : diethyl ether, 3:2 by volume.

«/ ,Piah were added 4*d&yV after flooding'the ecosystem, removed 3 days later,
    and processed individually.

f/  Snails were added on the day of flooding, removed 7 days later, and processed
    in 2 batches of IS snails each;  average batch weight =* 0.204 g.

g/  Algae were filtered from the surface water 7 days after flooding the ecosystem.

h/  Koaan numerals <* unknown compounds.
                                       Ill

-------
Table  55.-Concentration*  of  [  CJdieldrin and degradation products in  the  •oil5/

           sediment of  a model ecosystem 12 days after  flooding the ecosystem

           with
Compound
i£/
II
Dieldrin
XXI
IV
V
VI
VII
VIII
IX
X
XI
XII
Extractable 14C
Sample wt (g)

Dieldrin
equivalents, ppm
Rf£/ Acetone extract Methanol extract3/
.93
.90
.85
.79
.66
.49
.41
.34
.31
.25
.17
.03
.00


0.0041
0.0183
0.6062
0.0054
-0.0107
0.0058
0.0040
0.0108
0.0032
0.0037
0.0026
0.0022
0.0049
O.6819
100.000
0.0007;
0.0022,
0.0716
• 0.0005
0.0012$
0.0005
0-0002
0.0013-

0.0005
0.0003
0.0003
0.0007
0.0800
100. OOO
a/  No corn germinated in this ecosystem.

b/  Ecosystem was flooded with water 20 days after application of  [14c]dieldrin
~"   to the soil.

c/  Silica gel GF-254, c-haxane  s diethyl ether, 3:2 by volume.

d/  Methanol extract is from the sample previously extracted with  acetone.

c/  Roman numerals • unknown compounds.
                                      112

-------
                                                    PENTACHLORONITROBENZENE
                                                        TOTAt. RESIDUE
                                                       Animals
                         Calculation of the above estimates;
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total
Corn^7
Soil (II)
Air
Total maximum
mass, g:
(No.
""( 8)
( 4)
(13)
( 8)
( 1)
(I)
(28)
)' X
3.
9.
0.
0.
25.

3.
mass ™
36' •
09 -
0333 -
890 -
5

39 -
( 1)3718



^^ Total
concentration, «*"««> »•«'
total W8/8
26.
36.
0.
7.
25.
96.
94.
3718

9
4
433
12
5
4
9

[5000
1
0
1
2
0

9
0
V
:39
.441
.77
.44
.677

.25
.858
g-(I+II
(mass) (cone.)
37.
16.
0.
17.
17.
88.
878
3190
:)] - 1721
4
0
766
4
3
9



Total residue as
a % of applied
dose (5000 ug)
0.
0.
<0.
0.
0.
1.
17.
63.
34.
7
3
1
3
3
6
6
8
4
a/  Proportion at 14 days  postplanting;  the corn, having been consumed and/or demol-
    ished by the animals,  is not present as an entity at the termination of  the system.


Fig. 43.-Terminal environmental distribution of [  CJpentachloronitrobenzene plus
         metabolites in a  soil-terrestrial model ecosystem.
                                             113

-------
20 i

:planeing
i—
Ul
t>
o
o>
»
.
u
n

-------
27 •
26 "•
f "'
1».
* "
* 22 •
9
1
21 '•

20
fEP 2*
0.00878 {EM 102 1,(
•• I {UN 881
; 1 Before
rt nnoac hydrolysis
UtUUoaO
; O-.OC
, o.oc
o.oc
o.oc
'o.oc


m
816
761
668

fEP 22Z fEP 10Z
JQ
-------
Table 56.-Concentrations of  [  CJpentachloronitrobenzene and degradation.



         ""products in the soil of a model -ecosystem 20 days after application



          of  [  c]pentacaloronitrobenzene to the soil
Compound
PCNBS/
«a^
IS/
n
in
IV
V
VI
VII
VIII
IX
X
Extractable 14C
Unextractable 14C
Total 14C
Sample wt (9)
Rf*/
.98
.91
.75
.62
.49
.46
.33
.25
.18
.10
.03
.00




Pentachloronitrobenzene equivalents, ppoi
Acetone extract Methanol extract—/
0.351 0.018
O.U7 0.011
0.024
0.006
0.010
0.092 0.009
0.004
0.005
0.010
• 0.010
0.029
0.078 0.035
0.736 0.073
0.049
0.858,
100.000
a/  Silica gel GF-254, diethy1 ether : n-hexane, 7:3 by volxime.



b/  Methanol extract is from the sample previously extracted with acetone.



c/  Pentachloronitrobenzene.



d/  Pentachloroaniline.



e/  Roman numerals * unknown compounds.
                                      116

-------
 Table 57 .-Concentrations of [  c]Pentachloronitrobenzene and degradation



           products in cornS/ after a 14-day exposure in a model ecosystem
Pentachloronitrobenzene equivalents, ppm^/
Compound KfS/
KSB&/ 0.97
PCA£/ o.sa
I?/ 0.46
II 0.22
III 0.19
IV 0.11
V 0.05
VI O.OO
Extractable 14C
Unextractable ?-4C , _ . . ^
Total 14C
Average bio-
sample wt (g)
Root
2.649
2.043
0.538

0.119
0.140
0.220
7.369
13.078
10.612 _(.
23.690
0.715
Shoot
0.098
0.036
0.020
0.001
0.002
0.009
0.021
0.098
0.285
. ' 0.477 -
0.762
1.334
Entire plant
1.081
0.815
0.219
0.001
0.047
0.060
0.095
2.706
5.024
4.223
9.247
2.049
a/    ^cPentachloronitrobenzene was applied to the soil beneath each seed.




b/  Average of triplicate determinations.




c/  Silica gel G)?-'2S4f diethyl ether j ii-hexane, 7:3 by volume.




d/  Pentachloronitrobenzene»




e/  Pentachloroaniline.




f/  Roman numerals = unknown compounds.
                                        117

-------
Table 58.-Concentrations of  [c]Pentachloronitrobenzene and degradation

          products in invertebrates after a 5-day exposure in a model ecosystem
Pentachloronitrobenzene
Compound
PCNB^ "
PCA^/
1^
II
III
IV
V
VI
Extractable 14C
Dnextraetable 14C
Total 14C
Average bio-
sample wt (g)
*£*/
.94
.84
.40
.29
.14
.06
.03
.00




Armadi 1 lidiun£' Estigmene
{pillbug) (caterpillar)
0.511
0.033



<0,001
0.010
0.063
0.617
1.152
1.769
0.033
0.973
0.588
0.014



0.014
0.101
1.690
0.748
2.438
0.890
equivalents ,
Liroax
(slug)
0.042
0.032

0.005
0.051
0.030
0.013
0.137
0.310
0.131
0.441
9.092
pp^/
Lumbricus
(worm)
0.146
0.037
0.015

0.111
0.053
0.061
0.125
0.548
0.844
1.392
3.355
a/  Average of duplicate determinations for caterpillars and worms; single
    determination for pillbugs and slug.

b/  Silica gel GF-254, diethyl ether :  ri-hexane, 7:3 by volume.

c/  Three pillbugs were processed together;   batch weight = 0.100 g.

d/  Pentachloronitrobenzene.

e/  Pentachloroaniline.

f/  Roman numerals = unknown compounds.
                                      118

-------
Table 59.-Concentrations of [  CJpentachloronitrobenzene and degradation products in the prairie vol«

          5-day exposure in a model ecosystem
                                                                                                      after a
Pentachloronitrobenrene equivalents, ppta
_. Remaining
Compound RfS/ JJ
PCNB4/
DT*H^/
ri««Vi r •
&
XI
in
IV
V
VI
VII
VIII
Extractable 14C
Unextractable 14
Total 14C
Biosample wt (g)
96
82
76
55
46
20
19
12
05
00

C


0.^39
0.753


0.027
0.018

0.107
0.320
1.364
0.912
2.276
5.155
Uterine
Skin Uterus Liver
0.036 0.051 0.092 0.018
0.634 0.266 0.231 0.137

0.004
' . 0.012
• 0.005
..„ 0.006
0.006 0.037
0.007 ./; 0.011 0.045 0.029
0.683 , 0.357 0.368 0.221
0.035 , 0.320 0.078 0.175
0.718 - 0.677 0.446 0.396
0.130 3.729 0.019 1.364
Brain Carcass
0.037 0.024
0.045 0.091
0.117

0.002
0.002
0.003
0.012 0.001
0.013 0.003
0.224 0.126
0.012 0.038
0.236 0.164
0.585 13.594
Body
totalsS/
0.051
0.251
0.003
<0.001
0.009
O.003
O.002
0.002
0.025
0.070
0.416
0.261
0.677

a/  Silica gel GF-254, diethyl ether > rv-hexane. 7:3 by volume.
b/  Internal organs,'other than those specified,'were combined and processed as an individual sample.
c/  Body totals were calculated using live body weight (25.527 g).
d/  Pentachloronitrobenzene.
e/  Pentachloroaniline.
£/  Roman numerals = unknown compounds.

-------
Table 60.-Relat!ve affinities of 7 body-parts of the prairie vole^-  for

           f  Cjpentachloronltrobenzene plus Its metabolites, and
           '•-.rr.
          comparisons with the relative masses of the body-parts.
Body-parts
(organs and tissues)
Skin
Carcass^7
Liver
BraiTi
Uterine fat
Uterus
Remaining organs-

Residue wt in body-part
as a 1 of total residue
wt in enti.re body
14.62
12.89
3.13
0.80
0.54
0.05
67.96
99.99
Body-part" wt as a %
of enti re body wt
15.17
55.31
5.55
2.38
0.53
0.08
20.98
100.00
a/  Vole from a soil-terrestrial model ecosystem treated with
         pentach 1 oron i t robenzene .
b/  Carcass * the eviscerated body (the removed organs and tissues  are
    listed above);  it consists predominately of muscle and bone.

£/  The gastrointestinal tract + contents, kidneys + adrenals,  heart,
    lungs, mammary g.lands, ventral central neck gland, parotid  glands
    and small amounts of fat tissue were analyzed collectively; most
    (ca. 3/4) of the mass consisted of the gastrointestinal tract  •*•
    contents.
                                      120

-------
Table 61.-Concentrations of [  CJpentachloronitrobenzene and degradation products
in the water  of  a model ecosystem 7  days  after flooding the ecosystem with
Peatachloronitrobenzene equivalents, ppm
Compound
PCNB*/
PCA2/
•&
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV ' ' ' '
XV
Extractable 14C
Unextractable 14C
Total extractable
Unextractable 14C
b/ Ether-extractable Ether-extractable
~ before hydrolysis after hydrolysis^/
.96
.84
.68
.59
.46
.44
.33
.23
.20
.16
.10
.09
.07
.05
.04
"" .02 .
.00


"c
after hydrolysis
0.00015
0.00034
0.00007
0.00003
0.00003
0.00023
O.O0002
0.00002


0.00005




0.00004
0.00008
0.00106
0.00760


14C loss during hydrolysis
14
Initial C in water
Sample volume (1)


0.00017
0.00027



0.00004


0.00002
0.00004
0.00043
0.00024
0.00006
0.00006
0.00003
0.00006
0.00063
0.00205
0.00484
0.00311
0.00484
0.00083
0.00878
l.OOO
a/  Ecosystem was flooded with water 20 days after application of  [14c]penta-
    chloronitrobenzene to the soil.
b/  Silica gel GF-254, da-ethyl ether : iv-hexane, 7:3 by volume.
c/  The "Unextractable" of the preceding column was adjusted to 0.012 N HC1 and
    maintained at 55-56°C for 18-24 hours.
d/  Pentachloronitrobenzene.
e/  Pentachlbroaniline.
f/  Roman numerals <* unknown compounds.
                                      121

-------
 Table 62.-Concentrations  of  [14c]pentachloronitrobenzene and degradation

          products  in  aquatic organisms  in  a model ecosystem flooded with

          waterS/
Compound RfS/
PCNB5-/ .92
PcavS/ .79
iV .65
II .45
III .06
IV .00
Extractable 14C
Unextractable 14C
Total 14C
Average bio-
sample wt (g)
Pentaehloronitrobenzene
Gambusia*/
(fish)
0.171
0.684

0.062
0.007
0.060
0,984
0.734
1.718
0.343
equivalents, pp»='
PhysaS/
(snail)
0.350
0,544
0,026
0,096
0.039
0.133
1.188
0.413
1.601
0.012
a/  Ecosystem was flooded with water 20 days after application of  [14c]penta-
    chloronitrobenzene to the soil.

b/  Average of triplicate determinations for fish;  single determination  for
    snails.

c/  Silica gel GF-254, diethyl ether : iv-hexane, 7«3 by volume.

d/  Fish were added 4 days after flooding the ecosystem, removed 3  days later,
    and processed individually.

e/  Snails were added on the day of flooding;  15 snails were removed 7 days
    later and processed as single batch;  batch weight «= 0.183 g.

t/  Pentachloronitrobenzene.

g_/  Pentachloroaniline.

h/  Roman numerals » unknown compounds.
                                      122

-------
                                                     PENTACHLOROPHENOL
                                                         TOTAI, RESIDUE
                        (16%)
                         Corn
Animals
                          •Calculation of the above estimates:
Ecosystem

Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total
Corn^
Soil (II)
Air
Total max:
mass, |
(No.) X mass
(8) 3.78
( 4) 6.31
(13) 0.033
( 8) Q.937
( 1> 45.3
(I) .
(38) 3.39
( 1)3766

ffMtftt
P
- total
30.
25.
0.
7.
45.
109
• 129
- 3766

Mean
concentration,
ug/s
•v ••
2 0.551
2 0.212
429 0.618
50 1.45
5 0.530

6.30
0.-634
[5000 ug-(I+n
Total
residue, tig:
,
(mass) (cone.)
16.7
5.35
0.265
10.9
24.1
57.3
812
2388
->] - 2555
Total residue as
a % of applied
dose (5000 ug)
0.3
0.1
<0.1
0.2
0.5
1.1
16.2
47.8
51.1
a/  Proportion at 14 days postplanting;   the corn,  having been  consumed an<}/or demol-
    ished by the animals, is not present as  an  entity  at the termination of the system.


Fig.. 46.-Terminal environmental distribution of [   CJpentachlorophenol plus metabolites
         in a soil-terrestrial model ecosystem.
                                              123

-------
K>
20 1
15
B
•H
U
3
IX
CO
8.
• 10
3 .
I
*
w 5 •
$ .


0
^ 0,1
i











{EP 19Z
CM 21Z
UN «* 0,0'
j
fEP 16Z
6,30377 c^L L
0.04422 I
1,25 0,0 0,01860
Soil . Corn Air Earthworm Slug Plllbug Caterpillar Vole
                                                                                       PPM

                              Fig. 47.—Suomary of the fate of [  G]pentachlorophenol In a soil-terrestrial model ecosystem.   The total   C-
                                        resldues ate expressed as pentachlorophenol equivalents,  ppm (w/w), and their subdivisions are EP  •
                                        extractable parent compound,  EM - extractable metabolites of the parent Compound,  and UN  - unextractable
                                        products remaining In the processed sample.  On day zero, the corn  seeds were planted and the soil wasr
                                        treated with pentachlorophenol at one Ib Al/acre.  On days 10 and IS, the Invertebrates and the Vole were
                                        added, respectively.

-------
27. •
26 •
1* 25 •
J
1 " '
w
1
. 23 •
4J
HI
m 22
o
I?
21 •
20
fa? 8*
0,00818 
-------
Table 67.-ReJatfve affinities of 7 body-parts of the prairie vole^  for

           [ ' (fjpentachlorophenol plus Its metabolites, and comparisons

          wi'ih the relative masses of the body-parts.
Body-parts
(organs and tissues)
Liver
Carcass-
Skin
Brain
Uterine fat
Uterus
Remaining organs-

Residue wt In body-part
as a % of total residue
wt In entire body
15.58 ,
11.65
5.1*
0.78
O.Mi
0.15
66.27
100.01
Body-part wt as a %
of enti re body wt
\.t
5.72
A3. 19
13.75
1.26
2.12
0.26
33.70
100.00
a/  Vole from a soil-terrestrial model ecosystem treated with
    ['^(fjpentachlorophenol.

b/  Carcass = the eviscerated body (the removed organs and tissues are
    listed above); it consists predominately of muscle and bone.

£/  The gastrointestinal tract + contents, kidneys + adrenals, heart,
    lungs, mammary gVands, ventral central neck gland, parotid glands
    and small amounts of fat tissue were analyzed collectively; most
    (ca. 3A) of the mass consisted of the gastrointestinal tract +
    contents.
                                      130

-------
 Table 68 .-Concentrations of [ ^pentachlorophenol and degradation products

           in tha water of a model ecosystem 7  days after flooding the ecosystem

           with
                                      Pentachlorophenol equivalents,  ppm
                      Rf*/
Ether-extractable
before hydrolysis
Ether-extractable
after hydrolysis^/
»d/ gg
J*** .90
iV .73
PCP— ' .69
II .54
III .46
IV .36
V .34
VI .31
VII .22
VIII .19
IX .16
X .12
XI .05
XII .04
XIII - : .00
Extractable 14C
Onextractable 14C
Total extractable WC
Onextractable 14C after hydrolysis
14C loss during hydrolysis
Initial 14C in water
Sample volume (1)
0.00051
0.00005
0.00069
0.00002
0.00001
0.00003







0.00004
,Qi 00004 '
0.00139
0. 00695





0.00010

0.00044
0.00001
<0. 00001
0.00001
0.00001
0.00002
0.00002
0.00002
0.00001
0.00003
0.00004
0.00007
t-J, v ' 0.0001-1
0.00089
0.00296
O.OO228
0.00296
0.00324
0.00848
l.OOO
a/  Ecosystem was flooded with water 20 days after application of  [14c]penta-
    cblorophenol to the soil.
b/  Silica gel GF-2S4, benzene  : n-hexane  : acetic acid,  90t5:5 by volume.
c/  The "unextxactable'* of the preceding column was adjusted to 0.012 N HC1 and
    maintained at 55-56°C for 18-24 hours.

£/  Chloxanil  (tetrachloro-£-benzoquinone).
e/  Ronan numerals * unknown compounds.
f/  Pentachlorophenol.
                                       131

-------
Table 69.-Concentration* of  [c]pentachlorophenol and degradation products
           in aquatic organisms in a model ecosystem flooded With
Compound
&
PC*S/
jh/
XX
III
IV
V
VI
VII
VIII
Extractable 14C
Onextractable 14C
Total 14C
Average bio-
sample wt (g)
-*
.92
.65
.64
.52
.40
.37
.16
.07
.04
.00

,


Pentachloropbenol
Caabusia3/
(fish)
0.082
0.779
-
0.161
0.021


0.010
0.016
0.055
1.124
0.636
1.760
0.310
equivalents, ppm=«
PhvsaS/
{snail)
0.041
0.046
0.006
0.186
O.«17
0.024
0.029
0.035
0.113
0.353
0.850 .
1.665
2.515
0.016
a/  Ecosystem was flooded with water 20 days after application of  [14c]penta-
    chlorophenol to the soil.
b/  Average of triplicate determinations for fish;  single determination for
    snails.
c/  Silica gel GF-254, benzene : n-hexane : acetic acid, 90:5:5 by •volume.
d/  Fish were added 4 days after flooding the ecosystem, removed 3 days later,
    and processed individually.
e/  Snails were added on the day of flooding;  15 snails were removed 7 days
    later and processed as a single batch;  batch weight » 0.243 g.
f/  Chloranil (tetrachloro-£-benzoquinone).
£/  Pentachlorophenol.
h/  Roman numerals * unknown compounds.
                                      132

-------
                                                         CAPTAN

                                                      TOTAL RESIDUE
                                                       Animals
                          Calculation of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Animal total (1)
Corn^
Soil (11)
Air
Total maximum
mass, g:
(NO.
('»)
( 3)
(13)
( 8)
( 1)

(27)
) X
3.
5.
0.
0.
24.

3.
mass -
37
20
0336
722
54

39 -
( 1)3842



Mean
concentration,
Total
residue, ug:
total wg/g (mass) (cone.)
'27.
15.
0.
5.
24.
73.
91.
3842

o v
6
437
78
54
4
5

[5000
0.
0.
0.
0.
0.

0.
0.
US
181
069
470
299
119

396
165
-]
4.
1.
0.
1.
2.
10.
36.
634
- 4355
88
08
205
73
93
8
2


Total residue as
a Z of applied
dose (5000 yg)
0
<0
<0
<0
0
0
0
12
87
.1
.1
.1
.1
.1
.2
.7
.7
.1
a/  Proportion at 14 days postplanting;  the corn,  having  been  consumed  and/or demol-

    ished by the animals, is not present as an entity  at the  termination of  the system.




                                                r!4
Fig. 49.-Terminal environmental distribution of [  Cjcaptan plus metabolites in a soil-

         terrestrial model ecosystem.
                                              133

-------
20 .

15
9 '

-------
                                     27
Ul
I
u
I
I
t
I
IM
O
«
                                     25
                                     23
                                     22
                                     21
                                     20
IBP OZ
I 8,00291 
-------
Table 70.-Concentrations of  [  CJeaptan and degradation products in the* soil



          of a model ecosystem 20 days after application of  [*4c]captair to



          the soil
Compound
IS/
II
III
Captan
IV
V
VI
VII
VIII
Extractable 14C
Unextractable 14C
Total 14C
Sample wt (g)
MS/
.98
.89
CO. QlSf
• 3* » OJL
.51
.18-. 38
.15
.06
.04
.00




Captan equivalents, ppm
Acetone extract Methanol extract-
O.OOO8
0.0038
0.0025
0.0017 0.0001
0.0011
0.0006
0.0020 0.0001
0.0002
0.0092 0.0029
0.0217 0.0033
0.1397
0.1647
100.0000
a/  Silica gel GF-254, diethyl ether :  n_-hexane, 7:3 by volume.




b/  Methanol extract is from the sample previously extracted with acetone.




c/  Roman numerals « unknown compounds.




d/  Rf range denotes streak on TLC plate.
                                      136

-------
Table 71.-Concentrations of  [*4c]captan and degradation products in corn*'



          after a 14-day exposure in a model ecosystem
Compound
&
II
III
IV
Cap tan
V
VI
VII
VIII
IX
X
XI
Extractable 14C
Unextractable 14C
Total 14C
Averager bio-
sample wt (g)
RfS/
0.97
0.89
0.83
0.72
0.51
0.34-0.54S/
0.32
0.29
0.24
0.13
0.06
0.00





Root
0.002
0.001
0.001

0.001




0.002
0.001
0.065
0.073
0.294
0.367
0.672
Captan equivalents.
Shoot
0.006
0.010

0,007
0.005
0.004
0.001
0.002
0.002
0.011
0.018
0.064
0.130
0.28O
0.410
1.491
ppm&/
Entire plant
0.005
0.007

-------
Table  72.-Concentrations of {  cjcaptan and degradation products in invertebrates^

          after a 5-day exposure in a model ecosystem
Captan equivalents , ppm— -
Compound
X*
II
III
Captan
IV
V
VI
VII
14
Ex tract able C
14
Unextractable C
Total 14C
Average bio-
sample wt (g)
_-b/ Anuadillidium— Estigmene
(pillbug) (caterpillar)
.95 0.119 0.086
.30-.74S/
.70 0.014
.49 0.053 0.019
.30
.05-. 30
.05 0.013
.00 0.167 0.066
0.339 0.198
0.131 0.101
0.470 0.299
0.034 0.722
Limax
(slug)



0.020
0.005

0.004
0.027
0.064
0.005
0.069
5.204
Lumbricus
(worm)

0.033



0.01$

0.089
0.137
0.044
0.181
3.366
a/  Average of duplicate determinations for caterpillars and worms;  single
    determination for pillbugs and slug.

b/  Silica gel GF-254, diethyl ether :  n-hexane, 7:3 by volume.

£/  Three pillbugs were processed together;  batch weight * 0.101 g.

d/  Roman numerals = unknown compounds.

e/  Rf range denotes streak on TLC plate.
                                      138

-------
c
                       Table 73".-Concentrations of  [i4c]captan and degradation products in the prairie vole after a 5-day exposure in
                                 a model ecosystem
Captan equivalents, pptn
Compound RfS<
l& .89
II .80
III . •' .71 '
G
Captan . 46
IV ' ' . .05
V .00
Extractable 14C
pnextractable 14C
Total 14C
Biosample wt (g)
Uterus Brain

0.326 0.228
0.018

0.013
0.040 0.001
0.366 0.260
0.076 0.019
0.442 0.279
0.019 0.473
< Liver

- 0.124
,
0.022
" 0,006
0.051
, 0.203
0.065
0.268
1.234
Remaining
organs!?


0.033


0.056
0.089
0.129
0.218
6.790
Skin
0.029
0.044

0.002
0.001
0.002
0.078
0.046
0.124
3.092
Uterine
Carcass
fat
O.OO7
0.021
0.010
O.O42 0.001

-------
Table 74.-Relative affinities of 7 body-parts of the prairie vole^-7  for

          rl Jf~T
          I  CJcaptan plus its metabolites, and comparisons with the
            ?rt
          relative masses of the body-parts.
Body-part
(organs and tissues)
Carcass-
Skin
Liver
Brain
Uterine fat
Uterus
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
19.71
13.09
11.31
A. 51
0.41
0.27
50.70
100.00
Body-part wt as a %
of entire body wt
*i*f
51.18
12.90
5.15
1.97
0.39
0.08^
28.33
100.00
a/  Vole from a soi1-terrestrial model ecosystem treated with   <
    [1J*c]captan.

bY  Carcass » the eviscerated body (the removed organs and tissues are
    listed above); it consists predominately of muscle and bone.

£/  The gastrointestinal tract +• contents, kidneys + adrenals,  heart,
    lungs, mammary glands, ventral central neck gland, parotid  glands
    and small amounts of fat tissue were analyzed collectively; most
    (ca. 3A) of the mass consisted of the gastrointestinal  tract +
    contents.
                                      140

-------
Table  75--Concentrations of  [  cjcaptan and degradation products  in the water

          Of a model ecosystem 7 days after flooding the ecosystem with water*
Compound
&
II
III
Captan
IV
V
VI
VIX
VIII
XX
Extractable 14C
Onextractable 14C
Total extractable
Onextractable 14C
Captan
equivalents, ppm
fb/ Chloroform-extractable Chloroform- extractable
^^ before hydrolysis after hydrolysis^/
.98 0.000002
.79 0.000004
.58 0.000003
.55 0.000003
.25 0.000006
.18
.13
.08
.02 0.000008
.00 0.000023
0.000049
0.002555
14C
after hydrolysis
**C loss during hydrolysis
Initial C in water
Sample volume (1)




0.000003

0.000012
0.000014
0.000019
0.000004
0.000018
0.000070
0.001143
0.000119
0.001143
0.001682
0.002944
1.000
a/  .Ecosystem was flooded with water 20 days after application of [-^c]captan
    to the soil.

b/  Silica gel GF-254, dxethyl ether : iv-hexane, 7:3 by volume.

cf  Tha "unextractable" of the preceding column was adjusted to 0.012 N HC1
    and maintained at 55-56°C for 18-24 hours.

d/  Roman numerals = unknown compounds.
                                      141

-------
Table 76..-Concentrations of  [  cjcaptan and degradation products in aquatic

          organisms  in a model ecosystem flooded with water^/

Compound RfS'
!•£/ .98
II .97
Captan .57
III .27
IV .05
V .00
Extractable 14C
Unextractable 14C
Captan equivalents,
Gambusia*/
(fish)
0.715

0.021

O.OO4
0.056
0.296
0.082
ppmb/
PhysaS/
(snail)
0.026
0.018
0.048
0.032
0.039
0.104
0.267
0.558
Total 14C
0.378
0.625
Average bio-
  sample wt  (g)
0.243
0.016
a/  Ecosystem was flooded with water 20 days after application of  [14c]captan
    to the soil.

b/  Average of triplicate determinations for fishj  single determination for
    snails.

c/  Silica gel GF-254, diethyl ether : £-hexane, 7:3 by volume.

d/  Fish were added 4 days after flooding the ecosystem, removed 3 days later,
    and processed individually.

e/  Snails were added on the day of flooding;  15 snails were removed 7 days
    later and processed as a single batch;  batch weight * 0.238 g.

f/  Roman numerals ** unknown compounds.
                                      142

-------
                  Terrestrial animals
                                                           PARATHION
                                                         TOTAL RESIDUE
                 Aquatic animals
                          Coco
Soil sediment
                             Calculation of th« above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole ,
Total maximum
mass, g:

(
(
(No.)
8)
5)
(13)
(
%(
8)
1)
X
4.
7.
0.
0.
32.
Mean
concentration ,
mass " total
29 34
58
032
277
37
0
2
0 32
.3
.9
.416
.22
.0
ug/8
1.29
2.31
9.71
13.5
- ,0.304
Total
residue, tig:
(mass) (cone.)
44
87
4
30
. 9
.3
.5
.04
.0
.73
Total residue as
a Z of applied
dose (5000 yg)
0.9
1.8
0.1
0.6
- 0.2





Terrestrial
animal4/total (I)
Cornfe/
Soails
Fish
Aquatic
animal total (II)
Surface water (III)
Soil sediment^' (IV)
Air

(30) 3.39 -
(50) 0.008O -
( 3) 0.392 -


< 1)7000
( 1)3272 -

107
102
0.400
1.18

1.58
7000
3272

42.9
1.35
0.223


0.00741
0.&30
[5000 iig-(I+II+III-HV}]
176
4376
0. 540
0.263

0.803
51.9
2061
- 2710
3.6
87.5
0.011
0.005

0.016
1.0
41.2
54.2
a/  The terrestrial arlma1? (and their residues) were removed from the system at the ter-
    mination of the terrestrial phase.
W  Proportion at 14- days postplantittg;  the corn, having been consumed and/or demolished by
~   Che animals, is not present as an entity at the termination of the terrestrial phase, and
    Its residue is distributed among animals, air, and soil.
_c/  The direct interaction of corn, air, and terrestrial animals with the soil occurred prior
    to flooding the system.

Fig. 52.-Terminal enviranaeaeil-distribution-of '[l C-]parachion plus metabolites la a soil-
         terrestrial model ecosystem.
                                            143

-------
o
a.
n
20 '
19 .
18 '
14 -
12 •
11 -
10 -
0.!
4




O.C
[EP 182
577 { EM 152 0.3
. I. UN 67Z '•
0.05059 PARAT.UON

0.01
_ „ (EP 252
42.9 
-------

32 ..





5
u
1
S- 27 .
i
1 "
•3
25 •
1
U
£ 24 -
w
*N
0 23
1
22 •

21 .
20








0,
0,

0.

0.

0.

0.

0,
0,






«tt

ffip 45,
00741 JEM 22% l.j
V ^
>*y hydrolysis
1
00740
1
00662
1
00618
1
00526
I
00451
1
C0116 0,i



PARAT1UON
S
| yy Vy
0 V *^-\ y-**°«

55 {EM " 0.2
> ' c i

*


0,(

v


;

1

0,63
i





{EP 4Z
EM47Z
UN49Z




1






0,5?
[EP sz
fl^EM 13Z
k Ira 82Z





Water
removed











(EP 18Z
EM 1SZ
UN 67Z

r 12





if
VI
postflood;
6 £
1
5 .
S
• * &
a
•H
3 o
41
•S?
. 2 *

. 1
. 0
  Surface water
                               Snails
                                                     Pish
                                                                           Sediment
                                           PPM
Fig.
54.—Sunmary of the fate of [  CJparathion in the aquatic  phase;  an extension  of  a  soil-terrestrial
     model ecosystem (see Fig.  S3).   The barren terrestrial phase was  flooded  20  days postplantlng
     and sna  s, Daphnia and mosquito larvae were added to the system;  the  fish were added 4  days
     later,  ihe total   C residues   are expressed as  parathion equivalents, ppm  (w/w),  and their
     subdivisions arc EP a extractable parent compound, EM - extractable metabolites of  the parent
     compound, and UN <* unextractable products remaining in the processed sample.

-------
Table 77 .-Concentrations of  [  CJparathion and degradation products in the
          soil and sediment of a model ecosystem
— Parathion equivalents, ppm
Compound
Parathion
!§/
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
XXI
Extractable *4C
Onextractable 14C
Total 14C
Sample wt (g)
Rf£/
.96
.78-. 93S/
.79
.69
.20-. 68
.55-. 66
.58
.45-. 52
.52
.20-. 47
.43
.37
.18-. 31
.30
.17
.13
.09-. 12
.04-. 08
.07
.04
.01-. 04
.00




Acetone
extract
0.0825
0.0037
0.0009
0.0072


0.0008
0.0008
0.0005

0.0008
0.0010
0.0026
0.0037
0.0052
0.0147


0.0025
0.0044

0.0244
0.1557


SoilS/
Methanol
extract!/
0.0216


0.0020

O.OO05


0.0002
0.0012




0.0010
0.0033
0.0004

0.0014

0.0006
0.0047
0.0369
0.3839
0.5765
100.0000
Sediment*/
Acetone
extract
0.0286
0.0035

0.0025

0.0007
0.0004
0.0009


0.0021
0.0009
0.0037

0.0040
0.0173

0.0039

0.0051

0.0219
0.0955


Methanol
extract
0.0008



0.0013



•





0.0017
0.0048


0.0023


0.0052
0.0161
0.5179
0.6295
100.0000
a/  Soil samples were taken 10 days after crop treatment.
b/  Sediment samples were taken 22 days after crop treatment, 12 days after
    flooding the ecosystem with water.                                  i
c/  Silica gel GF-254, diethyl ether : nj-hexane, 7:3'by volume.
&/  Methanol  extract is from the sample previously extracted with acetone.
e/  Roman numerals « unknown compounds.
f/  Rf range denotes a streak on the TLC plate.
                                      146

-------
Table  78.-Concentrations of  [14c]parathion and degradation products  in cover' grown
           in  a model  ecosystem
Parathion equivalents
Compound
Parathion
I*/
II
HI
IV
V
VI
VII
VIII
IX
X
XI
XII *
XIII
Extr actable
*,
.94
.91
.60
.52
.41-.50S/
.26-. 45
.35
.25
.11-. 20
.17
.14
.09
' "<:.OS"
.00
14C
Onextzactable 14C
Total 14C
"
Average biosanple wt (g)

Root
0.183
0.028
0.009




0.069
0.002
0.003
0.002
0.008
* 6.005
0.155
0.464
0.598
1.062
0.557
Day 12
Shoot
49.305


1.724
0.101
0.597
0.045
0.306


0.527
0.260
01361'-'
9.054
62.280
17.923
SO. 203
1.196

Entire
plant
31.608
0.012
0.003
1.161
0.072
0.379
0.033
0.215
0.001
0.001
0.371
0.164
* 0.223
6.174
40.417
12.283
52.700
1.753

Root
0.168

0.012




0.004
0.007
0.003
O.001
O.104
" 0.015
0.325
0.639
1.071
1.710
0.693
, ppn-'
Day 14
Shoot
15.185


2.898

1.125

0.314
0.068

0.202
0.307
" "0.622
20.526
41.247
21.513
62.760
1.322


Entire
plant
10.853

0.004
1.931

0.744

0.197
0.054
0.001
0.141
0.231
0.425
13.672
28.253
14.685
42.938
2.015
a/  [c] Parathion was applied to the com leaves 10 days after planting the seeds;
    plants were harvested on indicated post-planting days.
b/  Average of triplicate determinations.
c/  Silica gel GF-254, diethyl ether : n-hexane, 7:3 by volume.
d/  Roman numerals ° unknown compounds.
a/  ftf range denote)) & streak on the TLC plate.
                                            147

-------
                             Table  79. — Concentrations of  [  cjparathion and degradation products  in  the  air of  a model ecosystem 0, 1, and 2
*-
00
                                                                 r-14
                                         days  after  applying  the  [_ Cjparathion  to  the  foliage.
R a/
Compounds f
Parathlon . 94
li' .33
II .02-. 33^'
III .03 .32
IV .04-. 23
V .03
VI .00
14
Extractable C
14
Unextractable C
Sum traps 1 & 2
14
Pre-extraction C
14
Extractable C
14
Unextractable C
Extraction losses
Air sample wt. (g)-
Parathlon equivalents.
Day 0
Hexane- Hexane-
extractable. , extractable ,
from trap 1- froa trap 2-
0.01838
0.00003
0.00008



0.00031
0.01880 0.00054
0.05226 0.00115
0.07723
0.01934
0.05341
0.00448
108.00
ppm
Day 1
Hexane- Hexane-
extractable extractable
from trap 1 from trap 2
0.00679


0.00005
0.00004
0.00002
0.00690 0.00018
0.03866 0.00109
0.04933
0.00708
0.03975
0.00250
108.00

Day 2
Hexane Hexane-
extractable extractable
from trap 1 from trap 2
0.00448
0.00005
0.00005


0.00012
0.00470 0.00003
0.03306 0.00069
0.04031
0.00473
0.03375
0.00183
108.00
                             £/   Silica  gel  GF-254, dlethyl  ether : hexane,  7:3  by volume.
                             b/   in-Hexane  extract of  trapping  solvent  (ethanolamlne:2-methoxyethanol, 1:2  by volume)  in trap 1,  the trap connected
                                  directly  to the ecosystem container.
                             c/   The n-hexane extract of* the trapping  solvent  (ethanolamlne : 2-methoxyethanol,'-l:2 by volume)  in trap 2.vas not
                                  chromatographed; trap 2 was connected In series  to trap 1.
                             &l   Roman numerals » unknown compounds.
                             e/   R«  range  denotes a streak on  TLC plate.
                             II   Air wa. trapped for  3 hr during daylight at a  flow rate of 10 ml/sec,  and 1 t of  air was  assumed to weigh 1 g.
1  I

-------
Table 80.—Concentrations of  [  cjparathion and degradation products in inverte-
           brates after a 5-day exposure in a model ecosystem.
Parathion equivalents, ppn—
Compounds
Parathion
I*'
II
III
IV
V
VI
VII
VIII
IX
14
Extractable C
Unextractable C
Total 14C
Average bio-
sample wt. (g)
Rf~
.88
.56
.34
.30
.22
.18
.12
.08
.04
.00




Lwnbricua
(worm)
0.556
0.048





0.044

0.027 ,
0.675
0.617
1.292
4.286
Limox
(slug)
1.472
0.452
0.005
0.008

0.003
0.016
0.064

0.158
2.178
0.128
2.306
7.578
Axmodi. I liditon^-
(pillbug)
1.969
0.759





0.156

0.359
3.243
6.463
9.706
0.032
Eatigmene—
(caterpillar)
3.188
1.238

0.006
0.083
0.027


0.178
0.338
5.058
8.468
13.526
0.277
&f  Average of duplicate determinations for worm and caterpillar; single determina-
    tion for slug and pillbug..
b/  Silica gel GT-254, diethyl ether : n-hexane, 7:3 by volume.
cj  Two pillbugs were analyzed together as the extract; both were dead when sampled.
Aj  One determination was based on a dead caterpillar.
e/  Roman numerals • unknown compounds.
                                         149

-------
Table 81.-concentrations of [14c]parathion and degradation products in the prairie vole after a 5-day



          in a model ecosystem
Parathion equivalents, ppra
Compound Rf— '
Parathion . 87
•& .63
II .15
III .04
IV .00
Retractable 14C
Unextractable 14C
Total 14C
Biosample wt (g)
Remaining
organs^/

0.078
0.023
0.037
0.118
0.256
0.837
1.093
7.085
a/ [ cj Parathion was applied to the
b/ Silica gel GF-254
c/ Internal organs.
d/ Autoradiographic
e/ Body totals were
f/ Roman numerals =
, diethyl ether s
other than those
Liver


0.006

0.015
0.021
0.128
0.149
2.162
Skin
0.028


0.001
0.001
0.030
0.101
0.131
5.948
corn foliage 5 days
n_-hexane »
specified,
Uterus Uterine
and ovaries*/ CarcaSS fat*/ Brai"





0.037
0.028
0.065
0.164
before the
0.016



0.001 0.010
0.017 0.035 0.010
0.036 0.015 0.018
0.053 0.050 0.028
15.824 0.173 0.639
vole was added to the ecosystem.
Body
totals^/
0.013
0.017
0.006
0.008
0.028
0.073
0.231
0.304
31.995

7:3 by volume.
were combined and analyzed as one sample.
analysis of extracts of these organs
calculated using
unknown compounds
the sum of
.
was unsuccessful because of low radioactive
the weights of dissected organs; live body weight -



content.
31.596 g.


-------
      82.'-Relative affinities of 7 body-parts of the prairie  vole^-  for

           [  c}parathIon plu? Its metabolites, and comparisons with  the

           relative masses of the body-parts.
isody-parts
lorgans and tissues)
Carcass^'
Skin
Liver
Brain
Uterus + ovaries
Uterine fat
Remaining organs-

Residue wt In body-part
as a % of total residue
wt in enti re body
8.71
8.00
3.31
0.18
0.10
0.09
79.61
100.00
Body-part wt as a %
of entire body wt
49.46
18.59
6.76
2.00
0.51
0.5*»
22. 14
100.00
a/  Vole from a soil-terrestrial model ecosystem treated with
~    1*C pa rath I on.
         pa rath I

b/  Carcass * the eviscerated body  (the removed organs and tissues are
    listed above); it consists predominately of muscle and bone.

c/  The gastrointestinal tract * contents, kidneys •*• adrenals, heart,
~   lungs, mammary glands, ventral centra) neck gland, parotid glands
    and small amounts of fat tissue were analyzed collectively; most
    (ca. 3/4) of the mass consisted of the gastrointestinal tract +
    contents.
                                      151

-------
Table 83.-Concentrations of  [14c]parathion and degradation products in the water

          of a model ecosystem 7 days after flooding the ecosystem with water*/
                                        Parathion equivalents-, ppm
Compound
Ether-extr actable
before hydrolysis
Ether-extractable
after hydrolysis^/
Parathion . 90
l3/ .73-.84S/
II .68
III .39-. 66
IV .59
V .10-. 46
VI .35
VII .29
VIII .24
IX .17-. 22
X .16
XI .11
XII .07
XIII .03
XIV .00
Extractable 14C
Dnextractable 14C
Total extractable 14C
Unextractable ^4C after hydrolysis
* C loss during hydrolysis
Initial 14C in water
Sample volume (1)
0.00029 ' 0.00013
0.00006
Q. 00013 ' 0.00009
0.00007
0.00003
0.00017
0.00004
0.00003
0.00002
0.00003
0.00012
0.00070
0.00012 0.00013
0.00010
0.00032 0.00031
0.00193 0.00096
0.00545 0.00379
0.00289
0.00379
O. 00073
0.00741
1.000
a/  Ecosystem was flooded with water 20 days after application of  [14c]parathion
    to the corn foliage.

b/  Silica gel GF-254, diethy1 ether : in-hexane, 7:3 by volume.

c/  The "un ex tractable" of the preceding column was adjusted to 0.012 N BC1 and
    maintained at 55-56°C for 18-24 hours.

d/  Roman numerals » unknown compounds.

e/  Rf range denotes a streak on the TLC plate.
                                      152

-------
                             r!4
Table 84.-Concentrat Ions of  [  CJ pa rath Ion and degradation product?  In

          aquatic organisms  from a model ecosystem flooded with water^-  .
Parathion equivalents, j>pm—
Compounds R.—
Parathion .95
|iX .I8-.903/
II .72
III .14
IV ' .03'. 12
V .09
VI .00
Extractable 1AC
14
Unextractable C
Total 14C
v t *
Average biosample wt. (g}'
G ambus la—
(fish)
0.008
0.029
0.016

0.014
0.047
0.114
0.109
0.223
"0.392 '
Physa^
TsnaTl)
0.023
0.080


0.039

0.132
0.274
1.080
1.354
0.0083
a/  Ecosystem was flooded with water 20 days after application of the
    [^CJparathion to tn« foliage.

b/  Average of triplicate determinations for fish; single determination
    for snal1.

£/  S'HIca gel GF-254, diethyl ether :  nrhexane, 7:3 by volume.

jd/  Fish were added 4 days after flooding the ecosystem, removed 3 days
    later, and processed individually.

«/  Snajls were added on the day of flooding, removed 7 days later, and
    processed In one batch of 15 snails; total batch weight = 0.124 g.

f/  Roman numerals " unknown compounds.

£/  R, range denotes a streak on the TLC plate.
                                        153

-------
                                                     METHYL  PARATHION
                                                        TOTAL RESIDUE
                                                         Aquatic animals
                                        Soil sediment
                             Calculation of the above  estimates:
Ecosystem
component
   Total naximua
      mass, g:

(No.)  X nass •  total
                                                  „
                                          Total
                                        resldue'
                                                                             Total residue as
                      concentration,  _"_ _ 1 ^.81    a Z  of  applied
                                                  Vg/g
                                                             (mass) (cone.)
                                                        dose  (5000  jig)
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
( 8)
( 5)
(13)
( 8)
( 1)
3.86
5.59
0.077
0.930
20.1
30.9
28.0
1.00
7.44
20.1
3.07
0.955
6.66
2.36
0.532
94- B
26.7
6.66
17.6
10.7
1.9
0.5
0.1
0.4
0.2
Terrestrial
   animali'total (I)
Cornt'
Snails
Fish
(32)    3.39
(50)    0.013
( 3)    0.329
                 87-4
                108
                 0.650
                 0.987
24.5
 1.19-
 0.236
 156
2658
   0.774
   0.233
 3.1
53.2
 0.015
 0.005
Aquatic
animal total (II)
Surface water (III)
Soil sediment^/ (IV)
Air


( 1)7000
( 1)3435


1.64
- 7000 0.00667
- 3435 0.455
[5000 ug-(M-IM-IIM-IV)]

1.01,
46.7
1563
- 3233

0.020
0.9
31.3
64.7
a/  The terrestrial animals (and their residues)  were removed from the system at the termina-
    tion of the terrestrial phase.
b/  Proportion at 14 days postplanting;  the corn,  having been consumed and/or demolished by
    the animals, is not present as  an entity at the termination of the terrestrial phase, and
    its residue is distributed asong animals, air,  and soil.
£/  The direct interaction of corn, air,  and terrestrial animals vith the soil occurred prior
    to flooding the system.

                                                r!4 T
Fig. 55.-Terminal environmental distribution of [CJmethyl parathion plus metabolites in a
         soil-terrestrial model ecosystem.
                                          154

-------
Cn
Ui
20'

19 '
. 18 '
§
£ 16
a

•!"'
"8
»p 13

12
11 -
10
0,3
t


•










0,(
fBT « -
EH UZ 0,!
Uff 82X t
METHYL PARATHION
, 0,0;
j




0,2;
fEP 21
21.5 ed) 0,1
mi "
^o*
•-


'647 3,(
^

i
< ^ }
!777
t.
1950 ,
1029 0.(
{EP 3Z fEP 6Z fEP 2Z
EM 55Z 0,955 *
fEP 1Z
>32
-------
32 •


'


j?
4J
§
.-4
a.
S 27 •
o
o.
n tr
1 26 •
I " '
n
S? 24 •
«4
0
„ 23 .
2
22 -

21 .
20 .

METHYL PARATinON


m __
-HO.


TEP ix
0,00667 36
-------
Table 85.-Concentrations  of [  c]methyl parathlon and degradation products
           in the  soil and sediment of a model ecosystem
Methyl parathion
Compound
IS/
Methyl parathion
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
Extractable 14C
Onextractable 14C
Total 1«C
Sample wt (g)
RfS/
.98
.93
.88
76-. 86^
.80
.70
58-. 67
20-. 67
48-. 64
.45
28-. 44
18-. 42
.25
16-. 21
.19
.16
.13
.08
03-. 07
.03
.00




Acetone
extract
0.0024
0.0133

0.0025

O.0137


0.0014
0.0006
0.0012

0.0008
0.0009
.

0.0019
0.0048

0.0037
0.0127
0.0599


SoilS/
Methanol
extracts/
0.0004
0.0015


0.0001
0.0039
0.0002




0.0005


'
0.0003
0.0006
0.0007

0.0006
0.0032
0.0120
0.3256
0,3975
100.0000
equivalents
, ppm
Sediment^/
Acetone
extract
0.0018
0.0011
0.0076
0.0020

0.0032


0.0017
0.0004

0.0021



0.0005
0.0009
0.0038
0.0043

0.0118
0.0412
0
0
100
Methanol
extract
0.0006
0.0002
<0.0001


0.0005

0.0006






0.0002
0.0002
0.0007
0.0016


0.0020
0.0066
.4069
.4547
.0000
a/  Soil samples were taken 1O days after crop treatment.
b/  Sediment samples were taken 22 days after crop treatment, 12 days after
    flooding the ecosystem with water.
c/  Silica gel GF-254, diethyl ether  : rt-hexane, 7:3 by volume.
d/  The methanol extract is from the sample previously extracted with acetone.
e/  Roman .numerals =» unknown compounds.
tf  Rf range denotes a streak on the TIC plate.
                                      157

-------
 Table  86.-Concentrations  of [c] methyl parathion and degradation products  in corn^/

           grown  in  a model  ecosystem
Methyl parathion equivalents, ppm"/
Compound
IS/
Methyl parathion
XI
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
XXI
Retractable 14C
Dnextractable 14C
Total 14C
Average biosample
"Rf£/
.96
.90
70-. 88^
.84
.73
.67
37-. 66
47-. 63
21-. 62
.44
.36
22-. 34
.25
03-. 24
.22
.17
04-. 16
.15
.11
.08
.04
.00



wt (g)

Root
0.005
0.030
0.004
0.014

0.076
0.008

0.008

0.023
0.002
0.004
0.006

0.002
0.003



0.003
0.301
0.489
0.480
0.969
0.1)25
Day 12
Shoot

12.826
0.047
2.495
10.549

0.280
0.826
0.031

0.045


0.055
0.234

0.206
0.416
0.216
0.950
21.573
50.749
15.244
65.993
1.268

Entire
plant
0.002
8.933
0.001
0.031
2.018
7.251
0.001
0.229
0.521
0.025
0.008
0.037
0.002
0.002
0.038
0.164
0.001
0.135
0.271
0.172
0.651
14.919
35.412
10.661
46.073
1.793
Day 14
Root Shoot

0.017 0.919

0.095
0.075 8.505


0.348

0.027

0.003


0.004 0.175

0.008 0.121
0.308
0.097
0.463
0.557 14.495
0.691 25.526
0.397 12.029
1.088 37.555
0.595 1.074
*
Entire
plant

0.596

0.061
5.486


0.223

0.010

0.001


0.115

0.080
0.198
0.061
0.295
9.505
16.631
7.869
24.500
1.669
a/   [14c] Methyl parathion was applied to the corn leaves 10 days after planting the
    seeds;  plants were harvested on indicated post-planting days.
b/  Average of triplicate determinations.
£/  Silica gel GF-254, diethyl ether t n-hexane, 7:3 by volume.
d/  Roman numerals * unknown compounds.
e/  Rf range denotes a streak on the TLC plate.
                                            158

-------
 TableS7. — Concentrations of [  c]methyl parathion and degradation pro-
            duets in the air of a model ecosystem one day after applying
                r!4 i
            the I  CJmethyl parathion to the foliage.
Methyl parathion equivalents, ppw
Compounds
Methyl parathion
Id/
II
14
Extractable C
14
Uhextractable C
a/ Hexane-extractable
f*~ from trap li/
.84 0.00012
.38 0.00001
.00 0.00000
0.00013
0.04624
Hexane-extractahle
from trap 2°-'



0.00002
0.00025
 Sum traps. 1 & 2
                14
 Pre-extraction   C
               14
   Extractable   C
                 14
   Unextractable   C
  1 Extraction Tosses ~

 Air sample vt. (g)-
  0.04950
  0.00015
  0.04649
  0.00286

108.00
 a./  Silica gel CF-254, diethyl ether : hexane, 7:3 by volume.
 Jb/  tv-Hexane extract of trapping solvent (ethanolaalne : 2-methoxyethanol,
     1:2 by volume) in trap 1, the trap connected directly to the eco-
     system container.
 c/  The n-hexane extract of the trapping solvent (ethanolamine : 2-
     methoxyethanol, 1:2 by volume) in trap 2 was not chrooatographed;
-'    trap 2 was' connected In series to trap 1.
 &/  Rooanr numerals = unknown compounds.
 ej  Air was trapped tot 3 hr'during daylight at "a flow irate of 10 ml/sec,
     and 1 L of Air was assumed to weigh 1 g-
                                       159

-------
           invt
Table 88.—Concentrations of [  C]methyl parathlem and degradation products in
           invertebrates after a 5-day exposure in a model ecosystem.
Compounds
i"
Methyl parathion
II
III
IV
V
VI
VII
VIII
IX
Extractable C
14
Unextractable C
Total 1AC
Average
biosample wt. (g)
V"
.97'
.81
.66
.60
.54
.20
.12
.08
,04
.00




Methyl
Lvmbnaite
(worm)

0.092
0.020
0.415


0.004
0.011
0.074
1.164
1.780
1.291
3.071
3.858
parathion
Limax
(slug) •
-
0.053


0.428
0.005
0.021
o.oao

0.197
0.784
0.171
0.955
5,587
eouivalents,.
(pillbug)
0.029
0.150
0.093
1,653



0.064

0.757
2.746
3.911
6.657
0,077
PP«a/ j,
i&/ Estigmene
(caterpillar)
0.169
0.224


0.540




0.259
1.192
1.164
2.356
0.930
£/  Average of duplicate determinations for worm and caterpillar; single determina-
    tion for slug and pillbug.
b/  Silica gel GF-254, diethyl ether : £-hexane, 7:3 by volume,
jc/  Three pillbugs were analyzed together as the extract.
&l  Roman numerals •= unknown compounds.
                                           160

-------
Table 89.-Concentrations of [c]methyl parathion and degradation products in the prairie vole after a 5-day
          exposure   in a model ecosystem
Methyl parathion equivalents! ppn
Compound Rf-/
Methyl parathion ,81
II .25-.74S/
III .68
IV . .53
V .39
VI .15-. 39
VII .22
VIII .14'
IX .06
X .00
Bxtractable 14C
Unextr actable 14C
Total 14c
Biosample wt (g)
Remaining
organsfZ/
0.011
0.027
0.027

0.043
0.083
0.122
0.313
1.511
1.824
5.206
» * «ui.ver
and ovariesS.'
-



_,
0.285
0.069 ,
0.354
0.080-
0.004
0.002

0.005

0.009
0.020
0.196
0.216
1.044
Skin
0.015

0.004

0.006
0.025
0.078
0.103
2.969
Carcass
0.006
0.006
0.003
0.001
0.001

0.003
0.020
0.042
0.062
10.140
M.




0.012
0.012
0.044
0.056
0.622
totals?/
O.003
0.005
0.001
0.003
0.007
<0.001
Q.007
0.001
O.013
0.021
0.035
0.097
0.435
0.532

a/  [14CJMethyl parathion was applied to the corn foliage 5 days before the vole was added to the ecosystem.
b/  Silica gel GF-254, diethyl ether : jn-hexane, 7:3 by volume.
o/  Internal organs, other than those specified, were combined and analyzed as one sample.
d/  The extract of these organs was not chromatographed.
e/  Body totals were calculated using live body weight (20.140 g).
ij  Roman numerals = unknown compounds,
3/  Rf range denotes a streak on the TLC plate.

-------
Table 90.-Relative-affinities of 6 body-parts of the prairie vole^-  for

           [  c]methyl parathion plus Its metabolites, and comparisons

          with the relative masses of the body-parts.
Body-parts
(organs and tissues)
Carcass-
Skin
Liver
Brain
Uterus + ovaries
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
5.81
2.88
2.11
0.33
0.26
88.61
100.00
Body-part wt as a %
of entire body wt
50.55
U.80
5.20
3.10
0.40
25.95
. 100.00
a/  Vole from a soil-terrestrial model ecosystem treated with
"~               parathion.
b/  Carcass «= the eviscerated body (the removed organs and tissues are
    listed above); it consists predominately of muscle and bone.

£/  The gastrointestinal tract + contents, kidneys + adrenals, heart,
    lungs, mammary glands, ventral central neck gland, parotid glands
    and small amounts of fat tissue were analyzed collectively; most
    (ca. 3A) of the mass consisted of the gastrointestinal tract +
    contents.
                                      162

-------
Table  91.-Concentrations  of [   cjmethyl parathion  and degradation products in

the water  of a model ecosystem 7 days after flooding  the ecosystem with
                                     Methyl parathion  equivalents,  ppa
Compound
RfS/
Ether-extractable
before hydrolysis
Ether-extractable
after hydrolysisS/
Methyl parathion
li/
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
Extractable 14C
Unextractable 14C
Total extractabla
Onextractable 14C
.94 0.00009
.81 0.00002
.72 O.OO014
.19-.712/ 0.00010
.63
.53-. 61
.50
.34-. 47
.32
.18-. 30
.18
.14 O.OOOO7
.12 0.00020
.07 0.00003 ,
, V03 , ^ >
.00 0^00025
0.00090
0.00427
14C
after hydrolysis
MC loss during hydrolysis
Initial 14C in water
Sample volume (1)

0.00006

0.00004

0.00001
0.00002
0.00003
0.00003
0.00001
0.00003
0.00003
0.00006
0.00002
0.00008
0.00013
0.00028
0.00083
0. 00326
0.00173
0.00326
0.00168
0.00667
l.OOO
a/  Ecosystem w, 3 flooded with water 20 days after application of  P4cJmethyl
    parathion to the corn foliage.

b/  Silica gel GF-254, diethyl ether : n_-hexane, 7i3 toy volume.

c/  The "unextractable" of the preceding column was adjusted to 0.012 N HC1 and
    maintained at 55-S6°C for 18-24 hours.

d/  Roman numerals = unknown compounds.
e/  R£ range denotes a streak on the TLC plate.
                                       163

-------
Table 92.—Concent rat ions of  P Cjmethyl parath Ion and degradation products  in
          T"3<_^r<                                                        /
          aquatic organisms  from a model ecosystem flooded with Mater— .
Methyl perathion equivalents, pog?—
Compounds R,—
& .99
Methyl para th ion .89
II .2A-.752-'
Ill .60
IV .20
V .05-. 16
VI .05
VII .00
Extractable lJ*C
Unextractable C
Total C
Average biosample Ytt. (g)
Gambus I a—
(fi£hj

0.038

O.OU


0.011
0.017
0.080
0.156
0.236
•i >
0.329
Physa^-7
(snai 1)
0.00& -

0.052 '

0.008
0.010
0.005
0.072
0.155
1.036
U91
0.013
a/  Ecosystem was flooded with water 20 days after application of  the
                parathion to  the foliage.
b/  Average of triplicate determinations for fish; single determination  for
*~   snail.

£/  Silica gel GF-25'ii diethyl ether  : ^-hexane, 7=3 by volume.

d_/  Fish were added ^ days after flooding the ecosystem, removed  3  days  later,
~   and processed  individually.

e/  Snails were added on the day of flooding, removed 7 days  later, and
    processed in one batch of 15 snails; total batch weight "  0.192 g.

f/  Roman numerals • unknown compounds.

£/  R, range denotes a streak on the TLC plate.
                                          164

-------
                   Terrestrial animals
                                                              HEXACHLOROBENZENE

                                                                  TOTAL  RESIDUE
                                                                (soybean system)
                           t   /    XN
                         ,*•-/      X
                                                        Aquatic  animals
                          .62
                        Soybeans   Soil (Drummer)  sediment
                            Calculations of the above  estimates:
                          Total maximum
Ecosystem
component
                       (No.) X mass - total
     Mean           Total
                 residue, us:
concentration,   	 __ J^ _ _

     vg'8       (mass)(cone.)
                                                                                  regldue
                                                                             a z of applied

                                                                             dose (500° "8)
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
(10)
{ 8)
(20)
(10)
( 1)
3.62
6.76
.0697
1.18
21.6
36.2
54.1
1.39
11.8 *
21.6
4.46
.195
1.53
.656'
.695
161
10.5
2.13
7.74
15.0
3.2
.2
.04
.2
.3
Terrestrial
   animal*/ total (I)
Soybeans^/            (34)
Snails                (50)
Fish                  ( 3)
                                       125
                              .718   »    24.4       1.15
                              .101   -     5.05       .801
                              .168   -     .504     2.38
                    196
                     28.1
                      4.05
                      1.20
3.9
 .6
 .08
 .02
Aquatic
animal total (II)
Surface water (III)
Soil sediment^.' (IV)
Air


( 1)7000
( 1)4130


5.55
• 7000
• 4130
[5000 ug-(IH


.00117
.829
•II+UI+IV)

5.25
8.19
3424
] - 1367

.1
.2
68.5
27.3
a/  The terrestrial animals (and their residues) were removed from the system at the termina-
    tion of the terrestrial phase.
b_/  Proportion at 14 days postplanting;  cha soybeans, having been consumed and/or demolished
    by the animals, is not present  as an entity at  the  termination of the terrestrial phase,
    and its residue is distributed  among animals, air,  and soil.
£/  The direct interaction of soybeans,  air,  and terrestrial animals with the soil occurred
    prior to flooding the system.

                                                r!4 i
 Fig. 58.'Terminal environmental distribution of [  Cjhexachlorobanzene plus metabolites  in a
          soil-terrestrial model ecosystem.
                                           165

-------
ON
20-
-
15-
I -
4J
c
a
§,10-
* -
)t system
Ul
i i i
vy
or
s-

_
0-
1.
J









fEP 97% fEP 70%
06SEM " fEP 99% 0.695{EM 26%
^ IUH 2% 0.01882 JEM 0% ^ VJ» "
J
1.
>







fEP 69% O'W
L5
-------
ON
                                                                                                                           0.829
                                                                   CEP 90X
                                                                  
§•
•w
g 23 -
u
1
o 22 -

1
21
20 -
^ v"" »*
i
t^ 45Z
EM 10Z O.E
im 45Z ,
T
0,00123 ,

0,0!

)099
0,00118




*

0,00113




0.00094




0,00091
0,0(
1070 °
,01 Im III 2.

•*

0,
[EP571 i
58 <( EM 30Z •
Lira isz



3


^
•
HEXACIILOROBENZENE
(Soybean system)
j*
j^?^V
\ H'
''"T^1
'o - i.
Water
removed














ftP 97Z
nr < EM IZ
UD l^ujj 2Z
8

• 7
6
!
1 5 I
*H
S
s.
' * »
J^
•8

3 §
B
S?
H4
• 2 °
»
2
• 1
- 0
                                       Surface  water
Snails
                             Fish
Sediment
                                                                                   PPM
                                Fig. 60 .—Summary  of the  fate of  £ CJhexachlorobenzene (soybean system) In the aquatic phase; an extension of a
                                          soil-terrestrial model  ecosystem  (see Fig.   ).  The barren terrestrial phase was flooded 20 days post-
                                          planting,  and snails, daphnia and mosquito larvae were added to the system) the fish were added 4 days later.
                                          The total  l^C-reslduea  are expressed as hexachlorobenzene equivalents, ppm (u/w), and their subdivisions
                                          are EP - extractable parent  compound, EM - extractable metabolites of the parent compound, and UN •
                                          unextractable products  remaining  in the processed sample.

-------
                              r!4 i
Table 93. — Concentrations of  [  Cjhexachlorobenzene and degradation products



           in the soil and sediment of a node! ecosystem in which soybeans



           were grown.


Hexachlorobenzene equivalents ,
PPm
Soil-7 . Sediment^'
Compound f
HCB^ .94
I-' .49
II .42
III .27
IV .22
V .00
14
Extractable C
14
Unextractable C
Total 16C
Sample wt (g)
Acetone Methanol Ace pone
extract extract^./ extract
0.9180 0.1051 0.6879
0.0020
0.0007
0.0003
-
0.0038 0.0066 0.0003
0.9218 0.1117 0.6912
0.0252 0.
1.0587 0.
Methanol
extract
0.0612
'-
-
0.0004
0.0001
0.0001
0.0618
0760
8290
100.0000 100.0000
a/  Soil samples were taken 20 days after application of  [  Cjhexachlorobenzene

    to the soil.



b/  Sediment samples were taken 28 days after application of  [  cj hexachloro-

    benzene to the soil, 8 days after flooding the ecosystem with water.



£/  Silica gel GF-254; _n-hexane : acetone : acetic acid, 40:10:1 by volume.



d_/  Methanol extract is from the sample previously extracted with atetone.



el  Hexachlorobenzene.



fj  Roman numerals » unknown compounds.
                                       168

-------
Table  94.—Concentrations of  [  C]hexachlorobenzene and degradation  pro-



           ducts  in  soybean plants —  after a 14-day exposure  in  a model



           ecosystem.

Compound
HCB^7
I*7
PCP
V
vni
X
XI
XIV
14
Extractable C
14
Unextractable C
Total 14C
Average bio-
sample wt (g)
V
.92
,90
.48
.40
.30
.20
.03-. IS^7
.00

*


Hexachlorobenzene equivalents, ppm—
Root
1.096
0.340
0.052
0 015
-
0.006
0.017
0.011
1.537
• 0.036 '
1.573
0.516
Shoot
0.024
0.011
0.005
0.002
0.002
0.002
0.002
0.001
0.051
0.005
0.057
0.202
Entire plant
0.794
0.248
0.039
0.011
<0.001
0.005
0.013
0.009
1.119
0.028
1.147
0.718
a/   |_  cjHexachlorobenzene was applied to  the soil beneath each  seed.



W  The roots of 6  soybean plants were combined and analyzed as  an  Individual

    sample; the shoots were similarly processed.



e/  Silica gel GF-254; ti-hexane  : acetone  : acetic acid, 40:10:1 by volume.



&J  HCB • hexachlorobenzene; PCP - pentachloxophenol.



e/  Roman numerals  ** unknown compounds.



f/  R, range denotes a streak on the TIC plate.
*—    £
                                        169

-------
Table  95. — Concentrations of £  C]hexachlorobenzene and degradation products in the air^-  from a model
           ecosystem in which soybeans were grown.
Compound
                       R C/
                       Rf~
                                                   Hexachlorobenzene equivalents, ppm
                                                  	Trap l£/	
                                  Day 0
Day 1
                                                            Day 5
              Day llj
                                                                                      Day 15
                                                                            Day 19
HCB^
II
PCP
III
IV
V
.97
.82
.71
.57
.50
.27
.00
                                 0.05090
      14
Total   C, Trap 1
Total 14C, Trap 2-'
    14
Sum   C, Traps 1 & 2
Sample vt  (g)5-
                                 0.05090
                                 0.00019'
                                 0.05109
                                              0.01422
                                              8.00102
                                              0.00032
                                              0.00018

                                              0.00027
                                              0.00014
                                              0.01615
                                              0.00018
                                              0.01633
                                                           0.00740
                         0.00245
                                                                                     0.00537
                                                                                     0.00024
                                       0.01862
0.00007
0.00015

0.00762
0.00012
0.00774
                                                                        0.00245
                                                                        0.00007
                                                                        0.00252
                                      0.00561
                                      0.00018
                                      0.00579
                                                                           0.01862
                                                                           0.00020
                                                                           0.01882
                               108.00000    108.00000    108.00000    108.00000    108.00000    108.00000
&l  Air was trapped for a 3-hour daylight period at a flow rate of 10 ml/sec on specified days after
    application of[l^c]hexachlorobenzene to the soil.
W  Trap 1 was connected directly to the ecosystem container and contained 75 ml of acetonitrile as the
    trapping solvent; the trapping solvent was ehromatographed.
c/  Silica gel GF-254; iv-hexane : acetone : acetic acid, 40:10;1 by volume.
&/  HCB •* hexachlorobenzene; PCP •» pentachlorophenol.
e/  Roman numerals «* unknown compounds.
£_/  Trap 2 was connected in series to trap 1 and contained 75 ml of trapping solvent  (ethanolamine :
~   2-methoxyethanol, 1:2 by volume); the trap 2 solvent was not ehromatographed.
gj  One liter of air was assumed to weigh 1 g.

-------
Table 96. —Concentrations of  [C]hexachlorobenzene and degradation products
           in invertebrates after a 5-day exposure in a model ecosystem con-
           taining soybean plants.
Hexachlorobenzene equivalents, ppm
Compound
HCBi/
I*'
PCP
II
III
IV
V
VI
VII
VIII
DC
14 '
Extrac table C
14
Unextractable C
Total IAC
Average biosample
_ a/ Aimadillidium — E8tigmen&~
V (pillbug) (caterpillar)
.89
.59
.51
.45
.39
.34
.25
.18
.07
.03
.00
"•


wt (g)
1.488
-
-
0.005
-
-
-
-
-
0.002
0.002
1.497
0.037
1.534
0.070
0.564
0.017
0.002
0.003
0.001
0.001
0.001
-
0.001
<0.001
<0.001
0.590
0.065
0.655
1.180
Limax-
(S!UR)
0.153
0.006
0.006
0.001
0.001
-
<0.001
0.012
0.001
0.001
0.001
0.182
0.013
0.195
6.756
Lumbricue^-
(earthworm)
4.100
0.103
0.028
0.019
0.006
0.005
0.003
-
0.002
0.002
0.002
4.270
0.191
4.461
3.616
£/  Silica gel GF-254; n-hexane : acetone : acetic acid, 40:10:1 by volume.
b_/  Three pillbugs were processed together; batch weight » 0.209 g.
c/  Three caterpillars were processed together; batch weight - 3.541 g
d/  Three slugs were processed together; batch weight - 20.268 g.
e/  Three earthworms were processed together; batch weight • 10.849 g.
fj  HCB * hexachlorobenzene; PCP » pentachlorophenol.
£/  Roman numerals • unknown compounds.
                                       171

-------
Table 97 . — Concentrations of £  C] hexachlorobenzene and degradation products in the prairie vole after a 3-dayS-
           exposure in a model ecosystem in which soybeans were grown.
Hexachlorobenzene equivalents,
ppra
e.
_ b/ Remaining
Compound f
«»y*p°f n *>
HLir~ . o<£
I*/ .62
II .56
III .48
IV .42
V .36
VI .34
VII .29
VIII .28
IX .15 .
X .21
XI .16
XII .11
XIII .05
XIV .00
Extractable I4C
14
Unextractable C
Total C
Biosanple wt (g)

1


0
0

0
0

37-fc
0
0
0
0
0
1
0
1
2
Skin
.419
-
-
.110
.046
-
.011
.006
-
-
.003
.002
.002
.001
.002
.602
.108
.710
.762
organ s^.'
1.


0.
0.

0.
0.


0.
0.
0.
0.
0.
1.
0.
1.
2.
159
-
-
064
030
-
Oil
008
-
-
003
002
005
002
002
286
050
337
292
Carcass
0.296
0.127
0.047
0.015
0.023
0.006
0.003
0.003
0.004
-
0.002
0.001
0.002
0.002
0.003
0.534
0.015
0.549
11.843
a/ The vole died 3 days after being placed In the ecosystem,
remaining in the ecosystem when the vole
b_/ Silica gel CF 254
c/ Internal organs.
d/ Body total's were
was added
; n-hexane : acetone : acetic acid.
other than those
calculated using
specified, were
intact
dead body
Brain
0.250
0.049
-
-
0.027
-

-
0.015
-
-
-
-
-
0.013
0.354
0.002
0.356
0.452
probably from
Liver
0
0
0
0
0




0


0
0
0
0
0
0
1
.048
.013
.022
.032
.017
-

-
-
.010
-
-
.004
.008
.005
.159
.014
.173
.171
starvation;
GI
0
0
0
0
0
<0
<0



0
0
0
0
0
0
0
0
2
the
tract
.088
.016
.016
.005
.003
.001
.001
-
-
-
.001
.001
.001
.002
.001
.134
.017
.151
.566

Body ..
totals^'
0.484
0.073
0.029
0.031
0.024
0.003
0.004
0.003
0.003
0.001 •
0.002 -
0.001
0.002
0.002
'0.003
0.665
0.030
10.69S ,'
-
few soybean shoots
had been consumed.
40:10:
1 by volume.
combined and processed
weight
(21.639 g).

as



•

an individual sample.




e/ Hexachlorobenzene.
Jf/ Roman numerals ~
fj Rj range denotes
unknown
a streak
compounds
.








on the TLC plate.

-------
Table 93.—'Relative affinities of 6 body-parts of the prairie vole^  for
            r!4 i
            {_  CJhexachlorobenzene (soybean system) plus its metabolites,

            and comparisons with the relative masses of the body-parts.

Body- part
(organs and tissues)
Carcass-
Skin'
GI tract
Liver
Brain
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
43.25
3U39
2.57
1.34
1.07
20.37
99.99
Body-part wt as a %
of entire body wt
• 56.17
13.10
12.17
5.55
2.14
10.87
100.00
a/  Vol« from a soil-terrestrial model ecosystem treated with
         hexachlorobenzene.
b/  Carcass » the eviscerated body (the removed organs and tissues are
    listed above); it consists predominately of muscle and bone.

£/  The kidneys + adrenals, heart, lungs, mammary glands, ventral central
    neck gland and paratid glands were analyzed collectively.
                                      173

-------
                              rl4
                              [Jit •
                                CJhexachlorobenzene and degradation products in the water of a model ecosystem
           (in which soybeans were grown) 7 days after flooding the ecosystem with waterS/.
                                                   Hexachlorobenzene equivalents, ppm
                                          Surface water
              Leachate—
               Rc/
Compound        f
Ether-extractable
before hydrolysis
                                                 Ether-extractable
                                                 After hydrolysis
Ether-extractable
before hydrolysis
Ether-ext raqtable
after hydrolysis
HCB£/
PCP
nil/
IV
V
VI
VII
VIII
IX
X
XI
14
Extractable
Unextractable
.90
.59
.44
.37
.27
.23
.17
.10
.06
.03
.00
5*c
0.00053
0.00003
0.00004
0.00001
-
0.00001
0.00001
- ,
-
0.00001
<0. 00001
0.00064
0.00007
0.00002
0.00003
0.00001
0.00001
0.00003
<0. 00001
0.00008
0.00002
0.00002
-
0.00029
0.00027
0.00105
0.00005
0.00003
0.00002
-
0.00001
0.00001
-
-
0.00001
<0. 00001
0.00118
0.00004
0.00001
0.00001
0.00001
0.00001
0.00001
<0. 00001
<0. 00001
<0. 00001
<0. 00001
<0. 00001
0.00009
0.00027
Total extractable C
Unextractable l^C after hydrolysis
* C loss during hydrolysis
Initial 14C in water
Sample volume (1)
0.00093
0.00027
-0.00003
0.00117
1.00000
0.00127
0.00027
0.00028
0.00182
1.00000
a/  Ecosystem was flooded with water 20 days after application of [  (fjhexachlorobenzene to the soil.
b/  One liter of water was withdrawn through the tap at the jar bottom over a period of 1 hr.
£/  Silica gel GF-254; iv-hexane : acetone : acetic acid, 40:10:1 by volume.
Al  The "unextractable" of the preceding column was adjusted to 0.012 N HC1 and maintained at 55-56 C for
      18-24 hr.
ej  HCB - hexachlorobenzene; PCP - pentachlorophenol.
if  Roman numerals «• unknown compounds.
                                                        ,-t.

-------
                              1-14
Table 100—Concentrations of  [  c] hexachlorobenzene and  degradation
           products  in aquatic organises In a model ecosystem  (In which
           soybeans  had been  grown)  flooded with water—  .
Compound
uafil
&
ii
in
IV
V
VI
VIX
VIII
IX •"'''* ' "•' '
X
14
Extract able C
14
Unextractable C
Total UC
Average biosample wt
Rf~
.92
.77
.61
.47
.42
.38
.24
.19
.10
.05 l
.00



(g)
Hexachlorobenzene
Gambuaiar-
(fish)
1.361
-
-
0.041
'
0.057
0.024
-
0.295
>"•--- ' 6.067
0.237
2.082
0.300
2.383
0.168
equivalents, ppra
Phye^
(snail)
0.458
0.061
0.087
-
0.036
0.039
0.005
0.015
-
0.050
0.017
0.768
0.033
0.801
0.101
                                                                   rl4 1
a/  Ecosystem was flooded with water 20 days after application of  [  Cj-
    hfWachlorobenzen* to the soil.
b/  Silica gel GF-234; n-hexane : acetone : acetic acid, 40:10:1 by  volume.
£/  Fish were added 4 days after flooding the ecosystem; 2  fish  (alive)
~   were removed 3 days later and processed together.
d/  Snails were added on the day of flooding; 15 snails were  removed 7 days
    later and- processed as a batch; batch weight * 1.510 g.
ef  Rexachlorobenzene.
f/  Roman* 'riumer-al's » unknown compounds.
                                        175

-------
                Terrestrial animals
                         -*-/
I   4%
V
 x   ^'
  Corn
                                                              HEXACHLOROBENZENE
                                                                 TOTAL RESIDUE
                                                                 (corn system)
                                Aquatic animals
                                  Soil  (Drummer) sediment
                           Calculations of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Total maximum „ Total
MS6' S: concentration, "^due- «'•
(No.
(10)
( 8)
(20)
(10)
( 1)
) X mase -
3.71 -
6.50 «
.0695 -
.829 -
46.5
total
37.1
52.0
1.39
8.29
46.5
. Ug/g
.584
.228
4.09
.347
2.88
(mass) (cone.)
21.7
11.9
5.69
2.88
134
Total residue as
a % of applied
dose (5000 ug)
.4
.2
.1
.06
2.7
Terrestrial
   animal^' total (I)
Cornk/                (46)
Snails                (50)
Fish                  ( 3)
      1.64
        .095
        .182
145
 75.4
  4.75
   .546
2.64
 .546
1.13
176
199
  2.59
   .617
3.5
4.0
 .05
 .01
Aquatic
animal total (II)
Surface water (III)
Soil sedimentS.' (0V)
Air


( 1)7000
( 1)4352


5.30
• 7000 .00173
• 4352 .818
[5000 ug-d+II+III+IV)]

3.21
12.1
3560
- 1249

.06
.2
71.2
25.2
a/  The terrestrial animals (and  their residues) were removed from the system at the ter-
    mination of the terrestrial phase.
b/  Proportion at 14 days postplanting, the corn, having been consumed and/or demolished by
    the aninals, is not present as an entity at the termination of the terrestrial phase, and
    its residue is distributed anong animals, air, and soil.
c/  The direct interaction of corn, air, and terrestrial animals with the soil occurred prior
    to flooding the system.


Fig. 61>-Terminal environmental distribution of [  c]hexaehlorobenzene plus metabolites in  a
         soil-terrestrial model ecosystem.
                                             176

-------
20-
15-
postplanti
M
o
w
5 -
I "
M
& 5-
,
W 2\ 0.0 0,0 0.0 0.0
s T
'\
HEXACHLOROBENZENB
fEP 99% * (Corn system)
[373 JEM 0%, a
^ L-LJC
IT
2775 {EP 99%, EM 0%, UW 1% °'
1.25 0.0 0. 03106 (EP 99%, EM o%, UN 1%
      Soil
                Corn
                                  Air
                                                earthworm       Slug
                                                            PPM
Pillbug
Caterpillar
                                                                                                           Vole
Fig. 62 •—Summary of the fate of [  c]hexachlorobenzene (corn system)  in a soil-terrestrial model ecosystem.   The
          total 14C residues are expressed as hexachlorobenzene equivalents,  ppm (w/w),  and their subdivisions are
          EP = extractable parent compound, EM = extractable metabolites of the parent  compound,  and UN = unextract-
          able products remaining in the processed sample.   On day zero, the corn seeds were planted and the  soil
          was treated with hexachlorobenzene at one Ib Al/acre.  On days 10 and 15,  the invertebrates and the vole
          were added, respectively.            ,'

-------
00


28 •
27 •
26 •
M
B
*4
U
3 25 -
0.
4J
0>
O
a.
B 24 •
1
I 23 -
01
° 22 -
9)
<
21 •
22 -

fEP 452
0, 00173 i EM 92 0.5
A l™ «6*
0.00096




0,00075


0,00075


0,00077


0,00063


0,00060
O.OC
-048 0,
fEP 592
46 « EM 372 1,
. I.UN 42 ,





fEP 372
13 
-------
                              r!4 -i                             '
Table 101. — Concentrations of  (_ Cjhexachlorobenzene and  degradation products

           la  the soil and sediment of a model ecosystem in which  corn  is

           grown.

Hexachlorobenzene equivalents ,
ppra
Soil-' Sediment-'
Compound f
nr»tiS/ o£
nl*ij™^ «5ns
I-^ .52
II .44
III .27
IV .18
V .00
14
Extractable C
14
Unextractable C
Total UC
Sample wt (g)
Acetone Methanol Acetone
extract extract^/ extract
0.8310 0.0729 0.6287
0.0023
0.0016
0.0009
_
0.0040 0.0007
0.8310 0.0769 0.6342
0.0411 0.
0.9490 0.
100.0000 100.
Methanol
extract
0.0724
-
-
-
0.0001
-
0.0725
1111
8178
0000
£/  Soil samples were taken 20 days after application of  [ cjhexachlorobenzene
    to the soil.

b/  Sediment samples were taken 28 days after application of  [  cjhexachloro-
    benzene to the soil, 8 days after flooding the ecosystem with water.

c/  Silica gel GF-254; n-hexane : acetone : acetic acid, 40:10:1 by. volume.

d/  Methanol extract Is from the sample previously extracted with acetone.

e/  Hexachlorobenzene.

ft  Kenan numerals •» unknown compounds..
                                         179

-------
                             -14
                              [14 T
                                CJhexachlorobenzene and degradation pro-
ducts in corn— after a 14-day exposure in a model ecosystem.
Compound
HCB^7
!«/
II
III
IV
PCP
V
VI
VII
IX
X
XII
XIII
XIV
Extractable C
14
Unextractable C
Total 1AC
Average bio-
sample wt (g)
Rc/
Rf
.94
'.90
.61-.8&£7
.58
.51
.44
.42
.37
.35
.21-. 35
.18
.14
.06
.00




Hexachlorobenzene equivalents, ppm-
Root
2.912
1.607
-
0.516
0.099
0.052
0.057
-
0.036
-
0.023
0.016
0.018
0.030
5.366
0.145
5.511
0.758
Shoot
0.037
0.018
0.069
0.017
0.004
0.004
0.002
0.002 ••
-
0.004
0.001
0.001
0.002
0.001
0.162
0.018
0.180 .
0.883
Entire plant
1.365
0.752
0.037
0.247
0.048
0.026
0.027
0.001
0.017
0.002
0.011
0.008
0.010
0.015
2.566
0.077
2.643
1.641
     t!4 ~\
       CI Hexachlorobenzene was applied to the soil beneath each seed..
b/  The roots of 6 corn plants were combined and analyzed as an individual
    sample; the shoots were similarly processed.
c/  Silica gel GF-254, n-hexane :  acetone :  acetic acid, 40:10:1 by volume.
d/  HCB • hexachlorobenzene; PCP » pentachlorophenol.
e/  Roman numerals «• unknown compounds.
fj  R, range denotes a streak on the TLC plate.
                                         180

-------
00
                          Table 103- — Concentrations of [  CJhexachlorobenzene and degradation products in the air—  from a model
                                     ecosystem in which corn was grown.
R £/
Compound f
HCB^ . 96
Te/ .
I— .41
II .26
Total 14C, Trap 1
Total UC, Trap 2-f
Sum C, Traps 1 & 2
Sample wt (g)^
Hexachlorobenzene
Trap
Day 0
0.03089
-
-
0.03089
0.00017
0.03106
108.00000
Day 1
0.02759
-
-
0.02759
0.00016
0.02775
108.00000
Day 5
0.01357
-
-
0.01357
0.00016
0.01373
108.00000
equivalents,
Day 11
0.00387
0.00001
0.00003
0.00391
0.00010
0.00401
108.00000
p-pm
Day 15
0.00504
-
-
0.00504
0.00013
0.00517
108.00000

Day 19
0.02570
-
-
0.02570
0.00026
0.02596
108.00000
                          £/  Air was trapped for a 3-hour daylight period at a flow rate of 10 ml/sec on specified  days  after  appli-
                              cation of  [  G]hexachlorobenzene to the soil.

                          W  Trap 1 was connected directly to the ecosystem container and contained  75 ml of  acetonitrlle as the
                              trapping solvent; the trapping solvent was chromatographed.

                          £/  Silica gel GF-254; ii-hexane : acetone : acetic acid, 40:10:1 by volume.

                          d/  Hexachlorobenzene

                          £/  Roman numerals *> unknown  compounds.

                          1]  Trap 2 was connected in series to  trap 1  and contained 75 ml of  trapping solvent (ethanolamine : 2-methoxy-
                              ethanol, 1:2 by volume);  the trap  2 solvent was not  chromatographed.

                          £/  One liter  of air was assumed to weigh 1 g.

-------
Table 104.-Concentrations of [  Cj hexachlorobenzene and degradation products
           in invertebrates after a 5-day exposure in a model ecosystem con-
           taining corn plants.

Hexachlorobenzene eauivalents, opm
Compound
HO*/
!*/
PCP
II
III
IV
V
VI
VII
VIII
IX
14
Extractable C
14
Unextractable C
Total UC
Average biosample
R a/ Armadillidiuir- Eetigmene—
f (pillbug) (caterpillar)
.90 3.848
.64
.55
.46
.39
.32
.23
.17
.07 0.031
.03 0.039
.00 0.041
3.959
0.133
4.092
wt (g) 0.070
0.286
0.012
0.002
0.001
0.001
<0.001
0.001
-
0.006
0.008
0.013
0.330
0.016
0.346
0.829
d/
(slufO
0.156
0.006
0.015
0.001
0.001
-
0.001
0.027
0.003
0.002
0.003
0.215
0.013
0.228
6.503
e/
(earthworm)
0.530
0.024
0.006
0.002
0.001
0.001
<0.001
-
<0.001
<0.001
<0.001
0.564
0.020
0.584
3.709
a/  Silica gel GF-254; n-hexane : acetone : acetic acid, 40:10:1 by volume.
b_/  Three pillbugs were processed together; batch weight = 0.209 g.
£/  Three caterpillars were processed together; batch weight = 2.488 g.
d/  Three slugs were processed together; batch weight - 19.510 g.
ej  Three earthworms were processed together; batch weight = 11.127 g.
if  HCB = hexachlorobenzene; TCP = pentachlorophenol.
£/  Roman numerals = unknoxm compounds.
                                         182

-------
Oo
to
                             Table 105.-Concentrations of I   QJ hexachlorobenzene and degradation products in the prairie vole after a 5-day


                                        exposure in a model ecosystesa in which corn was. grown.

Hexaehlorobenzene equivalents, ppm
Compound. •
sr
ii
in
IV
V
VI
VII
IX
X
XI
XTI
XIII -
XIV
Extract able
D ^
. f
.84
.59
.57
.49
.42
.40
.32
.27
.15-. 43^
.22
.17
.11
.05
.00
"c
14
Unextractable C
Total UC
Biosample wt
(B)
Fat
9.497
-
0.195
0.129
-
-
-
-
-
-
-
-
9.821
0.040
9.861
2.395
Remaining
organs?-'
5.128
-
0.179
0.058
-
-
-
-
0.014
-
-
-
0.015
5.394
0.040
5.435
6.136
Skin
2.877
f —
0.199
0.083
-
0.020
0.014
-
0.006
0.004
0.003
0.003
0.002
3.211
0.239
3.450
5.623
Carcass
1.328
0.289
0.126
0.147
0.101
0.044
-
-
-
0.017
0.012
0.010
0.007
0.011
2.092
0.128
2.220
22.799
Brain
0.841
0.125
-
0.025
0.060
-
-
-
-
-
-
-
0.021
0.016
1.088
0.008
1.096
0.771
a/ Silica gel GF-254; o-hexane : acetone : acetic acid, 40:10:1 by volume.
b/ Internal organs, other than those specified, were combined and processed as
cj Body totals were calculated using live body weight (46.481 g).
d/ Hexachlorobenzene.
GI tract
0.676
0.028
0.033
0.007
-
0.003
-
-
0.001
0.001
0.003
0.002
0.005
0.759
0.042
0.801
5.616
an individual
Liver
0.112
0.018
0.029
0.120
0.066
-
-
-
0.025
-
-
0.007
0.024
0.009
0.410
0.090
0.500
2.903
sample.
Body .
totals^'
2.269
0.145
0.067
0.141
0.080
0.021
0.003
0.002
0.002
0.011
0.006
0.006
0.006
0.009
2.768
0.110
2.878
-

                             e/  Roman numerals » unknown compounds.

                             f/  R. range denotes a streak on the TLC plate.

-------
Table 106. -Relative affinities of 7 body-parts of the prairie vole^  for
           r!4 n
           L  Cjhexachlorobenzene (corn system) plus its metabolites, and

           comparisons with the relative masses of the body-parts.

Body-part
(organs and tissues)
Carcass-
Fat
Skin
GI tract
Liver
Brain
c/
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
37.84
17.66
14.50
3.36
1.08
.63
24.92
99.99
Body-part wt as a %
of entire body wt
49.30
5.18
12.15
12.14
6.28
1.67
13.27
99.99
&l  Vole from a soil-terrestrial model ecosystem treated with
    L  Cjhexachlorobenzene.

b/  Carcass = the eviscerated body (the removed organs and tissues are
    listed above); it consists predominately of muscle and bone.

cJ  The kidneys + adrenals, heart, lungs,  mammary glands, ventral central
    neck gland, parotid glands and small amounts of fat tissue were
    analyzed collectively.
                                     184

-------
oo
01
                       Table  107.-Concentrations of  [C]hexachlorobenzene and degradation products in the water of a model ecosystem
                                   (in which corn was grown) 7 days after flooding the ecosystem with water8./.

Hexachlorobenzene equivalents, ppm
Surface water
Compound
yf
ii
PCP
III
IV
V
VI
VII
VIII
IX
X
XI
14
Extractable
Unextraccable
„£/
Rf
.92
.70
.65
.58
.44
.38
.28
.24
.18
.10
.06
.03
.00
C
14C
Ether»extr actable
before hydrolysis
0,00078
-
0.00006
0.00004
0.00002
-
0.00001
0.00001
-
-
0.00001
<0. 00001
0.00093
-
Ether-extractable
after hydrolysisS/
0.00015
0.00001
-
0.00001
0.00002
0.00001
0.00001
0.00001
-
0.00001
0.00001
0.00001
<0. 00001
0.00025
0.00022
Leachate—
Ether-extractable
before hydrolysis
0.00295
-
0.00018
0.00006
0.00004
-
0.00002
0.00001
-
-
0.00002
0.00001
0.00329
-
Ether-extractable
after hydrolysis
0.00015
0.00003
0.00003
0.00001
0.00001
0.00002
0.00002
0.00002
0.00002
0.00003
0.00002
<0. 00001
0.00001
0.00037
0.00035
                                          14
                       Total extractable   C
                       Unextraccable   ^C  after hydrolysis
                       ^C  loss  during hydrolysis
                       Initial  1*C  in  water

                       Sample volume (1)
0.00118
0.00022
0.00033
0.00173
1.00000
 0.00366
 0.00035
-0.00009
 0.00392
 1.00000
                       £/   Ecosystem was  flooded with water  20  days  after  applicatior  of  [  c]hexachlorobenzene  to  the  soil.
                       b/   One  liter of water was withdrawn  through  the  tap  at  the jar bottom over  a  period of 1 hr.
                       £/   Silica  gel GF-254; jv-hexane : acetone s acetic  acid, 40:10:1  by  volume.                           Q
                       dj   The  "unextractable1  of the preceding column was adjusted  to 0.012 N  HC1  and maintained at  55-56 C  for
                              18-24 hr.
                       e/   HCB  - hexachlorobenzene;  FCP  =  pentachlorophenol.
                       T/   Roman numerals °  unknown  compounds.

-------
Table io&.-Concentrations of [1AC]hexachlorobenzene and degradation

           products in aquatic organisms in a model ecosystem  (in which
                                                    /
           corn had been grown) flooded with

Compound
HCB^/
I#
II
III
IV
V
VI
VII
VIII
IX
X
14
Extractable C
14
Unextr actable C
Total 14C
Average biosample wt
*y
.92
.75
.59
.47
.43
.39
.24
.18
.10
.04
.00



(g)
Hexachlorobenzene
Gambusic^-
(fish)
0.420
-
-
0.020
-
0.014
0.006
-
0.063
0.098
0.229
0.850
0.277
1.127
0.182
eauivalents, pom
(snail)
0.319
0.046
0.044
-
0.032
0.021
0.008
0.009
-
0.027
0.017
0.523
0.023
0.546
0.095

    hexachlorobenzene to the soil.

b_/  Silica gel GF-254; n-hexane : acetone : acetic acid, 40:10:1 by volume.

£/  Fish were added 4 days after flooding the ecosystem; 2 fish  (alive)
    were removed 3 days later and processed together.

&l  Snails were added on the day of flooding; 15 snails were removed  7  days
    later and processed as a batch; batch weight »  1.429 g.

e/  Hexachlorobenzene.

fj  Roman numerals = unknown compounds.
                                    186

-------
                    Terrestrial
                                                                   PHORATE

                                                                 TOTAL RESIDUE
                                                       (Drummer sllty clay loam soil system)
                                                          Aquatic animals
                           Corn
Soil (Drummer) sediment
                             Calculations of the above estimates:


Earthworms
Slugs
Pillbugs
Caterpillars
Vole _ ,
Total maximum
mass, g : con

(No
(10)
( 8)
(20)
(10)
( 1)

. ) X mass "
3.85 -
8.58 -
.0478 <•
.980 -
20.3 *"' -

total
38.5
68.6
.956
9.80
20.3
Mean
icentration.,
Ug/g
.457
.376
.864
.459
,. .128
Total T<
residue, ug: i

(mass) (cone.)
17.6
25.8
.826
4.50
2.60
3tal residue as
i 2 of applied
lose (5000 ug)

0.4
0.5
.02
.09
.05 '
Terrestrial
   animal**/ total (I)
Cornk'                (50)   1.48
Snails                (50)    .118
Fish                  (6)    .156

Aquatic
   animal total (II)
Surface water (III)   ( 1)7000
Soil s«diments£/ (IV) ( 1)4505
Air
   138
    74.0
     5.90
      .93*
                                                    1.59
                                                     .226
                                                     .527
                                          6.84
                                       7000          .0471
                                       4S05          .546
                                       [5000 ug-d+IH-III+IV)]
 51.3
118
  1.33
   .493
                               1.82
                             330
                            2460
                            2157
1.0
2.4
 .03
 .01
                   .04
                  6.6
                 49.2
                 43.2
 a/  The terrestrial animals (and their residues)  were removed from the system at the ter-
     mination of the terrestrial phase.
 b/  Proportion at 14 days postplanting; the corn, having been consumed and/or demolished by
     the animals, is not present as an entity at the termination of the terrestrial phase,
     and its residue is distributed among animals, air, and soil.
 £/  The direct Interaction of corn, air, and terrestrial animals with the soil occurred prior
     •to flooding tha system.

•                                                 r!4 1
 Fig. 64.-Terminal environmental distribution of [  CJphorate plus metabolites in a soil
          (Druanaer)-terrestrlal model ecosystem.
                                           187

-------
00
oo
20-
15-
SP •
post plants
H
O
OT
1 -
§ '
in
m 5-
o
o
S -
0-
0.






1.
tsp is
EM 84ft
, w m o.o:
/
fEp 2% o.o:
1.59-^EM 55%
. lUN 43%
/^ v





K n
0.0(


o.o:

!E? 20
SM 42ft
,„,» - „ M5W
, tun 99%
fEP 3» fEP 15 fEP 0% fEP OS fEP 11<5
.131
-------
CD
VO
(EP 4Z
n OiR i EM 71Z
28 •

27 -
26 •
Jf
'u
a
 extractable parent compound, EM • extractable metabolites of the parent compound, and UN -
                                        unextractable products  remaining in  the processed sample.

-------
                             r!4 -i
Table 109.-Concentrations of |_  Cjphorate and degradation products in the
           Drummer silty clay loan eoil and sediment of a model ecosystem.
Phorate equivalents , pprc
Compound
PS/
pso2
Px
II
V
PxS02
PSO
VI
VII
VIII
PxSO
IX
14
Extractable C
14
Unextractable C
Total 14C
Sample wt (g)
Rc/
Rf
.9,
.fiS
.78
.65
.58
41-. 48^
.37
.31
.21
11-. 20
.09
.06
.00


Acetone
extract
0.0086
0.3495
0.0011
0.0032
-
0.0075
0.2625
0.0063
0.0017
0.0036
0.0033
0.0081
0.6554

Soil*7
Methanol
extract^'
0.0010
0.0309
0.0001
0.0010
-
0.0002
0.0285
0.0001
0.0003
0.0004
0.0003
0.0049
0.0677
0.1286
0.8517
100.000
Sediment-
Acetone
extract
0.0165
0.1916
0.0014
0.0004
0.0017
0.0013
0.0051
0.1570
0.0007
0.0014
0.0010
0.0040
0.0076
0.3897
0.
0.
100.
Methanol
extract
0.0054
0.0092
O.OOOj.
0.0001
0.0002
-
0.0001
0.0033
-
-
-
0.0002
0.0008
0.0194
1364
5455
0000
1-14 -I
    soil.
                                                              r!4 i
W  Sediment samples were taken 28 days after application of  [_  Cjphorate to
    the soil, 8 days after flooding the ecosystem with water.
£/  Silica gel GF-254; benzene : acetone, 4:1 by volume.
d/  Methanol extract is from the sample previously extracted with acetone.
e/  P-phorate; PSO, » phorate sulfone; Px » phoratoxon; PxSO- = phoratoxon
    sulfone; PSO ° phorate sulfoxide; PxSO = phoratoxon sulfoxide.
_f/  Roman numerals ° unknown compounds.
£/  Rf range denotes a streak on the TLC plate.
                                        190

-------
 Table 110.-Concentrations of [  CJphorate and degradation products in conA
            after a 14-day exposure in a model ecosystem containing Drummer
            silty clay loam soil.
Compound
&
pso2
Px
11^
III
PxS02
PSO
V
VI
VXI
PxSO
VIII >
IX
14
Extractable C
14
Unextractable C
Total l*C
Average Bio-
sample wt (g)
RC/
Rf
.93
.76
.57
.48
.41
.34
.30
.18-. 28^
.14
.10
.06
-.03
.00




Phorate
Root
0.011
0.412
0.014
0.004
0.004
0.039
0.068
0.032
0.022
0.013
0.027
- 0.041 ,
0.022
0.709
0.747
- 1.456
0.534
equivalents ,
Shoot
0.053
0.597
0.014
0.004
0,007
0.041
0.224
0.015
0.011
0.011
0.010
0.015
0.023
1.025
0.647
1.672
0.946
ppm-
Entire plant
0.038
0.530
0.014
0.004
0.006
0.041
0.168
0.021
0.015
0.012
0.016
0.024
0.022
0.911
0.683
1.594
1.480
     r!4 T
 a/   L C]Phorate was applied to the soil beneath each seed.
 b/   The roots of 6 corn plants were combined and analyzed as an individual
     sample;  the shoots were similarly processed.
 cj   Silica gel CF-254; benzene : acetone, 4:1 by volume.
 dy   P » phorate;'PS02 » phorate sulfone; Px - phoratoxon; PxS02 - phoratoxon
     sulfone;  PSO • phorate sulfoxide; PxSO ° phoratoxon  sulfoxlde.
.&/   Roman-  numerals • unknown compounds.
 f/   Rr range denotes a atreak on the TLC plate.
 ^™    t               •                     * *               4
                                     191

-------
vo
K>
                          Table 111•-Concentrations of [  c]phorate and degradation products in the air—  from a model ecosystem
                                     containing Drumner silty clay loam soil.
Phorate equivalents, ppm
Trap ik/
Compound
&
PS02
I-
II
PSO
III
IV
V
14
Total C, Trap 1
14 o/
Total C, Trap 2&'
Sum C, Traps 1 & 2
Sample wt (g)-''
Rf-
.95
.83
.b7
.45
.38
.20
03-. 16^
.01



Day 0
0.02730
-
-
0.00008
0.00236
0.00004
- 0.00005
0.00003
0.02986
0.07001
0.09987
108.00000
Day 1
0.01022
-
-
-
0.00043
-
-
-
0.01065
0.08683
0.09748
108.00000
Day 5
0.00115
-
-
-
0.00007
-
-
-
0.00122
0.02545
0.02667
108.00000
Day 11
0.00001
0.00015
-
-
0.00002
-
-
-
0.00018
0.00163
0.00181
108.00000
Day 15
0.00033
-
0.00002
-
0.00003
0.00002
-
-
0.00040
0.01091
0.01131
108.00000
Day 19
0.00014
0.00002
-
-
0.00003
-
-
-
0.00019
0.02775
0.02794
108.00000
                          a/ Air was trapped for a 3-hour daylight period at a flow rate of 10 ml/sec on specified days after appli-
                             cation of |/^c] phorate to the soil.
                          b/ Trap 1 was connected directly to the ecosystem container and contained 75 ml of acetonitrile as the
                             trapping solvent; the trapping solvent was chromatographed.
                          £/ Silica gel GF-254; benzene : acetone, 4:1 by volume.
                          cl/ P • phorate; FSC^ ~ phorate sulfone; PSO «• phorate sulfoxide.                               ;
                          e/ Roman numerals = unknown compounds.
                          fj Rj range denotes a streak on the TLC plate.
                          £/ Trap 2 was connected in series to trap 1 and contained 75 ml of trapping solvent (ethanolaraine s 2-methoxy-
                             ethanol, 1:2 by volume); the trap 2 solvent was not chromatographed.
                          h/ One liter of air was assumed to weigh 1 g.

-------
Table 112.-Concentrations of  [  CJphorate and degradation products in inverte-
           brates after a 5-day exposure in a model ecosystem containing
           Drummer silty clay loam soil.
Phorate equivalents, ppm
Compound
pl/
pso2
I*/
11
PSO
III
PxSO
V
VI
VII
14
Extractable C
14
Unextractable C
Total UC
Average biosample
R a/ Armadi.llidi.um-' Estigmene^
*f (pillbug) (caterpillar)
,92
.75
.68
.51
.28
09-. 26^
.08
.05
.03
.00



wt (g)
-
0.029
0.179
0.021
-
0.283
-
0.018
0.060
0.590
0.274
0.864
0.048
0.049
0.030
0.012
0.024
-
0.006
-
0.003
0.014
0.138 " '
0.320
0.459
0.980
Limas~
(slue)
-
0.014
0.234
-
-
0.085
0.004
-
0.004
0.341
0.035
0.376
8.579
Lumbriaus—
(earthworm)
0.003
0.005
0.047
0.006
0.081
0.012
0.005
0.003
-
0.003
0.165
0.292
0.457
3.848
&/  Silica gel GF-254; benzene : acetone, 4:1 by volume.
b/  Three pillbugs were processed together; batch weight = 0.143 g.
£/  Three caterpillars were processed together; batch weight •» 2.941 g.
d/  Three slugs were processed together; batch weight = 25.737 g.
e/  Three earthworms were processed together; batch weight = 11.545 g.
fj " P « phorate; PSO- " phorate sulfone; PSO = phorate sulfoxide; PxSO
    phoratoxon sulfoxide.
£/  Roman numerals = unknown compounds.
h/  R. range denotes a streak on the TLC plate.
                                       193

-------
V£>
                                                       rl4
                         Table 113.-Concentrations of  \_ CJ phorate  and  degradation products in the prairie vole after a 5-day


                                     in  a model ecosystem containing Drummer silty  clay loam soil.
exposure
Phorate equivalents, ppm
Compound
Ra/
f GI tract
P^X .95
I- .69-. 91-'
II
III ,4
IV
V
PSO
VII
PxSO
VIII
IX
Extractable C
14
Unextractable C
Total UC
Blosample wt (g)
.67
1-.93
.54
.42
.28
.12
.09
.04
.00

ai/ Silica gel GF-254; benzene
b/ Internal organs
0.003
0.007
0.009
-
0.019
0.037
0.032
-
0.006
0.004
0.008
0.125
0.266
0.391
3.075
: acetone,
Liver
<0.001
0.001
0.001
-
0.005
0.017
0.013
0.002
0.001
0.004
0.005
0.049
0.067
0.116
1.015
4:1 by
, other than those specified,
c/ Body totals were calculated using live body
AJ P = phorate; PSO = phorate
e/ Roman numerals
sulfoxide
; PxSO =
Remaining
organs^/
-
0.002
-
0.002
0.042
0.003
-
0.005
0.001
0.003
0.058
0.035
0.093
1.908
volume.
were combined
weight (20.302
Skin
0.001
0.003
0.006
-
0.010
0.011
0.004
-
<0.001
-
0.035
0.048
0.083
2.476

and processed
E).
Carcass
0.002
0.003
0.008
-
0.003
0.0)2
0.006
-
0.006
-
0.003
0.043
0 033
0.076
11.051

Brain
0.002
-
0.010
0.019
0.011
0.004
-
0.004
0.001
0.003
0.054
0.017
0.072
0.640

Body
totals^/
0.002
0.003
0.006
<0.001
0.007
0.019
0.010
<0.001
0.005
0.001
0.003
0.056
0.071
0.128
-

as an individual sample.



phoratoxon sulfoxide.
« unknown compounds.
f_/ Rf range denotes a streak
on the TLC
plate.






-------
Table 114 .- Relative affinities of 6 body-parts of the prairie vole^' for
              CJphorate (Drummer-soil system) plus its metabolites, and

           comparisons with the relative masses of the body-parts.
     Body-part
(organs and tissues)
Remaining organs—
Residue wt in body-part
as a % of total residue
   wt in entire body
Body-part wt as a
 of entire body wt
61 tract
Carcass
Skin
Liver
Brain
46.37
32.51
7.92
4.55
1.77
15.25
54.80
12.28
5.03
3.17
                                  6.87
                                    9.46
                                 99.99
                                   99.99
aj  Vole from a soil-terrestrial model ecosystem treated with
    [, CJphorate.

b/  Carcass = the eviscerated body (the removed organs and tissues are
    listed above);  it consists predominately of muscle and bone.

c/  The kidneys + adrenals, heart, lungs, mammary glands, ventral central
    neck gland, and parotid glands were analyzed collectively.
                                   195

-------
Table 115.—Concentrations of [  cjphorate and degradation products in the water of a model ecosystem (con-
           taining Drummer silty clay loam soil) 7 days after flooding the ecosystem with waterS/.
                                                          Phorate equivalents, ppm
                                          Surface water
                                       Leachate—
Compound
                           Ether-ex tract able
                           before hydrolysis
Ether-extractable
after hydrolysis^
                                                                  /
Ether-extractable
before hydrolysis
Ether-extractable
after hydrolysis
V- .94
PS02 .85
Li/ .78
II .60
Px .57
III .53
IV .47
V .43
PxS02 . 40
PSO .32
VII .13
PxSO . 08
IX .03
X .00
14
Extractable C,
Unextractable C
14
Total extractable C
Unextractable * 'C after
0.00005
0.02055
0.00017
-
0.00030
0.00004
-
0.00003
0.00009
0.00381
0.00006
0.00024
-
0.00020
0.02554
-
0
hydrolysis 0
l^C loss during hydrolysis 0
Initial 14C in water
Sample volume (1)
0
1
a/ Ecosystem was flooded with water 20 days
b/ One liter of uater
c/ Silica gel GF-254;
d/ The ' Unextractable'
ej P = phorate; FS(J2 =
PxSO = phoratoxon
was withdrawn through
benzene : acetone, 4:1
0.00002
0.00021
0.00006
0.00009
0.00005
-
f
-
-
0.00053
0.00019
0.00010
0.00011
0.00026
0.00162
0.01576
.02716
.01576
.00418
.04710
.00000
0,00019
0.07557
0.00280
•-
O.OOC9C
0.00009
-
0,00012
0.00020
0.00842
0.00011
0.00054
-
0.00032
0.08934
-
0
0
0
0
1
0.00004
0.00053
0.00029
-
0.00053
-
0.00026
-
0.00014
0.00040
0.00033
0.00056
0.00045
0.00113
0.00466
0.05261
.09400
.05261
.00929
.15590
.00000
after appllcatJon of [ cj phorate to the soil.
the tap at the jar
by volume.
of the preceding column was adjusted to
phorate sulfone; Px
sulf oxide.
= phoratoxon; PxS02

bottom over a period of 1
.
0.012 N HC1 and maintained
= phoratoxon sulfone; PSO

hr.
*•»
at 55-56 C for 18-24 hr
= phorate sulfoxide;

f/ Roman numerals » unknown compounds.

-------
116. -Concentrations of
                                     rate and degradation products in
           aquatic organisms in a model ecosystem containing Drummer
                                                      a/
           Kilty clay loam soil and flooded with water— .
Compound
p*/
pso2
Px
II
III
PxS02
PSO
V
VI
PxSO
VII
VIII
IX
14
Extractable C
14
Onextractable C
Total UC
Average biosample wt
Rb/
.95
.85
.74
.66
.61
.45
.39
.34
.14
.11
.08
.05
.02
.00

(g>
Phorate
Gcmbuaicf-
(fish)
.0.063
0.090
0.016
0.003
0.006
-
0.004
0.065
0.006
0.018
0.011
0.009
0.015
0.015
0.321
0.207
0.528
0.156
equivalents, ppm
Physo^
(snail)
0.004
0.054
0.010
-
0.004
0.002
0.001
0.013
0.002
0.001
0.001
0.001
0.002
0.014
0.109
0.117
0.226
0.118
_./ w _ _ 	 j 	 	 	 £i 	 _j_j 	 • ._t_ 	 * 	 ^rt j— 	 _ £ •_ 	 	 i j 	 A.J 	 	 £ \ ^ r*\ .
    phorate to the soil.
b/  Silica gel GF-254; benzene : acetone, 4:1 by volume.
c/  Three fish were added 4 days after flooding the ecosystem; 3 fish
    (dead) were removed 2 days later; 3 more fish were added 6 days
    after flooding the ecosystem; 3 fish (alive) were removed 1.3 days
    later; the fish were processed in 2 batches (as removed); since the
    parent compound and metabolite contents of the 2 batches were
    similar, the results were averaged.
d/  Snails were added on the day of flooding; 15 snails were removed /
    days later and processed as a batch; batch weight *• 1.776 g.
£/  P - phorate; PSO- = phorate sulfone; Px = phoratoxon; PxSO_ * phoratoxon
~~   sulfone; PSO = phorate sulfoxide; PxSO - phoratoxon sulfoxide.

tl  Roman numerals <* unknown compounds.
                                    197

-------
                                x
                  Terrestrial  animals
                          t  /    N
                         '—<      X
                        (10,5%;
                                                                   PHORATE

                                                               TOTAL RESIDUE
                                                       (Bloomfield loamy sand system)
                          Corn
             Soil  (Bloomfield) sediment
                            Calculations of the above estimates:
Ecosystem
component
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
Total maximum „ Total
Mean . ,
mass, g: . residue, vg:
' 6 concentration, He
(Ko
(10)
( 8)
(20)
(10)
( 1)
.) X mass -
2.13 -
1.79 •=
.0507 =
.872 -
22.8
total
21.3
14.3
1.01
8.72
22.8
Ug/g
1.91
2.03
1.40
2.01
.335
(mass) (cone.)
40.7
29.1
1.42
17.5
7.64
Total residue as
a % of applied
dose (5000 ug)
0.8
0.6
0.03
0.4
0.2
Terrestrial
   animal!/ total (I)
Corn£/                (50)    1.62
Snails                (50)     .0997
Fish                  ( 8)     .170
                  68.1
                  81.0
                   4.99
                   1.36
             6.48
              .821
              .772
 96.4
525
  4.09
  1.05
Aquatic
  animal total (II)
Surface water (III)
Soil sediment£/ (IV)
Air
( 1)7000
( 1)3770
   6.35                      5.14
7000          .0832         582
3770          .281         1059
[5000 pg (I+II+III+IV)]  -  3257
 2.0
10.5
  .08
  .02
                   .1
                 11.6
                 21.2
                 65.1
a/  The terrestrial animals (and their  residues) were removed  from  the system at  the ter-
    mination of the terrestrial phase.
b_/  Proportion at 14 davs postplanting;  the  corn, having been  consumed and/or demolished by
    the animals, is not present as an entity at the temination of  the terrestrial phase,
    and its residue is distributed among animals, air, and soil.
£/  The direct interaction of corn,  air,  and terrestrial animals with the  soil occurred prior
    to flooding the system.


 Fig.  67.-Terminal  environmental distribution of [  CJphorate plus metabolites in a soil
          (Bloomfield)-terrestrial model ecosystem.
                                         198

-------
VO
20-
•
1 ii-
& •
3
i '
s- •
a10-
CO
>,
3 -
I ;
o
a
.
0-
0.
i













f£p 1% [EP 1%
518 \ EM 84* ( 0,335S EN m
™ 1 1 I7D ft* W«^^^l
. IIM ic» (BP "% |m| «i»
v ^u« o» Q^ Qij2i}9
-------
O
O
28 0,281 |EM s*z
1

27
26 -

CO
•H-
c 25 -
«
*-H
a
u
CO
8. 24 -
«
5"
•o
B 23 -
1 -JEM29Z 0.





fEP 10Z
772 < EM 61Z
|^UN 29Z




%
0.0








PHORATE
(Bloorofield sand system)

f
«C^jO),P S CH, S Crt
0 0,51
Water
removed












*
t





{EP 1Z
EM 84Z
UN 15Z
8

. 7
. 6
to
c
"8
5 ^
u
2
i
4 Q
>>
•o

, §
u
to
X
ID



1
• 0
                                       Surface water
Snails
                             Fish
                                                          Sediment
                                                                                    PPM
                                                                r!4
                               Fig.  69. — Summary. of the fate of  [ Cjphorate  (Bloomfleld  loamy  sand  system)  In  the  aquatic phase;  an  extension
                                         of B soil-terrestrial model  ecosystem (see  Fig.    ).   The barren  terrestrial  phase was  flooded  20  days
                                         postplanting,  and  snails, daphnia and mosquito larvae  were  added  to the system;  the  fish  were added 4 days
                                         later.  The total  ^C-reslduea  are expressed  as  phorate  equivalents, ppjn (w/w) ,  and  their subdivisions
                                         are EP  -  extractable parent  compound,  EM *•  extractable metabolites  of  the  parent compound, and  UN  -
                                         unextractable  products  remaining In  the  processed  sample.

-------
Table  117.-Concentrations of  £ Cjphorate and degradation products in the
           Bloomfield loamy sand soil and sediment of a model ecosystem.
Phorate equivalents, ppm
Soil^
Compound
P£;
PSO
J.f/2
Px
II
III
IV
V
PxS02
PSO
VI
VII
VIII
PxSO
IX
14
Extrac table C
14
Unextractable C
Total C
Sample wt (g)
Rf~
.96
.87
.77
.65
.58
.52
.47
39-. 4fra/
.37
.32
.22
10-. 20
.09
.06 ,
.00


Acetone
extract
0.005?
0.2703
0.0013
0.0011
0.0082
0.0006
0.0007
0.0020
0.0096
0.0991
0.0006
0.0014
0.0024
0,0025
0.0070
0.4126
0
0
100
Methanol
extract^/
0.0015
0.0095
0.0001
0.0003
-
-
0.0003
0.0002
0.0057
-
-
0.0001
0.0003
0.0108
0.0288
.0770
.5184
.0000
Sediment^'
Acetone
extract
0.0043
0.0838
0.0011
0.0002
0.0009
0.0005
0.0005
0.0007
0.0044
0.0408
0.0004
0.0011
0.0005
0.0023
0.0036
0.1451
0.
0.
100.
Methanol
extract
0.0069
0.0141
0.0003
0,0001
0.0004
-
-
-
0.0002
0.0027
-
-
-
0.0003
0.0022
0.0272
1088
2811
0000
a/  Soil samples were taken 20 days after application of  [_  Cjphorate to the
    soil.
                                                              r!4 i
b/  Sediment samples were  taken 28 days after application of  |_  Cjphorate to
    the soil, 8 days after flooding the ecosystem with water.
£/  Silica gel GF-254; benzene : acetone, 4:1 by volume.
&l  Methanol extract is from the sample previously extracted with acetone.
e/  P = phorate; PSO_ - phorate sulfone; Px » phoratoxon; PxSO, •» phoratoxon
~~   sulfone; PSO ° pHorate sulfoxide; PxSO = phoratoxon sulfoxide.
SJ  Roman numerals " unknown compounds.
£/  R. range denotes a streak on the TLC plate.
                                     201

-------
Table  118.-Concentrations of [  c] phorate and degradation products in corn^-
           after a 14-day exposure in a model ecosystem containing Bloomfield
           loamy sand soil.

Compound
id/
PS02
is/
Px
11
III
IV
PxSO.,
PSO
V
VI
VII
PxSO
VIII
IX
14
Extractable C
14
Unextractable C
Total UC
Average biosample
R*'
Kf
.94
.88
.78
,70
.62
.54
.46
.40
.33
.16-. 30^
.15
.08
.05
.02
.00

wt (g)
Phorate
Root
0.015
0.976
0.027
0.013
0.024
0.007
0.015
0.204
0.64B
0.068
0.033
0.222
0.255
0.276
0.531
3.314
2.036
5.350
1.169
eauivalents
Shoot
0.062
2.160
0.047
0,030
0.025
0.016
0.027
0.337
0.694
0.118
0.041
0.196
0.278
0.355
2.403
6.789
2.629
9.418
0.447
b/
, pom-
Entire plant
0.028
1.304
0.032
0.018
0.024
0.009
0.01,8
0.241
0.661
0.082
0.035
0.215
0.261
0.298
1.049
4.275
2.200
6.476
1.616
    r!4
    r   i
a/  [  Cj Phorate was applied to the soil beneath each seed.
b_/  The roots of & corn plants were combined and analyzed as an individual
    sample; the shoots were similarly processed.
£/  Silica gel GF-254; benzene : acetone, 4:1 by volume.
d/  P «= phorate; PS02 = phorate sulfone; Px = phoratoxon; PxSO, = phoratoxon
    sulfone; PSO • phorate sulf oxide; PxSO = phoratoxon sulf oxide.
e/  Roman numerals " unknown compounds.
£./  Rf range denotes a streak on the TLC plate.
                                      202

-------
Table  119.-Concentrations of |_  CJphorate and degradation products in the air—  from a model ecosystem
           containing Bloomfield loamy sand soil.
                                                         Phorate equivalents,  ppm
                                                                 Trap l£'
Compound
                                  Day 0
                                               Day 1
                                       Day 5
                                          Day 11
                                          Day 15
                             Day 19
pi/
PSO,
II  '
lit
PSO
IV
V
VI
PxSO
VII
  .96
  .85
  .79
  .74
  .57
  .40
  .27
  .23
.14-.2
  .11
  .00
      14
Total   C, Trap 1
Total IAC, Trap 2&/
    14
Sum   C, Traps 1 & 2
Sample wt 
-------
Table ^.-Concentrations  of  [14C]phorate and degradation  products  in  inver-
            tebrates  after  a 5-day exposure  in a model  ecosystem containing
            Bloomfield  loamy sand soil.

Phorate equivalents , ppm
Compound
P£/
pso2
I*/
II
PxS02
PSO
III
rv
PxSO
V
VI
VII
14
Extractable C
14
Unextractable C
Total UC
Average biosample
_ a/ Armadillidiion- Estigmene^-
f~ (pillbug) (caterpillar)
.88
.76
.67
.52 0.551
.33
.27 0.023
10-. 28^
.11
.08 0.429
.05
.02 0.022
.00 0.076
1.101
0.297
1.398
wt (g) 0.051
0.172
0.158
" -
0.075
0.016
0.042
-
0.014
0.037
-
0.044
0.138
0.696
1.311
2.007
0.872
Limas-
(slue)
-
0.129
0.015
1.218
-
0.081
-
0.014
0.063
0.005
-
0.009
1.534
0,499
2.033
1.788
Lumbriews—
(earthworm)
0.014
0.314
-
0.136
0.007
0.236
0.025
0.052
-
0.014
0.014
0.021
0.833
1.077
1.910
2.129
a/  Silica gel GF-254; benzene : acetone, 4:1 by volume.
b/  Three pillbugs  (alive.) were processed  together; batch weight  =  0.152  g.
_£/  Three caterpillars (alive) were processed  together; batch weight  =  2.616  g.
&J  Three slugs  (dead) were processed  together; batch weight «=  5.363  g.
_e/  Three earthworms  (dead) were processed together; batch weight « 6.387 g.
_£/  P " phorate; PSOj " phorate sulfone; PxSC>2 ° phoratoxon sulfone;  PSO  =
    phorate sulfoxide; PxSO = phoratoxon sulfoxide.
_£/  Roman numerals  * unknown compounds.
h/  R  range denotes a streak on the TLC plate.
                                          204

-------
N>
o
en
                                                       [14 T
                                                         CJphorate and degradation products In the prairie vole after a 5-day


                                    in a model ecosystem containing Bloomfleld loamy sand soil.
                                                                                                     exposure

Phorate equivalents, ppm
Compound
&
I*/
II
III
IV
V
PSO
VI
PxSO
VIII
IX
14
Ex tract able C
14
Unextractable C
Total 14C
Blosample wt (g)
Ri'
Rf
.96
75-. 93^
.69
48-. 94
.55
.43
.31
.17
.09
.04
.00

Gt tract
0.009
0.017
0.030
-
0.181
0.148
0.008
0.011
0.009
0.015
0.028
0.456
0.113
0.569
4.395
Liver
0.002
0.013
0.006
-
0.009
0.028
0.033
0.003
0.007
0.021
0.022
0.144
0.419
0.563
1.255
Remaining
organs—^
-
0.006
-
0.009
0.050
0.006
-
0.005
0.002
0.009
0.087
0.251
0.338
1.048
Skin
0.003
0.008
-
0.049
0.018
0.023
-
0.002
0.001
0.001
0.105
0.171
0.276
3.200
Carcass
0.003
0.006
0.004
-
0.020
0.025
0.016
-
0.007
-
0.004
0.085
0.166
0.251
12.248
Brain
0.009
-
0.040
0.015
0.016
0.018
-
0.005
0.005
0.007
0.115
0.084
0.199
0.655
Body .
totals^
0.004
0.008
0.010
0.001
0.054
0.049
0.016
0.002
0.006
0.004
0.009
0.163
0.172
0.335
22.801
                         aj  Silica gel GF-254,* benzene : acetone, 4:1 by volume.


                         W  Internal organs, other than those specified, were combined and processed as an individual sample.
£/  P « phorate; PSO •* phorate sulf oxide; PxSO


AJ  Roman numerals = unknown compounds.
                                                                          phoratoxon sulf oxide.
e/
                                range denotes a streak on the TLC plate.

-------
Table  122rRelative affinities of 6 body-parts of the prairie vole^-   for

           [  CJphorate (Bloomfield soil system) plus its metabolites,

           and comparisons with the relative masses of the body-parts.

Body-part
(organs and tissues)
Carcass—
GI tract
Skin
Liver
Brain
c/
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
40.15
32.71
11.55
9. 24
1.71
4.63
99.99
Body-part wt as a %
of entire bodv wt
53.72
19.28
14.03
5.50
2.87
4.59
99.99
_a/  Vole from a soil-terrestrial model ecosystem treated with
    [14CJphorate.

b_/  Carcass = the eviscerated body  (the removed organs and  tissues  are
    listed above); it consists predominately of muscle and  bone.

c/  The kidneys f adrenals, heart,  lungs, mammary glands, ventral central
    neck gland, and parotid glands  were analyzed collectively.
                                     206

-------
                       Table 123.-Concentrations of [  C] phorate and degradation products  in the water of a model ecosystem (containing

                                  Bloomfield loamy sand soil)  7 days after flooding the ecosystem with waters./.
to
o

Phorate equivalents, ppm
Surface water
c/
Compound -f
P*' .92
PS02 .81
Ii/ .74
II .68
Px .57
III .53
V .42
PxS02 . 38
PSO . 31
VI .23
VII .15
VIII .09
PxSO ,08
IX .03
X .00
14
Extractable C
Unextractable **C
14
Total extractable C
Ether-extractable
before hydrolysis
0.00010
0.03313
0.00063
-
0.00040
0.00004
0.00003
0.00030
0.00361
-
0«0001S
-
0.00037
-
0.00017
0.03891
_
0
Unextrectable C after hydrolysis 0
*-^C loss during hydrolysis 0
Initial 14C in water
Sample volume (1)
0
1
a/ Ecosystem was flooded with water 20 days
b/ One liter of water
£/ Silica gel GF-254;
j|/ The "unextractable
e/ P = phorate; PS02
~ PxSO » phoratoxon
was withdrawn through
benzene : acetone, 4:1
Leaehate— '
Ether-extractable Ether-extractable
_ after hydrolysi&H/ before hydrolysis
0.00007
0.00050
0.00016
0.00014
0.00012
-
-
i. 0.00010
: 0.00055
0.00005
0.00021-
0.00011
0.00030
-
0.00028
0.00259
0.02484
.04150
. 02484
. 01684
.08318
.00000
0.00030
0.12212
0.00124
-
0.00068
0.00014
0.00022
0.00054
0.01243
-
0.00023
-
0.00074
-
0.00052
0.13916
_
0.
0.
0.
0.
1.
Ether-extractable
after hydrolysis
0.00018
0.00435
0.00027
0.00034
0.00007
0.00022
_
0.00020
0.00056
0.00012
0.00044
0.00028
0.00041
0.00033
0.00034
0.00811
0.06068
14727
06068
01911
22706
00000
r!4 i
after application of |_ CJ phorate to the soil.
the tap at the jar
by volume.
" of the preceding column was adjusted to
«• phorate sulfone; Px
sulfoxide.
= phoratoxon; PxS02
-*
bottom over a period of 1

hr.

0.012 N HC1 and maintained at 55-56uC for 18-24 hr.
• phoratoxon sulfone; PSO

•= phorate sulfoxide;

fj Roman numerals « unknown compounds.

-------
                              rl4
table  i24rConcentrations of  [  CJphorate and degradation products in
           aquatic organisms in a model ecosystem containing Bloomfield
           loamy sand soil and flooded with

Compound
&
PSO,
*y
Px
II
III
PxS02
PSO
IV
V
VI
PxSO
VII
VIII
IX
14
Extractable C
14
Unextractable C
Total UC
Average bio sample wt
Rb/
Rf
.94
.85
.7?
.65
.60
.48
.39
.34
.15
.13
.10
.08
.05
.02
.00

(g)
Phorate
Gambusi^
(fish)
0.075
0.161
0.019
0.004
0.004
0.002
0.009
0.171
0.009
0.005
0.017
0.022
0.009
0.017
0.023
0.547
0.225
0.772
0.170
ecmivalentSj ppm
Fhysc^-1
(snail)
0.019
0.122
0.012
-
0.007
0.006
0.003
0.015
-
0.004
0.005
0.002
0.002
0.004
0.056
0.257
0.565
0.822
0.100
a/  Ecosystem was flooded with water 20 days after application of  [  CJ-
    phorate to the soil.
b_/  Silica gel GF-254; benzene : acetone, 4:1 by volume.

cj  Three fish were added 4 days after flooding the ecosystem; 2 fish
    (dead) were removed 1 day later and 1 fish (dead) 1.2 days later;
    2 more fish were added 5 days after flooding the ecosystem; 2  fish
    (dead) were removed 1 day later; 3 more fish were added  6 days after
    flooding the ecosystem; 2 fish ( sick' ) and 1 fish  (dead) were re-
    moved 1.3 days later; the fish were processed in batches (as removed);
    since the parent compound and metabolite contents of the 5 batches  were
    similar, the results were averaged.
&l  Snails were added on the day of flooding; 15 snails were removed 7
    days latez and processed as a batch; batch weight «= 1.77* g.

£/  P «• phorate; PSO- « phorate sulfone; Px «= phoratoxon; PxSO. • phoratoxon
    sulfone; PSO = phorate sulfoxide; PxSO = phoratoxon sulfoxide.

fj  Roman numerals = unknown compounds.
                                    208

-------
                 Terrestrial animals
                                                                    SIHAZINE
                                                                 TOTAL RESIDUE
                                  Aquatic animals
                         Corn
              Soil (Drummer) sediment
                             Calculations of the above estimates:
Ecosystem
component
    Total maximum                          Total       To£al resldue ag

  __  •"••_»!	concentration,  JTl ^1 H.8!    a % of applied
 (No.) X mass- total       «'«       (mass) (cone.)    dose (5000 pg)
Earthworms
Pillbugs
Caterpillars
Vole
( 8)
(20)
(10)
( 1)
2.91
.100
.909
23.8
m ^
a
s*
"
23.3
2.0
9.09
23.8
4.90
2.01
.444
.0771
114
4.02
' 4.04
1.83
2.3
.08
.08
.04
Terrestrial
   animali'total (I)
Cornk/
Snails
Fish
Aquatic
   animal total (II)
Surface water (III)
Soil sediments/ (IV)
Air
(37)   2.67
(50)    .155
( 3)    .275
( 1)7000
( 1)4306
  58.19
  98.8
   7.75
    .825
1.39
 .133
 .207
124
137
  1.03
   .171
   8.58                      1.20
7000          .0586        410
4306          .888        3824
[5000 ug-(I+II+III+IV)J -  641
2.5
2.8
 .02
 .003
                                 .02
                                8.2
                               76.5
                               12.8
a/  The terrestrial animals (and their residues) were removed from the system at the termina-
    tion of the terrestrial phase.
b_/  Proportion at 14 days postplanting; the corn, having been consumed and/or demolished by
    the animals, is not presented as an entity at the termination of the terrestrial phase,
    and its residue is distributed among animals, air, and soil.
c/  The direct interaction of corn, ajr, and terrestrial animals with the soil occurred prior
    to flooding the system.
 Fig. 70 .-Terminal  environmental distribution of
          terrestrial model ecosystem.
                                                 [14
                             'cjsimazine plus metabolites in a soil-
                                         209

-------
20-

15
postplant
M
O
n
•o
I :
ST
«» 5-
o
$ .
_
0-
1.










CEP 71* CEI> 2«
Mi01 3* fa n% 0.0771^EM15%
^ ^UN26% o.on^J™ ?% * I™ e«
y
1.








CEP 32% 0.01
39 
-------
                                                                                            0,888
2B •

'27 -
26 -
* 25 -
a
u
i
a 24 •

(Q
•o
*

*. 23 •
a
X
a>
•M
0 22 .
41
21
* i

20 J
^ \UN 38Z
*" 1
fEP SOZ
0, 05859 1 KM ez 0,1
|
0,05516
0,05171

0,0^





1958





0,01391





0,03835




0,02812


fEP 77 Z
53 
-------
                              f-14 T
Table 125.-Concentrations of  [  CJsimazine and degradation products in the



           soil and sediment of a model ecosystem.

Simazine eauivalents, ppm
Soil*7
Compound f
Simazine . 68
I-1 .35
A-7 .26
II .04
III .00
14
Extractable C
14
Unextractable C
Total UC
Sample wt (g)
Acetone
extract
0,8741
0.0009
0.0284
0.0022
0.0050
0.9106
0.
1.
100.
Methanol
extract^/
0.1408
0.0001
0.0071
0.0013
0.0019
0.1512
3733
4351
0000
Sediment-7
Acetone
extract
0.4703
0.0010
0.0137
0.0014
0.00-41
0.4905
0.
0.
100.
Methanol
extract
0.0559
0.0002
0.0024
0.0004
0.0007
0.0596
3382
8883
0000
                                                         r!4
&l Soil samples were taken 20 days after application of  [_  CJsinazine to

   the soil.



b/ Sediment samples were taken 28 days after application of  [  CJsimazine  to

   the soil, 8 days after flooding the ecosystem with water.



£/ Silica gel GF-254; benzene : acetone, 4:1 by volume.



d/ Methanol extract is fron the sample previously extracted with acetone.



e/ Romar numerals *= unknown compounds.



fj 2-chloroi 4-amino, 6- ethylamino-£-triazine.
                                      212

-------
Table  126-Concentrations of  [  CJslmazlne and degradation products  in



           corn—  after a 14-day exposure in a model ecosystem.
Compound
Simazine
II
&
III
IV
V
VI
VII
14
Extractable C
14
Unextractable C
Total 1AC
Average biosample
Rf
.61
.25-. 52^
.38
.29
.22
.15
.08
.04
.00


wt (g)
Simazine
Root
0.593
0.003
0.015
0.011
0.006
0.008
0.037
0.375
1.048
0.335
1.383
2.022
equivalents
Shoot
0.079
-
-
0.016
0.013
0.024
0.177
0.794
1.103
0.293
1.396
0.651
b/
, PPm-
Entire plant
0.448
0.019
0.003
0.011
0.012
0.008
0.012
0.071
0.477
1.061
0.325
1.386
2.673
     r-14
—I   [  CjSimazine was applied to the soil beneath each seed.



b/  The roots of 3 corn plants were combined and analyzed as an individual

    sample; the shoots were similarly processed.



_£/  Silica gel GF-254; benzene : acetone, 4:1 by volume.



d/  Roman numerals «• unknown compounds.



e/  R, range denotes a streak on the TLC plate.



£/  2-Chloro, 4-amino, 6-ethylamino-^-triazine.
                                     213

-------
                           Table 127.-Concentrations of [_  cjsimazine and degradation products in the air—  from a model ecosystem.
10

Compounds
Id/
II
Simazine
III
A-7
IV
V
VI
VII
VIII
IX
Total 1 C, Trap 1
Total UC, Trap I-1
14
Sum C, Traps 1 St 2
E/
Sample wt (z)
R c/
Rf
.89
.76
.70
.41
.30
.26
.18
.13
.09
.04
.00


Simazine equivalents, ppm
Trap Lk/
Day 0
0.00001
-
0.00005
-
<0. 00001
<0. 00001
<0, 00001
0.00003
0.00001
0.00001
-
0.00011
0.00056
0.00067
108.00000
Day 1
0.00001
<0. 00001
0.00007
<0. 00001
-
-
<0. 00001
-
-
-
-
0.00008
0.00020
0.00028
108.00000
Day 5
0.00001
0.00001
0.00010
-
<0. 00001
-
-
-
-
-
<0. 00001
0.00012
0.00022
0.00034
108.00000
Day 11
<0. 00001
0.00001
0.00012
-
-
-
-
-
-
-
<0. 00001
0.00013
0.00034
0.00047
108.00000
Day 15
0.00001
<0. 00001
0.00005
-
0.00001
-
-
-
-
-

-------
                              r!4 i
Table  128 ^Concentrations of  |_ Cjsimazine and degradation  products  in inverte-



           brates  after  a 5-day exposure  in  a model ecosystem.
Simazine equivalents,
Compound
£/
Simazine
II
i&
III
IV
V
VI
VII
14
Extractable C
14
Unextrac table C
Total UC
Average- biosaaple
V"
.74
.58
.39
.22
.12
.07
.06
.04
.00



vt (g)
Amadi I lidium-
(pillbug)
-
0.213
0.022
0.365
0.026
-
0.209
-
0.157
0.992
1,022
2.014
-0.100
Estigmene^-
(caterpillar)
-
0.292
-
0.052
-
-
-
0.003
' 0.006
0.353
0.091
0.444
0.909
ppra
iMmbricus—
(earthworm)
0.076
3.244
-
0.662
0.051
0.069
0.095
0.099
~ 0.367
4.663
0.236
4.900
2.909
a/  Silica gel  GF-254; benzene : acetone, 4:1 by volume,



b_/  Three pillbugs were processed together; batch weight =» 0.301  g.



£/  Three caterpillars were processed  together; batch weight -  2.727  g.



df  Three earthworms  were  processed  together; batch weight - 8.728 g.



_e/  Roman numerals «  unknown  compounds.



tj  2-ChloroT 4-amina, 6-ethylamiao-£-triazin«.
                                         215

-------
N>
                        Table 129.-Concentrations  of  £  CJsimazine  and degradation products  in  the prairie vole after a 5-day exposure in
                                   a model  ecosystem.

Simazine equivalents, ppm
Compound
&
Simazine .
II
III
A-'
IV
V
B
VI
VII
VIII
14
Extractable C
14
Unextractable
Total UC
Biosample wt (g)
'i
94
86
7i
58
JS
25
20
13
08
04
00

C


Skin
-
0.0615
0.0263
0.0094
0.0010
0.0002
0.0005
0.0006
0.0006
0.0004
0.0007
0.1012
0.0627
0.]639
3.8457
Liver
_
0.0020
-
-
0.0004
-
-
0.0008
0.0005
-
0,0005
0.0042
0.1349
0.1391
1.2176
Remaining
organsS.'
-
0.0054
-
-
-
-
-
-
-
-
_
0.0054
0.0601
0.0655
1.7057
GI tract
0.0037
0.0127
0.0044
0.0010
0.0007
0.0004
0.0003
0.0003
0.0008
0.0013
0.0022
0.0278
0.0284
0.0562
4.0524
Carcass
-
0.0077
0.0007
0.0004
o.oooe
0.0003
0.0004
0.0008
0.0002
0.0001
0.0007
0.0119
0.0434
0.0553
11.3177
Fat
-
0.0039
-
-
•
-
-
0.0010
O.C017
-
0.0002
0.0068
C.0480
0.0548
0.7254
Brain
_
0.0029
-
-
-
-
-
-
-
-
0.0012
0.0041
0.0397
0.0438
0.7117
Body .
totals^1
0.0006
0.0164
0.0053
0.0019
0.0006
0.0003
0.0003
0.0006
0.0004
0.0004
0.0009
0.0277
0.0494
0.0771
-
                        af   Silica gel  GF-254;  benzene : acetone,  4:1  by  volume.
                        b/   Internal  organs,  other  than  those  specified, were  combined and  processed as  an individual sample.
                        £/   Body  totals were  calculated  using  live body  weight (23.8200 g).
                        d/   Roman numerals  =  unknown  compounds.
                        £/   A - 2-chloro, 4-amino,  6-ethylamino-£-triazine;  B  =  2-chloro, 4,6-diamino,-£-triazine..'

-------
Table 130.-Relative affinities of 7 body-parts of the prairie vole^   for
           r!4 i
           [^  Cjsimazine plus its metabolites, and comparisons with  the

           relative masses of the body-parts.

Body-part
(organs and tissues)
Skin
Carcass-'
GI tract
Liver
Fat
Brain
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
34.32
34.10
12.40
9.22
2.17
1.70
t. 6.09 , ,
100.00
Body-part wt as a %
of entire body wt
16.31
48.00
17.19
5.16
3.08
3.01
7.23
99.98
a/  Vole from a soil-terrestrial model ecosystem
~~   [14c]siraazine.
treated with
b/  Carcass » the eviscerated body (the removed organs and  tissues are
    listed above); it consists predominately of muscle and  bone.

cJ  The kidneys + adrenals, heart, lungs, mammary glands, ventral central
    neck gland, parotid glands and small amounts of fat tissue were
    analyzed collectively.
                                    217

-------
Table 131.—Concentrations of  [  CJsimazine and degradation pro-


           ducts in the water of a model ecosystem 7 days after

                                            a/
           flooding the ecosystem with water— .

Compound f
Simazine .57
A— 77
A • ££
1^ .03
II .00
14
Extractable C
14 e/
Unextractable C—
14
C Loss during extraction
14
Initial C in water
Sample volume (1)
Simazine equivalents, ppm
Surface water
0.04684
0.00315
0.00009
0.00005
0.05013
0.01033
-0.00187
0.05859
1.00000
&/  Ecosystem was flooded with water 20 days after application  of

    1-14 1
    |_  CJsimazine to the soil.



b/  Silica gel GF-254; benzene : acetone, 4:1 by volume.



cj  2-Chloro, •i-aminoj 6-ethylamino-£-triazine.



d_/  Roman numerals =» unknown compounds.



&J  The water, after ether extraction, was not subjected  to  the


    usual hydrolysis procedure.
                                 218

-------
                              [1A <•
                                Cjsimazine and degradation products in

           aquatic organisms in a model ecosystem flooded with water—
Compound
I*/
Simazine
t&
II
III
IV
V
VI
VII
• 14
Extractable C
14
Unextractable C
Total 1AC
Average biosample wt
*(y
.86
.65
.31
.27
.21
.14
.10
.06
.00

'

(8)
Simazine
Gambuaia*
(fish)
0.022
0.096
0.018
0.001
0.001
0.001
0.002
0.002
0.010
0.153
" " 0.054
0.207
0.275
equivalents, ppm
Phyea^
(snail)
-
0.103
0.005
-
-
-
-
0.003
0.002
0.113
0.020
0.133
0.155

    Simazine to the soil,

b/  Silica gel GF-254; benzene : acetone, 4:1 by volume.

£/„ Fish were added 4 days after flooding the ecosystem; 2 fish  (dead)
    were removed 1 day later and 1 fish  (dead) 2 days later; fish were
    processed individually and the results averaged.

d/  Snails were added on the day of flooding; 15 snails were removed  7
    days later and processed as a batch; batch weight = 2.324 g.

e/  Roman numerals » unknown compounds.

ff  2-Chloro, 4-amino, 6-ethylamino-s_-triazine.
                                     219

-------
                  Terrestrial animals
                                                                 TRIFLURALIN

                                                                 TOTAL RESIDUE
                                                         Aquatic  animals
                        Soybeans    Soil (Drummer)  sediment
                            Calculations of the above estimates:
Total maximun,
Ecosystem
component
                                                                 Total
                       (No.) X mass - total
                   concentration,

                        V8/8
                                   (mass)(cone.)
                                                                             Total residue gs
                                                                              a % of appUed

                                                                              d°8e (5°°° vg)
Earthworms
Slugs
Pillbugs
Caterpillars
Vole
( 8)
( 1)
(20)
( 5)
( 1)
1.90 =
.545 -
.0798 •=
.850 -
18.3
15.2
.545
1.60
4.25
18.3
4.29
.472
.587
.326
.224
65.2
.257
.937
1.39
4.10
1.3
.005
.02
.03
.08
Terrestrial
   animals/total (I)
Soybeans^/            (21)    .486
Snails                (50)    .182
Daphnia               (1)    .907
Pish                  (12)    .224

Aquatic
   animal total (XI)
Surface water (III)   ( 1)7000
Soil Bediment£/ (IV)  ( 1)4204
Air
              39.9
              10.2
               9.10
                .907
               2.69
                                        12.7
                                    - 7000
                                      4204
                                       sooo M
            [s
                                                   1.56
                                                    .571
                                                    ,146
                                                    .0591
                          .00913
                          .882
  71.9
  15.9
   5.20
    .132
    .159
   5.49
  63.9
3708
1151
 1.4
  .3
  .1
  .003
  .003
  .1
 1.3
74.2
23.0
a/  The terrestrial animals (and their residues) were removed from the system at the termina-
    tion of the terrestrial phase.
b_/  Proportion at 14 days postplanting, the soybeans, having been consumed and/or demolished
    by the animals, is noc present as an entity at the termination of the terrestrial phase,
    and its residue is distributed among animals, air, and soil.
£/  The direct interaction of soybeans, air, and terrestrial animals with the soil occurred
    prior to flooding the system.


Fig.  73.-Terminal  environmental  distribution of  [  cjtrifluralin plus metabolites in a soil-
         terrestrial model ecosystem.
                                          220

-------
Ni
NJ
20-
-
15-

B
19
r-l
I10;
1 •
8
ti '
sr 5-
IH
0
. -
0-
{EP 79% (EP 27%
EM 11% , - f 0.221^ 39%
UN ld% n mil,?} A 4.UN 34%
0. 03143 \ EM 4% T








/
fEP3a% o.o:
1.56^EM 32%
,





[UN 30%

0.0(

0.0(
0.0(
v [UN 9%
CEP 76% (EP 55% TEP 54% TEP 31% (EP 64%
L713
-------
                                28
                                27 -
N>
N)
KJ
                           a
                           o

M
•o
o
o
•-i
5 a
o
o.
09
X
- 4 -3
I
IJ
a
1 >>
J 0)
o
o
- 2 •£
1

0
Surface water Snails Daphnia Fish Sediment
PPM

                                Fig. 75. — Summary  of  the  fate  of  [  c]trlfluralln  In  the aquatic phase; an extension of a soil-terrestrial model
                                          ecosystem (see  Fig.   ).   The barren  terrestrial phase was  flooded 20 days postplantlng and snails,
                                          Daphnia,  and mosquito larvae were  added  to  the system; the  fish were added 4 days  later.  The total
                                          l^C-resldues are  expressed as trlfluralln equivalents, ppm  (w/w), and their subdivisions are EP »
                                          extractable parent compound, EM -  extractable metabolites of the parent compound,  and UN • unextract-
                                          able  products remaining in the processed sample.

-------
Table  133<-Concentrations of  [ c] trifluralin and degradation products in

           the soil and sediment of  a model  ecosystem.
Trifluralin equivalents, ppm
Soila/
Compound
l^
jj/
II
A
III
IV
V
B
VI
C
0
VII
VIII
IX
E
X
XI
XII
XIII
Extractable C
14
Unext rateable C
Total 14C
Sample wt (g)
Rf-
.95
.91
.87
.81
.72
.68
.61
.55
.46
.39
.33
.27
.25
.21
.15
.10
.07
.03
.00

Acetone
extract
-
0,7872
-
0.0213
-
0.0032
-
0.0115
-
0.0047
0.0118
0.0015
-
0.0020
0.0092
0.0045
0.0061
0.0079
0.0237
0.8946
0.
1.
100.
Methanol
extract^:'
-
0.1008
-
0.0033
-
0.0005
-
0.0015
-
0.0007
0.0016
0.0002
-
0.0002
0.0006
0.0018
'0.0013 "
0.0018
0.0068
0.1211
1116
1273
0000
Sediment-
Acetone
extract
0.0072
0.0905
0.0061
0.0070
0.0024
0.0028
0.0061
0.0382
0.0049
0.0074
0.0149
0.0106
0.0054
0.0114
0.0183
0.0087
0.0159
0.0355
0.1300
0.4233
0.
0,
100.
Methanol
extract
0.0011
0.0155
0.0017
0.0010
0.0003
0.0004
0.0007
0.0107
0.0008
0.0008
0.0020
0.0014
0.0010
0.0009
0.0023
0.0019
0.0038
0.0093
0.0194
0.0750
3841
8824
0000
                                                          rl4 T
a/. Soil samples were taken 20 days after  application  of  |_ CJ trifluralin to
    the soil.
                                                              rlA T
W  Sediment samples were taken 28 days  after application of  [   Cj trif luralin
    to the soil, 8 days after flooding the ecosystem fcith water.

£/  .Silica gel GF-2545 n_-hexane : acetone,  10:1 bv  volume.

    Mettianol extract is from the sample  previously extracted with acetone.

    Roman numerals - unknown compounds.
-d/

 £/

 f/
    T •» trifluralin; A - a,a,a-trlfluora-2,6-dinitro-N-propyl-p_-toluidiue;
    B » IJ,»-dipropyl-3-nitro-5-trifluoromethyl-o_-phenylenediamine;  C - 2,6-
    dlnitr*-4-trifluoromethylaniline;  D  -  2-ethyl-5-trifluoromethyl-7-nitro-l-
    propylbenzimidazole;   E «  2-ethyl-5-trifluorotnethyl-7-nitrobenzinidazole.
                                       223

-------
Table  134^Concentrations of  [  c]trifluralin and degradation products in
                         a/
           soybean plants'  after a 14-day exposure in a model ecosystem.

_ , Trifluralin equivalents .
Compound
Tl/
A
l-f
II
B
C
D
III
IV
V
E
VI
VII
VIII
14
Extractable C
14
Unextractable C
Total 1AC
Average bio sample
Rf
.84
.68
.63
.55
.46
.36
.31
.26
.22
.18
.13
.09
.05
.00


wt (g)
Root
0.866
0.044
0.011
0.043
0.018
C.024
0.103
0.015
0.012
0.015
0.013
0.023
0.117
0.172
1.476
0.599
2.076
0.334
b/
ppm-
Shoot Entire plant
0.005
0.079
-
-
0.002
0.005
0.010
-
-
0.005
0.004
0.004
0.018
0.111
0.243
0.164
0.407
0.151
0.598
0.055
0.007
0.029
0.013
0.018
0.074
0.011
0.008
0.012
0.011
0.017
0.086
0.153
1.092
0.464
1.556
0.486
a/   [  CJTrifluralia was applied to the soil beneath each seed.

b/  The roots of 3 soybean plants were combined and analyzed as an individual
    sample; the shoots were similarly processed.

£/  Silica gel GF 254; n_-hexane : acetone, 10:1 by volume.
d/  T = trifluralin; A •= 
-------
NJ
                            Table  135rConcentrations of [  C]trifluralln and degradation products in the air—  from a model eco-
                                       system.

Compound
T-X
A
B
C
D
I—
II
E
III
IV
V
VI
VII
14
Total .,C, Trap lf/
Total C, Trap 2-
Sum l^C, Traps 1 & 2
R/
Sample wt (g)^
R £/
.78
.67
.47
.32
.26
.22
.16
.12
.09
.07
.05
.03
.00




Trifluralin equivalents,
Trap ll/
Day 0
0.00009
0.00005
0.00114
0.00066
0.00119
0.00136
0.00603
0.00079
0.00048
0.00098
0.00">47
0.00551
0.00644
0.02719
0.00042
0.02761
108.00000
Day 1
0.00530
0.00003
0.00001
0.00001
0.00002
0.00001
-
0.00004
-
-
0.00004
0.00003
0.00008
0.00557
0.00036
0.00593
108.00000
Day 5
0.00279
0.00001
0.00001
0.00001
0.00001
0.00001
-
0.00004
-
-
0.00003
0.00002
0.00005
0.00298
0.00135
0.00433
108.00000
Day 11
0.00278
• 0.00001
0.00001
-
0.00001
<0. 00001
-
0.00003
-
-
0.00002
0.00001
0.00006
0.00293
0.00218
0.00511
108.00000
ppm
Day 15
0.01293
0.00009
0.00002
0.00002
0.00002
0.00001
-
0.00015
-
-
0.00010
0.00008
0.00027
0.01369
0.00344
0.01713
108.00000

Day 19
0.02738
0.00019
0.00006
0.00004
0.00005
0.00002
-
0.00027
-
-
0.00018
0.00016
0.00033
0.02868
0.00275
0.03143
108.00000
                            a/  Air was trapped for a 3-hour daylight period at a flow rate of 10 ml/sec on specified days after
                                application of  [  cjtrifluralin to the soil.

                            b/  Trap 1 was connected directly to the ecosystem container and contained 75 ml of acetonitrile as the
                                trapping solvent; the trapping solvent was chromatographed.

                            £/  Silica gel GF-254; ri-hexane : acetone, 10:1 by volume.

                            d/  T = trifluralin;  A = a,a,a-trifluoro-2,6-dinitro-N-propyl-p_-toluidine;  B = ]J,N-dipropyl-3-nitro-5-
                                trifluoromethyl-o-phenylenediamlne;  C= 2,6-dinitro-4 trifluoromethylanillne;  D" 2-ethyl-5-
                                trifluoromethyl-7-nitro-l-propylbenzlmidazolej  E = 2-ethy1-5-trifluoromethy1-7-nitrobenzimidazole.

                            e/  Roman numerals " unknown conpounds.

                            J?/  Trap 2 was connected in series to trap 1 and contained 75 ml of trapping solvent  (ethanolamlne :
                                2-methoxyethanol, 1:2 by volume); the trap 2 solvent was not chromatographed.

                            £/  One liter of air was assumed to weigh 1 g.

-------
                             r!4 -i
Table  136.-Concentrations of [  Cjtrifluralin and degradation products  in inverte-
           brates after a 5-day exposure in a model ecosystem.
Trifluralin equivalents, ppin
Compound
Ti/
A
!*/
8
C
D
II
E
III
IV
V
VI
14
Extractable C
14
Unextractable C
Total UC
Average biosample
Rr
.84
.77
.75
= 59
,42
.34
.29
.17
.11
.09
.04
.00



wt (g)
Armadiliidium— Estigmene^-
(pillbug) (caterpillar)
0.182 0.209
0.067
-
-
-
0.017 0.009
-
-
-
-
0.093
0.129 0.025
0.421 0.310
0.166 0.016
0.587 0.326
0.080 0.850
Limas—
(slug)
0.257
0.019
0.007
0.003
0.010
0.005
-
-
-
0.018
0.028
0.057
0.404
0.069
0.473
0.545
e/
(earthworm)
2.349
0.075
-
0.039 .
0.048
0.120
0.036
0.039
0.085
0.050
0.306
0.443
3.590
0.700
4.291
1.902
ji/' Silica gel GF-254; n-hexane : acetone, 10:1 by volume.
b/  Three pillbugs were processed together; batch weight «= 0.239 g.
_£/  Two caterpillars were processed together; batch weight = 1.700 g.
&f  Only one slug (dead) was recovered from ecosystem and processed.
ej  Two earthworms were processed together; batch weight «• 3.804 g.
f/  T = trifluialin; A = a,a,a-tnfluoro-2,6-dinitro-lv-propyl-p_-toluidine;
    B » N^N^dipropyl-S-niuro-S-trifluoromethyl-o-phenylenedianine; C =  2,6-
    dinitro-4-trifluoromethylaniline; D = 2-ethyl-5-trifluoromethyl-7-nitro-l
    propylbenzimidazole; E = 2-ethyl-5-trifluoromethyl-7-nitrobenzimidazole.
%J  Roman numerals » unknown compounds.
                                        226

-------
N>
ro
                        Table 137."Concentrations of [  cjtrifluralin and degradation products in the prairie vole after a 1.75-day^
                                   exposure in a model ecosystem.
Trifluralin equivalents, ppm
Compound
I*>
Tl/
A
B
C
D
II
E
III
IV
14
Extractable C
14
Unextractable C
Total C
Biosample wt (g)
R b/
f
.90
.80
.66
.52
.39
.31
.17
.10
.04
.00


GI tract
0.007
0.142
0.008
0.010
0.001
0.004
0.007
0.023
0.023
0.093
0.318
0.184
0.502
3.400
Skin "
0.017
0.197
0.012
0.006
0.004
0.036
0.009
0.012
0.017
0.031
0.341
0.116
0.457
2.431
Remaining
organs^.'
-
0.018
0.005
0.006
0.002
0.007
0.012
0.010
0.022
0.078
0.160
0.091
0.251
1.139
Liver
—
-
-
-
0.002
0.002
0.004
-
-
0.083
0.091
0.057
0.148
0.909
Brain
-
-
-
-
—
0.011
-
-
0.102
0.113
0.007
0.121
0.541
Carcass
_
0.014
0.003
0.002
0.003
0.001
0.003
0.004
0.005
0.013
0.048
0.033
0.081
9.860
Body
totals
0.004
0.061
0.005
0.004
0.002
0.007
0.005
0.009
0.011
0.041
0.149
0.076
0.225
18.281
                        &J  The vole died 1.75 days after being placed in the ecosystem, probably from starvation; essentially no
                            soybean shoots were present in the ecosystem when the vole was added; rabbit chow was added but not eaten.
                        jb/  Silica gel GF-254; jn-hexane : acetone, 10:1 by volume.
                        c/  Internal organs, other than those specified, were combined and processed as an Individual sample.

                        d/  Roman numerals • unknown compounds.
                        e/  T =• trifluralin; A » ct,a,a-trifluoro-2,6-dinitro-N^propyl-£-toluidine; B - ^,N-dipropyl-3-nitro-
                             5-trifluoromethyl-jn-phenylenedian>ine; C - 2,6-dinitro-4-trlfluoromethylaniline; D - 2-ethyl-5-
                             trifluoromethyl-7-nitro-l-propylbenzimidazole; E » 2-ethyl-5-trifluoromethyl-7-nitrobenzimidazole.

-------
 Table  138:-Relative affinities of 6 body-parts of the prairie  vole^-  for
             f 14 i
             L  Cjtrifluralin plus its metabolites, and comparisons with

            the relative masses of the body-parts.

Body-part
(organs and tissues)
GI tract
Skin
Carcass-
Liver
Brain
c/
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
41.58
27.11
19.46
3.28
1.59
6.98
100.00
Body-part wt as a %
of entire body wt
18.60
13.30
53.94
4.97
2.96
6.23
100.00
 ajj  Vole from a soil-terrestrial model ecosystem treated with
     [14c]trifluralin.

 b_/  Carcass = the eviscerated body (the removed organs and  tissues  are
     listed above); it consists predominately of muscle and  bone.

 cj  The kidneys t adrenals, heart, lungs, mammary glands, ventral central
;,    neck gland, and parotid glands were analyzed collectively.
1
                                     228

-------
Table 139.-Concentrations of [  cjtrifluralin and degradation pro-
           ducts in the water of a. model ecosystem 7 days after
                                            a/
           flooding the ecosystem with water— .

Compound
D£/
E
1^
II
III
14
Extractable C
Unextractable 14C-/'
T> k/
Rf
.26
.12
.06
.02
.00


14
C Loss during extraction
14
Initial C in water
Sample volume (1)


Trifluralin equivalents, ppm
Surface water
0.00093
0.00028
0.00043
0.00127
0.00162
0.00453
0.00453
, 0.00007
0.00913
1.00000
a/  Ecosystem was flooded with water 20 days after application of
    [14CJtrifluralin to thfe soil.

b/  Silica gel GF-254; ii-hexane : acetone, 10:1 by volume.

£/  D = 2-ethy1-5-trifluoromethyl-7-nitro-l-propylbenzimidazole;
~~   E •» 2-ethyl-5-trifluoromethyl-7-nitrobenzimidazole.

d/  Roman numerals = unknown compounds.

£/  The water, after ether extraction, was not subjected to the
    usual hydrolysis procedure.
                                 229

-------
Table  1/iOrConcentrations of  [  c]trifluralin and degradation products in

           aquatic organisms in a model ecosystem flooded with water— .
Trifluralin equivalents
Compound
£'
1&/
A
B
C
D
II
III
E
IV
V
VI
VII
14
Extractable C
14
Unextractable C
Total UC
Average bios ample
Rb/
Rf
.87
.77
.62
.43
.33
.31
.27
.22
.12
.08
.06
.04
.00



wt (g)
Garribusia—
(fish)
0.015
0.007
0.001
0.007
0.002
-
0.002
-
0.002
-
-
0.006
0.008
0.050
0.009
0.059
0.224
a/ Ecosystem was flooded with water 20 days
"~ trif luralin to the soil.
b/ Silica gel GF-254; iv-hexane :
£/ Three fish were added 4 davs
acetone, 10
(snail)
0.016
0.170
0.011
0.069
0.013
0.004
0.011
0.007
0.014
0.012
0.019
0.067
0.098
0.511
0.060
0.571
0.182
after application
:1 by volume.
after flooding the ecosystem;
, ppm
Daphn-U^-'
(water flea)
_
0.012
0.002
0.037
0.003
0.004
-
-
0.002
0.002
0.002
0.009
0.043
0.116
0.031
0.147
0.907
, rU-T
°f L cj-

3 fish (dead
    were removed 5 hr later; 3 more fish were added 4.2 days after flooding
    the ecosystem; 3 fish (dead) were removed 17 hr later; 3 more fish were
    added 5 days after flooding the ecosystem; 2 fish (dead) were removed 1 hr
    later and 1 fish (dead) 2.5 hr later; 3 more fish were added 5.14 days
    after flooding the ecosystem; 3 fish (dead) were removed 0.5 hr later;
    the fish were processed in batches (as removed), and the results averaged.

&/  Snails were added on the day of flooding; 15 snails were removed 7 days
    later and processed as a batch; batch weight * 2.730 g.

e/  Daphnia were added on the day of flooding, removed 7 days later, and pro-
    cessed as a batch; many organisms constituted the biosample.

f_/  Roman numerals * unknown compounds.
&/  T " trif luralin; A = a,o,a-trifluoro-2,6-dinitro-N^propyl-£-toluidine;
    B = N^-dipropyl-3-nitro-5-trifluoromethyl-o-phenylenediamine; C *> 2,6-
    dinitro-4-trifluoromethylaniline; D - 2-ethyl-5-trifluoromethyl-7-nitro-l-
    propylbenzimidazole; E « 2-ethyl-5-trifluoroaethyl-7-nitrobenzimidazole.
                                      230

-------
                                                                      2A5-T
                                                                  (Isooctyl ester)
                                                                   TOTAL RESIDUE
                 Terrestrial animals
                                                         Aquatic animals
                          Com
             Soil (Drummer) sediment
                            Calculations of the above estimates:
Ecosystem
Component
    Total maximum           Mean           Total             regldue ag

   __nass'8:	concentration,   ^""^ »*j_    a 2 of applied

 Wo.) i^als"-  total       U8/8       TmassKconc.)    dose (500° «>
Earthworms
Pillbugs
Caterpillars
Vole
< 8)
(20)
(10)
( 1)
i v ' 1
2.15 -
.0580 -
.912 -
26.3
17.2'
1.16
9.12
26.3
1.81
2.69
.163
.0361
31.1
3.12
1.49
.949
.6
.06
.03
,.02
Terrestrial
   aniraaia/ total (I)
Cornk/
Snails
Daphnia
Fish
(45)
(50)
( 1)
( 6)
2.76
 .168
 .367
 .233
 53.8
124
  8.40
   .567
  1.40
1.09
 .193
 .231
 .149
 36.7
135
  1.62
   .131
   .208
 .7
2.7
 .03
 .003
 .004
Aquatic
animal total (II)
Surface water (III)
Soil sediment^ (IV)
Air


( 1)7000
( 1)4306


10.4
- 7000 .0673
• 4306 .795
• [5000 yg-(I+II+III+IV)]

1.96
471
3423
• 1067

.04
9.4
68.5
21.3
a/  The terrestrial animals (and their residues) were removed from the system at the termina-
    tion of the terrestrial phase.
W  Proportion at 14 days postplanting; the corn, having been consumed and/or demolished by
    the animals, is not present as an entity at the termination of the terrestrial phase, and
    its residue is distributed among animals, air, and soil.
£/  The direct interaction of corn, air, and terrestrial animals with the soil occurred prior
    to flooding che system.

                                                 r!4 i
Fig. 76 .-Terminal environmental distribution of  [  CJ2,4,5-T (isooctyl ester) plus metabolites
          la a soil-terrestrial model ecosystem.
                                           231

-------
                                             EP
to
CO
to
20 1
.
-
15 •

§ -
t;
5r '
», 5-
o
41
-
-
0-
1,07^EM3^% fEP 17% 0.0361^EM 5A
>









^ yjM 01* Q Q117CJEH 8% i V.1™ 46
/ 'l
fEP 2% 0.0
1.09sEM 66%
/






, (JUN 32%
0.0


0.0

k [UN 75%
[EP 18% [EP 0% [EP 0% [EP 22%
37651EM 9% 1.81
-------
Ni
co
CO
2ft -
27 -
26 .
S 25 -
o.
0
o
P.
a 24 .
•o

« 23
a
X
a

flooding
••^
u
0)
a

•°
a
^ u
10
a
o
' 2 u

<
1

0
                                         Surface water
                                                                    Snails
                                                                    114,
Daphnla
                                                                                                  Fish
                                                                                                                               Sediment
                                                                                          PPM
                                   Fig. 78 . — Summary  of  the fate  of  [  C]2,4,5-T  in the  aquatic phase;  an  extension  of  a soil  terrestrial  model
                                            ecosystem (see Fig.    ).   The barren terrestrial  phase  was flooded  20 days postplantlng and snails,
                                            Daphnla,  and mosquito larvae  were  added to  the system;  the fish were added 4 days later.   The total
                                            l^C-resldues are expressed as 2,4,5-T equivalents, ppm  (w/w),  and their subdivisions  are EP - extract-
                                               ire parent compound,  EM » extractable metabolites of the  parent compound, and  UN • unextractable
                                             products remaining In the processed  sample.

-------
                             r!4 T
Table 141.-Concentrations of L  C]2,4,5-T (ieooctyl ester) and degradation

           products in the soil and sediment of a model ecosystem.


2,4
,5-T (ester)
Soil*'
Compound
2,4,5-T (ester)
I-7
II
III
IV
V
VI
VII
14
Extractable C
14
Unextractable C
Total UC
Sample wt (g)
Rc/
Rf
.88
.77
.34
.28
.11
.08
.04
.00




Acetone
extract
0.0321
0.0043
0.0207
-
0.0043
0.0034
0.0039
0.2265
0.2952
0.
1.
100.
Methanol
extract^/
0.0076
0.0014
0.0095
-
0.0010
0.0008
0.0127
0.0853
0.1183
6612
0747
0000
equivalents ,
ppm
Sediment-
Acetone
extract
0.0224
0.0033
0.0300
0.0173
0.0029
0.0023
0.0360
0.2354
0.3496
0
0
100
Methanol
extract
0.0036
-
0.0047
0.0019
-
-
0.0041
0.0459
0.0602
.3855
.7953
.0000
                                                         r!4 1
a/  Soil samples were taken 20 days after application of [_  Cj 2,4,5-T (isooctyl
    ester) to the soil.

b/  Sediment samples were taken 28 days after application of  [  CJ 2,4,5-T
    (isooctyl ester) to the soil, 8 days after flooding the ecosystem with
    water.

cl  Silica gel CT 254; n-hexane : acetone, 10:1 by volume.

&l  Methanol extract is from che sample previously extracted with acetone.

e/  Roman numerals « unknown compounds.
                                      234

-------
                              r!4 i
Table 142:-Concentrations of  [  Cj2,4,5-T  (isooctyl ester)  and  degradation pro-



           ducts in corn—  after a 14-day exposure in a model ecosystem.

t 2,4,5-T (ester) equivalents, ppm^'
Compound
2,4,5-T (ester)
&
II
III
IV
V
VI
VII
VIII
14
Extract able C
14
Unextractable C
Total UC
Average Biosample
Rf~
.88
.42
.33
.17
.13
.10
.06
.03
.00



wt (g)
Root
0.029
0.031
-
0.006
0.002
0.005
0.025
0.611
0.372
1.081 ,
0.498
1.579
1.740
Shoot
0.003
0.008
0.005
-
-
-
0.005
0.076
0.073
0.170
0.089
0.259
1.024
Entire plant
0.019
0.022
0.002
0.004
0.001
0.003
0.018
0.413
0.261
0.743 "
0.347
1.090
2.764
    r!4
a/  [  CJ2,4,5-T (isooctyl ester) was applied to tha soil beneath each seed.



b_/  The roots of 3 corn plants were combined and analyzed as an individual

    sample; the shoots were similarly processed.



£/  Silica gel GF-254; n-hexane : acetone, 10:1 by volume.



d/ Roman numerals - unknown compounds.
                                      235

-------
NJ
U>
cr>
                           Table 143.-Concentrations of [  c]2,4,5-T (isooctyl ester) and degradation products In the air^  from &
                                      model ecosystem.
2,4,5-T (ester) equivalents, ppm
., Trap lA/
Compound
2,4,5-T (ester)
l-f
II
III
IV
V
VI
VII
Total 14C, Trap 1
14 e/
Total C, Trap 2-
14
Sum C, Traps 1 & 2
Sample wt (g)—
Rf~
.80
.32
.27
.19
.14
.09
.04
.00


Day 0
0.00170
0.00003
0.00001
<0. 00001
0.00001
<0. 00001
0.00003
0.00046
0.00224
0.00038
0.00262
108.00000
Day 1
0.00097
0.00003
-
0.00001
<0. 00001
<0. 00001
<0. 00001
0.00001
0.00102
0.00058
0.00160
108.00000
Day 5
0.00127
0.00060
-
-
0.00002
0.00001
0.00001
0.00003
0.00194
0.00310
0.00504
108.00000
Day 11
0.00134
0.00045
-
-
0.00006
0.00003
0.00005
0.00006
0.00199
0.00143
0.00342
108.00000
Day 15
0.00136
0.00054
-
-
-
0.00006
0.00003
0.00003
0.00202
0.00563
0.00765
108.00000
Day 19
0.00195
0.00076
-
-
-
0.00006
0.00005
0.00007
0.00289
0.00887
0.01176
108.00000
                           &l  Air was trapped for a 3-hour daylight period at a. flow rate of 10 ml/sec on specified days after
                               application of [^CJ2,4,5-T (isooctyl ester) to the soil.
                           b_/  Trap 1 was connected directly to the ecosystem container and contained 75 ml of acetonitrile as the
                               trapping solvent;  the trapping solvent was chromatographed.
                           £/  Silica gel GF-254; n-hexane : acetone, 10:1 by volume.
                           Al  Roman numerals = unknown compounds.
                           e/  Trap 2 was connected in series to trap 1 and contained 75 ml of trapping solvent (ethanolamine :
                               2-methoxyethanol,  1:2 by volume); the trap 2 solvent was not chromatographed.
                           f/  One liter of air was assumed to weigh 1 g.

-------
                             rl4 T
Table  144-Concentrations of [  CJ2,4,5-T (isooccyl ester) and degradation pro-



           ducts in invertebrates after a 5-day exposure in a model ecosystem.
Compound
2,4,5-T (ester)
I-X
II
III
IV
V
VI'
14
Extractable C
14
Unextractable' C
Total 14C
Average biosample
V"
.82
.39
.27
.09
.04
.02
.00

,

wt (g)
2,4,5-T
Azmadi 1 lidium—
(pillbug)
-
-
0.009
-
-
-
1.284
1.293
1.402
2.695
0.058
(ester) equivalents
Estigmene^-
(caterpillar)
0.035
0.010
0.022
-
-
-
0.068
0.135
, , 0.027
0.163
0.912
, pom
Liaribricus—
(earthworm)
0.007
-•
0.052
0.019
0.627
0.197
0.287
1.189
' 0.626
1.815
2.147
£/  Silica gel CT-254; ii-hexane : acetone, 10:1 by volume.



W  Three pillbugs were processed together; batch weight = 0.174 g.



c/  Three caterpillars were processed together; batch weight •* 2.736 g.



d/  Only one earthworm was recovered from ecosystem and processed.



e/  Roman numerals ° unknown compounds.
                                         237

-------
N>
U>
00
                                                     C14 n
                                                       Cj2,4,5-T (Isooctyl ester) and degradation products in the prairie vole after a

                                  5-day exposure in a model ecosystem.

2,4,5-T (ester) equivalents, ppm
R a/
Compound £
Td/
i. •
II
III
IV
V
VI
VII
14
Extractable C
14
Unex tract able
Total UC
Biosample wt (g)
48
41
31
23
13
06
00
C

Remaining
organs*!/
0.0017
-
-
0.0012
0.0025
-
0.0411
0.0465
0.0342
0.0807
1.5449
Skin
-
-
-
0.0054
-
-
0.0187
0.0241
0.0425
0.0666
4.3030
GI tract
0.0006
0.0019
0.0031
0.0018
0.0018
0.0184
0.0127
0.0403
0.0233
0.0636
3.5239
Liver
0.0003
0.0003
0.0007
0.0003
0.0003
0.0012
0.0155
0.0186
0.0122
0.0308
1.5488
Fat
0.0022
-
-
-
0.0029
-
0.0082
0.0133
0.0127
0.0260
0.6983
Carcass
_
-
0.0007
-
-
-
0.0112
0.0119
0.0073
0.0192
12.5614
Brain
-
-
-
-
-
-
0.0083
0.0083
0.0037
0.0120
0.5371
Body .
totals-
0.0003
0.0003
0.0008
0.0012
0.0005
0.0025
0.0138
0.0194
0.0167
0.0361
-
                       a/  Silica gel GF-254; n-hexane : acetone, 10:1 by volume.

                       b_/  Internal organs,  other than those specified, were combined and processed as an individual sample.

                       c_/  Body totals were  calculated using live body weight (26.2900 g).

                       d/  Roman numerals «  unknown compounds.

-------
Table  146.-Relative affinities of 7 body-parts of the prairie vole^  for
            r!4 n
            L  CJ2,4,5-T (isooctyl ester) plus its metabolites, and com-

           parisons with the relative masses of the body-parts.

Body-part
(organs and tissues)
Skin
Carcass—
GI tract
Liver
Fat
Brain
c/
Remaining organs-
Residue wt in body-part
as a % of total residue
wt in entire body
30*19
25.43
23.64
5.02
1.91
• - - -68
13.14
100.01
Body-part wt as a %
of entire body wt
17.41
50.82
14.26
6.26
2.83
2.18 < '
6.25
100.01
aj  Vole from a soil-terrestrial model ecosystem treated with
    [L4CJ2,4,5-T  (isoQctyl ester).

W  Carcass = the eviscerated body (the removed organs and tissues are
    listed above); it .consists predominately of muscle and bone.

c/  The kidneys + adrenals, heart,  lungs, mammary glands, ventral central
    neck gland, parotid glands and small amounts of fat tissue were
     naljrzed -collectively,
                                    239

-------
                              r!4
Table 147/-Concentrations of [  CJ2,4,5-T (isooctyl ester) and
           degradation products in the water of a model ecosystem
                                                         a/
           7 days after flooding the ecosystem with water— .

Compound
1^
II
III
IV
V
VI
14
Extractable C
Unextractable 14C-/
Rf
.39
.26
.11
.06
.02
.00


14
C loss during extraction
14
Initial C in water
Sample volume (1)


2,4,5-T (ester) equivalents, ppm
Surface water
0.00007
0.00007
0.00007
0.00022
0.00048
0.00061
0.00152
0.06454
0.00124
0.06730
1.00000
aj  Ecosystem was flooded with water 20 days after application of
    [  Cj2,4,5-T (isooctyl ester) to the soil.

b/  Silica gel GF-254; n_-hexane : acetone, 10:1 by volume.

cf  Roman numerals = unknown compounds.

jd/  The watet, after ether extraction, was not subjected  to  the
    usual hydrolysis procedure.
                                240

-------
                              rl4
Table 148.-Concentrations of  [  CJ2.4.5-T  (isooctyl  ester)  and  degra-
           dation products in aquatic organisms  in a model  ecosystem
           flooded with water^.

Compound
ii/
2,4,5-T (ester)
II
III
IV
V
VI
VII
VIII
14
Extractable C
14 '
Unextractable C
Total 14C
Average biosample
V"
.80
.73
.40
.25
.19
.11
.07
.05
.00

-

wt (g)
2,4,5-T
Gambuaice—
(fish)
0.004
0.007
0.002
0.037
0.005
0.003
0.001
0.017
0.028
0.104
0.045
0.149
0.233
(ester) equivalents, ppm
Phyec^
(snail)
-
0.009
-
0.021
0.003
0,008
0.006
0.029
0.094
0.170
0.023
0.193
0.168
Dophnior-
(water flea)
-
0.014
-
0.021
0.009
0.002
0.001
0.005
0.140
0.192
0.040
0.232
0.567

~~   2,4,5-T  Cisooctyl ester) to the soil.
b_/  Silica gel GF-254; tv-hexane : acetone, 10:1 by volume.

_c/  Three fish were added 4 days after flooding  the ecosystem;  2  fish
    (dead) vere removed 5 hrs later and 1 fish (dead) 1 day  later;
    three more fish were added 5 days after  flooding the ecosystem;  1
    fish (dead) was reiooved 15 hrs later and 2 fish (dead) 1 day  later;
    the fish were processed individually or  in pairs (as removed), and
    the results averaged.

d/  Snails were added on the day of flooding; 15 snails were removed 7
~~   days later and processed as a batch; batch weight - 2.525 g.

e/  Daphnia  were added on the day of flooding, removed 7 days later,  and
    processed as a batch; many organisms constituted the biosample.

£/  Roman numerals ° unknown compounds.
                                    241

-------
TV le 149,
-------
                14
Table 150. Total   C metabolites expressed as alclrin equivalents, ppm,



 in individual orcanisms of different species from four model



 ecosystems; two systems contained a vermiculite substrate and two



 contained a Drummer loam  soil substrate; the statistics are the



 arithmetic mean » standard error, and analvsis of variance K values



 with significant differences indicated by an asterisk (factors are nt



 soil and vermiculite).                       .
Verniculite
A
svstens
3
Drumnor
A
loan soil svstens
B

CORII (entire plant)
3.801
8.789
5.306
6.331
6.720
8.32''
7.462+0.629
Between fictors,
,
1.918
2.194

2.056-0.138
Between factors,
12.86<5
5.566
3. 956
5.559
7.934
3.67"
7.436*1.297
FO.OOl[L,2j°170
-
3.099


("3.099)
Vosri^r1"-*
1.565
1.453
0.506
1.540
0.749
0.650
1.077+1.201
O,1** wit'iin factors
' SLUGS '"-
0.2C6
0.533
0.7'n
0.5n+n.12'»
,A within factors,
CATLRPTUJVUS
5.146
4.232
S.Si1
4.323:0.463
Between factors,
4.5/0
3.757
2.539
3.622+0.590
Between factors,
'.017
2. 399
''.633
2.42TS-*0.205
^o.ioii^r9-04
r
'2.1J56 -
2.669

2.313±0.144
Fn infi ,1*«.»
0.235
0./83
0.7<»7
0.521*". 14"
' O.lo£2j8jj* "'
ILL'BUCS
1.207'
1.376
1.213
1.290+0.0/9
;* wit'iin factors.
0.635
1.415
0.419
0.570
0.947
0.533
0.767'0
F0.05i'A5r15!3

0.71?
0.433'
0.23"
0.480+0

0.663
0.238

0.451*0
p r ..«•> in
n ml •» « 1 •






.150
0.0466




.nil





»124




.213

                                243

-------
                 14
Table 151. Total   C-metabolites  expressed as aldrln equivalents,  ppm,



  in duplicate corn samples  at  each of  three postplanting  ages (6, 10,



  and 14  days) from four  different model  ecosystems; two of  the systems



  (VA and VB)  contain  a vermiculite substrate and  two  (SA  and SB)



  contain a natural soil  substrate.
0) 
-------
                                                      14
Table 152.  Ecosystems containing vermiculite:  total   Ometabolites expressed as



  aidrin equivalents, ppm, in the  individuals of various species, and  the



  variation within individual samples.
Ecosysten A
Age,
days
6
10
14
15
15
15



Component
Corn
Corn
Corn
Slug
Caterpillar
Pillbug



Xl
8.801
5.306
6.720
1.918
5.146
4.570




8
6
8
2
4
3



y Y
X2 X3
.789
.331
.822
.194
.282 3.542
.757 2.539




8
5
7
2
4
3



X
.795
.819
.771
.056
.323
.622



s
0.008
0.725
1.436
0.195
0.803
1.022



C.V
0.
12.
19.
9.
18.
28.



.(%)
097
5
1
48
6
2 '


Ecosystem B

6
10
14
15
15
15

Corn
Corn
Corn
Slug
Caterpillar
Pillbug

12.868
J.956
7.994
3.099
2.017
2.956

5
5
8

2
,2

.566
.559
.670

.599 2.663
.669

9
4
8

2
2

.217
.758
.332

.426
.813

5.163
1.133
0.473

0.356
0.203,

56.
23.
5.

14.
7.

0
8
74

7
21
Summary of
Systems

s
0.008
0.195
0.203
0.356
0.478
0.725
0.803
1.022
1.133
1.486
5.163

Average
within
vidual

A and R

C.V.(%)
0.097
5.74
7.21
9.48
12.5
14.7
18.6
19.1
23.8
23.2
56.0

C.V.
indi-
s amplest
18%.
                                          245

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                                                          14
Table 153' Ecosystems containing Drummer loan soil:  total   C-netabolites


 expressed as aldrin equivalents, ppm, in the individuals of various species,



 and the variation within individual samples.
Ecosvstem ,A
Age,
days
6
10
14
15
15
15
15




6
10
14
15
15
15


Component
Corn
Corn
Corn
Slug




Caterpillar
Earthworm
Pillbug




Corn
Corn
Corn
slug








Caterpillar
Pillbug

Xl
I.b65
0.506
0.749
0.286
0.2S5
1.205
1.207


T*

0.685
0.419
0.947
0.245
0.712
0.663


1
1
0
0
0
1
1



\ X3
.453
.540
.650
.533 0.720
.488 0.797
.897 0.681
.376 1.288



4V
1.509
1.023
0.700
0.513
0.523
1.261
1.290



s
0.079
0.731
0.070
0.218
0.258
0.610
0.085



C.V
5
71
10
42
49
48
6



.(%)
.25
.5
.0
.4
.3
.4
.55


cosvstcn B

1
0
0
0
0
0

.415
.570
.538
.275 0.282
.438 0.239
.238

1.050
0.495
0.743
0.267
0.480
0.451

0.516
0.107
0.23°
0.020
0.215
0.301

49
21
38
7
44
66

.1
.6
.9
.36
.7
.6
Sunmry of
Systens

s
0.020
0.070
0.079
0.035
0.107
0.215
0.218
0.258
0.289
0.301
0.516
0.610
0.731

Average
within
vidual
A nnd B

C.V. (%)
5.25
6.55
7.36
10.0
21.6
38.9
42.4
44.7
43.4
49.1
49.3
66.6
71.5

C.V.
indi-
samples:
                                                                             36%
                                        246

-------
Table 154.-Pesticides in the aquatic phase subsequent to the terrestrial
           phase— .
Parent compound
                                      14
                                Total   C-pesticidal residue, ppm
                              (with %• parent cotrpound in parentheses)
Accumulation in wate
 7 days after flooding
                                              b/
Mean accumulation in
  fish and snails^/
FUNGICIDES
PCP
PCNB
HCB
Captan
0.00848
0.00878
0.00173
0.00294
( 8)
( 2)
(47)
(0.1)
2.14
1.66
0.838
0.602
(23)
(16)
(48)
( 6)
Trifluralin (soybeans)       0.00913    ( 0)
2,4,5-T (isoo<:tyl aster)     0.06730    ( 0)
Simazine                     0.05860    (80)
                                             HERBICIDES
                                0.315
                                0.171
                                0.170
            (21)****
            ( 5)***
            (62)**
                                            INSECTICIDES
Dieldrin (no crop)
ParathioniL/ , ,
Methyl parathion—
Phorate
0.00390
0.00741
0.00667
0.04710
(40)
( 4)
( 1)
(0.1)
VARIABLE SOIL /CROP
Dieldrin (vertaiculite)
Phorate (loamy sand)
HCB (soybeans)
0.02200
0.08320
0.00117
(41)
(0.1)
(42)- •
8.16
0.787
0.713
0.377
(94)
( 3)
( 8)
( 7)*
(CO! IP ARE ABOVE)
66.4
0.796
1.59
(91)
( 6)**
(57)
aj  Except where indicated, all systems contained silty clay loam soil
    and .corn.      • •  . .
b/ -.The mass of water was ca. 1.75 x greater than the mass of soil.
£/  Fish were exposed for 3 days, unless they died earlier, and snails
    for 7 days.     -  .
d/  The-parathions were applied.to corn foliage 10 days prior to flooding,
    all others were applied to soil 20 days prior to flooding.

*   Asterisks demark those residues that were lethal to fish; the more
    numerous the asterisks, the more rapid the kill.
                                     247

-------
Table 155.-Transfer of pesticides to surface water subsequent to their
         .exposure to a terrestrial environment:   the total   C-pesti-
          cidal residue in water seven days post-flooding,  expressed
          as a percent of the initial pesticide application
Fungicides
PCNB 1 . 23 %
PCP 1.19 %
Captan 0.412 %
HCB 0.242 %
Herbicides
2,4,5-T (iso- 9.42 %
octyl estei)
Simazine 8.20 %
Trifluralin 1.28 %
Insecticides
Phorate 6.60 %
Parathion 1.04 %*
Me. parathion 0.934 %*
Dieldrin 0.546 %
* Applied to corn foliage 10 days prior to flooding;   all of the other
  compounds were applied to soil (silty^clay loam) 20 days prior to
  flooding.
                                   248

-------
Table  156TA synopsis of Che differences in the terrestrial environmental
           fates of phorace as Induced by varying the type of

compound
Phorate in S.C.L.
Phorace in L.S.
Total 14C-insecticidal residue
Persistence in soil 20
days after application^'
61Z (1)-'
35Z (1)
Mean accumulation in
terrestrial animals^-'
0.457 ppm (3)
1.54 ppa (2)
a/  S.C.L. * silty clay loam soil;  L.S. » loamy sand.
W  Percent of the applied dose.
cl  Five species exposed for five days.
d_/  Each value in parentheses is the percent parent compound in the total
    residue;  it describes the parent compound's resistance to degradation.
Table 1" —A synopsis of the differences in the terrestrial environmental
           fates of aldrin as induced by varying the type of soiUL'


                                Total 16C-insecticidal residue
      Parent      	
     compound        Persistence in soil 20         Mean accumulation in
                     days after application^/       terrestrial animalsi'

  Aldrin in S.C.L.     ca. IOOZ  (67)1/                0.689 ppm   (6)
  Aldrin in vertnic.         42Z  (14)                  2.92  ppm   (7)

a/  S.C.L. » silty clay loam soil;  vermic. « vermiculite.
W  Percent of the applied dose.
cj  Five species exposed for five days.  ,         .            • <  -
A/  Each value in parentheses is the percent parent compound in the total
    residue;  it describes the parent compound's resistance to degradation.
Table 158.-A synopsis of the differences in the terrestrial environmental
           fates -of HCB2/ as induced by varying the type of crop


                                 Total ^C-fungicidal residue
      Parent      _________________________^___-_^_^___
     compound        Persistence in soil 20         Mean accumulation in
                     days after, application^'        terrestrial animals^'

  BCB (soybeans)            74Z  (96)1/                1.51 ppm  (85)
  HCB (corn)                &7Z  (95)                  1.63 ppm  (83)

a]  Hexachlorobenzene was applied to silty clay loam soil, not the crop.
b_/  Percent of the applied dose.
c/  Five species exposed fur five days.'
d_/  Each value in parentheses is the percent parent compound in the total
    residue;  it describes the parent compound's resistance to degradation.
                                       249

-------
Table  159rINSECTICIDES applied *o Vertniculitc.  a synopsis and differentia-
           tion of their terrestrial environmental fates
Parent
compound
Dieldrin
Aldnn
Fonofos
Total C-insecticidal residue
Persistence in vermiculitc .
20 days after application-^
68%
42%
9%
<86>£/
(14)
( 8)
Mean accumulation in
terrestrial animals"/
3.65 ppm (70)
2.92 ppm ( 7)
0.571 ppn ( 1)
a/  Percent of applied dose.
b/  Five species exposed for five days  (only caterpillar and vole data
    available for fonofos).
c/  Each value in parentheses is the percent parent compound in the total
    residue   it describes the parent compound's resistance to degradation.
Table 160."^NSECTICIDDS applied to Corn growing in Silty Clay Loam Soil*
           a synopsis and differentiation of their terrestrial environ-
           mental fates
Parent
compound
Parathion
Methyl parathion
Total 14C-insecticidal residue
Accumulation in soil
10 days after application^'
0.577 ppm (18)£/
0.398 ppm ( 4)
Mean accumulation in
terrestrial animals—
5.42 ppra (31)
2.72 ppm ( 4)
a/  Maximum value possible in soil   1 25 ppm.
b/  Five species exposed for five days.
c/  Each value in parentheses is the percent parent compound in the total
    residue;  it describes the parent compound s resistance to degradation.
Table 161-INSECTICIDES applied to Corn growing in Vermiculite   a synopsis
           and differentiation of their terrestrial environmental fates
Parent
compound
DDT
Methoxy ch lor
Total 14C insecticidal residue
Accumulation in vermiculite
XO days after application—
1.73 ppm (65)^
1.44 ppm (62)
Mean accumulation in
terrestrial animals.—
22.3 ppm (39)
3.03 ppm (26)
a/  Maximum value possible in vermiculite - 2.08 ppm.
b/  Five species exposed for five days.
£/  Each value in parentheses is the percent parent compound in the total
    residue,  it describes the parent compound s resistance to degradation.
                                        250

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Table  162."FUNGICIDES applied to Silty Clay Loam Soil,  a synopsis  and  dif-
           ferentiation of their terrestrial environmental  fates
Parent
compound
HCB
PCNB
PCP
Captan
Total *4C-fungicidal residue
Persistence in soil 20
days after application^
67% OS)5/
64% (43)
48% (19)
13% ( 1)
Mean accumulation in
terrestrial animals"'
1.63 ppia (83)
1.34 ppm (19)
0.672 ppm (15)
0.228 ppm (12)
a/  Percent of the applied doso.
b/  Five species exposed for five days.
£/  Each value in parentheses is the percent parent compound in  the  total
    residue;  it describes the parent compound's resistance to degradation.
Table 163.-HERBICIDES applied to Silty Clay Loam Soil:  a synopsis and dif-
           ferentiation of their terrestrial environmental fates


                                 Total 14C-herbiCiiial residue
      Parent      	.                    	
     compound        Persistence in soil 20         Mean accumulation in
                     days after application^.'        terrestrial animals°-'
Simazine
Trifluralin
2,4,5-T isooctyl
ca.

ester
100%
78%
74%
(70)£/
(79)
f 4)
1
1
1
.86
.36
.17
ppra
ppm
ppm
(41)
(44)
( 5)
a/  Percent of the applied dose.
b/  Four species (no slugs) exposed for five days.
c/  Each value in parentheses is> the percent parent compound in the total
    residue;  it describes the parent compound's resistance to degradation.
Table 144.-INSECTICIDES apJ>l4>edi_to.Silty Clay LoBW-Soi-1   a synopsis and
           differentiation of" their terrestrial environmental fates

                                Total ^C-msecticidal residue
      Parent      	
     compound' " '     Persistence ifir soil 20         Heart accumulation ip
 *                    days after application—        terrestrial animals—

  Alarm              ca. 100*  (67)-'                 0.689 ppm  (6)
  Phorata                  6U  ( 1)                    0.457 ppm  (3)

a/  Percent of the applied dose.
b/  Five species exposed for five days.
c/  Each value in parentheses is the  percent parent compound in the total
    residuat  it describes the parent compound's resistance to degradation.
                                       251

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                     Table 165.-Grand summary: fate of   C-fungicides in terrestrial-modular model ecosystems^'
NJ
Ln
to
Ecosystop.
component and
postplanting age
at analysis
(cays)
Substrate (^0)
Air (5)^X
Corn (14)
Earthworm (15)
Slug (15)
Pillbug (15)
CaterpUlar (15)
Vole (20)
Water (?7)
Sediment (28)
Srail (27)
Fish (27)
Total 14C-fungicidal Extractable parent Resistance to degradation
residues (ppm) 14C-fungicidal compounds (ppm) <% of extractable parent com-
pound present in total residue)
HCB
0.949
0.014
2.64
0.584
0.228
4.09
0.347
2.88
0.0017
0.818
0.546
1.13
PCNB
0.858
0.017
9.25
1.39
0.441
1.77
2.44
0.677
0.009
...
1.60
1.72
PCP
0.634
0.078
6.30
0.551
0.212
0.618
1.45
0.530
0.008

2.52
1.76
Captan HCB PCNB PCP Captan HCB PCHB PCP Captan
0.165 0.904 0.369 0.119 0.002 95.26 43.01 18.77 1.09
0.094
0.396 1.36 1.08 1.01 0.004 51.52 11.68 16.03 1.01
0.181 0.530 0.146 0.046 0.0 90.75 10.50 8.35 0.0
0.069 0.156 0.042 0.035 0.028 68.42 9.52 16.51 40.58
0.470 3.85 0.511 0.022 0.053 94.13 28.87 3.56 11.28
0.299 0.286 0.973 0.541 0.019 82.42 39.88 37.31 6.35
0.119 2.27 0.051 0.037 0.002 78.82 7.53 6.98 1.68
0.003 0.0008 0.0002 0.001 <0.0001 47.06 1.71 ^ 8.14 0.10
0.701 '•• ••' •" 85.70 "• . "•
0.025 0.319 0.350 0.046 0.048 58.42 21.88 1.83 5.82
0.378 0.420 0.171 0.779 0.021 37.17 9.94 44.26 5.56
                     a/  Ecosystems contained Drummer silty clay loam

                     b_/  Total l^C-fungicidal residues only;  percent
soil;    C-fungicides were applied to the soil on Day 0.

extractable parent compound was not determined.

-------
 DDT*

 DIELDRIN


 METHOXYCHLOR*

 ALDRIN

 FONOFOS


 ALDRIN
 DIELDRIN
(No corn
germinated)
 PENTACHLORONITROBENZENE,,
 PENTACHLOROPHENOL
 PARATHION'
METHYL PARATHION*
CAPTAN
        Substrate:
         V - venniculite
         S - silty  clay loam soil:
                    a
Animals;
Air; *Postemergent
      application;    10%
Fig. 79 . — Environmental distributions of the total   C-pesticidal residues (% of
         the"applied dose)  at  the termination of the terrestrial phase of various
         model ecosystems dosed with a given pesticide.  The plants, having been
         consumed and/or demolished by the animals, are not present as an entity
         at the termination of the system.  (Calculations and more detailed
         distributions are presented in the text.)
                                   253

-------
       0.030
       0.027
       0.024
    B
    o.
    o.
    oi   0.021
    0)
    u
    
-------
    2.50
     0.00
                                      Days Postplanting
                                  14,
Fig. 81 .  —Translocations of total   C-pestic±dal residues from soil to air during
          3-hour daylight trapping periods.  In the PCNB and captan systems, pesti-
          cide was applied to the soil on Day 0 (equivalent to 1.25 ppm).  In the
          parathlon system, pesticide was applied to corn foliage on Day 10.
                                        255

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           SOIL
PENTACHLORONITROBENZENE
PENTACHLOROPHENOL
                            * * * • •
PARATHION
METHYL PARATHION
                                               • • • •
CAPTAN
                          • *•••••••»«
                         • ••••••••••
                          • •••••••••I
          SEDIMENT
PARATHION
METHYL PARATHION
                                                                       • • • I
             Extr^ctable  parent
             compound;
Extractable
metabolites;
Unextractable
products
                                                                        10%
Fig.  82.—Proportions  (%) of extractable parent compound, extractable metabolites,
         and unextractable products detected in the  total l^C-pesticidal residues
         in soil and  sediment.
                                    256

-------
Ln
               0 100
               0 075
i 0.050
E
               0 023
                     Ca
                            AIR
                            nay 5
                           PCP

                                    IHCB

                                     1
                                     •
                10.0
               S
               H
               8
               J
                 2.3
                      CORN
                     (Z maye)
                      Day 14
                           PCP
                       Cap
                            JL
                                             1.23
                                             0.94
                                             0.63
                                             0.31
                                              4.0
                                              3.0
                                              2.0
                                              i.o
                                            SOIL
                                        (alley clay loan)
                                            Day 28
                                                            ,v™
                                                        PCP
                                                                    A"
                                                                  HCB
 Cap

1
                                         CATERPILLARS
                                           IE  aarea)
                                            Day 15
                                                             PCNB

                                                                            "
                                                                            3.0
                                                                            2.0
                                                                            1.0
                                                                           4.0
                                                                            3 0
                                                                            2.0

    VOLES
I'M. oohrogaeter)
    Day 20
                                                                                    HCB

                                                                                    I
                                                                                       PCP

                                                                                                           4.0
                                                                                                           3.0
                                                                                                           2.0
                                                                                                           1 0
                                                                                         Md
                                                                                        1
                                                                                                                            HCB
                                                            PILLBUGS
                                                           (A.  oulgare)
                                                             Day 15
                                                                                                                         PCNB
                               il
                                                                   HCB


                                                           —
                                                           I
 £. maxunue)
   Day 15
                                                                                                          4 0
                                                                                                          3.0
                                                                                                          2.0
                                                                                                          1.0
                                                                                           PCHB
      PCP   •   HCB
 %   m   I   n
                                                             EARTHWORMS
                                                             (L. terrestne)
                                                                Day 15
                                                                                                                                   Aid
I
                                                                   PCP
                                                                   1        n

   Fig.
                     83. — Total    C-pesticidal residues  (black bars)  and  parent  compounds (white  bars) in the components
                           of terrestrial model ecosystems  at the  indicated postplanting  periods.   The silty clay loam soil
                           in each  system was treated at planting  with a single pesticide at a rate simulating one Ib AI/
                           acre.  Invertebrate animals were added  to the systems  at Day 10,  and the voles  at Day  15.  All
                           animals  were analyzed after a 5-day exposure within the systems,  and the plants after  14 days.

-------
ro
m
oo
             c
             o
S
o
               0.009
               0.008
               0.007
               0.006
               0.005
             2 0.004
             0 0.003
               0.002
               0.001
                       PCNB
                       WATER
                                        PCP
                                Dield
                        Cap
                              HCB
                                             FISH
                                             (G.  affinis)
                                                                               Dield
                                                                    I
                                                                     PCNB
                                                             PCP
SNAILS
(Physa ep)
Dield

 I
                                                                                                             PCP
                                                                              -  Cap
              Pig. 84 .— Total l^C-pesticidal residues  (black bars)  and parent compounds (white bars) in the aquatic
                        phase of a soil-terrestrial model ecosystem treated with [14c]dieldrin compared with those
                        treated with fungicides.  The barren terrestrial  phases were flooded 20 days after dosing the
                        --oils.  The snails were added at i.he time of flooding, and the fish were added 4 days later;
                        water, fish and snails were analysed 7 days postflooding.

-------
        8, 5
        a
        o
        
-------
 DIELDRIN

 DDT
                          -f^^r .^r J^T ^^r .^r- ^J^J^J
                          ;  .^r ,^r  ^r ^r ^ V^v^vC
 PARATHION
 METHOXYCHLOR
 PENTACHLORONITROBESZEWE
 PENTACHLOROPHENOL
 ALDRIN
 ETHYL  PARATHION
 FONOFOS
            Extractable parent
            compound;
Extractable
metabolites;
Unextrac table
products
j^ »[
Fig. 86 . — Mean proportions (%) of extractable parent compound, extractable
         metabolites, and unextractable products detected in the total l^C-
         pesticidal residues in terrestrial animals as averaged over 5 species
          (earthworms, slugs, pillbugs9 caterpillars, and voles) from terrestrial
         model ecosystems; only the dieldrin residue was predominately parent
         compound.  (Degradation within each species and the nature of the
         metabolites is described in the text.)
                                     260

-------
      1
      o.
      o
      g
      u
      o
      o
Fig.
     87
         1.0
         0.9
         0.8
         0.7
         0.6
         0.5
         0.4
         0.3
         0.2
         0.1
     VOLES FROM

     SYSTEMS CONTAINING

    -SILTY CLAY LOAM SOIL
              *Postemergent application
c
Tt
M

t-t
V
                        o

                        I
                        o.
                        o
                        o
                        W
                        u

                        H
            J=
            U
            CO

            CO
            Pu
                  11.9
                                                          3.6
                   3.2
                                                          2.8
                                                2.4
                                                2.0
                                                          1.6
                                                1.2
                                                0.8
                                                0.4
                   VOLES FROM

                   SYSTEMS

                   CONTAINING

                   VERMICULITE
                        14
•Accumulations of total   C-pesticidal residues  (black bars)  and  parent  compounds
 (white bars), in'voles (entire body) from modeJ,  ecosystems  containing  either  a

 vermiculite substrate or a silty clay loam soil.  The voles  were analyzed after
 a 5-day exposure within a given model ecosystem.  Each  system was dosed with a
 single pesticide at a rate simulating one Ib Al/acre; the  mode of application

 was either preemergent to substrate or postemergent  to  foliage,  as indicated.
 No corn germinated in the soil system treated with dieldrin;  the system was

 drenched with water instead ot normal sprinkling.
                                           261

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DIELDRIN


DDT


METHOXYCHLOR


PENTACHLORONITROBENZENE


PENTACHLOROPHENOL


ALDRIN


PARATHION


CAPTAN


METHYL PARATHION


FONOFOS
             Extractable parent
             compound;
Extractable
metabolites:
Imextractable
products
                                                                           10%
    88 •"" Proportions  (%) of extractable parent compound, extractable metabolites,
         and unextractable products detected in the total 1/*C-pesticidal  residues
         in the  entire vole body.   Oesradation within individual vole  orsans and
         ttie nature of tae metabolites is described in the text.)
                                     262

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 DDT


 DIELDRIN  w


 DIELDRIN  (s)


 ALDRIN  (s)


 ALDRIN  w


 HG  (soybeans)


 HCB  (corn)
 SIMAZfNE

 2,14,5-T  (iaooctyl ester)


 PRORATE  (sand)


 TRIFLURALIN


^PHORATE  (s)         ,    -


 CAPTAN


 METHOKYCHLOR

 PCNB


 PCP


 P/VRATHION


 RETH?L PARATHION  '   • '

• •*••*••*•••••*<
»*•***•••••*•••
*•••••*«••••••!
• •••••*••*•*•••
         QBZJ Skin
         I5(f3 (washed.),

.•ermiculite;    S !
D     Other orpins,
     especially liver;

•  soil
                                                                          10%
                                                          Gastrointestinal
                                                          tract + contents
                                                          (•approxiaate where
                                                            indicated).
 Fi9-89  —Proportions- (%)  of the  total 14C-pesticidal residue (jjg)  detected in
           the entire vole  located in- various organs.  These are distributions
           of sc'tuaj. quantities, not concentrations.  The carcass is the body
           m&nus i*ts viscera and skin;  it Consists predominately of muscle and
           bone   (Detailed distributions are described in the text  and are
           compared with the relative masses of the organs.)
                                         263

-------
    D.
    c
    o
    c
    HI
    u
    o
    o
        0.8
        0.7
        0.6
        0.5
        0.4
        0.3
        0.2
        0.1
               VOLES FROM
               SYSTEMS CONTAINING
               SILTY CLAY LOAM SOIL
             " *Postemergent application
11.4
                                                        3.6
                                                        3.2
 2.8
 2.4
 2.0
 1.6
 1.2
 0.8
                                                        0.4
VOLES FROM
SYSTEMS
CONTAINING
VERMICULITE
*
I

I
                   I
Fig. 90-—Accumulations of total "C-pesticidal residues (black bars) and parent com-
          pounds (white bars) in voles (carcass) from model ecosystems containing
          either a vermiculite substrate or a silty clay loam soil.  The voles were
          analyzed after a 5-day exposure within a given model ecosystem.  Each system
          was dosed with a single pesticide at a rate simulating one Ib Al/acre; the
          mode of application was either preemergent to substrate or postemergent to
          foliage, as indicated.  No corn germinated in the soil system treated with
          dieldrin; the system was drenched with water instead of the normal sprinklin
                                          264

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 DIELDRIN
 PARATHION
 PENTACHLOROPHENOL
 PENTACHLORONITROBEN2ENE
DDT
METHYL  PARATHION


METHOXYCHLOR


CAPTAN
ALDRIN
           Extractable parent
           compound;
Extractable
metabolites;
^7*3 Unextractable
!•!«! products
10%
Fig. 91 .— Proportions  (%) of extractable parent compound,  extractable metabolites,
          and unextractable products detected in the total  l^C-pesticidal residues
          in the vole carcass.  The carcass is the body minus its viscera and skin;
          it consists predominately of muscle and bone.  (Degradation within other
          vole organs and the nature of the metabolites is  described in the text.)
                                      265

-------
                                       *
                                       o
 I
 (X
 c
 o
 C
 0)
 u
 c
     44
     40
     24
20
     16
     12
      CORN IN
      SYSTEMS CONTAINING
      SILTY CLAY LOAM
      SOIL
                                 CO
                                 C-
                                 4J
                                 a)
                 o
                 a
                 c.
                 o
                      TICTTLITF
                                                    * Poster^ergdnt  application
                                                      to  foliage
                                                                                u
                                                                                o
                                                                           (U
24
76
6
94
98
2
99!
i :
                                  14
Fig.92 .—Concentrations of total   C-pesticidal  residues (black bars) and
         parent compounds  (white  bars)  in entire corn plants 14 days
         postplanting, and the proportions (%)  of the residues (ug, not
         concentration) located in shoots and roots.  Postemergent applica-
         tions directly to corn toliage were made 10 days postplanting,  and
         preemergent applications to  soil were conducted at the time of
         planting.  Each system was dosed with a single pesticide at a rate
         simulating one Ib Al/acre.
                                    266

-------
 METHOXYCHLOR*
 DDT'
                                                         '•'••••••••••••••••••••'p
 METHYL PARATHION
 DIELDRIN


 ALDRIN


 FONOFOS
     IN
PENTACHLOROPHENOL
PENTACHLORONITROBENZENE
       IExtractable parent
       conpou:-*!':
Extractable
metabolites;
                                10%

•^Unextractable *Posteinergent  foliage
  products;      application
    Sh » corn shoots; P' * corn roots; V » vermiculite; S * silty clay loam soil.

Fig.93 .—Proportions (%) of extractable parent  compound, extractable metabolites,
         and unextractable products detected in the total ^C-pesticidal residues
         from corn shoots and rootsv  Plan-ts dosed by post emergent application
         were analyzed 4 days after dosing,  and plants from systems treated with
         a preemergent soil application were analyzed 14 days after dosing.
                                      267

-------
    METHOXYCHLOR
   DDT
    PARATHION*
    METHYL PARATHION
   DIELDRIN
   ALDRIN
 V
   FONOFOS
   ALDRIN
   PENTACHLOROPHENOL
   PENTACHLORONITROBENZENE   s
   CAPTAN
                                                                            10%
          Extractable
          parent compound;

         venniculite; S «= silty clay loam soil.
Extractable
metabolites;
Unextractable
products;
*Postemergent
 foliage
 application
Fig. 94 .—Proportions (%)  of  extractable parent compound, extractable metabolites, and
         unextractable products detected in the total  ^C-pesticidal residues  from
         entire corn plants  from terrestrial model  ecosystems.  Plants dosed by post-
         emergent application were analyzed 4 days  after dosing, and plants from
     ,    systems treated  with a preemergent soil application were analyzed 14  days
         after dosing.

                                       268

-------
    25
    20
 S
 a.
 o.
 e
 o
6
a
o
    15
    10
             CORN  ROOTS
               (Z.  mays)
                Day  14
25
20
15
                           a.
                           u
10
         CORN SHOOTS
           CZ. wot/sj  '
            Day 14
                                                                            O-i
                                                                            CJ
                                                                            P-.
Fig. 95".—Total   C-pesticidal residues (black bars) and parent compounds (white
         bars) in corn roots and shoots 14 days after treating, at the time of
         planting, the silty clay loam soil in each system with a single pesti-
         cide at a rate simulating one Ib Al/acre.
                                         269

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                          MATERIALS AND METHODS

MODEL ECOSYSTEM DESCRIPTION

     The basic ecosystem unit was a 19-liter wide-mouth glass carboy 46 cm
high with a base diameter of 26 cm.  The metal lid, which was on the carboy
only when air was being trapped, was equipped with inlet and outlet stain-
less steel tubing to periodically monitor pesticide vapors in air, and a
plastic stopcock containing a copper wire-mesh filter was added at the base
of the carboy to sample leachates.  Each carboy contained either 400 g of
vermiculite (Terra-Lite, W. R. Grace and Co., Cambridge, Mass.) or 3000 g
of Drummer silty clay loam soil (Particle diameter 2.4-4.8 mm).  Fifty corn
seeds (Zea mays, Pioneer Hi-Bred 3334A, Pioneer Hi-Bred International, Inc.,
St. Joseph, 111.) were planted in each ecosystem carboy at a depth of 1 cm.
Vermiculite ecosystems were sprinkled with two liters, and soil ecosystems
with one liter, of standard reference water (Freeman 1953) containing
the following concentrations of salts, in ppm:  MgSO^, 34.6; K2S04, 6.5;
MnS04, 0.135; CaCl2, 14.0; NaHCOs 25: NfyNOs, 3.0; K.2HP04, 0.84; CaC03,
57.5; Na2Si03, 26.9; and FeCl3} 0-72, at a final pH of 7.9.  Each ecosystem
was weighed after planting and initial watering, and again 7 and 14 days
later at which times enough distilled water (ca. 600—700 ml) was added
with a sprinkler to restore the initial wet weight of the system, thus
simulating two rains and compensating for the evaporation of water.  Both
the vermiculite and the soil, when used in conjunction with the standard
reference water, provided satisfactory mineral nutrition and texture for
the growth of corn, cotton and soybeans.  Both substrate-water combinations
also sufficiently supported, for the duration of the experiments, the
various invertebrate and vertebrate animals added during the terrestrial
phase of the ecosystems.  Furthermore, both substrates readily permitted
extraction and determination of radiolabeled components.  Flooding the
ecosystem with 7 liters of standard reference water on Day 20 provided
sufficient mineral nutrition to maintain the various aquatic organisms for
the duration of the aquatic phase.

     The ecosystem units were housed in a 244 x 132 x 198-cm walk-in
environmental growth chamber (PGW 36, Controlled Environments, Pembina,
N. Dak.) which was operated at the following parameters: Light/dark phase,
12:12 hours; continuous air circulation; day air temperature, 26°C;
night air temperature, 19°C; day substrate temperature, 24-26°C; night
substrate temperature 20-21°C; relative humidity, 50%; light intensity at
substrate surface, 1000 foot-candles.  The individual ecosystem carboys
were open (covered with nylon mesh screening) to the surrounding "controlled
environment" during most of the 27-day experimental period.  They were
semi-closed only during the hours when air was being trapped.  (The
semi-closed state accounted for only 2.8% of the total experimental time
in those ecosystems with preemergent pesticide applications, and only 2.3%
of the total time in those ecosystems with postemergent application.)
                                    270

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MODEL  ECOSYSTEM OPERATION

     For  preemergent  application of  the  pesticide,  a  total of  5 rag of radio-
labeled compound in one  ml of  acetone was  injected  (20 pi per  injection)  at
a  depth of  one  cm into the substrate immediately  beneath each  of the  50
uniformly dispersed corn seeds at the time of  planting (Day 0).  For  post-
emergent  application  of  the pesticide, a total of 5 mg of radiolabeled
compound  in one ml of acetone  was applied  to the  surface of each leaf of  each
corn plant  (20  ji per plant) on Day  10 postplanting.   The 5-mg rate of
application for the 545-cm2 growth area  of the model  ecosystem corresponds
to about  one pound of active ingredient  (AI) per  acre for 1.12 kg/ha),
thus simulating the commonly used treatment rate  in the field.  For each
type of application,  a control ecosystem unit  similarly planted with  corn
seeds  and  maintained under the same conditions as  the experimental unit
was teated  with acetone  alone.

     The  ecosystems were maintained  for  a  total of  27 days, the first 20
days as the terrestrial  phase  and the last; 7 days as  the aquatic phase
(Figs. 96 and 97);  several pesticides were investigated using  only the
terrestrial phase.  In the preemergeat application  (Day 0) ecosystems,
air was sampled for '3 daylight hours on  Days 0, 1,  2,  5, 11 and 19, and
two corn  plants were  removed for analysis  on Days 6,  10 and 14.  In the
postemergent application (Day  10) ecosystem, air  was  sampled for three
daylight  hours  on Days 10,  11,  12, 15 and  19,  and three corn plants were
removed for analysis  on  Days 12 and  14.  In all ecosystems, invertebrate
animals   usually 20 pillbugs and 10  each of the caterpillars,  slugs and
earthworms)  were added on Day  10' (after  corn plant-sampling or  after pes,ticide
application).   Three  of  each type of invertebrate animals were  removed for
analysis  on Day 15  (after air.sampling,  if applicable).  The-vole was
added  to  the ecosystem on Day  15, supplied with a cup of fresh water  daily,
and removed for analysis on Day 20.  Any readily  visible plant shoots and
invertebrate animals  remaining in the terrestrial phase were removed  on
Day 20 and  discarded; the Substrate  was  then mixed  well and sampled for
analysis* ^  After substrate sampling  on Day 20r the  ecosystem was flooded
with 7 liters of standard reference  water, and 50 snails,  about 300
'mosquito  larvae and about 300  daphnia were added;  the latter two organisms
were supplied primarily  to serve as  food for the  fish.   The surface water
was mixed slightly  and sampled for radioactive content daily.   Three  fish
were added  on Day 24  (4  days after flooding) and  removed for analysis on
Day 27; snails,  any algae,  and any remaining daphnia  were also removed
for analysis on Day 27.   One liter of surface  water and, if desired,  one
liter  of  leachate were collected for analysis  on  Day  27.  The  remaining
surface water was decanted from the  ecosystem  and discarded.   In earlier
ecosystems,  the wet sediment was left in the ecosystem container for  5
days and  then mixed and  sampled for  analysis.   In more recent  ecosystems,
the wet sediment was  sampled on Day  28.
                                     271

-------
K>
               Plant
               seeds
                                       Add
                                  invertebrates
    Sample
invertebrates;
   add vole
  Analyze vole;
     remove
   remaining
     plants
  and animals;
     s.imple
   substrate
      Analyze flshk
      snails, algae
      and daphnia;
Add      sample   Sample
fish    leachate sediment
                                   Sample air
                                                                                                                                 or
           Day 0-1-2-3-4-5-6-7-8-9 -10-11-12-13-14-15-16-17-18-19-20-21-22-23-24-25-26-27-28	32
Apply
pesticide
to
substrate;
add water
                                                 Sample plants
                                          Add
                                         water
  Add
 water
                                               Terrestrial Phase
                                                                                    Sample surface water
     Flood
   ecosystem;
  add  nails,
mosquito larvae
  and daphnia
            Decant
            water
                                                                                        Aquatic Phase
                    Fig. 96.  Time  sequence  for  the model ecosystem  (preemergent pesticide application)

-------
    Plant
    seeds
             Add
        invertebrates
        Sample
    invertebrates;
       add  vole
  Analyze vole;
     remove
   remaining
     plants
  and animals;
     sample
   substrate
      Analyze fish,
      snails, algae
      and daplmia;
Add      sample   Sample
fish    leacliate sediment
                                                 Sample air
                                            Ml
                                                                                       or
    Add
    water
 Add        Apply
water     pesticide
         , to plants
    J
Sample-
plants
      Add
     water
                                    Terrestrial Phase
                                                                                    I   I    I    I   I   I    II
           Sample surface water

     Flood                       Decant
   ecosystem;                    water
  add snails,
mosquito larvae
  and dapltnia
                                                              Aquatic  Phase
Day 0-1-2-3-4-5-6-7-8-9 -10-11-12-13-U-15-16-17-18-19-20-21-22-23-24-25-26-27-28	32
        Fig. 97 .  Time sequence for the model ecosystem (postemergent  pesticide  application)

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MODEL ECOSYSTEM ORGANISMS

     Miarotu£ ochrogaster (Wagner), the prairie vole, was selected as the
apex of the food web of the model ecosystem because voles ("field mice")
are possibly the most abundant mammals in the world, and the praicie vole
is particularly abundant in the central portion of the United States.
Jameson (1947) states that the activities of voles, especially those of the
genus Microtus, attracted the attention of Aristotle, who wrote:  "The
rate of propagation of field mice in country places, and the destruction
that they caus"e, are all beyond telling.  In many places their number is
so incalculable that very little of the corn crop is left to the farmer..."
The voles utilized in the ecosystems were from a laboratory colony derived
from wild animals captured in Illinois.  The animals were bedded on cleaned,
processed and unground rice hulls (J. B. Hunt Co., Stuttgart, Ark.) and
Pel-I-Cel Pelleted Corn Cob Laboratory Animal Waste Absorbent (Paxton
Processing Co., Inc., Paxton, 111.) in standard metal mouse cages,, and
maintained on a diet consisting of Purina Laboratory Rabbit Chow Checkers
(Ralston Purina Co., St. Louis, Mo.).  The vole is present in the model
ecosystem during the terminal 5 days of the terrestrial phase, and at the
end of this period, it not uncommon to find that many of the other or-
ganisms of the system have been consumed.  In those systems containing corn,
the first food preference of the vole appears to be corn, and the garden
slugs appear to be the least palatable.

     Estigmene acrea (Drury), the saltmarsh caterpillar, was chosen
principally because of the considerable amount of information available
in our laboratory regarding its ability to metabolize a variety of pesticides.
It is the insect component of the model ecosystem, and thus represents the
reportedly most abundant form of terrestrial life in nature.  The early
fifth instar larvae are active feeders on all of the crops that have been
tested in the model ecosystem.  The caterpillars were reared in 1-oz
plastic pill cups containing a synthetic diet modified from that of
Vail et al. (1967) by the addition of sorbic acid, cholesterol, wheat
germ oil, linolenic acid and inositol.

     L-imax maximus L. 3 a garden slug representing the phylum mollusca, was
chosen because it is the most hardy of the slugs tested from the surrounding
agricultural area.  In abundance of species, mollusks comprise the largest
invertebrate phylum aside from the arthropods.  The animals were success-
fully maintained at 15°C in 8-inch-tall round or rectangular glass battery
jars containing 3-4 cm of sand and covered with perforated aluminum foil.
The sand was moistened with distilled water and sprinkled with Purina
Dog Chow.  Jars were cleaned and the sand and food replaced twice weekly.

     Lumbriaus tevrestx^is L.,an earthworm belonging to the phylum
Annelida, was used in the model ecosystem because it is representative of
the abundant invertebrate fauna that lives predominately beneath the soil
surface.  They were successfully maintained at 15°C in a large porous wooden
box containing 3-4 inches of rehydrated Buss Bed-ding (Buss Manufacturing
Co.,Lanarck, 111.).  The bedding was kept moist with distilled water.  Each
cubic foot of bedding was sufficient to support 150 small worms or 50 large
worms.
                                     274

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     Armad-il'Lidium vulgare  (Latretlle) is one of the pillbugs, which  are
the only terrestrial representatives of the crustaceans.  Pillbugs  possess
several similarities to the Insecta including a chitinous exoskeleton and
problems of maintaining water balance during the elimination of nitrogenous
metabolic wastes.  Evaluation of the metabolic potential and the  tendency
for pesticides to accumulate in pillbugs will provide valuable information
for comparison to the data already available on the interactions  of pesti-
cides in insects.  They were maintained at 21°C and 70% relative  humidity
in plastic cake boxes (perforated lids) containing 2-3 cm of a moistened
mixture of soil, gravel and wood chips, and were fed sweet alyssum
(Lobularia maritima  (L.) Desv.) and small pieces of potato tuber.

     The following organisms were used in the aquatic phase of the  model
ecosystem: Daphnia magna (water flea), Culex pipiens quinquefaaeiatus
(mosquito larva), Physa sp. (snail) and G
-------
     phorate j),0-diethyl _S-(2-ethylthio)-methyl phosphorodithionate [CH_-  C]



       (9.7 mCi/tnmol)-A


                               14
     hexachlorobenzene [ring U-  Cj (20- mCi/mmol)-N



     pentachlorophenol [ring-D-  C] (14.05 mCi/mmol~N


                                     14
     pentachloronitrobenzene [ring U-  C (14.5 mCi/mmol)-N



     captan N- (trichlorornethylthio-4-cyclohexane-l, 2-dicarboxlmide



       [14C-C13] (23.8 mCi/mmol)-n


                                                             14
     simazine 2-chloro-4,6-(ethylamino)-syrn-triazine [ring D-  C]



       (18.27 mCi/mmol)-n



     trifluralin 1? ,N-dipropyl-2,6-dinitro-4,trifluromethylaniline



       [ring U-14C] (15.16 mCi/mmol)-N


                                                                         14
     2,4,5-T isoctyl ester isoctyl 2,4,5-trichlorophenoxyacetate [ring-U-  C]



       (11.81 mCi/mmol-N



     Before application to the model ecosystems, the radiolabeled chemicals



were adjusted to the following specific activities:



                                                   dpm/ g    mCi/mmol



     DDT                                           22,163      3.54



     methoxychlor                                  10,340      1.61



     aldrin                                        18,851      3.10



     dieldrin                                      21,263      3.68



     parathion                                     31,736      4.16



     methyl parathion                              47,258      5.60



     fonofos                                       24,366      2.70



     phorate                                       72,150      8.45



     hexachlorobenzene                             41,518      5.33



     pentachlorophenol                             21,238      2.55



     pentachloronitrobenzene                       32,463      4.32




    code A - Amersham Corp., M = Malinckrodt  Chemical Works, N = New  England

    Nuclear Corp.,  S = synthesized by Dr.  J.  R.  Sanborn.



                                    276

-------
     captan                                        22,063      2.99

     simazine                                      44,179      4.00

     trlfluralin                                   46,751      7.05

     2,4,5-T isooctyl ester                        42,156      6.95

 SUBSTRATE ANALYS-JS

     Substrates analyzed by this procedure included soil or vermiculite
 sampled on Day 20 of the ecosystem, and soil or vermiculite sediment sampled
 on Day 28 or 32, after the aquatic phase  (8 or 12 days after flooding the
 ecosystem and 1 or 5 days after removing  the surface water).  The substrate
was thoroughly mixed with a spatula and three random 100-g samples taken.
One sample was stored in the refrigerator in an air-tight container for
 future use, if necessary; the second was placed in a 130°C oven for dry
weight determination, the third sample was analyzed for radioactive
components according to the following procedure (Fig. 98).

     Repeated comparisons of Soxhlet extraction of a soil sample with 500
ml of acetone for a 24-hour period, followed by a similar extraction with
 500 ml of methanol, with the homogenization-filtration procedure outlined
below indicated that the latter was a more efficient procedure.  The sample
was homogenized with 200 ml of acetone in a 200-ml Sorvall Omni-Mixer cup
at Setting 6 for 15 minutes.  The cup was kept on ice during the procedure.
The homogenate plus two 20-ml acetone'rinses of the cup were suction-
filtered through Whatman No. 2 filter paper in a Buchner funnel at full
bench vacuum.  The filter cake was rinsed twice, each with 20 ml of
acetone, and the total acetone filtrate retained for further processing.
The filter cake was then returned to the Omni-Mixer cup, 200 ml of
absolute methanol added and the homogenization and filtration procedures
repeated, with appropriate methanol rinses.  The total methanol filtrate
was retained for further processing.  In earlier ecosystems, the filter
 cake was discarded without further analysis.  In more recent ecosystems,
 the filter cake was dried to constant weight and aliquots were combusted in
a Packard Tri-Carb Sample Oxidizer in order to determine the unextractable
radioactive content.

    ..The -acetone and methanol filtrates  (extracts) were transferred, with
appropriate rinses of the filtration flasks, to 250-ml volumetric flasks,
made up t'o' the volume mark" with the appropriate solvent, and mixed thoroughly.
Triplicate 0.1-ml samples of the acetone extract and L.0-ml samples of the
methanol extract were added to scintillation vials containing Aquasol
 (Universal L.S.Ck Cocktail, New England Nuclear, Boston, Mass.) in order
to determine the radioactive content.

     The acetone extract was then transferred to a 1-liter separatory funnel
along with 400 ml of diethyl ether and -a. few grams (5-6) of sodium
bisulfite.  The residual acetone extract was rinsed out of the volumetric
 flask with portions of the ether.  The separatory funnel was shaken well,
                                   277

-------
                              Substrate - 100 g
                                        Homogenize in large
                                        Sorvall Qnsni—Mixer cup
                                        with 200 ml acetone;
                                        suction-filter, with
                                        cup rinses
              I
          Filtrate
                              Filter cake
                Sample for radio-
                activity;   add a
                few grams  sodium
                bisulfite;  extract
                with 400 ml ether
                                     Homogenize in ilarge
                                     Sorvall Omni-Mixer
                                     cup with 200 ml
                                     methanol;  suction-
                                     filter, with cup
                                     rinses
Acetone/ether
    phase
 Water
 phase
Filtrate
Filter cake
        Sample
        for radio-
        activity;
        concen-
        trate
     Sample
     for radio-
     activity
      Sample for
      radioactivity;
      concentrate
        Dry to
        constant
        weight
     TLC
Discard
    Auto-
 radiography
                                           TLC
                      Auto-
                   radiography
                   Combust to
                    determine
                   "unextract-
                    able 14C"
Fig. 98 .  Substrate analysis procedure  (vermiculite/soil/sediaent)
                                       278

-------
accompanied by frequent venting, and the water phase permitted  to  settle out.
The water phase was collected, the volume measured, and  triplicate
1.0-ml samples added to Aquasol vials.  The water phase  was  then discarded.
The volume of the acetone/ether phase  (extract) was measured, and  triplicate
0.2 or 0.5-ml samples were added to Aquasol vials.

     The acetone/ether and methanol extracts were concentrated  individually
to small volumes in a rotary evaporator.  The evaporation  flask contents were
then transferred, with appropriate rinses, to 15-ml screw-capped centrifuge
tubes for final concentration under a  stream of nitrogen.  Samples of  the
concentrated extracts were analyzed by means of thin-layer chromatography
and autoradiography.

AIR TRAPPING AND ANALYSIS

     The ecosystem carboy was fitted with a metal lid  containing two pieces
of stainless steel tubing, the inlet tubing projecting into  the carboy about
28 cm (ending about 10 cm above the surface of the substrate in the terrestrial
phase), and the outlet tubing projecting into the carboy only about 4  cm.
The inlet tubing was connected by means of silicone rubber tubing  to a
needle valve which in turn was connected to a Silent Giant aquarium pump
(Aquarium Pump Supply, Inc., Prescott, Ariz.), providing a slight  positive
pressure within the carboy.  The outlet tubing was attached  by  means of a
short piece of silicone rubber tubing  to the first of  two  gas traps which
were connected in series and terminated with a flow meter.   (The vapor
trap preceding the two gas.traps shown .in the illustration (Fig. 1)
was not routinely used in these experiments; it was used only in con-
comitant studies involving long-term gas trapping.)  The gas traps consisted
of 125-ml gas washing bottles fitted with teflon joint sleeves  and standard
taper tops containing glass tubing which terminated in fritted  glass
cylinders of extra coarse porosity.  The two bottles were mounted in
4-liter Dewar flasks packed with crushed ice.  The first trap (closest
to the ecosystem carboy) contained 75  ml of either acetonitrile of a mixture
of 2-methoxyphenol and ethanolamine (2:1 by volume), and the second trap
contained 75 ml of the aforementioned  mixture.  The air  was  routinely
trapped for a three-hour daylight period at a flow rate  of 10 ml/sec
on Days 0, 1, 2-, 5, 11 and 19 of those ecosystems which  had  received
preemergent application  (Day 0) of the pesticide to the  substrate, and
on Days 10, 11, 12, 15 and 19 of those ecosystems in which the  pesticide
had been applied to the corn foliage (postemergent) on Day 10.

     Following each trapping period (Fig- 9S)» the tubing  between  the
ecosystem carboy and Trap 1 was rinsed with fresh Trap 1 solvent and the
rinse added to Trap 1.  Similarly, the tubing between  Trap 1 and Trap  2
was rinsed with fresh Trap 2 solvent and the rinse added to  Trap 2.
The contents of each trap were mixed thoroughly, the volume  measured,
and triplicate 1.0-ml samples added to scintillation vials containing
Aquasol in order to determine the level of radioactivity.
                                    279

-------
                                Aquarium pump
                                Ecosystem jar
                                   Trap 1
                       (75 ml acetonitrile or mixture*- }
               Rinse tubing
               and trapping
               bottle with
               fresh trap-
               ping solvent
                      Trap 2
                  (75 ml mixture^)
                                 Flow meter
                                 (10 ml/sec)
Aceto-
nitrile
or
Mixture
     Sample for
     radioactivity;
     concentrate
  TLC
 Auto-
radiog-
 raphy
                Sample for
                radioactivity;
                extract with
                hexane 2 x 50 ml
         Rinse tubing and
         trapping bottle
         with fresh trap-
         ping solvent;
         sample for
         radioactivity;
         extract with
         hexane 2 x 50 ml
                                                Hexane
                                                extract
                                                    Mixture
                                                     phase
 Hexane
 extract
            I
         Mixture
          phase
                   Sample
                   for radio-
                   activity;
                   concentrate
                        Sample
                        for radio-
                        activity
Sample
for radio-
activity ;
concentrate
Sample
for
radio-
activity
                           TLC
            Discard
                TLC
                   Discard
                                                 Auto-
                                              radiography
               Auto-
            radiography
 a/  2-methoxyethanol : ethanolamine,  2:1 by volume
 Fig.99 .   Air  trapping and analysis procedure
                                        280

-------
     Where acetonitrile was the trapping solvent, the acetonitrile after
trapping was evaporated to a small volume in a rotary evaporator.  The
evaporation flask contents were then transferred, with ether rinses, to a
15-ml screw-capped centrifuge tube for final concentration under a stream
of nitrogen.  Samples qf the concentrate were analyzed by means of
thin-layer chromatography and autoradiography.

     Where the mixture was the trapping solvent, the mixture after trapping
was transferred to a 250-ml separatory funnel and extracted two times,
each with 50 ml of hexane.  The hexane extracts were combined, the volume
measured, and triplicate 1.0-ml samples added to vials containing dioxane-
based scintillation fluid.  The extract was concentrated as usual and
analyzed by Tieans of thin-layer chromatography-autoradiography.  The
mixture phase was collected, the volume measured, and triplicate 1.0-ml
samples added to Aquasol vials.  The remainder of the mixture phase was
discarded.

WATER ANALYSIS

     Daily, after gentle stirring of the surface water, triplicate 1.0-ml
samples were withdrawn and added to scintillation vials containing Aquasol
in order to determine radioactive content.  On Day 27 of the ecosystem
(7 days after flooding), one liter of surface water was withdrawn and
analyzed by the procedure outlined below (Fig. 100).  For selected eco-
systems, one liter of leachate was drained from the bottom of the ecosystem
on Day 27 and also analyzed by the following procedure.

     The water was transferred to a 2-liter separatory funnel and extracted
three times, each with 250 ml of diethyl ether  (or chloroform if the
pesticide was insoluble in the ether).  The ether extracts were combined,
the volume measured, and triplicate 1.0-ml samples added to scintillation
vials containing dioxane.-based scintillation fluid-  The ether extract
was retained for further processing.

     The water phase was collected, the volume measured, and triplicate
1.0-ml samples added to Aquasol vials.  The water was then transferred
to a 2-liter standard taper Erlenmeyer flask, followed by 1 ml of
concentrated hydrochloric acid (= final concentration of 0.012 N, pH 0.2)
and a magnetic stirring bar.  The flask was fitted with a Snyder column
and heated at 556-56°C, with stirring, for 18-24 hours in order to hydrolyze
conjugated compounds present in the water.  After the hydrolysis period,
the water was cooled to''room temperature, the volume measured, and triplicate
1.0-ml samples added to Aquasol vials.

     The hydrolyzed water was then transferred to a 2-liter separatory
funnel and extracted with ether (or chloroform) as before.  The ether
extracts were combined, the volume measured, and triplicate 1.0-ml samples
added to vials containing dioxane-based fluid.  The ether extract was
retained for further processing.  The water phase was collected, the
volume measured, and triplicate 1.0-ml samples added to Aquasol vials.
The remainder of the water phase was discarded.
                                   281

-------
                              Water - 1 liter
                                       Sample for radioactivity;
                                       extract with ether 3 x  250 ml
         Ether extract
Water phase
                 Sample for
                 radioactivity;
                 concentrate
              TLC
             Auto-
          radiography
                                       I
                                 Ether extract
       Sample for radioactivity;
       add 1 ml cone. HC1  (=*•
       0.012N);  hydrolyze 18-24
       hours at 55-56°C;  sample
       for radioactivity;  ex-
       tract with ether 3 x
       250 ml
              1
          Water phase
                                         Sample
                                         for radio-
                                         activity ;
                                         concentrate
                 Sample for
                 radioactivity
                                      TLC
           Discard
                                     Auto-
                                  radiography
Fig.100.  water analysis procedure (surface water/leachate)
                                       282

-------
     The two  ether  extracts, before  and after  hydrolysis, were  concentrated
 Individually  to small volumes  in a rotary  evaporator.   The  evaporation
 flask  contents were then  transferred, with appropriate  rinses,  to  15-ml
 screw-capped  centrifuge tubes  for final concentration under a stream of
 nitrogen.   Samples  of the concentrated extracts were  analyzed by means of
 thin-layer  chromatography and  autoradiography.

 CORN ANALYSIS

     Two corn plants were removed from the substrate on Days 6, 10 and 14
 of those ecosystems which had  received preemergent application  (Day 0)
 of the pesticide  to the substrate, and three plants  were removed on Days
 12 and 14 of  those  ecosystems  in which the pesticide had been applied to
 the corn foliage  (postemergent) on Day 10.  Care was taken  to retain the
 maximum portion of  the root system of each plant.  Roots were rinsed
 free of adhering  substrate and blotted dry.  The plant  was  severed
 at the crown, and the root and shoot portions  weighed.   Root and shoot
 portions were processed individually (Fig. 101).  Any readily visible
 plant  shoots  still  present at  the end of the terrestrial phase  (Day 20)
 were removed  and  discarded.

     The sample was cut into small pieces  and  homogenized with  10  ml of
 acetone in  a  50-ml  Sorvall Omni-Mixer cup  at Setting 6  for  5 minutes.
 The homogenate was  transferred to a  15-ml  screw-capped  graduated centrifuge
 tube,  along with  a  5-ml rinse  of the cup,  and  centrifuged in a  clinical
 centrifuge  at medium speed for 5 minutes.  The supernatant  was  transferred
 to a, 25-ml  graduated cylinder.  The  pellet was resuspended  in 5 ml of
 acetone, mixed well, and  again centrifuged.  This supernatant was  combined
 with the first supernatant and mixed well, the volume was measured,  and
 triplicate  0.1 or 0.2-ml  samples were added to scintillation vials
 containing  Aquasol  in order to determine radioactive content.   The
 supernatant (extract) was retained for further processing.

....   The centrifuge tube  containing  the pellet (residue) was rotated so
 that the contents coated  the lower walls of the tube.   The  residue was
 permitted to  air-dry, and was  then pulverized  with a pointed spatula or a
 glass  rod.  A small amount (about 0.5 ml)  of distilled  water was added
 to saturate the residue,  followed by 3 ml  of Protosol (Tissue and  Gel
 Sol'ubilizer,  New  England  Nuclear, Boston,  Mass.).  The  tube contents
 were thoroughly mixed by  vortexing and/or  with a glass  rod.  The tube
 was tightly capped  and incubated in  a 50°C .water bath for 48 hours with
 shaking; at least once during  the incubation period  the tube contents
 were'again  thoroughly mixed.   The dissolved residue  was then diluted to
 10 ml  with  Aquasol  and mixed well.   Triplicate 0.1 or 0.2-ml or other
 appropriate-size  samples  were  added  to Aquasol vials; when  a 0.5 or 1.0-m
 sample was  used,  0.05 or  0.1 ml of glacial acetic a'c-i'd  was  added in order
 to neutralize the vial contents and  minimize chemiluminescence.
 The remainder of  the diluted residue was discarded.
                                   283

-------
                                   Plant
                                      Rinse off adhering substrate;
                                      blot dry;  sever at crown;
                                      weigh shoot and root
                   Shoot
                                        Root
                       - - -Process  separately-
                                               .J
                                      Cut into small pieces;  homogenize in
                                      small Sorvall Omni-Mixer cup with 10 ml
                                      acetone;  centrifuge, with cup rinses
 Supernatant
        Sample for
        radioactivity;
        concentrate
     TLC
    Auto-
 radiography
                                Pellet
                 Combine
Re suspend in 5 ml acetone;
mix well;  centrifuge
                                Supernatant
                                          Pellet
                                               Air-dry; pulverize;
                                               add few drops water
                                               and 3 ml Protosol;
                                               mix well;  incubate
                                               at 50°C 48 hours
                                               with shaking;
                                               dilute to 10 ml
                                               with Aguasol;
                                               sample for radio-
                                               activity
                                                   Discard
Fig.
    101
Plant analysis procedure
                                      284

-------
     The acetone extract was concentrated to a small volume in a rotary
evaporator.  The evaporation flask contents were then transferred, with
acetone and ether rinses, to a 15-ml screw-capped centrifuge tube for
final concentration under a stream of nitrogen.  Samples of the concentrated
extract were analyzed by means of thin-layer chromatography and auto-
radiography.

 INVERTEBRATE ANIMALS ANALYSIS

     Organisms analyzed by this procedure (Fig. 102) included pillbugs,
slugs, caterpillars and earthworms.  These animals had been added to the
ecosystem on Day 10 (during the terrestrial phase).  Representative live
specimens (usually three of each type of animal) were removed 5 days
later for analysis; any invertebrate animals still present in the ecosystem
on Day 20 were removed and discarded.  Slugs, caterpillars and earthworms
were processed individually, and pillbugs either individually or in
batches of three.  If necessary, earthworms and slugs were rinsed free of
adhering substrate and blotted dry.  The animals were weighed and then
frozen.

     The organism was minced into small pieces and homogenized, a few
pieces added at a time, in a glass tissue grinder with a 8 ml (small
organism - pillbug, caterpillar) or 10 ml (large organism - slug, earthworm)
of acetone.  The homogenate was transferred to a 15-ml screw-capped graduated
centrifuge tube, along with a 3 or 5-ml rinse of the grinder, and centrifuged
in a clinical centrifuge at medium speed for 10 minutes.  The supernatant
was transferred to -either -another graduated centrifuge tube (small
organism) or a 25-ml graduated cylinder (large organism).  The pellet
was resuspended in 4 or 5 ml of acetone, mixed well, and again centrifuged.
This supernatant was combined with the first supernatant and mixed well.
In the case of the large organisms, the pellet wash was repeated if the
supernatant was still highly colored (yellow).  The supernatant volume
was measured, and triplicate 0.1 or 0.2-ml samples were added to scintilla-
tion vials containing Aquasol in order to determine radioactive content.
The supernatant (extract) was concentrated and analyzed by the same procedure
used for corn extracts.

     The centrifuge tube containing the pellet (residue)was rotated so that
the contents coated the lower walls of the tube.  The residue was permitted
to air-dry, and was "then pulverized with a pointed spatula or a glass rod.
Each small organism residue was processed en toto.  For the large organisms,
however, the total weight of the pulverized residue was recorded; triplicate
100-mg samples were weighed out and processed individually.  The residues
were processed by the same procedure used for corn residues except that
only 2 ml of Protosol were added to each tube.

VOLE ANALYSIS

     The prairie vole, which had been added to the ecosystem on Day 15,
was removed from the ecosysteraon Day 20, the end of the terrestrial phase,
and sacrificed by ether inhalation.  The animal was weighed, washed under
running tap water, rinsed in a water-acetone mixture, and air-dried
(Fig. 103.) After removal of the skin, the following internal organs and
                                    285

-------
                                 Organism
                                       Rinse off adhering substrate, if
                                       necessary;  blot dry;  weigh;  freeze
                              Frozen organism
                                       Mince into small pieces;  homogenize
                                       in glass tissue grinder with 8-10 ml
                                       acetone;  centrifuge, with grinder
                                       rinses
Supernatant
        Sample for
        radioactivity;
        concentrate
     TLC
    Auto-
 radiography
                Pellet
Combine
Resuspend in 4-5 ml acetone;
mix well;  centrifuge
                                 Supernatant
                          Pellet
                    Repeat pellet wash
                      if supernatant
                       still colored
                                                          Air-dry;  pulverize;
                                                          if large  pellet,  re-
                                                          cord total weight
                                                          and then  weigh out
                                                          100-rog samples; add
                                                          few drops water and
                                                          2 ml Protosol;  mix
                                                          well;  incubate at
                                                          50°C 48 hours with
                                                          shaking;   dilute to
                                                          10 ml with Aguasol;
                                                          sample for radio-
                                                          activity
                                                    Discard
Fig. 102.  Invertebrate animal analysis procedure (pillbugs/slugs/caterpillars/
          pupae/earthworms)
                                      286

-------
                                                       Vole
                  I
         Frozen snail organs
       (ProcBS* indlviduilly or
       in various combinations)
                                                           Sacrifice;  weli'h;  wa«h.
                                                           rlnoc;  dry  dissect;
                                                           vclph organs;  freeze orpans
                                              I
                                    Frozen tkln, carcass

                                    (Process indlvlduilly)
     I  r—
Supernatant
       for radio-
       activity,
       conceit-
       trite
    TLC
   Auto-   %
rrtdloi-rapiy
                    Mince into snail
                    hot-ioKPnLze in ~l*os tissue
                    "rindur with 3-10 ml acetone;
                    centrifuge, with
                    Tinaen
Pulloc
                                                         Supocnatant
                    Con! ino
     Rcsuspend in
     A-S ol acetone;
     nix well.
     centrifuge
                   Su|>cro3tant
                                       I
                                    Pellet
                                    repeat
                                    pellet
                                   wash if
                                 supernatant
                                    still
                                   colored
Saraplo
(or radio
activity;
concen-
trate
                           Preparative
                               TLC
                          
-------
tissues were dissected from the animal, weighed individually, and frozen:
brain; heart; lungs; liver; kidneys and adrenal glands; uterus and ovaries;
gastrointestinal tract and contents, abdominal, pectoral and uterine
adipose tissues, when present; mammary, parotid, and ventral central neck
glands.  The skin and carcass were weighed individually and then frozen. * •

     Individual internal organs were homogenized and analyzed by the same
procedure used for small invertebrate animals; when several 'internal' organs
were combined to be processed en masse, the procedure for large inverte-
brate animals was used.  The skin and carcass were processed'individually
as follows.  The sample was cut into small pieces with scissors or a razor
blade and then homogenized with 100 ml of acetone in a 200-ml Sorvall
Omni-Mixer cup at Setting 6 for 15 minutes (the skin pieces did not fully
homogenize).  The homogenate was transferred to five 30-ml Corex centrifuge
tubes, along with two 10-ml rinses of the cup, and centrifuged in a
Sorvall RC2-B centrifuge at 12,000 rpm for 10 minutes.  The supernatants
were transferred to a 250-ml graduated cylinder.  The pellets were combined
into two tubes, resuspended in 15 ml of acetone each, mixed well, and again
centrifuged.  These supernatants were combined with the first supernatants
and mixed well.  In the case of the carcass, the pellet wash was repeated
if the supernatants were still highly colored (yellow).  The supernatant
volume was measured, and triplicate 0.1 or 2-ml samples were added to
scintillation vials containing Aquasol in order to determine radioactive
content.  The supernatant (extract) was retained for further processing.

     The two pellets for each sample were permitted to air-dry and were
then combined and weighed.  Combined carcass pellets were pulverized with
a mortar and pestle, and triplicate 100-mg samples weighed out.  Skin •
pellets consisted of loose hair and small pieces of intact skin; triplicate
representative 100-mg samples were weighed out.  The residues were processed
by the same procedure used for corn residues except that only 2 ml of
Protosol were added to each tube.

     Each acetone extract was concentrated to a small volume in a rotary
evaporator.  The evaporation flask contents were then  transferredt with
acetone and other rinses, to a 15-ml screw-capped centrifuge tube ^or final
concentration under a stream of nitrogen.  At this stage, both the carcass
extract and the skin extract were largely oil; the oil layer in each case
contained essentially all of the radioactivity.  The bulk of the radio-
activity was recovered from the oil layer by means of  preparative thin-layer
chromatography on silica gel-impregnated glass fiber sheets  (ITLC-SG,
20x20 cm sheets, Gelman Instrument Co., Ann Arbor, Mich.) using acetonitrile
as the developing solvent.  The total non-oily area between the origin and
the solvent front of each sheet was cut into small squares and the
radioactive components eluted by leaching with about 40 ml of acetone
containing about 1% water, followed by an acetone rinse.  Elutes and rinses
from replicate sheets were combined and centrifuged to remove suspended
silica gel particles.  The resulting carcass and skin  supernatants  (extracts)
were concentrated and analyzed by the same prodedure used for corn extracts.
                                    288

-------
AQUATIC ORGANISM ANALYSIS

     Organisms analyzed by this procedure  (Fig. 104) included fish, snails,
daphnia and algae.  They were removed from the ecosystem on Day 27, the
end of the aquatic phase, the fish after a 3-day exposure, and the other
organisms after a 7-day exposure.  The three fish were processed individually,
the snails in hatches of 15, the daphnia en iuasse as a single sample,
and the algae as a single sample.  Fish and snails were blotted dry and
then weighed; daphnia and algae were suction-filtered to damp dryness and
then weighed.  If organisms could not be processed immediately, they were
frozen.

     The organism was minced into small pieces (necessary only for fish)
and homogenized in a glass tissue grinder  with 8 ml of acetone.  The
homogenate was transferred to a 15-ml screw-capped graduated centrifuge
tube, along with a 5-ml rinse of the grinder, and centrifuged in a clinical
centrifuge at medium speed for 10 minutes.  The supernatant was transferred
to a 25-ml graduated cylinder.  The pellet was resuspended in 5 ml of
acetone, mixed well, and again centrifuged.  This supernatant was combined
with the first supernatant and mixed well; the volume was measured,
and triplicate 0-1 or 0.2-ml samples were  added to scintillation vials
containing Aquasol in order to determine radioactive content.  The super-
natant (extract) was concentrated and analyzed by the same procedure used
for corn extracts.

     The pellets (residues) were processed by the same procedure used for
corn residues except'that only 2 ml of Protosol were added to each tube.

RADIOACTIVITY MEASUREMENTS

     The radioactive content of samples was measured by liquid scintillation
counting in a Packard Model'3320 Tri-Carb  Liquid Scintillation Spectrometer.
Aquasol was used for counting samples dissolved in aqueous or polar organic
solvents.  Samples dissolved in nonpolar organic solvents were counted in
a dioxane-based cocktail of the following  compositions naphthalene, 120 g;
p-bis-[2-(5-pheny1-oxazolyl)] benzene (POPOP), 0.05 g; 2,5-diphenyloxazole
(PPO), 7.0 g; and 1,4-dioxane, 1 liter.  All samples were counted for 10-
minute periods.  All counts were corrected for background and counting
efficiency.

THIN-LAYER CHROMATOGRAPHY AND AUTORADIOGRAPHY

     Thin-layer chromatographic analyses were carried out using 20x20-cm
and occasionally 5x20-cm glass plates coated with 0.25 or 0.5-mm-thick
layers of Silica Gel GF-254 (E. Merck, Darmstadt, Germany).  The plates
were activated in a 100° oven for one hour and stored in a desiccator box
until used.
                                    289

-------
                                 Organism
           (Process fish individually, other organisms • in batches)
                                       Blot dry or suction-filter
                                       damp-dry;  weigh;  freeze if
                                       not processed immediately
                         Fresh or frozen organism
                                       Mince into small pieces, if
                                       necessary;  homogenize in
                                       glass tissue grinder with
                                       8 ml acetone;  centrifuge,
                                       with grinder rinses
Supernatant
        Sample for
        radioactivity;
        concentrate
     TLC
    Auto-
 radiography
               Pellet
Combine
Resuspend in 5 ml
acetone;  roue well;
centrifuge
                                 Supernatant
                          Pellet
                                                          Air-dry; pulverize;
                                                          add few drops water
                                                          and 2 ml Protosol;
                                                          mix well;  incubate
                                                          at 50°C 48 hours
                                                          with shaking;
                                                          dilute to 10 ml
                                                          with Aguasol;
                                                          sample for radio-
                                                          activity
                                                    Discard
Fig. 104.  Aquatic organism analysis procedure (fish/snails/daphnia/algae)
                                        290

-------
     In most  cases, a.  sufficient quantity  of  concentrated  extract was
applied to assure  the  presence  of  at  least 10,000  dpm in the  spot.   If  the
extract contained  less than this quantity  of  radioactivity, the  total or
some fraction of the extract was applied so as  to  maximize the quantity
of radioactivity present  in the spot  without  overloading the  spot with
extract material.  Extract  samples were co-chromatographed with  authentic
unlabeled parent compound and any  available metabolites  of the parent
compound.  These unlabeled  compounds  were  also  spotted in  a separate lane
on each plate.  A  delimiting solvent  front line was marked 15 cm above
the orign on  each  plate.

     The following solvent  systems were employed for  development of  the
chroma to grams:

         DDT:  n-hexane:diethyl  ether  (24:1 by volume)

         Methoxychlor:  petroleum  etheridiethyl ether (17:3 by volume)

         Fonofosi  carbon tetrachloride:ethyl acetate (1:1 by volume),

           preferably  n^hexane:chloroform;  (4:1  by  volume), used  for  corn

         Aldrin, dieldrin:  ia-hexane:diethyl ether  (3:2 by  volume)

         Pentachlorophenol:  benzene :n_-hexane: acetic  acid  (18:1:1 by volume)

         Parathion, methyl  parathion, pentachloronitrobenzene, captan:      -  '

           dlethyl ether:n-hexane  (7:3 by  volume)

         Phorate,  simagine;  benzene:acetone  (4:1  by  volume)

         Trifluralin,  2,4,5-T isooctyl ester:   n-hexane:acetone  (10:1 by volume)

     Following total evaporation of the solvent from  the plates, the plates
were set with 8x10-inch sheets  of  x-ray film  (Kodak Blue Brand film, BB-5,
•Eastman Kodak Co., Rochester, N.Y.) for a  period of 2  weeks if the initial
spot contained at  least 10,000  dpm, or increasing  lengths  of  time if the
spots contained lower  levels of radioactivity.  Following  the exposure
period, the films  were developed (Kokak Liquid  X-ray Developer and Replenisher),
fixed (Kodak  Rapid Fixer  with Hardener), washed with  tap water,  and  air-dried.
The resulting autoradiograms were  traced,  and the  tracing  outlines stippled
onto the chromatograms  by means of a  dissecting needle.  The  chromatograms
were examined under short-wave  ultraviolet light for  the location of
authentic compound spots  (UV-absorbing against  the fluorescent background).
Coincidence of the authentic compound spots with the outlined spots  was
coasldered sufficient  for tentative identification of  the  radiolabeled
(outlined) spots»  . The outlined spots were scraped into  scintillation vials
containing dioxane-based  scintillation fluid  in order  to determine radioactive
ftontent.
                                      291

-------
 COST ANALYSIS  OF MATERIALS AND METHODS

     The terrestrial model ecosystems developed under this Contract were
designed for; operation in any reasonably well equipped biological laboratory.
Thereforej the design has been kept as simple as possible with especial
emphasis on the development of compact units that can be handled
economically in standard controlled environmental chamber equipment with
high intensity fluorescent lighting for plant, growth.  The most economical
sized chambers for routine work using the terrestrial model ecosystem
would appear to be the approximately 200 cubic* foot models such as
Sherer Gillette CEL 37-14 or Percival PT-80.  These are equipped to
maintain temperatures within + 2°F, under programmed conditions^and are
provided with light intensities of 5000 foot candles.  Units of this size
can handle 6 of the terrestrial model ecosystems simultaneously.   Their
cost is about $5000 each.  Larger walk-in environmental plant growth
chambers costing $8000-$10,000 can provide space for 10-12 terrestrial
model ecosystems with somewhat more convenience in working space.  Such
units are routinely used in almost every biological laboratory and. have a
life-time of many years.  Therefore, we have not included their price
in this Cost Analysis.

     Similarly, the provision of laboratory facilities for rearing the
test animals and for working up the information from each individual
terrestrial model ecosystm, using extraction, thin-layer chromatography,
radioautography and liquid scintillation counting involves standard
laboratory equipment.  Therefore, we have not included these facilities
in our Cost Analysis.

RADIOLABELED PESTICIDES

     These were provided by the Environmental Protection Agency specifi-
cally for the studies made under the "Substitute Chemicals Program."  The
individual cost is not known to us but can be estimated from comparable
prices by commercial suppliers.  The average cost of the following
l^C Labeled pesticides selected from the manufacturers catalogues I/:
aldrin, dieldrin, DDT, lindane, 2,4-D, hexachlorobenzene, paraquat, and
nicotine was $472 for 250 microcuries.  This quantity of radioactivity is
sufficient to treat 4 to 8 model ecosystems.  Therefore, the average cost
of the radiolabeled pesticide is estimated at $100 per individual ecosystem.
Custom syntheses of new materials is somewhat more expensive but these are
almost always available through the manufacturer who uses them routinely
in satisfying pesticide registration requirements.
—   Amersham Corp. 1978-79, New England Nuclear Corp. 1978
                                292

-------
MODEL ECOSYSTEM UNITS

     The costs involved with the basic terrestrial model ecosystem units
are outlined in Table 166.  These, averaged for the 22 terrestrial model
ecosystems as developed, were $8.03 per individual model ecosystem.

ECOSYSTEM BIOTA

     The costs involved in operating the  terrestrial model ecosystems
including the plants and animals are very modest and are indicated in
Table 166.  These averaged $1.34 per individual ecosystem.

CHEMICALS AND SUPPLIES

     The costs of the chemicals and supplies utilized for the basic
ecosystem units are itemized in Table 167.  These averaged $135.41 per
individual model ecosystem.

REARING SUPPLIES

     The costs of the dietary materials and supplies and in rearing the
various animals utilized in the model ecosystem units, i.e. isopod, slug,
salt marsh caterpillar, vole, mosquito larva, fish, etc. are itemized in
Table 168.  These averaged $12.18 per individual model ecosystem.

MISCELLANEOUS CONSUMABLE SUPPLIES

  -  - The costs of miscellaneous items involved in evaluating ttie results
of the model ecosystem studies, e.g. TLC plates, X-ray film for radio-
autography, chemicals for trapping volatiles, etc. are itemized in Table
^69.  These averaged $22.70 per individual model ecosystem.

TOTAL COST OF INDIVIDUAL MODEL ECOSYSTEM EVALUATION

Based on the itemization in Tables 166-169 and calculated as the average
cost of the 22 model ecosystems run under this Contract the following
cost is obtained for each individual model ecosystem determination.

     radiolabeled compound                  $100.00
     model ecosystem unit                      8.03
     biota                                     1.34
     chemicals                               135.41
     rearing supplies                         12.18
     miscellaneous consumable supplies        25.70

                          Total             $282.66

This figure does not include labor or depreciation of standard laboratory
equipment.
                                 293

-------
          Table 166.   Costs of Terrestrial Model Ecosystem Units
NJ
vO
*-
         A.
         B.
Expected



Eros>stera inic
1. Glass cjrbo>, 19-liter, wide-mouth,
'«ith metal screw-on lid
2. Stainless °teel tubing, 7.5 mm
ID x 3/8 OD
3. Silver solder
4. Neoprene '0 ring gasket, 13 cm OD
5. Polyeth>lene twistcock tap
6. Cooper raes'.i screening, 1" x 2"
7. Vinyl tubii-g, 1/2" ID x 1/8" wall
8. Silicone cement
9. Kylon itesh fabric, coarse, 8" x 8"
10. Rubber band, 1/8' x 2-1/2"
Ecosystem unit contents (excluding
animals)
1. Venalculite
or
Drcioirer silty clay loam soil
or
Bloonuield loamy sand
2. Corn seeds
or
Soybean seeds
3. Distilled water
4. Plastic cup, 2-oz
5. Tap water
Animals
1. PillbJg
2. Saltmarsh caterpillar
3. G?ide.i slug
4. Esrthwomi
5. Prairie vole
6. Snail
7 . Daphnia
8. Mosquito larvae
9. Mosquito fish
Quantity
per eco-
system

1

30'1

2g
1
1
1
2 cm
1/10 tube
1
6


400 g
or
3000 g
or
3000 g
50
or
50
2.1
3
60 ml

20
10
10
10
1
50
300
300
3
cost
per
Purchase Unit initial
unit price ecosystem

ea 9.00

ft 1.50


9.00

4.50

oz 12.00 12.00
ea .40
ea .75
sq. ft. 3.00
5 ft .96
tube 2 . 00
yd .59
1/4 Ib box .40


24 Ib bag 9.49

Collected free

Collected free
Free from seed company

Free from seed company
No charge
500/pkg 5.00
No charge

Collected free
Maintained in colony
Collected free
doz .75
Maintained in colony
Maintained in Indoor pond
Maintained in indoor pond
Maintained in insectory
Maintained in aquarium
.40
.75
3.00
.96
2.00
.59
.40


9.49








5.00





.75





Actual
cost per
initial
ecosystem

9.00

4.50

12.00
.40
.75
3.00
.96
2.00
.59
.40


9.49








5.00





.75





Expected
cost per
22 eco-
sys terns

144.00

4.50

12.00
4.80
3.75
3.00
.96
2.00
1.18
.40

'
9.49








5.00
•




15.00





Actual
cost per
22 eco-
systems

144.00

4.50

12.00
4.80
3.75
3.00
.96
2.00
1.18
.40


9.49








5.00





15.00






-------
        Table 167.  Costs of Laboratory Chemicals for Terrestrial Model Ecosystems
in
            Chemicals
            1.
            2.
            3.
            4.
            5.
            6.
            7.
            8.
            $.
           10.
           11.
           12.
           13.
           14.
           15.
           16.
K2S04
        7H,0
CaCla . 2H20
NaHCO}
           17.
           18.
           19.
           20.
           21.
           2i.
           23.
           24,
           25.
           i'».
           27.
           28.
           29.
           30.
           31.
           32.
        .  3H20
CaO
Ha2Si03 . 9H20
FeClj . 6HjO
Distilled water
Acetone, bulk technical
Acetone, reagent grade
Kcthanol-
Etaer (diethyl)
Hexane
  or '
Benrene
  or
Chloroform
  or-
Petroleum ether
  or
£' hyl acetate
Ethanol
Sodiun bisulfite
Iodine crystals
Cone. HC1
Glacial acetic acid
Protosol
(14c) Toluene standard
Dioxnne
PI'fJ
)•!« 01'
Nii>l tlali-nc
Aqucsol
Drierite desiccant  (indicating)
Dekasol  radioactive decontatalnant
Sod'um dichronate
Cone, sulfuric acid,  technical
Quantity
per eco-
system
639 mg
58.5 mg
1.8 mg
167.4 og
225 mg
27 mg
9.9 mg
289.8 rag
563.4 mg
10.8 mg
8 1
3 gal
2 1.
1 1.
4 1.
1 1.
or
1 1.
or
1 1.
or
1 1.
or
1 1.
SO ml
10 g
100 g
2 ml
100 ml
100 ml
5 ml
JO I.
70 g
•"> R
1.2 kg
3 1.
1 Ib
50 ml
2.5 Ib
15 btls

Purchase
unit
Ib
Ib
Itf
Ib
Ib
Ib
Ib
Ib
Ib
iV
No charge
5 gal
gal
gal
12 x 1 Ib
qt

Pt,
*
pt >

gal^.
*
Pt
pt-
Ib ^
Ib "-
6 Ib btl
5 Ib brl
500 ml -btl
10 ml
gal
100 8
j a
2.5 Ib
4-1. bti
Ib
qt
5 Ib
10 Ib btl

Unit
price
2.03
1.93
2.03
1.98
.97
1.66
1.68
1.35
5.00
2.24

11.75
4.04
4.46
22.05
3.28

.88

1.53

4.1Q

2.02
.94
2.27
9.97
2.86
8.16
57.00
25.00
14.49
16.80
5.f>0
8.46
45.00
2.71
6.00
5.02
.43
Expected
cost per
initial
ecosystem
2.03
1.93
2.03
1.98
.97
1.66
1.68
Io35
5.00
2,24
11.75
4.04
4.46
22.05
Actual
cost per
initial
ecosytem










11.75
4.04
4.46
22.05
Expected
cost per
22 eco-
sys terns
2.03
1.93
2.03
1.98
. .97
1.66
1.68
1.35
5.00
2.24
164.50
48.48
31.22
264.50
Actual
cost per
22 eco-
systems










164.50
48.48
31.22
264.50
                                                                                       avg.3.25
                                                                             .94
                                                                            2.27
                                                                            9.97
                                                                            2.86
                                                                            8.16
                                                                           57.00
                                                                           25.00
                                                                           43.47
                                                                           16.80
                                                                            •>.(>0
                                                                            8.46
                                                                           45.00
                                                                            2.71
                                                                            6.00
                                                                            5.02
                                                                            6.02
                                                                                         3.25
  .94
 2.27
 9.97
 2.86
 8.16
57.00

43.47
16.80
 5.60
 8.46
45.00
 2.71
 6.00
 5.02
 6.02
          71.50
  1.88
  2.27
  9.97
  2.86
  8.16
171.00
 25.00
883.89
268.80
 lf>.BO
186.12
765.00
  8.12
  6.00
 10.04
 12.04
             71.50
  1.88
  2.27
  9.97
  2.86
  8.16
171.00

883.89
268.80
 H>.80
186.12
765.00
  8.13
  6.00
 10.04
 12.04

-------
Tabla 168.  Costs of Rearing Supplies for Terrestrial Model Ecosystem
Quantity
per eco-
system
Teed di°t components
1 .
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
J6.
17.
18.
19.
20.
21.
22.
23.
24
25.
26.
honey
Is p water
Ijar
Casein, vitamin free
Alfalfa meal
Sucrose
Hheit germ
Wesson's salts
Alphacel
KOH
Vanderzant vitamin mixture
Sorbic acid
Methyl p-hydroxy benzoate
Ascorbic acid
Aureomycin
Cholesterol
Choline chloride
Wheat germ oil
Lxnolenic acid, technical
Inesitol
Fornaldehyde (37*)
Sweet alyssum
Dog chow
Fnbbit chow
Kouse chow
Tropical 'ish food
.4
760
12.
32
14
24
27
9
4.
1
9
1.
1.
3.
.
.
1
1.
.
.
1
8
ml
5 g
g
g
g
8
g
5 g
g
g
7 8
^ e
3 g
25 g
6 8
g
8 Lll
5 ml
6 g
ml
2 plants
1
5
5
.
Ib
Ib
Ib
25 oz
Purchase Unit
unit price

Ib
No charge
Ib
5 Ib
10 Ib
1 Ib
5 Ib
5 Ib
5 Ib
1 Ib
1 kg
200 «
100 g
50 g
5 g
25 g
200 g
Ib
250 g
100 g
Pt
Maintained
5 Ib
50 Ib
50 Ib
2 oz

1

11
10
5
1
t>
7
4
1
24
2
3
1
11
2
2
4
5
3


.09

.00
.95
.00
.89
.00
.30
.29
.21
.08
.50
.21
.75
.25
.44
.11
.35
.20
.00
.92
Expected
cost per
Initial
ecosystem

1

11
10
5
1
4
7
4
1
24
2
3
1
11
2
2
4
5
3


.09

.00
.95
.00
.89
.00
.30
.29
.21
.08
.50
.21
.75
.25
.44
.11
.35
.20
.00
.92
Actual Expected
cost per cost per
initial 22 eco-
ecosystem systems

1.

22.
10.
5.
5.
4.
7.
4.
1.
24.
2.
3.
5.
22.
2.
2.
4.
5.
3.
.

09

00
95
00
67
00
30
29
21
08
50
21
25
50
44
11
35
20 •
00
92
Actual
cost per
22 eco-
systems

t




















in greenhouse
1
6
11
2
.46
.78
.97
.89
1
6
11
2
.46
.78
.97
.89
1.46 • 1.
6.78 13.
11.97 23.
2.89 14.
46
56
94
45
1.46
13.56
23.94
14.45
Rearing supplies
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Moist newspaper
Cedar rhips
Crave]
Plastic pill cup, 1-oz
Cardboard lid for pill cup
Pill cup tray
Cotton dental wick
Ccllucotton circle, 8 inch diara
Brown wrapping paper, 15' x 600 ft
Fine nylon mesh, 10" x 10"
Cardboard ice cream carton w/lid, gal
Sand
Distilled water
Aluminum foil, 12" x 10 Ib
3
1
2
35
35
1
2
1
2
1
. 1
5
3
slits
cup
cups





ft


Ib
cups
ft
No charge
25 Ib
Collected
5000/pkg
1000/pkg
C.I
1000/box
300 ft rl
600 ft rl
yd
50/cs
100 Ib
No chge
10 Ib

3

.64

3

.64

3.64 3.

64

3.64
free
35
2

6
12
6
3
15
2
12
.50
.00
.50
.56
.94
.35
.00
.54
.24 '
.82
35
2
1
6
.50
.00
.00
.56
Included
6
3
15
.35
.00
.54
Inlcuded
Included
35.
2.
5.
6.
under III, fl. 8
6.
3.
15.
under I. D. 11
under I. D. 13
50
00
00
56

35
00
54













-------
Table 169.  Miscellaneous Consumable Supplies Specifically Required
1.   Acetonlcrlle
2.   Ethanolamlne
3.   4-Me thoxyphenol
4.   Silica gel Impregnated TLC
     plates, 20 cm*
5.   Silica gel GF-254
6.   Combustion cones for Packard
     oxldlzer
7.   X-ray film 8"xlO"
8.   X-ray developer
9.   X-ray fixer
10.  Sand
11.  Aluminum foil. 12" wide
12.  Vinyl tubing 1/8' ID x 1/16" wall
13.  Sillcone tubing 3/16" ID x 3/32" wall
14.  Teflon joint sleeve
15.  Wooden applicators

Quantity
per eco-
system
600 ml
150 ml
300 ml
8
100 g
10
12
1 qt
1 qt
5 Ib
2 ft
3 ft
8 in
2
5 dot


Purchase
unit
1 gal
1 gal
7 Ib btl
25/pkg
500 e
1000/pkg
50/pkg
1 Sal
1 gal
100 Ib
10 Ib rl
10 ft
1 ft
6/pkg
72 doz/bx


Unit
price
12.04
14.60
8.35-
24.25
15.82
65.20
25.00
2.47
2.03
2.24
12.82
0.63
0.46
1/.50
1.91
Expected
cost per
initial
ecosystem
12.04
14.60
8.35
24.25
15.82
6S.20
25.00
2.47
2.08
2.24
12.82
0.63
0.46
14.50
1.91
Actual
cost per
initial
ecosystem
12.04
14.60
8.35
24.25
15.82
65.20
25.00
2.47
2.08
2.24
12.62
0.63
0.46
14.50
1.91
Expected
cost per
22 cco-
systems
48.16
14.60
16.70
145.50
47.46
65.20
IjO CO
1A..82
12.48
2.24
12.82
1.2S
1.38
29.00
3.82
Actual
cost per
22 eco-
systens
43.16
14.60
16.70
U5.50
47.46
65.20
150 00
14.32
12.48
2.24
12.82
1.26
1.'3
2<).00
3.82

-------
                    REFERENCES

Jameson, E.  Natural History of the Prarie Vole (Microtus).
     University of Kansas Museum, Pubs. Natural History, Vol. 1,
     No. 7 (1947).
Vail, P.V., T.J. Henneberry, and R. Pengalden.  An artificial diet
     for rearing salt marsh caterpillar, Estigmene acrea (Lepidoptera;
     Arctiidae), with notes on the biology of the species.
     Ann. Entomol. Soc. Amer. 60, 134 (1967).
                             298

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