V-/EPA
                           United States
                           Environmental Protection
                           Agency
                         Environmental
                         Research Laboratory
                         Athens, GA30613
Research and Development    EPA/600/M-90/003    June 1990

ENVIRONMENTAL
RESEARCH    BRIEF
                   Degradation Kinetics of Chlorinated Aromatic
                Compounds in Saturated Subsurface Environments
             John E. Rogers1,  Jacobus Struijs2, Dorothy D. Hale3, and Frank Bryant3
Abstract
Results are presented to support the use of Monod kinetics
in describing the anaerobic  degradation of chlorinated
aromatic compounds  in  the  saturated subsurface
environment.  For all compounds studied,  a lag period was
observed before loss of the  compound was  detected.
However,  subsequent  additions  of compound  were
dechlorinated without a lag and at an increased rate. The
length of the lag was dependent on both the characteristics
of the fresh water sediment and the compound investigated.
Preliminary studies indicated that the population size of
dechlorinating organisms in some sediments can increase in
response to  the removal of a single chlorine  from the
chemical, 2,4-dichlorophenol.

Background
The regulation of hazardous and solid waste is continually
being refined as the understanding of the properties and
fates of  chemical  waste components  increases. This
increased knowledge has  resulted in  a number of adopted
and proposed amendments to  the Resource Conservation
and Recovery Act (RCRA) (PL 98-616). The Hazardous and
Solid Waste  Amendments of  1984  directed EPA  under
RCRA  section 3001 (h) to develop additional  hazardous
waste characteristics for  identifying  hazardous wastes. In
June 1986,  EPA  proposed  to  modify  the Toxtcity
 1 Environmental Research Laboratory,  Environmental  Protection
  Agency, Athens, GA 30613-7799

 2 National Institute of Public Health & Environmental Hygiene,
  Bilthoven, The Netherlands

 3 Technology Applications, Inc., c/o Environmental Research Laboratory,
  U.S. Environmental Protection Agency, Athens, GA 30613-7799
                      Characteristic. The existing characteristic uses the National
                      Interim Primary Drinking Water Standards (DWS) as toxicity
                      thresholds for listed individual chemical components of the
                      waste. These thresholds  are, in turn, combined with a
                      generic dilution/attenuation factor (100 times) to determine
                      the regulatory threshold. The proposed characteristic would
                      use chronic  toxicity reference levels, combined with a
                      compound-specific  dilution/attenuation factor,  to calculate
                      the regulatory threshold for individual waste toxicants in the
                      waste  leachate. A  subsurface (unsaturated and saturated
                      zone)  fate model is  used  to calculate the  dilution/
                      attenuation factors.

                      In  the proposed rules, the model  includes mathematical
                      equations  that rely on compound-specific hydrolysis and
                      soil adsorption data; these equations are coupled to others
                      using parameters  describing  a wide range of subsurface
                      environments. The resulting model calculates the degree of
                      attenuation and dilution a compound would undergo as it
                      migrates to a subsurface  drinking water source. Chemical
                      hydrolysis is the only transformation mechanism  currently
                      considered in the proposed  rule. Although the EPA
                      recognizes   that  biodegradation is  an  important
                      transformation process, it was considered insufficiently
                      understood to be included in the model at that time.
                      Research  at  EPA's Environmental Research Laboratory at
                      Athens, GA,  has  been aimed  at identifying key kinetic
                      expressions that describe anaerobic degradation  in the
                      saturated zone. The main  emphasis of this research is to
                      increase our  understanding of the  kinetics  of anaerobic
                      degradation to provide the scientific basis necessary for
                      reliably including biodegradation in  the  future  regulation of
                      hazardous and solid wastes.

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  Laboratory Procedures
  Collection and Treatment of Samples

  Sediment and water samples were collected from five ponds
  near Athens,  GA, in September 1986. Bolton's Pond  and
  Cherokee Trailer  Park Pond were sampled periodically over
  the 3 year period beginning September 1986. The samples
  were collected and treated as  follows. Sterile  Mason  jars
  were filled to capacity  with  sediment (0-10 cm)  and
  overlying  water  and capped  near the sediment/water
  interface. Additional site  water was  collected  near  the
  sediment surface  in sterile  1-L Erlenmeyer flasks. Both
  water and  sediment samples  then were  transported  to the
  laboratory and  placed in an  anaerobic  glovebox that
  maintained an atmosphere of  95%N2:5%H2.  All  further
  manipulations  of the water  and sediment were conducted in
  the  chamber.  Sediments  were  washed with  site  water
  through a 1-mm sieve (U.S. Standard Testing Sieve No. 18)
  to  remove organic  debris  and  stones.  Sediments
  subsequently were stored in crystallizing dishes for 3 weeks
  before being  used in  serum bottle  microcosms.  Such
  treatment allowed  removal of residual oxygen from  the
  sediments and restoration of methanogenic activity.
  Transformation  Assays

  Wet sediment containing  the equivalent of 10  g of dry
  sediment weight was  added  to  individual  125-ml  serum
  bottles. Sufficient  site water then was  added to bring  the
  final volume to 100 ml. One-to-five milliliters of an aqueous
  stock solution (200 ppm) of  chlorinated substrate  was added
  to separate reaction vessels to yield a final concentration of
  2 to 10  ppm. Bottles  were  capped  with  butyl  rubber
  stoppers, crimp sealed, and  incubated in the dark  in the
 anaerobic chamber at 25°C. The loss of the substrate then
 was  followed  over time.  At specific  intervals,  1.0-ml
 subsamples were  removed and  combined with  1.0 ml of
 hexane (PCBs), pentane (chlorinated benzenes), acetonitrile
 (chlorinated anilines, phenols  and benzoates), or ethanol
 (PCP, 2,4-D and 2,4,5-T) to  terminate biological activity and
 to dissolve any test chemical sorbed to the  sediment. The
 subsamples combined with acetonitrile or  ethanol  were
 centrifuged  at  3500 rpm (IEC HN-S CENTRIFUGE) and
 subsequently filtered through 0.22-nm filters before analysis
 or storage (4°C).  Subsamples treated with hexane and
 pentane  were  also centrifuged,  with the solvent phase
 subsequently analyzed for residual test chemicals.

 Autoclaved sediment slurries served  as sterile controls  In
 most cases,  sediments  were  autoclaved (Sybron/Castle
 3020) at  120°C (1.4 atm) for 30 minutes on  3 consecutive
 days. Some sediment samples, however,  were autoclaved
 only once for 30 minutes before the addition of a chlorinated
 substrate.  The  more  rigorous autoclaving  changes the
 sediment  properties and  causes  the  production  of
 compounds  that  interfere with  the  chromatographic
 determination of some chlorinated substrates and products.

 HPLC Analysis

 Chlorinated substrates in  sediment slurries  were quantitated
as follows. Sediment slurries mixed with equal volumes  of
acetonitrile  or ethanol were  centrifuged  for 10 minutes  at
3500  rpm (IEC HN-S CENTRIFUGE). The  supernatant
solutions  were filtered (0.22 urn,  Millipore, GVWP) before
analysis by  reversed phase HPLC.  The chromatographic
system consisted of a Rainin pump system coupled to a C-
  18 Dynamax Microsorb column (0.46 x 25 cm), a Knauer UV
  absorbence detector operated  at 280 nm  (chlorinated
  phenols, anilines and benzoates, and 2,4-D) or 290 nm (PCP
  and  2,4,5-T) and  a  Shimadzu  C-R3A integrator.  The
  chromatography solvent  for chlorinated  phenols  and
  benzoates  and 2,4-D was  methanol:water:acetic acid
  (60:38:2  v/v/v). For   chlorinated  anilines,  the solvent
  composition was  70:28:2 (v/v/v).  The  chromatographic
  solvent for  PCP and  2,4,5-T was  acetonitrile:water:acetic
  acid (60:38:2 v/v/v). Residual  substrates and products were
  identified by comparing their retention times with those of
  authentic standards.

  Gas  Chromatograph Analysis

  Concentrations  of chlorobenzenes were  quantified by gas
  chromatography. A 1.0-ml sediment  slurry sample was
  added to 1.0 ml of n-pentane containing  5 ppm lindane as
  an internal standard. The mixture  was vigorously  mixed for
  30 seconds and then centrifuged at 3900 X g. A  5-pl sample
  from the solvent phase was injected into  an  HP  5890 gas
  Chromatograph  connected to an HP 3399A integrator. The
  temperature  of  the  injection  port  was  270°C and  the
  temperature  of the  ECD detector  was 300°C. Nitrogen was
  used as the carrier and the auxiliary gas. An OV-I column
  (30 m X 0.25 mm with  0.5 nm film) was used. The column
  temperature  was maintained under isothermal conditions at
  180°C for quantification  of  substrate. A  programed
  temperature  gradient (initial  temperature of 40°C  for 4
  minutes,  followed by  10°C/min  increase  to 180°C  which
  was held for  15  minutes) was used  in the identification  of
  degradation intermediates.

  Identification of Products

 The identities of  intermediate metabolites were established
 by using  a combination of co-chromatography (HPLC and
 GC) with authentic standards and gas  chromatography-mass
 spectrometry (GC-MS).  GC-MS  was used to  confirm
 molecular weights and  numbers  of  chlorine  substituents
 Analyses were  conducted  on  iso-octane  extracts of
 sediment  slurries. Sediment  slurry samples (5  ml)  were
 mixed with 1 ml  of isooctane,  and after centrifuging (3500
 rpm), the isooctane  layer  was separated  from  the water
 phase and used  without further  purification. The extracts
 were  analyzed with  a  Finnigan 4500  GC-MS, interfaced to
 the Finnigan  Incos  data system.  The gas Chromatograph
 was equipped with a   DB-5  30-m x 0.25-mm  capillary
 column.

 Most Probable Number (MPN)  Determinations

 Numbers  of  2,4-dichlorophenol  (DCP)  dechlorinating
 microorganisms  in pond sediments  were  estimated  with
 most probable number  (MPN) techniques (1).  The dilution
 and incubation medium was prepared  by adding 2,4-DCP to
 sterile pond water to give a final concentration of'10 mg/L
 Sterile  pond water was  prepared by filtration through 0 22-
 tim membranes followed by autoclaving (30  minutes). Either
 4-fold or 10-fold  dilution series were  used  with 3 replicate
 MPN  tubes. Dilution  series were  prepared directly  from
 sediment slurries used in transformation assays. Autoclaved
 control tubes  were prepared  using autoclaved  sediment
 Following a 4-week  incubation period, a  1-ml subsample
 was removed  from each MPN tube, mixed  with  a  1-ml
volume  of acetonitrile  and  analyzed  for 2,4-DCP Tubes
were considered positive if the 2,4-DCP peak area was not

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 more than three times the peak area of the 4-chlorophenol
 (CP) product.  Numbers of dechlorinating organisms (with a
 95% confidence interval) were estimated from the number
 of positive tubes in selected consecutive dilutions using  an
 MS-DOS turbo pascal program utilizing  American Society of
 Microbiology guidelines for MPN determinations.

 Computer Simulations

 Theoretical  simulations of the fate of chlorinated aromatic
 compounds in sediment slurries  were  prepared using  a
 Monod  growth model  (26).  Two  basic assumptions were
 made.  First,  the  growth  rate  of the  dechlorinating
 microorganisms can be expressed by
       u = umax S / (Ks  +  S)
                              (1)
 where u is the specific growth rate, S is the concentration of
 chlorinated substrate, umax is the maximum specific growth
 rate, and  Ks is the half saturation constant (2). Second, the
 following mass balance equation applies,
S0
                 = S  + B/Y
(2)
 where S0 is the concentration of substrate at zero time, B0 is
 the concentration of bacteria  at zero time, and  Y is  the
 growth yield factor.  Y is treated here as  a  constant, as  has
 been  the practice of others (2-5). Because only changes in
 S are of interest, the term X can be substituted for B/Y.  If B
 is given in cells/L and Y in cells/mg (number of cells formed
 per mg parent compound  dechlorinated)  then  X  has  the
 units  of mg (parent compound)/!. Thus, X corresponds to
 the amount of "substrate"  required to produce a population
 density of B. By analogy, X0 corresponds to the amount of
 "substrate"  that could  be  equated to  the  formation of  the
 initial  population of specific degraders at time zero, i.e.  B0.
 Because Y is considered a constant,  u can be  represented
 as

       u  = 1/XdX/dt                  (3)
 Combining Equation 3 with Equation 1 yields

       dX/dt =  umax S X/(KS + S)      (4)

 Because  of the mass  balance Equation 2,  dX/dt  can  be
 assumed to equal -dS/dt, yielding

       - dS/dt  = umax S X/(KS  + S)    (5)

 Plots of S versus t were obtained by simultaneously solving
 Equations 4 and 5 using TUTSIM software.

 Results  and Discussion

 The object of this project was to develop kinetic models for
 predicting the anaerobic degradation  of  hazardous  organic
 chemicals in the saturated  zone,  and  in  particular,  the
 degradation of chlorinated aromatic compounds. Studies on
 the  anaerobic  degradation  of  dichlorinated  phenols  were
 conducted to develop the appropriate kinetic models. Where
 possible,  we refer to the work of others to illustrate how
 Monod kinetics may  also  appropriately describe  the
 degradation of a wide variety of compounds in the saturated
 zone.

 To provide perspective and to  ensure that  our conclusions
 have  breadth of application, the  degradation  of  the  six
dichlorophenol isomers was  investigated in the  sediments
from  five ponds near Athens, GA.  In addition  to  the
dichlorophenol isomers, the degradation of  PCP, 2,4-D and
2,4,5-T was investigated  using sediments  collected
 throughout the United States (in Georgia, Florida, and New
 York)  and the Soviet  Union. Although the data  are not
 presented here,  similar  results also  were observed with
 chlorinated anilines and  benzenes. In  all cases, the  initial
 dechlorination of the test  compounds was preceded by a lag
 period. Similar results have been observed for a variety of
 chlorinated  (3,6,9,10)  and  nonchlorinated  aromatic
 compounds (6,8,11,2,17,14,19). The length of the  lag was
 observed to  be  both  sediment-  (Tables  1  and 3) and
 compound-  (Tables 2 and  3)  dependent.  In those  cases
 where the test compound  was added  a second and third
 time (Figures 1 and 2) following the complete dechlorination
 of the previous addition, dechlorination was faster and  no
 lag was apparent. When  such an increase in the onset and
 rate of activity is observed,  the sediments are considered to
 have adapted to  the  dechlorination or  degradation of the
 particular compound under investigation (3,6,9,10,23).

 In some adapted  sediments or sludges,  the compound loss
 (3,6,9) and the formation of  methane and carbon dioxide is
 immediate (no  lag)  . Few, if any, degradation  intermediates
 are observed. At  the other end of the  spectrum are those
 adapted sediments  that remove only a  single  chlorine from
 the compound to  form a stable intermediate (9,10,23). In this
 research, for example, 2,4-DCP was converted to  4-CP in
 the sediment  from  one  pond, and  2,3-, 2,4-  and 2,6-DCP
 were converted to 3-, 4-, and 2- CP in the sediment  from
 another.  None of  the   monochlorophenols  was  further
 degraded. The conversion of 2,3- and 2,6-DCP to a mixture
 of monochlorophenols and  phenol  in some sediments was
 indicative of an intermediate  level of adaptation. The  direct
 conversion of  dichlorophenols  to methane  and  carbon
 monoxide was not indicated with either sediment.

 That  sediments can adapt  to  convert  dichlorophenols  to
 monochlorophenols suggests  that  the  dechlorination
 process provides  a selective advantage for the survival  of
 dechlorinating organisms. Brown et al.  (4) have calculated
 that the free energy released during  reductive dechlorination
 is exergonic. Therefore, one could expect that if this release
 of energy could  be coupled to the utilization  of  organic
 compounds in sediment, the conversion of 2,4-DCP to 4-CP
 observed  here could support biological growth, resulting  in
 adaptation.  Results  indicate   that  the  number  of
 dechlorinating  microorganisms,  as measured  by  MPN
 techniques,   increases  following  the  addition  of
 dichlorophenols to sediment slurries (Table 4). Although an
 increase in MPN units was not always observed, adaptation
 was  consistently  observed.  The  relative  importance  of
 induction (i.e., an  increase in enzymatic activity) and growth
 were not evaluated here.  It  is apparent  from these  studies,
 however, that both are occurring. Considering that the sterile
 controls  in these studies showed   no  loss of compound,
 abiotic processes  can reasonably be ruled out.

 Several other  mechanisms  have also been considered  in
 explaining the length of lag periods.  Others have suggested
 that  a lag period is required  for  mutation  and  genetic
 transfer (16,25). Also, certain environmental  factors  have
 been  implicated. These  include  limiting  nutrient
concentrations (13,24), preferential use of organic (12,13)  or
 inorganic  (7)  compounds before degradation of the  test
chemical,  recovery  from toxic  chemicals  (21), and the
predation of degrader populations by protozoa (26).

 Because we observed both  adaptation  and  an increase  in
the units of biological activity,  Monod growth  kinetics can be

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      Table 1. Persistence of 3,5-DCP in Fresh Water Sediment Slurries
                                            Residual 3,5-Dichlorophenol Concentration (mg/L)
                                                        Time i
Sediment
Bar H
Pond
Cherokee
Pond
2 -Boat
Pond
Sandy Creek
Nature Ctr.
Bolton's
Pond
(mg/L)
4.36
4.14
4.22
4.27
4.18
Table 2. Persistence of
(
Isomer
2,3-
2,4-
2,5-
2,6-
3,4-
3,5-
Initial
Doncentra'
(mg/L)
4.57
4.70
4.91
4.12
4.40
4.14
WeekO
3.30
4.18
4.14
4.14
4.22
4.22
4.27
4.27
3.78
4.18
Dichlorophenol
Week 2
3.48
4.36
4.14
4.14
4.22
4.22
4.27
4.27
4.18
4.18
Isomers
Week
3.57
4.36
3.74
4.09
0
4.18
4.00
3.74
2.87
4.18
in Fresh
4 Week 6 Week 8
4.35
4.36
0
0
0
4.12
4.27
4.27
0
4.18
Water Sediment
3.01
4.01
0
0
0
3.92
3.84
4.01
0
4.18
Week 1 0
3.23
4.14
0
0
0
4.04
4.24
4.24
0
4.18
Week 14
2.18
3.26
0
0
0
4.06
4.27
3.48
0
3.41
Slurries
Residual Dichlorophenol Concentration
tj Time of Incubation
Week 0
4.57
4.57
4.70
4.70
4.91
4.35
2.85
3.03
4.32
4.40
4.14
4.14
Week 2
3.60
3.33
4.45
4.75
396
402
4.02
3.25
3.60
3.71
4.14
4.14
Week
0
0
0
0
4.30
4.20
4.04
4.12
4.12
4.02
3.74
4.09
4 Week 6 Week 8
0
0
0
0
0
3.92
0
3.35
0
3.98
0
0
0
0
0
0
0
0
0
0
0
4.02
0
0
(mg/L)
Week 10
0
0
0
0
0
0
0
0
0
3.32
0
0

Week 12
0
0
0
0
0
0
0
0
0
4.02
0
0
Table 3. Lag Times and aT50 Values for PCP, 2,4-
        D, and 2,4,5-T in Fresh Water Sediment
        Slurries
                    Lag (days)
T50 (days)
PCP
East River, NY
Lake Borek, USSR
Cherokee Pond, GA
2,4-D
Wacissa Spr., FL
Lake Borek, USSR
Cherokee Pond, GA
2.4,5-T
Cherokee Pond, GA

19
14
>40

9
50
22

60

26
15
>40

16
55
46

60
a T50 is the time to observe a 50% decrease in con-
 centration, and should not be mistaken for a half life
 that is related to first-order kinetics (Moore ef a/.,
 EPA/600/3-89/080).
useful  in investigating the  dechlorination  of chloroaromatic
compounds in anaerobic saturated zone water. The length
of the lag period in this case is dependent on the values of
Ks, umax  and  X0. The  effects of  increasing  Ks  and
decreasing biomass are shown  in Figures 3 and 4. The
effects of decreasing umax would be similar to the effects of
decreasing biomass. Factors affecting the  lag period (such
as those described above) would presumably affect one or
all of these kinetic  parameters. Adaptation  is represented by
the theoretical curves in Figure 5.

Incorporating Monod kinetics into  a  subsurface  transport
and transformation model  requires a supporting database.
Unfortunately, such  a database  is currently  not  available.
This fact was recognized in 1988 with the  publication of an
anaerobic protocol  (40 CFR, Part 795,  Section  795.54) for
developing  anaerobic  degradation  data  for  organic
chemicals  of  interest  in  the  subsurface  environment.  A
geometric sampling approach was recommended for use in
providing data for rapidly and slowly degrading compounds.
Samples were to  be analyzed at 0,  4, 8, 16, 32, and 64
weeks. The protocol would be used to determine the length
of time  (lag) before which  detectable  degradation could be
observed and the  half-life of the chemical  following the lag
period.  Conceivably these  two  pieces of  information could
be incorporated into a fate model as  separate entities. The
methodology provided here is  a crude,  but conservative

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           6   12   18   24    30   36   42
                          Time (days)
                                   48  54
                 16
                      24    32    40    48
                          Time; (weeks)
                                   56
                                         64
Figure 1.
Loss of 2,6-DCP in Cherokee Pond (A) and Bolton's
Pond (B) sediment. Arrows denote additions of 2,6-
dichlorophenol.
(under  estimation of degradation  or  transformation  rate),
approximation to the direct use of Monod kinetics.

Acknowledgements

We wish  to  acknowledge the useful  and constructive
comments provided by Dr. N. Lee Wolfe and Dr. Susan A.
Moore in reviewing the manuscript.

References

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      6?

      I
  Figure 2.
                                                        120
                                                                       160
                                                                                      200
                                                                                                     240
                                                           Time (d)
Loss of 2,4-dichlorobenzoate ( D • D. 5 ppm) and the formation of 4-chlorobenzoate (O-O) in Cherokee Pond
sediment. Arrows denote additions of 2,4-dichlorobenzoate.
 Table 4. Mean Number (Log10 ± Standard Deviation, n = 5)
         of 2,4-Dichlorophenol Dechlorinating Organisms in
         Cherokee Pond Sediments Collected from Selected
         Sites During Various Seasons
Sampling Date
9/27/88
1/24/89
3/27/89
5/30/89
V
2.99 ± 0.88
3.62 ± 0.09
4.22 ± 0.31
4.03 ± 0.55
T|OSSb Sample
5.18 ± 1.20
4.54 ± 0.58
4.68 ±0C
4.37 ± 0.49
Control
3.56 ±1.01
3.78 ± 0.39
4.13 ± 0.33
3.65 ± 0.26
 a Time = 0
 b Time = complete dechlorination of 2,4-dichlorophenol to
  monochlorophenol
17.  Shelton, D.R., and J.M. Shelton. 1984. General method
    for  determining anaerobic biodegradation potential.
    Appl.Environ.Microbiol. 47:850-857.

18.  Simkins,  S.,  and  M.  Alexander.  1984.  Models  for
    mineralization kinetics with the variables  of  substrate
    concentration  and  population  density.  Appl  Environ
    Microbiol.  47 :1299-1306.

19.  Sleat, R.,  and J.P   Robinson.  1983.  Methanogenic
    degradation  of sodium benzoate in profundal sediments
    from a small eutrophic lake. J.Gen. Microbiol  129 141-
    152.
                                                                                                     100
                                                   Figure 3.  Theoretical plot representing the effect on the
                                                            lag of increasing the half saturation constant Ks.
                                                            S0 (4.6 mg/l); umax (0.15/d); X0 and Ks (mg/l) as
                                                            indicated.

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Figure 4.  Theoretical plot indicating the effect of decreasing
         bacterial population on lag. S0 (4.6 mg/l); umax
         (0.35/d); Ks (8 mg/l); X0 (mg/L) as indicated.
20. Smouse,  P.E.  1980.  Mathematical  models  for
    continuous  culture  growth  dynamics  of mixed
    populations  subsisting on  a heterogenous  resource
    base. 1.  Simple competition. Theor.Popul.Biol.  17:16-
    36.
21. Stephenson, T.,  J.N. Lester,  and  R.  Perry.  1984.
    Acclimation to nitrilotriacetic acid in the activated sludge
    process. Chemosphere 13:1033-1040.
22. Stewart, P.M.,  and  B.R.  Levin.  1973.  Partitioning  of
    resources and the outcome of interspecific competition:
    a  model  and some  general  considerations.  Am.Nat.
    107.107-198.

23. Struijs,  J.,  and  J.E.  Rogers.  1989.  Reductive
    dehalogenation of  dichloroanilines  by  anaerobic
    microorganisms in fresh and dichlorophenol-acclimated
    pond sediment. Appl.Environ.Microbiol. 55:2527-2531.
24. Vashon, R.D., W.J. Jones, and A.G. Payne. 1982. The
    effect of water hardness on  nitrilotriacetate removal and
    microbial  acclimation  in  activated sludge.  Water Res
    16:1429-1432.

25. Walker,  R.L.,  and  A.S.  Newman.  1956.  Microbial
    decomposition  of  2,4-dichlorophenoxyacetic  acid.
    Appl.Microbiol. 4:201-206.

26. Wiggins,  B.A.,  S.H. Jones, and  M.  Alexander. 1987.
    Explanations for  the acclimation  period preceding the
    mineralization  of  organic chemicals  in  aquatic
    environments. Appl.Environ.Microbiol. 53:791-796.
Figure 5.  Theoretical plot indicating adaptation. S0 (4.6 mg/L)
         each addition; umax (0.15/d); Ks (10 mg/l); X0 (0.1
         ug/l).

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