oEPA
                              United States
                              Environmental Protection
                              Agency
                          Robert S. Kerr Environmental
                          Research Laboratory
                          Ada, OK 74820
                             Research and Development
                                         EPA/600/S-92/001 February 1992 •
ENVIRONMENTAL
RESEARCH  BRIEF
               Biodegradation of Atrazine in Subsurface Environments

                                 James L. Sinclair* and Tony R. Lee*
 Abstract

 The pesticide atrazine is frequently detected in ground water,
 including ground water used as drinking water. Little information
 is available on the fate of atrazine in the subsurface, including its
 biodegradability. The objectives of this study were to evaluate the
 biodegradability of atrazine under differing conditions (oxygen
 status, prior exposure to atrazine, subsurface sediment texture,
 unsaturated  and saturated zone sediments) that would be
 commonly encountered in the subsurface. Samples of soil and
 sediment were taken from a borehole drilled at a location beside
 a highway near Stratford, Oklahoma which had  received
 applications of atrazine annually for 12 years. A second borehole
 was drilled 66 feet away in a field that had not received atrazine
 applications.  Samples were taken  from different depths with
 respecttothewatertableandsedimenttypes. Core material from
 the boreholes was used to make microcosms to study atrazine
 biodegradation.  Microcosms from Stratford, OK sediment were
 incubated aerobically. A samplef rom the Norman, OK landfill was
 used to make microcosms that were incubated anaerobically.
 Identical microcosms that had been sterilized by autoclaving were
 used as controls to differentiate biodegradation from abiotic
 processes. Most or all of the atrazine spiked into active and sterile
 microcosms made of surface soil from both Stratford locations
 had disappeared by 105 days of incubation as determined by
 HPLC analysis.  No  disappearance of atrazine was observed in
 either the active or sterile treatment of any of the subsurface
samples from either Stratford borehole.  A small amount (3.8%)
of MC ring labeled atrazine was mineralized to "CO2 by 161 days
   ManTech Environmental Technology, Inc., Roberts. Kerr
   Environmental Research Laboratory, Ada, OK.
                     in the active treatment of the surface soil from the Stratford
                     roadside.  Little or no atrazine was mineralized to CO  in
                     microcosms of the surface soil from the Stratford field oMhe
                     subsurface samples from  either borehole.  A slow decline of
                     atrazine was noted in the active treatment of the Norman landfill
                     sediments that were incubated anaerobically. Therefore, some
                     decline of atrazine concentration was noted in anaerobic
                     subsurface microcosms of Norman landfill sediments, but no
                     decline was observed in the aerobic Stratford subsurface sediment
                     microcosms.  Factors  responsible for the lack of atrazine
                     degradation in the Stratford microcosms may have included the
                     usually small bacterial populations in these samples and the
                     resistant nature of atrazine.

                     introduction

                     Within the last decade,  there have been many reports of the
                     occurrence of pesticides in ground water (Younos and Weigmann,
                     1988). One of the pesticides which occurs most commonly in
                     ground water is atrazine. Because of health concerns, there is
                     interest in factors which would affect the occurrence and fate of
                     atrazine in ground water. Typically, when atrazine is found in the
                     subsurface it is present in concentrations of 0.3 to 3 ppb (Younos
                     and Weigmann, 1988), which is at least an order of magnitude
                     lower than levels commonly  found in surface runoff waters
                     (Thurman et al., 1991). The amounts of atrazine which occur in
                     the subsurface are controlled by factors which are discussed in
                     Cheng and Koskinen (1986) and Helling and Gish (1986).

                     Predicting the fate of atrazine in the subsurface is difficult because
                     little work on the behavior of atrazine has been done in the
                     subsurface or with samples of subsurface material. Mostworkon
                     atrazine degradation was done in the 1960s and 1970s and was

                                              ^gA) Printed on Recycled Paper

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dona either with surface soil, water or with pure cultures of
microorganisms.  These studies indicated that atrazine was
moderately resistant to degradation in surface soils although
degradation rates varied considerably in different soils (Skipper
and Volk, 1972; Roeth et al., 1969).  Enough atrazine often
survived into the next growing season so that inhibition of sensitive
plants occurred. Mineralization of atrazine to CO2 was found to
proceed very slowly with only a few percent of added atrazine
being mineralized in several months time  (Skipper and Volk,
1972, and Dao et al, 1979).

A limited number of studies have been done  on atrazine
biodegradation  in the subsurface.  Roeth et al. (1969) reported
that atrazine was degraded 2 to 3 times faster in surface soil than
In subsurface soil from 14 to 24 inches and 36 to 48 inches deep.
Lavy et al. (1973) found that phytotoxic amounts of atrazine were
gone after 5 months at 15 cm, 17 months at 40 cm, and were still
present after41 months at 90 cm after atrazine amended soil from
these depths was reburied at these same depths in a soil pit in
Nebraska Obenhuber (1988) reported that atrazine had a hatf-
lifo of 556 days in aerobic subsurface microcosms, and 2632 days
in anaerobic microcosms based on "CO2 data. This report also
demonstrated  that alternating  aerobic-anaerobic treatments
speeded up the rate of degradation. These studies suggest that
 atrazine degradation proceeds at a slower rate in the subsurface
than in surface soil. Recent work on microbial populations and
 activities in the subsurface has shown that microbial abundances
 (Sinclair and Ghiorse, 1989, Sinclair era/. 1990) and activities
 (Hicks and Fredrickson, 1989) differ between different sediment
 types. Thus, H is likely that pesticide biodegradation will proceed
 at different rates in different types of subsurface sediment.

 This study was designed to provide more information on the
 biodegradation of atrazine  in the subsurface.   The  specific
 objectives were to determine if atrazine biodegradation occurs in
 the subsurface, and if so, at what rates in different parts of the
 profile  and in different sediment types.

 Materials and Methods

 Sites and Sampling

 A search was conducted for a site where atrazine had been
 regularly applied and which had other desired characteristics.
 These features were that the site was reasonably level, had
 permeable sediments which would  permit rapid downward
 movement of  water, and had  a nearby  location with similar
 geology but had not received applications of atrazine, and was
 near Kerr Lab. The only site that met these selection criteria was
 the roadside by highway 177 which had been sprayed with
 atrazine, glyphosate and sulfometuron methyl once a year for
 weed control. Atrazine had been applied annuallyforapproximately
  12years. The location was 4.2 miles north of Stratford, OKon the
 west side of Highway 177. Surface soil collected January 2,1989
 from the roadside was found to contain atrazine. A drilling was
  conducted June 9,1989 at the roadside to evaluate whether this
  s'rte would be suitable for this study. The subsurface strata were
  determined to be permeable to water; the water table level was
  found to be somewhat deep but still at an acceptable level for the
  migration of atrazine to ground water (10.59 m); and samples
  were taken for atrazine analysis.  A drilling to obtain samples for
  experiments was conducted on July 25,1989 in the roadside and
  July 26, 1989, 66 feet west of the roadside borehole in a field
  where atrazine had not been applied.  Samples were taken from
a number of depths where sediments having different textures
were found.  Samples from each borehole that will be discussed
in this paper are the following:
      Description

      Surface
      Unsaturated
      Saturated
Roadside
Depth (m)

 0.0-  0.1
 4.2-  4.5
11.8-12.0
   Field
Depth (m)

 0.0- 0.1
 3.8- 4.1
12.0-12.3
The subsurface samples used in the anaerobic treatment were
from the Norman, OK landfill (Beeman and Suflita, 1990). A hole
was dug with a backhoe to below the water table (1.5 to 2.0 M
deep). Samples were scooped into jars from at or slightly below
thewatertable. Sediments were anaerobic at thiss'rte, and rapidly
reduced resazurin.

The average annual temperature in central Oklahoma (including
Stratford and Norman) is 16 to 17 °C. The temperature of shallow
sediments varies with the seasons, howeverthe deeper sediments
are the average annual temperature. Seasonal variations were
noted in the temperature of the Norman landfill sediments due to
their shallow depth (S.A. Gibson, personal communication).

 Microcosms

 Microcosms were set up by  aseptically  weighing out 10 g of
 sediment and transferring this to a steriie 60 ml serum bottle. The
 bottles were stoppered with sterile 1 cm thick butyl rubber stoppers.
 Sediments were adjusted to 30% water content with sterile Milli-
 Q water.  Sterile microcosms were made by autoclaving for 8
 hours at 122 °C, after which, all manipulations of the microcosms
 were done in a laminarflow hood using aseptic technique. Sterile
 and active (nonsterile) microcosms were made from all samples.
 Three replicate microcosms were made for each treatment. The
 anaerobic Norman landfill sediments were weighed out  for
 microcosms in an anaerobic glovebox. One ml of a  1/100,000
 dilution of resazurin and a  0.1  ml of a 100  u,m solution of
 Na^S^H  O were added to each microcosm. The microcosms
 were incubated  at 22°C  in  the dark.  All microcosms were
 amended with  100 ppb of atrazine.

 Sample Characterization

 The following  properties  of  samples were determined: water
 content, particle size distribution, total organic carbon (TOG), pH,
 total nitrogen, ammonium nitrogen, total phosphorus, phosphate
 phosphorus, and 26 metals.

 Bacteria in samples were enumerated by plate counts using dilute
 peptone, trypticase, yeast  extract,  glucose  (PTYG) medium
 (Balkwill and Ghiorse, 1985). Directcountsof bacteria were made
 using acridine orange  direct  counting (AODC) procedures
 described in Balkwill and Ghiorse (1985).

  Extraction and Analyses

 Atrazine standards were obtained  from  EPA and  ManTech
  standards repositories in Cincinnati, OH and Research Triangle
  Park, NC, respectively. Standards were also made up from pure
  atrazine obtained from Chem Service (West Chester, PA).  Little
  difference was noted between these standards when they were
  compared.

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 The atrazine extraction method of Muir and Baker (1978) was
 tested to determine its efficiency for atrazine extraction from soil.
 Soil was spiked with 1 ppm of atrazine which was allowed to
 remain in the soil for 1 week before extraction.  Twenty  ml of
 absolute methanol were added to 10 g of soil and were shaken for
 one hour.  The methanol was poured into aTeflon centrifuge tube
 and centrifuged on a Sorvall RC2B centrifuge at 10,000 rpm using
 an SS34 rotor for 10 minutes. The supernatant was analyzed by
 high pressure liquid chromatography (HPLC) analysis and showed
 a95% recovery of atrazine. This method was adopted foratrazine
 extraction.

 Bond Elute C18 cartridges  (Analytichem International, Harbor
 City, CA) were investigated as a method to concentrate atrazine
 and remove soil organic matter from methanol extracts of soil. To
 increase the  polarity of the extract so that atrazine would be
 retained by the C18 material, the extract was diluted 10:1 with
 Milli-Q water. Two tests were run to determine how efficient the
 cartridges were at retaining the atrazine while the extract was
 being passed th roug h the cartridge. The first test was to run a 100
 parts per  billion  (ppb) solution of 10% methanol: 90% water
 through a  C18 cartridge. The second method was to stack two
 018 cartridges and measure the amount of atrazine which passed
 through the first cartridge into the second cartridge. After the
 extract was passed through the cartridges, 2.0 ml of absolute
 methanol was used to elute the atrazine from the  C18 material.
 Analysis of the eluate indicated that for the first method  of
 checking the extraction efficiency of the C18 cartridges, essentially
 all of the atrazine in  the  initial solution was recovered in the
 methanol eluate.  For the second method, it was found that 1.7%
 of the total amount of atrazine had passed through  the first
 cartridge into the second cartridge. Therefore, the  C18 cartridge
 method of concentrating  the extracts  was found to  be  very
 efficient and was selected as the method of concentration to be
 used.

 HPLC analysis was done using a Scientific Systems Inc. (SSI)
 isocratic HPLC system. Samples dissolved  in methanol were
 diluted 50:50 with Milli-Q water; and if any turbidity was noted, they
 were centrifuged in a Microfuge (Fotodyne, Gosheim, F.R. Germany)
 for 10 minutes. Samples were injected into a 50 u,l sample loop.
 A mobile phase of 28% acetonitrile, 68% water, 4% methanol and
 0.0002% acetic acid (v/V) at pH 4.6 gave the  best  results for
 separating atrazine from interfering peaks. Some samples were
 analyzed by increasing the methanol concentration stepwise up to
 7% with a corresponding decrease in the percentage of water. An
 Alftech C8150 X 4.6 mm column and an Alttech C8 guard column,
 both with 5 urn packing material were used.  A flow rate of 2.0 ml
 per minute was used initially and then reduced to 1.5 ml per minute
 later to reduce pressure and stress on the column. A  UV-VIS
 detector was used at 222 nm. The extraction method used in this
 study mobilized a considerable amount of soil organic matter. To
 prevent this organic matter from degrading the performance of the
 column and other parts of the system, regularf lushes and cleanings
 of the column and other parts were necessary including a 10
 minute methanol flush between each sample analysis followed by
 a 20 minute baseline re-equilibration flush with the mobile phase.

 Mineralization of the atrazine ring was determined by measuring
 MCO2 production from 14C ring-labeled atrazine added to the
 microcosms.  The amount  of 14C labeled atrazine added to the
 microcosms was 50,000 DPM with enough nonlabeled atrazine
 added to make up a total of 100 ppb.  CO was trapped in  0.25 ml
of 1 N NaOH in a centerwell apparatus (Kontes Glass, Vineland,
 NJ) suspended from the stopper of the bottle. One day before the
 bottles were sampled t% H2SO, was added to the bottles to drive
 off carbpnate-CO2. A pilot study using this method indicated that
 CO2 inside the bottles was almost completely removed by the CO
 trap after 1 hour and therefore this method is satisfactory for
 determining CO2 evolution in this type of microcosm (Ghiorse et
 al., 1989 and  Madsen et al., 1991). A search was conducted for
 a suitable scintillation cocktail which would give a high counting
 efficiency in the presence of the 1 N NaOH CO  absorbent. A 6:l
 ratio of Beckman Ready-Sblv EP cocktail (Beckman Instruments
 Inc., Fullerton, CA) to 1 N NaOH was found to give  equal counts
 to a 6:1  ratio of the same cocktail with water even  when  a
 precipitate formed in the NaOH and cocktail mixture. Therefore
 this cocktail was  used in the experiments.

 Results

 The physical,  chemical and biological properties of the Stratford
 samples recovered from the boreholes are listed in Table 1. The
 bacterial populations in all of the samples used in this experiment
 including those from  the  sandy strata were lower than usual
 (Sinclair and Ghiorse, 1989) with even the highest plate counts
 from these samples being less than 105 per gram  of sediment.
 The 12.0 m deep  sample from the field had <50 platable bacteria
 per g.   The  other characteristics showed differences in  the
 samples as would be expected. Nitrogen and phosphorus showed
 a general trend toward lower values with depth. Samples used for
 microcosms were analyzed for 26 metals (data not shown). There
 was little relation between the metals content of the samples and
 biological populations.

 Atrazine assays of the samples taken January 2,1989 from the
 roadside indicated that there was about 1 part per million (ppm)
 of atrazine in the surface soil. Another surface soil sample taken
 from the roadside March 13, 1989 had 9.3 ppb indicating that
 there was a loss of 99% of the atrazine over a period of 2 months
 and 11  days.  The temperatures during this time were  cold so
 biological activity would have been minimal.  There had been
 substantial rain and snow melt during this period and there was
 evidence of the flow of water in the  ditch. Therefore, it appears
 that most of the atrazine loss occurred as a result of surface runoff.
 At the time of the July, 1989 drilling 26 ppb atrazine was found in
 the surface soil and 0.46 ppb was found 4.2 m deep in the
 unsaturated zone (Table 1).

 The results of the atrazine disappearance experiment are shown
 in Figures 1 and 2.  Atrazine loss occurred at a steady rate in
 microcosms of both the active and the sterile treatments of the
 surface soil of the  roadside. By the end of the experiment at 161
 days, more than 80% of the atrazine originally spiked into the
 microcosms had been degraded or bound in both the active and
 sterile treatments in the roadside surface soil. In the surface soil
 of the field where atrazine had not been applied there was a sharp
 decline in concentration up to 77 days, after which atrazine had
 declined to below  the limit of detection in both active and sterile
treatments.  Data shown for microcosms of subsurface material
 (Figure 1) indicate that there was no atrazine loss from any of the
samples.  No  differences were noted between the active and
sterile treatments of the subsurface sample microcosms, and not
even abiotic hydrolysis was observed in the other subsurface
samples regardless of the differing characteristics of the samples.

By contrast, in subsurface samples taken from the Norman landfill
(Figure 2), a steady decline in the concentration of atrazine was

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                          Roadside
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                  Unsaturated Zone (4.2 m)
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                       	.—  Sterile
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                                                                   70
                                                                          20"


                                                                          10
             Unsaturated Zone (3.8 m)
                                                                                         Active
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                               Active
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Saturated Zone (12.0 m)
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                                                                                      50
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                         Tfme(days)                                                     Time (days)

                                          a" uysis T. Sh°wn for mfcw«»m» <>' *<>» and sediments from the Stratford, OK site. Panel
A  ho   mf                 .K       u       .                                                       ,       .
from ih» fii^ft T   T Pro'''* o^epth* from the roadside where atrazine had been sprayed. Panel B shows microcosms from a profile
from the field 66 ft. from the roadside where atrazine had not been sprayed. The error bars are ± 1 S.D.

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    70


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               Saturated Zone of Norman Landfill
            N
                             	D— Active
                             	»-_ Starila
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                        Time (days)

 Figure 2. Alrazlne level* a* determined by HPLC analysis are shown
 formIcroco*m»framthe*aUiraledzoneof theNorman Landfill. The
 error bar* are * 1 S.D.


 noted in the active treatment throughout the experiment. By the
 end of the experiment very little of the added atrazine was
 detectable.   In the sterile treatment,  it was not possible to
 determinewhethertherewas any degradation of atrazine because
 of interferences in the samples.

 The results of the atrazine mineralization experiment (Figure 3)
 indicated that there was a slow release of MC labeled CO, from
 labeled atrazine added to the surface soil of the roadside. By 161
 days of incubation, 3.8% of the activity originally added as labeled
 atrazine was released as "CO,,. Avery small amount of 14CO2 was
 released from the surface soil of the field in the nonsterile
.treatment as compared to the sterile treatment. By 161 days, this
 amounted to 0.4% of the total amount of activity added. Very little
 activity appeared in the CO2 traps of the microcosms of  the
 subsurface samples.  Most of the activity which was trapped
 appeared at 133 or 161 days and often appeared equally in the
 nonsterile and the sterile microcosms. Examples of nearly equal
 amounts of activity found in nonsterile and sterile treatments can
 be seen in the roadside sample from 11.8 m deep and the field
 samples from 3.8 and 12.0 m deep.  No clear example was
 observed where microcosms of  the nonsterile treatment of a
 subsurface sample had more activity in the CO2 trap than could be
 seen in the sterile treatment from the same subsurface sample.

 Discussion

 Most of the atrazine applied to the roadside appeared to be  lost
 to surface runoff, howeverthere was some penetration of atrazine
 into the upper part of the unsaturated zone.  The amount of
 atrazine which penetrated into the 4.2 m deep sample (0.46 ppb)
 was below the EPA's health advisory limit of 3 ppb of atrazine in
 ground water (USEPA, 1989) and detectable levels of atrazine
 were not found in deeper samples. Therefore, the indigenous
 microbial populations were exposed to atrazine in the surface soil
 and upper parts of the unsaturated zone of the roadside. Despite
 this prfor exposure in at least part of the profile, there was no
 evidence of  microbial acclimation to- atrazine in the surface or
 subsurface  of the  roadside  in the atrazine disappearance
 experiment.  In the roadside and the field, abiotic hydrolysis
seemed to be responsible for almost all of the atrazine breakdown
since nearly equal amounts of loss were observed in the active
and sterile treatments. There seemed to be a more rapid rate of
hydrolysis in the surface soil of the  field than in the roadside
atthoughthe reason forthis is not clear. The lack of biodegradation
of atrazine  in the subsurface samples may  not have been
unexpected, however the lack of abiotic hydrolysis was unusual
and the reason for this is not evident.

An objective of this work  was to determine how the rate of
biodegradation of atrazine differed in sediments having different
characteristics, such as texture or position with respect to the
water table. Regardless of differing characteristics, no atrazine
degradation was observed in  any of the subsurface samples. A
similar observation about atrazine biodegradation was made by
Konopka and Turco (1991).  Atrazine was apparently resistant
enough to degradation to mask any differences in biodegradation
which might beobserved in sediments which haddifferent microbial
population  sizes or types during the 161 -day time course of the
experiment. Degradation of atrazine was observed in the Norman
landfill sediments which were incubated anaerobically.  This
result illustrates that atrazine may degrade in the subsurface
under some conditions.

Very little complete mineralization of atrazine to CO2 was observed
in any sample. These results are similar to those of Skipper and
Volk (1972) and  others  who  also observed little atrazine
mineralization in surface or subsurface soils. There did appear to
be a microbial acclimation  effect in the roadside surface soil as
compared  to the field surface soil for atrazine mineralization.
Atrazine mineralization to CO2 appeared to be abiological process
because it  was only observed in the active treatment. About 10
times as much atrazine mineralization  occurred in the roadside
surface soil microcosms as  occurred in the field surface soil
microcosms. No evidence could be seenfor atrazine mineralization
in any of the subsurface sediment samples, ft is not clear why 14C
activity was found in the CO2trap cups of the sterile treatments of
several of  the subsurface  sediment  microcosms but not in the
sterile treatment surface soil microcosms, ft is unlikely that the
activity was due to MCO2formed by microbial contaminants in the
sterile subsurface sediment  microcosms because this activity
was noted in all of the replicates of these microcosms.

 It is difficult to judge how representative the results of these
 experiments are of atrazine biodegradation at other subsurface
 sites because of the lower than usual bacterial populations at the
 Stratford site (compared to Sinclair and Ghiorse, 1989 or Sinclair
 era/., 1990). Nonetheless, the microbial populations did have the
. ability to degrade alachlor even though alachlor had not been
 applied to this site. Dr. T.B. Moorman of the USDA in Stoneville,
 MS (1991 Abstr. Afner. Soc. Microbiol. Ann. Meeting Q94, p. 292)
 has reported that several percent of alachlor added to microcosms
 of some subsurface sediments from the  Stratford site was
 mineralized. Alachlor did degrade differently in samples having
 different textural characteristics  or position with respect to the
 water table. The alachlor degradation in the Stratford samples
 was reported to be  more rapid  than that found in  subsurface
 samples from Plains, GA (T.B. Moorman, personal communication,
 and Pothuluri et al, 1990). Therefore the slow rate of atrazine
 biodegradation in the subsurface of this site may be a reflection
 of the resistance of atrazine to degradation and its decreasing rate
 of degradation with depth in soil (Lavy et al., 1973). Nonetheless,
 because of the sparse bacterial populations and the lack of abiotic
 hydrolysis in the subsurface samples from this site, other sites

-------
            10
            4 .
                              Roadside
                             Surface Soil
                         	D— Active
                         —-»—• Sterile
                          SO
                                     100
                                                 150
B
                                                                           10
                                                                           *  .
          Field
                                                                                              Surface Soil
                                                                                                     D— Active
                                                                                                   —_—. Sterite
                                                                                         50
                                                                                                    100
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                          50
                                     100
                                                 150
                                                                                         50
                                                                                                    100
                                                                                                                150
           10
           6
                        Saturated Zone (11.8 m)
                                   Active
                                   Sterile
                         SO          100

                           Time (days)
                                                                          10
 Saturated Zone (12.0 m)
jk •   	o—  Active
«E»    —-«.—.  Sterite
   50          100

       Time (days)
Figure 3. The percent of MC evolved as «CO2-C from added "C ring-labeled atrazine is shown. Panel A shows the results from microcosms
of the roadside where atrazine had been sprayed and panel B shows the results from the field 66 ft. from the roadside where atrazine had
not been sprayed.

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should be studied to determine if atrazine degrades more readily
in the subsurface at other locations.

References

Balkwill, D.L. and W.C. Ghiorse. 1985.  Characterization of
subsurface bacteria associated with two  shallow aquifers in
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Disclaimer
The information in this document has been funded wholly or in
part by the United States Environmental Protection Agency. This
document has been  subjected to  the Agency's  peer  and
administrative review and has been approved for publication as
an EPA document.

Quality Assurance Statement
All research projects making conclusions or  recommendations
based on environmentally related measurements and funded by
the Environmental Protection Agency are required to participate
in the Agency Quality Assurance  Program.  This project was
conducted under an approved Quality Assurance Program Plan.
The procedures specified in this plan were used without exception.
Informationontheplan and documentation of thequalrty assurance
activities and results are available from the Project Officer.
                                                                        •ttU.S. GOVERNMENT PRINTING OFFICE: 1991 - 648-080/40I4S

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