Draft
                                                    8/16/88
AMBIENT AQUATIC LIFE WATER QUALITY CRITERIA  FOR

                 PHENANTHRENE
    U.S. ENVIRONMENTAL PROTECTION AGENCY
     OFFICE OF RESEARCH AND DEVELOPMENT
    ENVIRONMENTAL  RESEARCH  LABORATORIES
              DULUTH, MINNESOTA
         NARRAGANSETT,  RHODE ISLAND

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                                     NOTICES
This document has  been
                                 bv  the
                                                     Standards Division, Office
                                              ronmental  Protection Agency,  and



«°«c0.n«nj."f:nn""n:i.""'""' Pr0""CtS  d°eS  n0t  «»«'««, .„<.,....„,

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                                    FOREWORD
       Section 304(a)(l)  of the Clean Water Act requires the Administrator of
 the Environmental Protection Agency to publish water quality criteria that
 accurately reflect the latest scientific knowledge on the kind and extent of
 all identifiable effects on health  ,:d welfare that might be expected from the
 presence of pollutants in any body of water.   Pursuant to that end  this
 document proposes water  quality criteria for  the protection of aquatic life
 These criteria do not  involve consideration of effects on human health.

       This _ document  is a draft,  distributed for public review and comment
 After considering all  public comments  and making any needed changes,  EPA will
 issue the criteria in  final form,  at which time they will replacf any
 previously  published EPA aquatic life  criteria for the same pollutant.

 W«<-    I**? "'"/'"^oL?11?,1"7 criteria"  is  used in two sections  of the Clean
 r±L,AGJ'  SeCtl°n 30t(a)(1)  and section 303(0(2).   In section  304,  the term
 represents  a non-regulatory,  scientific  assessment of effects.   Criteria
 presented in this  document  are  such scientific assessments.   If  water quality
 criteria  associated  with specific  stream uses  are  adopted by a State  as  water
 quality standards  under  section  303, then they become maximum acceptable

 si                           can  be used to derive
      Water quality criteria adopted in State water quality standards could
have the same numerical values as criteria developed under section 304
However  in many situations States might want to adjust water quality criteria
developed under section 304 to reflect local environmental conditions before
assisTst*^ ^^ wate* 5uality standards.  Guidance is available from EPA to
assist States^in the modification of section 304(a)(l) criteria, and in the
development of water quality standards.  It is not until their adoption as
part of State water quality standards that the criteria become regulatory
                                    Martha G.  Prothro
                                    Director
                                    Office of Water Regulations and Standards
                                     iii

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                                ACKNOWLEDGMENTS
Loren J. Larson
(freshwater author)
University of Wisconsin-Superior
Superior, Wisconsin
Robert S. Carr
(saltwater author)
Battelle Ocean Sciences
Duxbury, Massachusetts
Charles E. Stephan
(document coordinator)
Environmental Research Laboratory
Duluth, Minnesota
David J. Hansen
(saltwater coordinator)
Environmental Research Laboratory
Narragansett, Rhode Island
                                     i v

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                                     CONTENTS
                                                      :                     Page
  Foreword	
                              	   i i i
  Acknowledgments	
                                 	   i v
  Tables..	
                                              	   v i


  Introduction	
                     	    1
 Acute Toxicity to Aquatic Animals	

 Chronic Toxicity to Aquatic Animals	
                                          	   4
 Toxicity to Aquatic Plants	
                                                           	   D
 Bioaccumulation..  .
                       			   5
 Other Data....
                   	   6
 Unused  Data....
                   	•	   7
 Summary	
                   	   9
 National Criteria...
                        	    9
 Implementation..
                    	   10
References.
                                                                           25

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                                     TABLES
1.
2.
3.

4.
5.
6.
                                                                     Page
Acute Toxicity of Phenanthrene to Aquatic Animals  	   12
Chronic Toxicity of Phenanthrene to Aquatic Animals  	        15
Ranked Genus Mean Acute Values with Species Mean Acute-Chronic
  Ratios	
                              	•	'	   ID
Toxicity of Phenanthrene to Aquatic Plants 	          ,g
Bioaccumulation of Phenanthrene by Aquatic Organisms 	   20
Other Data on Effects of Phenanthrene on Aquatic Organisms  	   21
                                      VI

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  [ntroduct i on
       Phenanthrene contains three fused aromatic rings and is one  of  the
  chemicals -known as polynuclear aromatic hydrocarbons  (PAHs).   It  commonly
  occurs in petroleum products and by-products  and  is used  in  several
  manufacturing processes,  including  the production  of  plastics.  Pyrosynthesis
  and early diagenesis  of  organic  matter,  particularly  steroids,  are important
  sources  of  phenanthrene  in aquatic  environments (Anderson et al.  1986).
  Concentrations  as  high as  1,200  Mg/kg  have  been reported  in  sediment
  (Varanasi et  al.  1985).
      Phenanthrene  is  a solid  at  room temperature,  with a melting  point of
  lOl'C  (Callahan et al. 1979).  It has  a molecular weight of  178.23, a vapor
  pressure of 6.8 X  1
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  classify phenanthrene as a PAH whose toxicity is not: greatly enhanced by



  photo-activation.




       A comprehension of the "Guidelines for Deriving Numerical  National  Water




  Quality Criteria for the Protection of  Aquatic Organisms and Their Uses"




  (Stephan et al.  1985),  hereinafter referred to as the Guidelines,  and the




  response to public comment  (U.S.  EPA 1985a) is necessary in  order  to




  understand  the following text,  tables,  and calculations.   Results  of  such




  intermediate  calculations as  recalculated  LCSOs  and  Species  Mean Acute Values




  are  given to  four significant  figures to prevent  roundoff  error  in subsequent



  calculations,  not to  reflect  the,  precision of  the  value.   The criteria




  presented herein  supersede  previous  national aquatic  life  water quality




  criteria for  phenanthrene (U.S  EPA  1980)  because  these  new  criteria  were




  derived using  improved procedures  and additional  information.  The  latest




  comprehensive  literature search for  information for this document  was




  conducted in July, 1986; some more recent  information was  included.








 Acute Toxicitv to Aquatic Animals




      Data that may be used,  a, >rding to the Guidelines, in the derivation of



 Final Acute  Values for phenanthrene are  presented in Table 1.  The acute




 toxicity of  phenanthrene has been measured  with nine freshwater species.   Call




 et  al.  (1986)  exposed six species  to phenanthrene in flow-through tests in




 which the concentrations were  measured.   The acute values were 96,  117,  126,




 375,  and 234 Mg/L  for the hydra,  Daphnia ma^na. amphipod, rainbow trout,




 and bluegill,  respectively.  An annelid,  Lumbriculu*  V.JMP^^  was more
resistant to phenanthrene  with  a  96-hr  LC50  of  > 419 Mg/L.   Eastmond et al.




(1984) and Milleman  et  al.  (1984)  conducted  static  tests  with  Daphnia  mama.



Their 48-hr ECSOs were  about 6  to  7  times  higher than the  value reported by




Call et al.  (1986).  Another Daphnia species, D.  £uiex, was  tested  by Geiger




                                        2

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  and  Buikema  (1981,1982)  and  Trucco  et  al.  (1983).   Trucco  et.al.,  reported  a




  48-hr  EC50 of.10,0  Mg/L,  which  is  close  to  the  value  obtained  by  Call et al.




  (1986)  for D.  ma^na.   Geiger and  Buikema reported  the 48-hr EC50 to be above




  the  highest  tested concentration.   Because this  result was from  a  test in




  which  the concentrations of  phenanthrene were  not  measured, and  data from a




  test with the  same  species in which the concentrations were measured are




  available which are  in agreement  with other data on  daphnids,  this later value




  was not used to calculate the mean acute value for D. pulex.   Data on the   '




  acute toxicity of  phenanthrene to insects  is limited to a single species,




  Chironomus tentans.  Millemann e,t al.  (1984) reported a 48-hr EC50 of




 490 Mg/L for the larva of this midge.   Milleman and co-workers also tested




 the fathead minnow, Pimephales firomejas. and reported the 96-hr LC50 to be



 greater than the highest tested concentration.




      Freshwater Species Mean Acute Values (Table  1) were calculated as




 geometric  means of  the available  acute  values,  .and Genus Mean  Acute Values



 (Table  3)  were  calculated as  geometric  means  of uie Species Mean Acute




 Values.  Of the  eight freshwater  genera for which mean acute  values are




 available, the  most sensitive genus, Hvdr-a.  is  at least  13  times  more




 sensitive  than  the  most resistant, Pimeohales.  The range  of values for the




 four most  sensitive genera, which  include three invertebrates  and one fish,  is




 a factor of 2.4.  The  freshwater Final  Acute  Value  for phenanthrene was



 calculated to be 59.63  Mg/L usnng  the procedure described  in the




 Guidelines and the  Genus  Mean Acute  Values  in Table 3.   The Final Acute Value




 is  lower than the lowest  freshwater  Species Mean  Acute Value.




     The acute toxicity of phenanthrene  to  resident North American  saltwater




animals has been determined with eight  species  of  invertebrates  and two




species of  fish (Table  1).  The acute values range  from  17.7 Mg/L (Battel-le




Ocean Sciences 1987) and 27.1 Mg/L (Kuhn and Lussier  1987)  for the  mysid,




                                       3

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  My$id°P3is ^Ma, to 600 ^g/L for the polychaete worm,  Neanthes



  arenaceodentata .(Rossi and Neff 1978).   The mysid is about five times  more



  sensitive than the next most sensitive  species,  the  Atlantic  siiverside,



  Menidia menidia.  and the range of sensitivites  of the  five most sensitive



  species is a factor of 8.4.   The  saltwater  Final  Acute  Value  for phenanthrene



  was calculated to be 15.46 n/L.  which  is  lower  than the  mean acute  value



  for the most sensitive saltwater  species tested.







  Chronic  Toxicitv  to  Aquatic  Animals




      The  available  data  that  are  usable according  to the  Guidelines  concerning



  the chronic  toxicity of  phenanthrene  are presented in Table 2.   Call et al.



  (1986) conducted  a  life-cycle  test, with Daphnia magna and  found  that




  163 Mg/L  prevented reproduction.  The total number of young per  test




 chamber was  reduced  by 45  and  46% at  phenanthrene concentrations of 57 and



 46 pg/L, respectively,  although those values were not found to be




 statistically different from the control due to variability amongst



 replicates.  The morta.;ty in the  control  treatment in this test was 25%.   The



 chronic  value is 96 Mg/L, and the  acute-chronic ratio is 1.214.




      In  an early life-stage test with rainbow trout,  no fish survived at



 66 »g/L  and survival  was reduced to  57%  at  8 Mg/L (Call  et al. 1986).




 Total biomass per  test  chamber at  the end of the  test was  reduced 75, 44,  33,




 and  9%.  in comparison to  the  control  treatment,  by phenanthrene concentrations



 of 32, 14,  8,  and  5 MgA,  respectively.  The chronic  value for this  species



 is 6.325 ng/L and  the acute-chronic  ratio is 59.29.




     The chronic toxicity  of  phenanthrene has been determined  in a  life-cycle



toxicity test  with the  saltwater mysid, Mvsidonsi.  h.hu (Kuhn and  Lussier



1987).   All mysids exposed  to  11.91 Mg/L died.  Survival,  growth,  and

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  reproduction were not significantly reduced by 5.549  ,ug/L.   However, '533




  fewer young per_reproducti ve  day were  produced in 5.549  ^g/L.   The  chronic




  value was  8.129  ^g/L (Table  2).   The  acute-chronic  ratio,  calculated  using



  this  chronic value  and the acute value  of  27.10 ng/L,  is  3.333




       The available  Species Mean  Acute-Chronic  Ratios  are  59.29,  1.214, and




  3.333 (Table 3).  This  range  is  too great  to allow  calculation  of a Final




  Acute-Chronic  Ratio  as  the geometric mean  of the  three ratios.   The ratio of




  1.214 was  obtained  with one of the most acutely sensitive tested freshwater




  species.   It is  used  as the freshwater Final Acute-Chronic Ratio, which




  results in  a  freshwater Final Chronic Value of 49.12 Mg/L.  However, this




  value must  be  lowered to 6.324 Mg/L (Table 2)  to  protect the important




  rainbow trout.  Because the ratio of 3.333 was obtained with the most acutely



  sensitive of the tested saltwater species,  it  is  used as the saltwater Final




 Acute-Chronic Ratio.  Division of the saltwater Final  Acute Value by 3.333



 results in  a saltwater Final  Chronic Value  of 4.638
 Toxicitv to Aquatic Plants





      Call  et aL.  (1986)  exposed the duckweed,  Lemna minor,  to phenanthrene.



 Frond production  was  reduced 36% by 658 Mg/L,  7% by 356 Mg/L,  and 24% by




 198 Mg/L.   Hsieh  et al.  (1980)  exposed a freshwater alga,  Selenastmm




 eapricornutnm.  to  phenanthren*  as  well  as  to  17  other PAHs  using an "algal




 lawn"  technique.   Although it  is difficult  to  relate  results  of  such tests  to




 phenanthrene  concentration in water,  it  is  noteworthy that  phenanthrene  was




 one of the  most toxic of the chemicals.  Data  in Table  6  also  suggest that




 algae might  be quite sensitive-  to  phenanthrene.   No data  are  available




concerning  the toxicity of phenanthrene  to  saltwater  plants.   A  Final  Plant




Value, as defined  in the Guidelines, cannot be obtained because  no  test  in

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  which the concentrations of phenanthrene were measured has been conducted with
  sensitive aquatrc plant species.
  Bi oaccumulation
       Carlson et al.  (1979)  studied the  uptake  of  phenanthrene  by  the  fathead
  minnow,  Pimephales promelas (Table 5).   In exposures  of'?,  14,  18,  21,  and 28
  days,  mean bioconcentration factors (BCFs)  were  1,875,  2,100,  3,700,  2,100 and
  2,820,  respectively.   The  effect  of particulate-bound phenanthrene  on uptake
  by the  fathead  minnow was  negligible  in  exposures  less  than  10  days,  although
  after  14  days the  presence  of  pa,rticulates  reduced  the  BCF  (Gerhart et  al'.
  1981).   In exposures  of  24  to  90  hr with either Daphnia magna  or  DaphnU
 £Hiez, BCFs  ranged from  300  to 600  (Eastmond et al. J.984; Newsted and Giesy
  1987; Southworth et al.  1978).  In  a 24-hr  exposure of  green alga, Selenastrun.
 .capricornutum, Casserly  et al. (1983) obtained a BCF  of 10.6 (Table 6).
      No data are available from which steady-state BCFs can be calculated or
 estimated  for saltwater  species.   However,   the extent to which phenanthrene
 bioconcentrates  in the blue mussel, Mvti 1 us eduMs. and the common rangia,
 RancOa cuneata,  has been determined in tests lasting < 24 hours (Table 6).
 Blue mussels exposed  to ^C-labeled phenanthrene for 8 hours'accumulated 68
 times the 0.3 /zg/L  in  the test solution  and 81  times the 1.9 Mg/L in a
 second  treatment  (Hansen et  al.  1978).   Less than 50%  of the phenanthrene was
 depurated from the  soft tissues within 24 hours;  after 12  days  5% remained.
 The  BCF was 32 after 24-hours exposure of the  common rangia  to  89  Mg/L
 (Neff et  al.  1976).
     No U.S.  FDA action level  or other maximum  acceptable  concentration  in
tissue. „  defined  in  the Guidelines,  is  available  for phenanthrene,  and,
therefore,  no Final  Residue Value  can be  calculated.

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  Other Data

       Additionaj._data on the lethal  and sublethal  effects  of  phenanthrene  on '
  aquatic species  are  presented in Table 6.   Rogerson et  al.  (1983)  reported  the
  acute toxicity thresholds  to  be  greater than  the  solubility  limit  for  two
  freshwater protozoans,  Colpidium colpoda  and  Tetrahvmena  elliotti.  in  18-hr
  and  24-hr  exposures,  respectively.   Millemann et  al.  (1984)  reported the 48-hr
  LC50  for a snail,  Phvsa  .^na,  to  be  greater than  the  highest concentration
  tested.  An  amphipod, Gammarus nmvus,  was more  sensitive  to  phenanthrene with
  a  48-hr LC50 of  460  n/L.   The ECSOs,  based on  death  and  deformity  of
  embryos and  larvae,  for  rainbow  trout,  Salrno  gairdneri. and  largemouth bass,
  Micropterus  salmonies. were reported to be 30 and 250 Mg/L,  respectively.
      Developmental rates and  survival  of  larval mud crabs were reduced in
  200 Mg/L.   The effect was greatest  at  a salinity of 5 g/kg than at  15 or 25
  g/kg (Laughlin and Neff  1979).   Respiration rate and growth  of larval crabs
 were reduced in < 37.5 Mg/L (Laughlin  and Neff  1980).  The phototaxis of
 barnacle nauplii, BaUnus amjjutri^, was inhibited by phenanthrene; the EC50
 was at 55%  of a saturated solution  (Donahue et al. 1977).

 Unused Data

      Some data  concerning the  effects of phenanthrene on aquatic  organisms  and
 their  uses  were not used because  the tests were conducted  with species  that
 are not  resident  in North America (e.g.,  Afolabi et  al.  1983; Freitag et  al.
 1984).   Results of  tests  conducted with brine  shrimp.  Artemia sp.  (e.g.,
 Foster and  Tullis  1984,1985) were not  used because  these species  are from  a
 unique saltwater  environment.  Eadie (1984), Covers  et al.  (1984),  Hallett and
 Brecher (1984), Neff  (1979,1982.,b),  and Richards  and  Shieh  (1986)  compiled
data from other sources.  Bartell  (1984) reported  computer simulated data
only.

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       Results were not used when the test procedures were not adequately
  described (e.g.," She 1 ford 1917; Solbakken et al. I984c; Strength et al.
  1982).  Except  in biocongentration test,, data were not used when phenanthrene
  was a component of an effluent, mixture, oil,  or sediment (e.g.,  Augenfeld et
  al. 1980-1981.1982;  Black 1983a.b;  Carr et al.  1986;  Casserly et  al.  1983;
  Dauble et al. 1981;  Gray et  al. 1983;  Grushko  et al.  1980;  Hall  et  al.  1984;
  Horning et al.  1984;  Lopez-Avila et al.  1985;  Palawski  et al.  1985;  Pickering
  1983;  Vandermeulen et al.  1985; Woodward et  al.  1981).   Data were not  used
  when the  organisms were  exposed to  phenanthrene  by  injection or gavage  (e.g.,
  Niimi  and  Palazzo  1986;  Solbakken and  Palmork  1981,1984a,b;  Solbakken  et  al.
  1983,1984a).  Histological studies  were  not  used (e.g.,  Gerhart and  Carlson
  1978).  Results  of some  laboratory  tests were not used  because the  tests  were
  conducted  in  distilled or deionized water without addition  of appropriate
  salts (e.g..  Abernethy et al.  1986; Bobra et al.  1983;  Zepp  and Schlotzhauer
  1983).

      Results  of  laboratory bioconcentration tests were  not  used when the  test
 was not flow-through or  renewal  (e.g., Landrum et al. 1985)  or when the
 concentration of phenanthrene  in the te.t solution was  not adequately measured
 (e.g.,  Geiger and Buikema 1982; Krahn and Malins 1982).   Studies  using
 radiolabeled phenanthrene in which only  radioactivity was measured in the
 water or in exposed organisms were not used (Freitag et al.   1985;  Geyer et al.
 1984).   Reports  of the concentrations  of phenanthrene in wild aquatic
 organisms  (e.g.,  Black et al.  1981b; Boehm et al. 1982;  Dunn and Fee 1979;
 Eadie et al.  1982;  Farrington et al. 1982;  Grahl-Nielson et  al.  1978;  Heit et
 al.  1980; Humason and  Gadbois  1982;  Kalas et  al.  1980;  Knutsen and Sortlund
 1982; Kveseth  and Sortlund  1982;  Lee et  al.  1981;  Maccubbin  et al. 1985;
Mackie et al.  1980; Malins et  al.  1985;  Mix  1982;  Mix  and Schaffer 1983a,b;
Pittinger et al.   1985; Pruell  et  al. 1984; Rainio et  al.  1986; Sirota  and  Uthe
                                       8

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  1981;  Sirota et al.  1983;  Vassilaros  et  al.  1982;  Veith  et  al.  1981)  were  not
  used to  calculate  bioaccumulation  factors  when  the  number of measurements  of
  the  concentration  in water was  too  small or  the  range of the measured
  concentration in water  was too  lar^e
                                   
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  National Criteria
       The procedures described in the "Guidelines for Deriving Numerical
  National Water Quality Criteria for the Protection of Aquatic Organisms  and
  Their Uses" indicate that,  except where a locally important  species  is very
  sensitive,  freshwater aquatic organisms and their uses  should not  be  affected
  unacceptably if the four-day average concentration of'phenanthrene does  not
  exceed 6.3  /ig/L more than once  every three  years  on the  average  and  if the
  one-hour average  concentration  doe.s  not ex.ceed  30 Mg/L more  than once
  every three years  on the  average.   Because  sensitive  freshwater  animals  appear
  to  have  a narrow  range  of  susceptibilities  to phenanthrene,  this criterion
  will  probably be  as  protective as  intended  only when  the magnitudes and/or
  durations of excursions are  appropriately small.
      The procedures  described in the "Guidelines  for  Deriving Numerical
 National Water Quality criteria for  the Protection  of Aquatic Organisms and
 Their Uses" indicate that, except where a locally  important  species is very
 sensitive,  saltwater aquatic organisms and their  uses should not be affected
 unacceptably if the four-day average concentration of phenanthrene does not
 exceed 4.6 Mg/L more than once every three years on the average and if the
 one-hour average concentration does not exceed 7.7 Mg/L more than once
 every three  years  on the average.

 Implementation
      As  discussed  in the Hater Quality  Standards Regulation (U.S. EPA 1983a)
 and  the  Foreword to this document,  a  water quality criterion for aquatic  life
 has  regulatory  impact only  after  it  has  been adopted in  a state  water quality
 standard.  Such  a  standard  specifies  a  criterion for a pollutant that  is
consistent with a particular  designated  use.   With the concurrence  of  the  U.S.
EPA.  states  designate one or  more uses  for each  body of water or segment
                                       10

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  thereof and adopt criteria that are consistent with the use(s) (U.S. EPA
  1983b,1987).  In^each standard a state may adopt the national criterion, if
  one exists, or,  if adequately justified, a site-specific criterion.
      Site-specific criteria may include not only site-specific criterion
  concentrations (U.S.  EPA 1983b),  but also site-specific,  and nossibly
  pollutant-specific,  durations of  averaging periods  and frequencies of allowed
  excursions (U.S.  EPA  1985b).   The  averaging periods of "one hour"  and "four
 days"  were selected by the  U.S.  EPA on the basis  of data  concerning how
 rapidly some aquatic  species  react  to  increases in  the concentrations of .some
 aquatic pollutants, and  "three  years"  is the  Agency's  best  scientific judgment
 of  the  average amount  of  time  aquatic  ecosystems  should be  provided between
 excursions (Stephan et al.  1985; U.S.  EPA 1985b).   However,  various species
 and  ecosystems react and  recover at  greatly differing  rates.   Therefore,  if
 adequate justification is provided,  site-specific and/or pollutant-specific
 concentrations, durations,  and frequencies  may  be higher or  lower  than  those
 given in national water quality criteria  for aquatic life.
     Use of criteria,  which have been adopted in state  water  quality
 standards,  for developing water quality-based permit limits and for designing
waste treatment facilities requires  selection of an appropriate wasteload
allocation model.   Although dynamic models are  preferred for  the application
of these criteria (U.S.  EPA 1985b),   limited data or other considerations might
require  the use of a steady-state  model (U.S.  EPA 1986).  Guidance on mixing
zones and the design of monitoring  programs is also available (U.S. EPA
1985b,1987).
                                      11

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