5EPA
           United States
           Environmental Protection
           Agency
            Environmental Research
            Laboratory
            Athens GA 3061 3
EPA/600/3-85/040
June 1985
            Research and Development
Rates, Constants, and
Kinetics
Formulations in
Surface Water Quality
Modeling
(Second  Edition)


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                                                 EPA/600/3-85/040
                                                 June 1985
       RATES, CONSTANTS, AND KINETICS FORMULATIONS
            IN SURFACE WATER QUALITY MODELING
                    (SECOND EDITION)

                            By
  George L. Bowie, William B. Mills, Donald B. Porcella,
Carrie L. Campbell, James R. Pagenkopf, Gretchen L. Rif-pp,
    Kay M. Johnson, Peter W.H. Chan, Steven A. Gherini

                 Tetra Tech, Incorporated
               Lafayette, California  94549

                           and
                  Charles E. Chamberlin
                Humboldt State University
                 Arcata, California 95521


                   Contract 68-03-3131
                     Project Officer

                 Thomas 0. Barnwell, Jr.
      Technology Development and Applications Branch
            Environmental Research Laboratory
                  Athens, Georgia  30613
            ENVIRONMENTAL RESEARCH LABORATORY
            OFFICE OF RESEARCH AND DEVELOPMENT
           U.S. ENVIRONMENTAL PROTECTION AGENCY
                  ATHENS, GEORGIA  30613

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                                DISCLAIMER

      The information in this document has been funded wholly or in part by
the United States Environmental  Protection Agency under Contract No. 68-03-
3131 to Tetra Tech,  Incorporated.   It has been subject to the Agency's peer
and administrative review,  and it  has been approved for publication as an
EPA document.  Mention of trade names or commercial products does not con-
stitute endorsement or recommendation for use by the U.S. Environmental
Protection Agency.

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                                 FOREWORD

      As environmental controls become more costly to implement and the
penalties of judgment errors become more severe, environmental quality
management requires more efficient analytical tools based on greater know-
ledge of the environmental phenomena to be managed.  As part of this Labora-
tory's research on the occurrence, movement, transformation, impact, and con-
trol of environmental contaminants, the Technology Development and Applica-
tions Branch develops management or engineering tools to help pollution
control officials achieve water quality goals.

      Basin planning requires a set of analysis procedures that can provide
an assessment on the current state of the environment and a means of predic-
ting the effectiveness of alternative pollution control strategies.  This
report contains a revised and updated compilation and discussion of rates,
constants, and kinetics formulations that have been used to accomplish these
tasks.  It is directed, toward all water quality planners who must interpret
technical information from many sources and recommend the most prudent course
of action that will minimize the cost of implementation of a pollutant con-
trol activity and maximize the environmental benefits to the community.

                                     Rosemarie C. Russo
                                     Director
                                     Environmental Research Laboratory
                                     Athens, Georgia

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                                 ABSTRACT
     Recent  studies are reviewed to  provide a comprehensive volume on  state-
of-the-art formulations used in surface water  quality modeling along with
accepted values for rate  constants and coefficients.   Topics covered
include:   dispersion, heat budgets,  dissolved oxygen saturation, reaeration,
CBOD decay,  NBOD decay,  sediment  oxygen demand,  photosynthesis,  pH  and
alkalinity,  nutrients, algae, zooplankton, and coliform bacteria.  Factors
affecting the  specific phenomena and methods of measurement are discussed in
addition  to  data  on rate constants.

     This report was submitted in fulfillment of Contract No.  68-03-3131 by
Tetra Tech,  Incorporated, under the  sponsorship  of the U.S. Environmental
Protection Agency.  The report covers the period June 1983 to April  1985t
and work  was  completed as of April 1985.
                                   IV

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                                 CONTENTS

Fdreword	   111
Abstract	    |v
Figures	   V1<1'
Tables	    x]
Acknowledgments	   XV1'

1.  Introduction 	    1
      1.1  Background	    1
      1.2  Purpose and Use of This Manual  	    2
      1.3  Scope and Arrangement of Manual 	    2
      1.4  General Observations on Model Formulations, Rate Constants,
           and Coefficients	    3
      1.5  References.	    4

2.  Physical Processes 	    6
      2.1  Introduction   	    6
      2.2  Advective Transport 	,	   11
      2.3  Dispersive Transport  	   17
      2.4  Surface Heat Budget	   61
      2.5  References	   76

3.  Dissolved Oxygen   	   90
      3.1  Dissolved Oxygen Saturation  	   90
      3.2  Reaeration	101
      3.3  Carbonaceous Deoxygenation	  .  135
      3.4  Nitrogenous Biochemical Oxygen Demand 	  158
      3.5  Sediment Oxygen Demand (SOD)  	  173
      3.6  Photosynthesis and Respiration  	  188
      3.7  References  ........  	  205

4.  pH and Alkalinity	231
      4.1  Introduction	231
      4.2  Carbonate Alkalinity System	231
      4.3  Extended Alkalinity Approach  	  236
      4.4  Summary	241
      4.5  References	242

5.  Nutrients	244
      5.1  Introduction	244
      5.2  Nutrient Cycles	  245
      5.3  General Modeling Approach for All Nutrients 	  247
      5.4  Temperature Effects 	  253
      5.5  Carbon Transformations  	  255
      5.6  Nitrogen Transformations   	  257

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        5.7   Phosphorus Transformations 	 ,.   265
        5.8   Silicon Transformations  	   265
        5.9   Algal Uptake   	268
        5.10  Excretion	271
        5.11  Sediment Release 	   272
        5.12  Summary	273
        5.13  References	274

6.  Algae	279
        6.1   Introduction	279
        6.2   Modeling Approaches  	   281
        6.3   Cell Composition	285
        6.4   Growth	287
        6.5   Respiration and Excretion  .	342
        6.6   Settling	345
        6.7   Nonpredatory Mortality 	   351
        6.8   Grazing	357
        6.9   Summary	363
        6.10  References	365

7.  Zooplankton	375
        7.1   Introduction	375
        7.2   Temperature Effects  	   376
        7.3   Growth	378
        7.4   Respiration and Mortality	400
        7.5   Predatory Mortality  	   409
        7.6   Summary	416
        7.7   References	418

8.  Coliform Bacteria  	   424
        8.1   Introduction	424
        8.2   Composition and Assay	426
        8.3   Modeling Coliforms 	   428
        8.4   Summary	449
        8.5   References .	450

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                                  FIGURES
Number                                                                 Page

 2-1       One-dimensional geometric representation for river
             systems. .... ...................       9
 2-2       Two-dimensional geometric representation for lake
             systems. ...
 2-3       Oscillation of velocity component about a mean value .  .      18

 2-4       Diffusion coefficients characteristic of various
             environments ............. .  ........      20

 2-5       Dependence of the horizontal diffusion coefficient
             on the scale of the phenomenon ............      31

 2-6       Okubo's diffusion data and 4/3 power lines  .......      32

 2-7       Factors contributing to tidal ly averaged dispersion
             coefficients in the estuarine environment .......      42

 2-8       Dispersion coefficients in streams ...........      54

 2-9       Clear sky solar radiation according to Hamon,  Weiss
             and Wilson (1954) ...................      65

 3-1       Predicte'd reaeration coefficients as a function of
             depth from thirteen predictive equations  .......      HI

 3-2       Comparisons of predicted and observed reaeration
             coefficients for the formula of Dobbins (1965) (a)
             and Parkhurst-Pomeroy (1972) (b) ...........      112

 3-3       Formula of Bennett and Rathbun (1972) compared against
             observed reaeration coefficients . ..........      113

 3-4       Calculated versus experimental reaeration coefficients
             for equations of (a) Tsivoglou and Wallace (1972),
             (b) Padden and Gloyna (1971), and (c) Parkhurst and
             Pomeroy (1972) ....................      114
                                   Vll

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Number
                            FIGURES  (continued)


                                                                       Page
 3-5       Reaeration coefficient versus energy dissipation
             (a) for flow rates between 10 and 280 cfs and
             (b) for flow rates less than 10 cfs ..........      115

 3-6       Field data considered by three different investigations.      H6

 3-7       Reaeration coefficient (I/day) vs. depth and velocity
             using the suggested method of Covar (1976) ......     H7

 3-8       Ratio of reaeration coefficient under windy conditions
             to reaeration coefficient without wind, as a
             function of wind speed ....... . ........     123

 3-9       Division of head loss structures by dam type ......     126

 3-10      Sources and sinks of carbonaceous BOD in the aquatic
             environment ......................     137

 3-11      Deoxygenation coefficient (k ,) as a function of depth. .     147

 3-12      Example computation of kR based on BOD measurements of
             stream water .....................     156

 3-13      Effect of reduced nitrogen concentration on
             nitrification rate as reported by Borchardt (1966) . .     162

 3-14      Effect of temperature on nitrification as reported
             by Borchardt (1966) ..................     166

 3-15      pH dependence of nitrification .............     167

 3-16      Nitrogenous biochemical oxygen demand versus travel
             time in Shenandoah River  ...............     171

 3-17      Diurnal variation of (P-R)  in Truckee River near
             Station 2B  ......................     198

 3-18      Concept of Stokes total time derivative .........     199

 3-19      Algal productivity and chlorophyll relationships for
             streams .....................  ...     202
 4-1       [SCn - SC.J plotted against reported alkalinity .....    239

 5-1       Nutrient interactions for carbon, nitrogen, and
             phosphorus ......................    246

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                             FIGURES (continued)


Number                                                                Page

 5-2       Nutrient interactions for silica 	     247

 5-3       Nitrogen cycle	     248

 5-4       Phosphorus cycle 	     249

 5-5       Effect of pH and temperature on unionized ammonia.  .  .  .     264

 6-1       Major types of temperature response curves for algal
             growth	     294

 6-2       Envelope curve of algal growth rate versus temperature
             for data compiled from many studies involving many
             different species	     298

 6-3       Temperature-growth curves for major algal groups ....     304

 6-4       Comparison of light response curves for algal growth .  .     312

 6-5       Michaelis-Menten saturation kinetics for algal growth
             limitation by a single nutrient	     324

 7-1       Growth  rate and grazing rate as a function of food
             supply for zooplankton with constant filtration rates
             and assimilation efficiencies	     380

 7-2       Comparison of the Ivlev and Michaelis-Menten functions
             with  the same half-saturation value	   388

 7-3       Comparison of reverse Michaelis-Menten formulation
             (a) and Canale et aJL 's, (1975, 1976) formulation (b) for
             filtration rate as a function of food concentration.  .     394

 7-4       Frequency histograms for zooplankton assimilation
             efficiencies 	     403

 7-5       Frequency histograms showing variations in zooplankton
             assimilation efficiencies with different food types.  .     404

 7-6       Frequency histograms of zooplankton respiration rates.  .     415

 7-7       Frequency histogram of nonpredatory mortality rates
             for zooplankton	     416

 8-1       Relationship between pathogen or virus decay rates and
             coliform decay rates based on figure presented by
             Chamberlin (1982)	     425

                                    ix

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                            FIGURES (continued)

Number

8-2       Typical mortality curves for coliforms as a function
            of time	

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                                   TABLES


Number                                                                 Page

 2-1       Major Reviews of Modeling State-of-the-Art 	      7

 2-2       Values for Empirical Coefficients a, and a?	     28

 2-3       Tidally Averaged Dispersion Coefficients for Selected
             Estuaries	     45

 2-4       Tidally Averaged Dispersion Coefficients 	     46

 2-5       References Related to Longitudinal Dispersion. .....     49

 2-6       Summary of Studies of Transverse Mixing in Streams ...     57

 2-7       Transverse Mixing Coefficients in Natural Streams and
             Channels	     58

 2-8       Summary of Field Data for Transverse Dispersion
             Coefficients 	     59

 2-9       Summary of Nondimensional Diffusion Factors in Natural
             Streams	     60

 2-10      Values for Short Wave Radiation Coefficients A and B  .  .     66

 2-11      Values for Empirical Coefficients	     69

 2-12      Evaporation Formula for Lakes and Reservoirs  	     71

 3-1       Methods Used by Selected Models to Predict Dissolved
             Oxygen Saturation	      91

 3-2       Solubility of Oxygen in Water Exposed to Water-
             Saturated Air at 1.000 Atmosphere Pressure  	      93

 3-3       Values for the Bracketed Quantity Shown in Equation 3-11
             to be Used with the Corresponding Temperatures and
             Pressures	      95

 3-4       Comparison of Dissolved Oxygen Saturation Values
             from Ten Equations at 0.0 mg/1 Salinity and
             1 atm Pressure	      97

                                    xi

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                             TABLES (continued)


Number

 3-5       Comparison of Dissolved Oxygen Saturation Values from
             Selected Equations at a Chloride Concentration of
             20,000 mg/1 (36.1 ppt Salinity)  and 1 atm Pressure .  .      98

 3-6       Reaeration Coefficients for Rivers and Streams 	     103

 3-7       Summary of Studies which Reviewed  Stream Reaeration
             Coefficients ..... 	     108

 3-8       Equations that Predict the Effects of Small Dams on
             Stream Reaeration. .	     '25

 3-9       Reported Values of Temperature Coefficient 	     127

 3-10      Sources of Stram Reaeration Data	     128

 3-11      Reaeration Coefficients for Lakes	     130

 3-12      Reaeration Coefficients for Estuaries	     132

 3-13      Values of the Temperature Compensation Coefficient
             Used for Carbonaceous BOD Decay.	     142

 3-14      Coefficient of Bed Activ.ity as a Function of Stream
             Slope	     143

 3-15      Deoxygenation Rates for Selected U.S. Rivers 	     144

 3-16      Expressions for Carbonaceous Oxygen Demand Used in
             Water Quality Models ..... 	     150

 3-17      Values of Kinetic Coefficients for Decay of
             Carbonaceous BOD	    152

 3-18      Expressions for Nitrogenous Biochemical Oxidation
             Rates Used in a Variety of Water Quality Models  ...     160

 3-19      Summary of Factors that Influence Nitrification	     164

 3-20      Temperature Correction Factor, #,  for Nitrification. .  .     165

 3-21      Case Studies of Nitrification in Natural Waters	     169

 3-22      Summary of Nitrification Rates  	     172
                                    xi i

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                             TABLES (continued)


Number                                                                 Page

 3-23      Some Typical Values of the Temperature Coefficient for
             SOD Rate Coefficients Used in Water Quality Models . .     179

 3-24      Model Formulations Commonly Used in SOD Computations . .

 3-25      Average Values of Oxygen Uptake Rates of River Bottoms .

 3-26      Measured Values of Sediment Oxygen Demand in Rivers
             and Streams,
                                                                       189
 3-27      Measured Values of Sediment Oxygen Demand in Lakes
             and Reservoirs ....................     190

 3-28      Measured Values of Sediment Oxygen Demand in
             Estuaries and Marine Systems .............     19"!
 3-29      Oxygen Produced per Mass of Algae ............     192

 3-30      Oxygen Consumed per Mass of Algae ............     193

 3-31      Summary of Methods to Predict Photosynthetic Oxygen
             Production and Respiration without Simulating Algal
             Growth and Death ...................     194

 3-32      Photosynthetic Oxygen Production and Respiration
             Rates in Rivers ....................     204

 4-1       Options and their Required Input Parameters for PHCALC .     240

 5-1       Comparison of Nutrient Models ..............     254

 5-2       Rate Coefficients for Carbon Transformations ......     256

 5-3       Rate Coefficients for Nitrogen Transformations .....     259

 5-4       Rate Coefficients for Denitrification ..........     262

 5-5       Rate Coefficients for Phosphorus Transformations ....     266

 5-6       Rate Coefficients for Silica Transformations ......     267

 6-1       General Comparison of Algal Models ...........     283

 6-2       Nutrient Composition of Algal Cells - Percent of
             Dry Weight Biomass ..................     286

 6-3       Nutrient Composition of Algal Cells - Ratio to Carbon. .     288


                                    xiii

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                             TABLES (continued)






Number
6-4

6-5
6-6

6-7
6-8
6-9
6-10

6-11
6-12

6-13
6-14
6-15
6-16
6-17
6-18
6-19
6-20
7-1
7-2
7-3
7-4
Nutrient Composition of Algal Cells - Ratio to
Chlorophyll a 	
Algal Maximum Growth Rates 	
Comparison of Temperature Adjustment Functions for
Algal Growth 	
Comparison of Light Limitation Formulations 	
Algal Saturating Light Intensities 	
Half-saturation Constants for Light Limitation 	
Half-Saturation Constants for Michael is-Menten
Growth Formulations 	
Comparison of Algal Growth Formulations 	
Half-Saturation Constants for Variable Stoichiometry
Formulations 	
Minimum Cell Quotas 	
Maximum Internal Nutrient Concentrations 	
Maximum Nutrient Uptake Rates 	
Half-Saturation Constants for Nutrient Uptake 	
Model-Specific Nutrient Uptake Parameters 	
Algal Respiration Rates 	
Phytoplankton Settling Velocities 	
Algal Nonpredatory Mortality Rates 	
General Comparison of Zooplankton Models 	
Zooplankton Maximum Consumption Rates 	
Zooplankton Maximum Filtration Rates 	
Zooplankton Maximum Growth Rates 	

289
291

3n5
319
320
321

327
329

332
333
334
339
340
341
346
352
358
377
382
383
384
                                    xiv

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                             TABLES (continued)


Number                                                                 Page

 7-5       Comparison  of Temperature Adjustment Functions for
             Zooplankton Growth and Consumption ..........    385

 7-6       Michael is-Menten Half-Saturation Constants for
             Zooplankton Consumption and Growth ....  ......
 7-7       Threshold  Feeding  Levels for Zooplankton  .  .  ......

 7-8       Comparison  of Zooplankton  Growth Formulations ......     396

 7-9       Zooplankton Assimilation Efficiencies ..........     401

 7-10      Zooplankton Respiration Rates ..............     410

 7-11      Zooplankton Mortality Rates ...............     413

 8-1       Factors Affecting Coliform  Disappearance  Rates .....     435

 8-2       Coliform Bacteria Freshwater Disappearance Rates
             Measured  Iji situ ...................     436

 8-3       Values for  Coliform-Specific Disappearance Rates  Used
             in Several Modeling Studies ......... ......     437

 8-4       Nutrient KS Values for Escherichia Coli .........     438

 8-5       Values of Co, C', k,  and k1  from the Ohio River .....     441

 8-6       Summary of  Decay Rates of  Tc,  Fc, and  Fs  ........     442

 8-7       Comparison  of kg Estimates  Based on Chamberlin and
             Mitchell  (1978) with Additional Values  ........     444

 8-8       Parameter Estimates for Lantrip (1983)  Multi-Factor
             Decay Models .....................      446

 8-9       Experimental Hourly T-90 Values ............      449
                                   xv

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                            ACKNOWLEDGMENTS

     Special  thanks are due to the  participants in the Rates  Manual Workshop
held at Tetra Tech, Lafayette during November  29-30, 1984 to  review the
first  draft  of the report.  These include Ray Whittemore (National Council
of  the Paper Industry for Air  and Stream  Improvement,  Inc.)» Steve
McCutcheon  (U.S.  Geological  Survey),  Kent  Thornton (Ford, Thornton, and
Norton, Inc.),  Vic Bierman  (U.S.  Environmental  Protection Agency), Tom
Barnwell  (U.S. Environmental  Protection Agency),  Don Scavia  (National
Oceanic and Atmospheric Administration), Tom Gallagher (HydroQual,  Inc.),
Carl  Chen  (Systech, Inc.),  Jerry Orlob (University  of California, Davis),
Lam Lau (National  Water Research  Institute, Ontario,  Canada), Bill  Walker
(private consultant),  and  Peter Shanahan  (Environmental Research and
Technology,  Inc.).  Betsy Southerland  (U.S. Environmental  Protection Agency)
was unable  to attend but also participated in  the review of the first draft.
The above individuals provided many useful comments  and references which
were incorporated  in the final report.

     Numerous other individuals also provided  reference materials during the
preparation of  this report.  Although  they are too numerous to mention here,
their  input  is  greatly appreciated.

     We would  also like to thank Trudy  Rokas, Susan Madson,  Gloria Sellers,
Belinda Hamm, and  Faye Connaway for typing and  preparing the report, and
Marilyn Davies  for providing most of the graphics.

     Finally, thanks are due most to Tom Barnwell and the U.S. Environmental
Protection Agency, Environmental Research Laboratory, Athens,  Georgia for
both funding  the project and providing technical input and guidance.
                                   xvi

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                               Chapter 1
                              INTRODUCTION

1.1 BACKGROUND

     The  use of mathematical models to simulate ecological  and  water quality
interactions in surface waters has  grown  dramatically over  the  past two
decades.   Simulation techniques offer an  integrated and relatively sound
course for  evaluating wasteload abatement alternatives.  Predictions  of
system behavior based upon mathematical  simulation techniques  may  be
misleading, however, particularly if the physical  mechanisms  involved are
not accurately represented  in the model.   Furthermore, even where the model
does faithfully describe mechanisms in the  prototype, poor results  may  be
obtained where  insufficient data are available to estimate rate constants
and coefficients.

     Much of the work  done  in  the  water quality modeling field has been
oriented  toward improvement  of models—toward incorporating better numerical
solution  techniques, toward an  expanded complement  of water quality
constituents simulated, and toward  realistic representations  of modeled
physical, chemical, and biological phenomena. There is, however, a need for
a  document that summarizes  the  rate  constants  and coefficients
(e.g., nitrification rates and reaeration  rates) needed in the  models.  This
document  is intended to satisfy that need.

     The  first edition of this document was published seven years ago  (Zison
e_t jil_., 1978).  Because an extensive body  of literature on rate constants
and modeling formulations  has emerged since that time, the  United  States
Environmental Protection Agency has sponsored an updating of the manual.  In
addition,  a workshop was held to  evaluate  the manual, to  review the
                                   1

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formulations  and associated coefficients  and  rate values,  and  to provide
further  data for  the final document.   As a result of the literature  review
and workshop,  a substantially new manual  has been produced.

1.2  PURPOSE  AND USE OF THIS MANUAL

     This manual  is intended for use  by practitioners  as  a  handbook—a
convenient reference on modeling formulations, constants, and rates commonly
used  in  surface  water quality simulations.   Guidance is  provided in
selecting appropriate formulations or  values of rate constants  for specific
applications. The manual also provides  a range of coefficient  values that
can be used to perform sensitivity analyses.  Where appropriate,  measurement
techniques for rate constants are also  discussed.

      It was impossible, however, to encompass all formulations or to examine
all recent reports containing rates data.   It is hoped, therefore, that the
user  will recognize the  desirability of seeking additional  sources where
questions remain about formulations or  values.  Data used  from  within this
volume should be recognized as representing a sampling from  a larger  set of
data.  It should also be noted that there are  often very  real  limitations
involved in  using literature values  for rates rather than  observed  system
values.  It is hoped that this document  will find its main use as a guide in
the  search for  "the correct value"  rather than as the sole source of that
value.

1.3  SCOPE AND ARRANGEMENT OF MANUAL

     In  preparing  this  manual, an  attempt was made  to   present  a
comprehensive set of formulations and  associated constants.   In  contrast to
the first edition (Zison e_t a_L,1978),  the manual has  been  divided into
sections  containing specific topics.   Following this introduction, chapters
are presented that discuss the following topics:

     i  Physical processes of dispersion and temperature
     ®  Dissolved oxygen

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     •  pH and alkalinity
     c  Nutrients
     •  Algae
     •  Zooplankton
     •  Coliforms

     The parameters that  are  addressed in this manual  are  those that
traditionally have been the  focus of water  quality management and the focus
for control of  conventional pollutants.   These include temperature,
dissolved oxygen, nutrients and eutrophication,  and coliform bacteria.
Higher organisms (fish, benthos) are not discussed, nor are the details  of
higher  trophic  levels in ecosystem models.  Also, hydrodynamic processes,
although important, are not dealt with in detail.
1.4  GENERAL  OBSERVATIONS ON  MODEL FORMULATIONS, RATE CONSTANTS, AND
     COEFFICIENTS
     Each rate value  or  expression used in  a model should  not be chosen  as
an "afterthought", but should be  considered  as an integral part of the
modeling  process.  A substantial portion of any modeling  effort should  go
into selecting  specific approaches  and formulations  based  upon the
objectives  of modeling, the kinds and  amounts of data available, and the
strengths  and  weaknesses of  the approach or formulation.  Once formulations
have  been  selected, a significant  effort should be made to determine
satisfactory value's for parameters.   Even  where the parameter  is  to  be
chosen  by  calibration, it is clearly  important  to  establish whether the
calibrated  value is within  a reasonable range or not.  Recent references  on
model  calibration include Thomann  (1983), National Council on Air and
Stream  Improvement (1982),  and Beck (1983).   Users should be aware that  an
acceptable  model  calibration does not imply that the model has predictive
capability.   The model may contain  incorrect  mechanisms, and agreement
between model predictions  and observations could have  been  obtained through
an unrealistic choice of parameter values.   Further, the future status  of
the prototype may be controlled by  processes  not even  simulated in  the
model.

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     Values  of many constants and coefficients are dependent upon the way
they are used  in modeling  formulations.   For example, while pollutant
dispersion is  an observable  physical  process,  modeling this process is
partly  a mathematical  construct.   Therefore, constants that are  used to
represent the  process  (i.e.,  dispersion  coefficients) cannot be chosen
purely on the  basis  of  physics  since  they also  depend on the modeling
approach.  For example,  to determine  the dispersion  coefficients  in  a
model application to an  estuary,  both the time and length  scales  of the
model  must be considered.   Whether  the model  is tidally averaged or
simulates  intra-tidal  variations,  and  whether the model is  1-, 2-, or 3-
dimensional,  all  influence the value of the appropriate dispersion
coefficient for that model.  Ford  and Thornton (1979) discuss  scale  effects
in  ecological  models,  and conclude  that inconsistent scales  for the
hydrodynamics,  chemistry, and  biology  may produce erroneous model
predictions.

     Since coefficient values are  never known with certainty, modelers are
constantly faced with  the question of how accurately rate  constants should
be known.  The  relationship between uncertainty in coefficient values and
model  predictions can be evaluated by performing sensitivity  analyses.   For
models with  few parameters, sensitivity  analyses are  generally
straightforward.   However, for complex models, sensitivity analyses are no
longer straightforward  since  many dynamic interactions  are  involved.
Sensitivity analyses  are discussed in detail in Thornton and  Lessem (1976),
Thornton (1983), and Beck (1983).

1.5  REFERENCES
Beck,  M.B.   1983.   Sensitivity  Analysis, Calibration,  and Validation.
Iji: Mathematical Modeling of Water Quality:  Streams, Lakes, and  Reservoirs.
International  Institute  for Applied Systems Analysis.  Editor:  G.T.  Orlob.
Ford,  D.E. and K.S.  Thornton.  1979.  Time and  Length  Scales  for  the One-
Dimensional Assumption and its  Relation to Ecological  Models.  Water
Resources  Research.   Vol.  15, No.  1, pp. 113-120.
National Council of the  Paper Industry for Air and  Stream Improvement,  Inc.
1982.   A  Study of  the  Selection,  Calibration and Verification of
Mathematical Water Quality Models. NCASI Tech. Bull. 367, New York.

                                  4

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Thomann,  R.V.   1982.  Verification of Water Quality  Models. Journal  of
Environmental  Engineering  Division, ASCE.  Vol.  108,  No. EE5, October,
pp.  923-940.

Thornton,  K.W. and A.S. Lessem.   1976.  Sensitivity  Analysis of the Water
Quality for  River-Reservoir Systems Model.  U.S.  Army Waterways Experiment
Station.   Misc. Paper Y-76-4.

Thornton,  K.W.   1983.  Sensitivity  Analysis in Simulation  Experimentation.
Encyclopedia  of Systems and Control.  Pergamon Press.

Zison, S.W.,  W.B. Mills, D. Deimer, and C.W. Chen.   1978.  Rates Constants
and Kinetics  Formulations in Surface  Water Quality  Modeling.  Prepared  by
Tetra Tech,  Inc., Lafayette,  CA,  for Environmental Research Laboratory,
USEPA, Athens, GA.  EPA-600/3-78-105.   335 pp.

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                                Chapter 2
                            PHYSICAL  PROCESSES

2.1  INTRODUCTION

     The purpose  of  this chapter is to give the reader an  overview of how
the major  physical processes  are incorporated  into water  quality  and
ecosystem  simulations.  Since a detailed review is beyond the  scope of this
report, the reader  is encouraged to review the articles listed  in Table  2-1
which  represent several of  the more complete  and  recent  reviews of the
state-of-the-art in physical process modeling.

     Physical  processes often simulated in water quality models  include flow
and circulation  patterns, mixing and dispersion, water temperature,  and  the
density distribution (which  is a function of  temperature,  salinity,  and
suspended solids concentrations) over  the water column.  It is  stressed that
quality predictions are very dependent upon the physical  processes and how
well these  are represented in the water quality simulations.    Despite  this
dependence,  the  modeler  often is forced to  make a trade-off  between
acceptable  degree of detail  in water quality vs. physical  process simulation
due to  cost or  other restrictions.   It is desirable  from the  standpoint of
both the engineer and ecosystem analyst, therefore, to select  the simplest
model  which satisfies the temporal  and spatial resolution required for water
quality and/or ecosystem simulation.   For example, the optimum  time  step for
dynamic  simulation of a fully-mixed impoundment would be  3-6 hours for
capturing diurnal fluctuations,  and daily or weekly for strongly stratified
impoundments  which normally exhibit slowly varying conditions.  In  terms of
spatial  resolution required,  the analyst  should take advantage of  the
possible  simplifications  of dominate physical characteristics (i.e.,
physical shape,  stratified layers,  mixing zones, etc.).

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           TABLE 2-1.  MAJOR REVIEWS OF MODELING STATE-OF-THE-ART


French,  R.H.   1983.  Lake Modeling:  State-of-the-Art.   In:   CRC Critical
Reviews  in  Environmental Control,  Vol. 13, Issue 4,  pgs. 311-357.

Harleman,  D.R.F.   1982.   Hydrothermal Analysis  of  Lakes  and Reservoirs.
Journal  of  the Hydraulics Division, ASCE.  Vol. 108,  No. HY3, pp. 302-325.

Johnson, B.   1982.  A Review  of  Multi-Dimensional  Numerical Modeling of
Reservoir  Hydrodynamics.  U.S.  Army Corps of Engineers, Waterways Experiment
Station.

Fischer, H.B.,  List, E.J., Koh,  R.C.Y. Imberger, J.,  and Brooks, N.H.   1979.
Mixing in  Inland and Coastal Waters.   Academic Press,  New York.

Hinwood,  J.B., and Wall is,  I.G.  1975.  Review of  Models of Tidal  Waters.
Journal  of  the Hydraulics Division, ASCE, Vol.  101,  No.  HY11, Proc. Paper
11693, November, 1975.

Orlob, G.T.,  ed. 1984.  Mathematical Modeling  of  Water  Quality:  Streams,
Lakes, and Reservoirs.  John Wiley and Sons, Wiley-Interscience, N.Y.,  N.Y.

Elhadi,  N. , A. Harrington,  I.  Hill,  Y.L. Lau,  B.G.  Krishnappan.  1984.
River Mixing:   A State-of-the-Art Report.   Canadian  Journal of Civil
Engineering.   Vol.  11, No. 11,  pp. 585-609,
2.1.1  Geometric Representation


2.1,1.1  Zero-Dimensional  Models


     Zero-di me nsiona 1  models  are used to estimate  spatially averaged
pollutant  concentrations  at minimum  cost.   These models predict a
concentration  field of the  form  C  =  g(t), where  t  represents time.  They

cannot predict  the fluid dynamics  of a  system, and the  representation is
usually  such  that an  analytical  solution is possible.  As an example,  the

simplest representation of  a lake  is  to consider  it  as  a  continuously

stirred tank reactor (CSTR).

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2.1.1.2  One-Dimensional  Models

     Most  river models  use  a  one-dimensional representation, where the
system geometry is formulated conceptually as  a linear network  of  segments
or volume sections  (see Figure 2-1).   Variation of  water quality
parameters occur  longitudinally  (in  the x-direction) as  the water is
transported  out  of one segment and into the  next.  The one-dimensional
approach is also a popular  method for simulation of small, deep  lakes, where
the  vertical  variation of temperature  and  other quality  parameters is
represented by a network of vertically stacked horizontal slices or volume
segments.

2.1.1.3  Multi-Dimensional  Models

     Water quality models of  lakes and  estuaries are often  two-  or three-
dimensional in order to represent the spatial heterogeneity of the  water
bodies.   Depending on the  system, two-dimensional representations  include a
vertical dimension with longitudinal segmentation for deep and narrow lakes,
reservoirs, or estuaries (Figure 2-2).

     Three-dimensional spatial representations  have been used  to  model
overall lake circulation patterns.  Part  of the reason for  this  need is the
concern with  the water quality  of the near-shore zone as well  as  deep  zones
of lakes.  In  addition, the  different water quality interactions  in these
zones can  lead  to changes in the  overall  lake  quality that  cannot  be
predicted  without this spatial  definition.

2.1.2 Temporal Variation

     Ecological models are  distinguished on a  temporal basis as  being  either
"dynamic"  or  "steady-state".  A strict steady-state assumption implies that
the  variables  in  the system  equations  do not change with time. Forcing
functions, or exogenous variables, that describe environmental  conditions
which are  unaffected by  internal  conditions  of the system, have constant
values.  Inflows and outflows are discharged to  and drawn from the  system at

                                   8

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                                                   I-
                            Control Volume, Xj
X.|   *  volume element

QO   =  water withdrawals from element X,
  xi                                1
QI   =  water discharged to element X.
  x.                             i

E    =  evaporation

F    =  precipitation

Q.j+1  =  advective flow to downstream element

Q. -|  =  advective flow from upstream element

AX   =  longitudinal  dimension of element
                                                        QI
Figure 2-1.  One-dimensional  geometric representation for  river systems  (Chen and Wells,  1975).

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a constant rate  and any  other hydrologic  phenomena  are also steady.
Insolation, light intensity, photoperiods, extinction  coefficients, and
settling rates are a  few examples of  additional forcing functions  which are
held constant in a  steady-state model.  Constant forcing functions  represent
mean  conditions  observed  in a system,  and  therefore  the model  cannot
simulate  cyclic phenomena.

     A wide variety of planning problems  can be analyzed by use of  steady-
state or  quasi-steady  (slowly varying) mathematical  models which provide the
necessary  spatial  detail for important water quality variables.  Certain
phenomena can achieve  steady-state conditions within a  short time interval
and  therefore  can be  modeled rather easily.  Steady-state or quasi-steady
representations are  particularly useful because  of their simplicity.
Examples of phenomena which have been modeled on a steady-state basis are:
1) bacterial die-off,  2)  dissolved oxygen concentrations  (under certain
conditions), and 3) nutrient distribution  and recycle.
                                                   tributary
                                                    inflow
       tributary
        inflow
                                                   horizontal
                                                  segmentation
                                      vertical
                                    segmentation
              outflow
    Figure 2-2.  Two-dimensional  geometric representation for lake
                systems (Baca  and Arnett, 1976).
                                  10

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     Many water quality  or  ecological  models for rivers  and  lakes  are
concerned with the  simulation of water  quality variables that  have
substantial temporal  variation and  are linked to  processes and variables
that vary  considerably.   For example,  the  seasonal distribution of certain
biological species  and  related  abiotic substances  may be  of major
importance.   In these instances, dynamic  models are required.

     The process of  selecting the  correct time and  length  scales  and then
matching  these with an  appropriate model demands both  an  a priori
understanding of the dominate physical, chemical and biological  processes
occurring within the  system, as well as an understanding of a given model's
theoretical basis and  practical  application  limits.  Proper  guidance for
model  selection and  application  best  comes from  a thorough  review of the
relevant literature  appropriate  to  the specific problem at  hand.   Ford and
Thornton (1979), for  example,  present a detailed discussion of  the  time and
 length scales appropriate for the  vertical one-dimensional modeling  approach
for reservoirs and  lakes.  The  references presented in Table 2-1 as well as
several others cited throughout  this chapter discuss model compatibility
requirements  for various water body types and  applications.

     The  remainder  of this chapter focuses on  advective  transport,
dispersive transport,  and the surface heat budget.

2.2  ADVECTIVE TRANSPORT

     The  concentration of a substance at a particular site within  a system
is  continually modified  by the  physical  processes  of  advection  and
dispersion which transport fluid constituents from location  to  location.
However,  the  total amount of a substance in a  closed system remains  constant
unless it is modified by physical,  chemical, or biological  processes.
Employing a Fickian type  expression for turbulent mass flux,  the three-
dimensional advection-diffusion  (mass balance) equation can be  written as:
               V«9C   W5C   d  IV  <9Cx   d  ,y 6>CN    9 ,y  <9Cv  _
               ~^ + ~dl ~ at (Kx di' ~ w (  y dy> " dl (Kz dl>  ~
                                   11

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where    c        = mean concentration of constituent, mass/volume
         u        = mean velocity in x-direction,  length/time
         v        = mean velocity in y-direction,  length/time
         w        = mean velocity in z-direction,  length/time
                                                    2
         K  ,K  ,K  = eddy diffusion coefficients, length /time
            i/
        2S       = sum of source/sink rates, mass/(volume-time)
         t        = time

     Difficulties exist in trying to correctly  quantify  the terms in  this
equation.  The unsteady  velocity  field  (u,v,w)  is  usually evaluated
separately  from Equation (2-1)  so that the pollutant  concentration, c,  can
be  prescribed.   The complete  evaluation of the velocity field involves the
simultaneous solution of the momentum, continuity, hydrostatic, and state
equations  in  three dimensions  (see  Leendertse  and  Liu, 1975; Hinwood and
Wallis, 1975).  Although sophisticated hydrodynamic  models  are available,
the detail  and  expense of  applying such models  are  often not justified in
water  quality computations,  especially for  long term or  steady-state
simulations  where only average  flow values are required.  For example, the
annual  thermal cycle for a strongly stratified reservoir  with a relatively
low inflow  to  volume ratio has  been successfully simulated with only a  crude
one-dimensional,  steady-state application of mass and energy conservation
principles.   On the other  hand,  simulation  of large, weakly stratified
impoundments dominated by wind  driven circulation  may require the ultimate,
full representation of the unsteady velocity field in  three dimensions.

     The purpose  of this section  is to briefly familiarize  the reader  with
the  various  types of approaches used to evaluate the  velocity field in  water
quality models.   Most hydrodynamic models internally  calculate hydrodynamics
with relatively little user  control  except  for specification of forcing
conditions  such as wind,  tides,  inflows, outflows  and bottom friction.
Thus,  the  following paragraphs  present only a summary discussion of the
approaches  used,  organized according  to the  dimensional  treatment of the
model.
                                   12

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2.2.1  Empirical Specification of  Advection

     This  is  the crudest  approach, in that  the  advective terms  of  the
advection-diffusion equation  (Equation 2-1) are  directly specified from
field data.  Empirical specification  is  quite common in  water quality models
for rivers,  but  is also often used in  steady-state  or slowly-varying estuary
water  quality models (e.g., O'Connor et: aj_.  (1973)).   In these types of
estuary models,  specification of the dispersion coefficients is  critical
since  dispersion must account for the  mixing which in  reality is caused by
the oscillatory  tidal action.  Due to  the highly empirical  treatment  of  the
physical  processes  in such models, the  model "predictions"  remain valid  for
only those conditions measured in  the  field.  These models cannot  predict
water  quality variations under other  conditions, thus increasing the demand
on field data  requirements.  Examples  of models  representative of the above
approach include .0' Connor et al_. (1973)  and Tetra Tech (1977).

2.2.2  Zero Dimensional Models for Lakes

     A coarse representation of  the  water system  as a  continuously stirred
tank reactor (CSTR)  is often sufficient for  problem applications  to some
lakes  where detailed hydrodynamics  are not required.   Since in this zero-
dimensional type of representation there  is  only a  single element,  no
transport direction can  be  specified.  The quantity of flow entering  and
leaving the system alone determines water volume changes within the element.
Examples  of zero-dimensional models  include lake  models  by Anderson et  al  .
(1976).

2.2.3  One-Dimensional Models for  Lakes

     For lake  systems with  long residence times  and stratification in  the
vertical  direction, vertical  one-dimensional representations are  common.
Horizontal layers are imposed and  advective  transport is assumed  to occur
only in the vertical direction.
                                     13

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     Generally the tributary inflows and outflows  are  assumed to enter  and
leave the  lake at water levels of equal density.   Since water is essentially
incompressible the inflow is assumed  to generate vertical  advective flow
(via the continuity equation) between all elements above the  level of entry.
The elements below this level, containing higher density water, are assumed
to be unaffected.  Examples of one-dimensional  lake models include Lombardo
(1972,  1973), Baca et _al_. (1974),  Chen and Orlob (1975),  Thomann et  aJL
(1975), Imberger et al_. (1977), HEC (1974),  Markofsky and Harleman (1973),
and CE-QUAL-R1 (1982).

     For lake or  reservoir systems  exhibiting  complex  horizontal interflows,
inflows, and outflows, semi-empirical formulations have  been developed  to
distribute  inflows  and to determine the  vertical  location  from  which
outflows arise,  depending on stratification conditions.   Examples  include
models by U.S.  Army  Corps of Engineers  (1974), Baca  e_t aj_.  (1976), and Tetra
Tech (1976).

2.2.4  One-Dimensional Models for Rivers

     Most river models represent  river  systems conceptually as  horizontal
linear networks  of segments or volume  elements.  The  process  of advection is
assumed to transport a constituent  horizontally by movement of  the parcel of
water  containing the constituent.  In general, there are two  approaches to
treat  the advection  in river  models.   One approach  requires field
calibration of  the river  flow  properties  by measuring flows  and  cross
sectional  geometry at  each model  segment over a range  of  flow magnitudes.  A
power  series  can then be developed for each cross section to interpolate or
extrapolate  for other  flow events.  Such dn  approach   is  especially
appropriate  for rivers exhibiting complex  hydraulic  properties  (i.e.,
supercritical  flows, cascades, etc.)  and when steady state solutions  are of
interest.   Examples  of such models  include Tetra Tech (1977).

     A second,  more rigorous approach for  simulating  river  advection
involves  the  simultaneous solution of  the continuity and momentum equations
for the portion  of the river under  study.  This approach  is  considered  more

                                   14

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"predictive"  than  the former since empirical flow data are required only for
model  calibration and  verification.   It  is  also more accurate  and
appropriate for  use in transient water  quality simulations.   In either case,
however, geometrical data on the cross-sectional  shapes of the  river  are
required.   Examples of models representative of the latter  approach include
Brocard and Harleman (1976), and Peterson et al_. (1973).

2.2.5  One-Dimensional and Pseudo-Two-Dimensional  Models  for Estuaries

     A natural extension  of the one-dimensional  river model has  been to
estuary systems, either  as  a  one-dimensional  representation  for narrow
estuaries  or as a system  of multiple interconnecting one-di rnens i onal
channels  for pseudo-representation of wider or multi-channeled  estuaries.
In either case,  advection is determined through the simultaneous solution of
the  continuity and momentum equations together with appropriate  tidal
boundary conditions.  These types of models are generally quite flexible in
their  ability to handle multiple inflows, transient boundary conditions,  and
complex geometrical configurations.   Two  primary approaches include  the
"link-node" network models  by Water  Resources Engineers (WRE) (1972),  and
the finite element model (Galerkin Method)  by Harleman et aj_.  (1977).

2.2.6  Two-Dimensional Vertically Averaged  Models for Lakes  and Estuaries

     Vertically  averaged, two-dimensional  models  have proven to be  quite
useful, especially in  modeling the  hydrodynamics and water quality of
relatively shallow estuaries and wind-driven lakes.  The  crucial assumption
of these models is the vertically well-mixed  layer that  allows for vertical
integration of the continuity, momentum, and mass-transport  equations.  Such
models are frequently employed to provide the horizontal  advection for water
quality models since they are relatively inexpensive to operate compared to
the  alternatives of large scale field measurement programs or fully three-
dimensional model  treatments.  There  exist well  over fifty models  which
would  fit  into  the two-dimensional,  vertically averaged classif'ication.
Examples of models that have been widely used  and  publicized include Wang
and  Connor (1975), Leendertse (1970),  Taylor  and Pagenkopf (1980), and
Simons (1976).
                                   15

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2.2.7  Two-Dimensional  Laterally  Averaged Models for Reservoirs  and
      Estuaries

     In  recent  years, laterally averaged models  have become  standard
simulation techniques for reservoirs or  estuaries  which exhibit significant
vertical  and longitudinal  variations  in  density  and  water quality
conditions.  The two-dimensional  laterally averaged models require  the
assumption of  uniform lateral mixing  in the  cross channel  direction.
Although this simplification eliminates one horizontal dimension,  the
solution of the  motion equations in the remaining longitudinal and vertical
dimensions requires a much more rigorous approach than  for the two-
dimensional vertically  averaged models.  In order to  correctly simulate the
vertical effects of density  gradients  on the  hydrodynamics  and mass
transport, both the  motion (continuity and momentum) and advective-diffusion
equations must be solved simultaneously.  In addition, such models  must also
treat  the vertical eddy  viscosity  (momentum  transfer due to  velocity
gradients) and  eddy diffusivity  (mass  transfer due to concentration
gradients) coefficients,  which  are  directly  related to  the degree of
internal mixing and  the  density  structure  over the water  column.
Mathematical  treatment of vertical diffusion and  vertical momentum transfer
varies  greatly  between models, and will be discussed further  in this
document.  Examples of laterally averaged reservoir  models  include Edinger
and Buchak  (1979) and Norton e_t aK (1973).  Examples  of laterally  averaged
models  developed for  estuaries include Blumberg (1977),  Najarian et al.
(1982)  and Wang (1979).

2.2.8  Three-dimensional Models for Lakes  and Estuaries

     Fully three-dimensional  and  layered  models  have been  the subject of
considerable attention over  the last decade.  Although still a developing
field,  there are  a  number of models  which  have  been applied to estuary,
ocean,  and lake  systems  with moderate  success.   As  with laterally
averaged two-dimensional models,  the  main  technical  difficulty in this
approach is in the  specification  of the internal turbulent momentum transfer
and  mass  diffusivities,  which are ideally  calibrated  with field

                                  16

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observations,  thus making availability of adequate prototype  data an
important  consideration.   An  additional  factor of great importance is the
relatively   large computation cost of  running three-dimensional models,
especially for long-term water  quality simulations.  In many  cases, the
effort and cost of running such  models is difficult to justify from  purely a
water quality standpoint.   However,  as computational costs  continue to
decrease  and sophistication of numerical techniques increases,  such models
will  eventually play an important  role in supplying  the  large scale
hydrodynamic regimes in water quality simulations.  Examples  of  the more
prominent three-dimensional models  include Blumberg and  Mel lor  (1978),
Leendertse  and Liu  (1975),  Sheng  and Butler (1982), Simons (1976)  and King
(1982).

 2.3  DISPERSIVE TRANSPORT

 2.3.1  Introduction

      The  purpose of this  section is to  show  how dispersive transport  terms
 are incorporated into the equations of  motion and continuity by temporal  and
 spatial averaging (a detailed discussion  of  this  subject  is also  given  by
 Fischer  e^t  al.  (1979)).  A consequence of temporal averaging of either
 instantaneous velocity or concentration is to produce a smoothed velocity or.
 concentration  response curve over  time.  Figure 2-3  illustrates  both
 instantaneous velocity and time-smoothed  curves.  The velocities V and  ¥ are
 related by

                              V =  V +  V                             (2-2)

where V   = instantaneous velocity,  length/time
       V   = time-smoothed velocity,  length/time
       V  = velocity  deviation from the  time-smoothed  velocity,
           length/time

The velocity component V  is  a  random component  of velocity which  vanishes
when  averaged over the appropriate  time interval (i.e., V = 0).
                                   17

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     By averaging, the stochastic components  are removed from the momentum
and mass conservation equations.  However,  cross product terms appear in the
equations,  such  as V'V and V'V in the case  of the momentum equation,  and
	      	       XX      X j
V'C'  and V'C'  in the case of the mass conservation equation  (where C1 is the
instantaneous concentration  fluctuation,  and  V^ and V^  are the random
velocity deviations in the x and y directions, respectively).  In the case
of the momentum  equation these terms are called turbulent  momentum  fluxes,
and  in the case of the mass conservation equation they are  called turbulent
mass  fluxes.  It is through  these terms  that  eddy  viscosity  and  eddy
diffusivity enter into the momentum and mass  conservation equations.

     To  solve the time-smoothed equations,  the time averaged cross  product
terms are expressed  as  functions of  time  averaged variables.  Numerous
empirical expressions  have been developed to  do this.  The expressions  most
often applied  are analogous to Newton's law  of viscosity in the case of
turbulent momentum transport and Pick's law of diffusion  in the  case of
turbulent mass  transfer.  Expressed quantitatively these relationships are
of the form:
        o
        3
        01
                                     V= time smoothed velocity
                                     V-instantaneous velocity
                                V
                                             V'-V-V
                                   TIME
      Figure 2-3.
Oscillation  of  velocity component about a mean
value (redrawn  after Bird et ji]_., 1960).
                                   18

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                                       9MV
                                       -                            (2-3)
                             V^CT = K g                             (2-4)

where  E   =  eddy viscosity,  mass/( length-time)
                                  2
       K   =  eddy diffusivity,  length /time
       V   =  time smoothed velocity in the x direction,  length/time
       /\
       £  =  time  smoothed concentration, mass/volume
       P  =  mass  density, mass/ volume

      In natural water  bodies  the turbulent viscosity and diffusivity  given
 by Equations  (2-3) and  (2-4)  swamp their counterparts  on  the molecular
 level.   The  relative magnitude between eddy di ffusivities and molecular
 diffusion coefficients is depicted graphically in  Figure 2-4.

      In addition  to  temporal  averaging, spatial  averaging is often  used to
 simplify three dimensional models to  two  or  one  dimensions.  As an
 illustration consider the vertically averaged mass transport equation.
 Before averaging,  the governing three dimensional  mass transport equation is
 typically written  as:

          c              c)
                                    .(V .   (V .   (QZ)         (2.5)

 where c       = the local  (time  smoothed) concentration, mass/volume
       u,v,w    = the  local  (time  smoothed)  water velocities,
                 length/time
                                                       2
       Q ,Q  ,Q, = the local  diffusive fluxes, mass/(length -time)
        x y   z
 Before  spatial averaging, the  local  concentration and velocities can be
 expressed by a vertically averaged term and a deviation term:
                                    19

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     10
       6-
     104-
     102-
 o
 CD
 CO
\
CN
 E
 o
UJ
o
LU
O
o
Z
O
00
     10°
10-2-
    io-4-
    10-6-
    10-8-
   10-10.
            EDDY DIFFUSION:
           ^— Horizontal, Surface Waters
            EDDY DIFFUSION:
           ^—Vertical,Thermocline and Deeper
              Regions in Lakes and Oceans
             •Heat in H20
                MOLECULAR DIFFUSION
               '— Salts and Gases in H2O
                  •Proteins in H20
                THERMAL DIFFUSION
               	Salts in
•                                          Ionic Solutes in
                                          Porus Media
                                          (Sediments,Soils)
    Figure  2-4.  Diffusion coefficients  characteristic of various
                environments (redrawn after  Lerman, 1971).
                               20

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                                c = ch  +  ch
                                u = uh  +  uh
                                v = vh  +  v^                            (2-6)
 where c,u,v  = previously defined
       ch     = vertically averaged concentration, mass/volume

                               h
                             o
       c/     =  deviation from  c,  at  any point  in  the water  column,
               mass/volume
       u. ,v.  =  vertically averaged water velocities, length/time

                                h        h
                            =  /udz,    /vdz                         (2-8)
                               0        0

      u/jV/ = deviation from  u. , v.  at any point  in the water column,
              length/time
      h     = local  water depth, length

Equation (2-5)  can now  be written in its vertically  averaged form:

      9ch   d(u.c.)   <9(v.c- )        r-
      -   + -*-  * -       - -   J  "x^h)*
It  is  noted that when  vertical integration is performed  on the three-
dimensional mass conservation equation,  cross  product terms appear in the
resulting two-dimensional equation,  just as they  do when temporal averaging
is done because  vertical gradients generally exist  in both the concentration
and velocity fields.  The horizontal turbulent diffusion  fluxes Q  r Q   are
usually  expressed in terms of the gradients of the vertically averaged
concentration and  the turbulent diffusion coefficient, which in general  form
are written:
                                    21

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                                  dC.       dC.
                         «x •  -xx -5? - Sy -5?                   <2-10a)
                                  dC.       dC.
                         Q  =  -e  —- - e   —-                   (2-10b)
                          y     yx  <9x    yy  ay

where e   ,  e   , e  , e   = turbulent eddy diffusion coefficients
       xx  xy  yx   yy

By analogy, the horizontal transport terms, u^c^ and v^c^, associated with
vertical  velocity variations  (i.e.,  differential advection),  are expressed
by means of the shear dispersion coefficients:
                                           i    -
                                       - Exy I*
                                 .  9C.     .  dC.
                        ,, i „, _  rd     n   ra    n                   /0
                        Vh - -Eyx ~ai  - Eyy ~gy

where E  ,E  ,E  ,E   = shear dispersion  coefficients
       xx  xy  yx yy

By combining Equations (2-10) and (2-11), the final form of the  vertically
averaged mass transport equation can be written as:
                                            h     + D
             dt     dx.        ay      dx \ xx   dx    xy   dy
                         -2.1 n  h —Li +  n   h
                         9y \  xy   <9x   yy
where D  ,D  ,D    = dispersion coefficients which account for mass  transport
       xx  xy yy
due to both concentration and velocity gradients over the vertical.

     One-dimensional  mass conservation equations  result when a  second
spatial  averaging is performed.  The  one-dimensional equations  express
changes along the  main flow axis.  As expected,  the diffusion terms are
again  different from their two-dimensional counterparts.  Consequently, the
type  and magnitude of  the diffusion terms  appearing in the  simulation
                                   22

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equations  depends not only on  the water body characteristics, but the model
used to simulate the water body.

2.3.2  Vertical Dispersive Transport

     Vertical dispersive transport of momentum and mass becomes important  in
lakes  or  estuaries characterized  by  moderate to great depths.   In a lake
environment,  vertical mixing  is  generally caused  by wind action on the
surface through which eddy turbulence is transmitted  to the deeper layers  by
the action of shear stresses.   In estuaries, typically the  vertical mixing
is induced by the  internal turbulence driven by the tidal flows, in addition
to surface wind effects.  Similarly, the internal mixing in deep reservoirs
is primarily  caused by  the flow-through action.   In  each environment,
however,  the amount of vertical mixing is controlled, to a  large extent,  by
the degree of density stratification in the water body.

     Treatment of vertical mixing processes  in mathematical  models  is
generally achieved through the  specification of vertical eddy viscosity (E )
and  eddy diffusivity  (K  ) terms,  as  previously discussed.  As observed  by
McCutcheon (1983), however, there  is little consensus  on  what values the
vertical  eddy  coefficients should have and  how eddy  viscosity and eddy
diffusivity are  related.  At present,  the  procedure for estimating  these
coefficients  is  generally limited to empirical techniques that range from
specifying a  constant E  and K   to  relating to  some  measure of stability,
i.e., the Richardson  number Ri .  In this  approach,  the ratio of the
coefficients  for stratified flow to  the coefficients for  unstratified  flow
is expressed as  a  function of  stability f(s):
                                    =  f2(s),                         (2-14)
                        and  EvQ=PrKvo                            (2-15)
                                    23

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where E   =  kzu+(l  -  z/h)  for shear layers  and Pr = the Prandtl  or Schmidt
       vo       *
number, which  is  generally close to  unity for  open-channel  shear  flow
(Watanabe  et  a_l_., 1984).
 In  addition

          k   = von Karman's  constant (-0.4), dimension!ess
          z   = distance above  the bottom, length
          u*  = shear velocity, length/time
          h   = depth of flow,  length

      A widely used formula which relates E /E   to  stability involves the
  Munk and Anderson  (1948) formulation  (as reported  by McCutcheon (1983)):

                           Ev/Evo = (1 + 10 Ri)'1/2                   (2-16)

  and
                           Kv/KvQ = (1 + 3.33 RiT3/2                 (2-17)
                      O
  where Ri = ^ _ /f|M j s dimension! ess                               (2-18)
       P  = density, mass/volume
       u  = the  mean horizontal velocity at a point z above the bottom,
            1ength/time
                                              2
       g  = acceleration of gravity, length/time

      As reported by McCutcheon (1983), in a recent  review of available data
  for stratified  water flows  (Delft, 1979) Equations  (2-16)  and (2-17) were
  found  to fit the data better than  several other similar formulations.
  Models by Waldrop (1978),  Harper  and Waldrop (1981),  Edinger  and Buchak
  (1979), O'Connor and Lung (1981), Najarian et al_.  (1982), and Heinrich, Lick
  and Paul (1981) use this  scheme.   In some models, the  coefficients and
  exponents  in  Equation  (2-16)  and  (2-17) are not adjusted, and any
  discrepancies  between field measurements and model predictions  are
  attributed  to the  inexactness of  the model.   In other models,  the
  coefficients  and exponents  are calibrated on a site  specific basis.

                                    24

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     For model simulations of mixing through and  below the thermocline, the
Munk and Anderson type formulas  appear to be less adequate  (McCutcheon,
1983).   Odd  and Rodger  (1978)  developed site specific  eddy viscosity
formulations for the Great Ouse Estuary in Britain:
                   Ev/Evo = (1  + bRi)"   for Ri£l                   (2

and
                   EV/EVQ = (1  + b)"n  for Ri>l                     (2-20)

where  b  and  n are coefficients.   The depth varying Ri  is  used  if Ri
increases  continuously starting at  the bed and extending over 75 percent or
more of the depth.  Where a significant peak in Ri occurs  in' the vertical
gradient,  that peak Ri  is  used  for all depths in  the  equation above.
McCormick and Scavia (1981) make a  correction for K   in Lake  Ontario and
Lake Washington studies  that  is  similar to corrections of E  by Odd and
Rodger.  Above the  hypo! imnion ,  they apply a  modification  of the Kent and
Pritchard (1959)  equation:

                              Kv -  u,/0RQ                          (2-21)

where RQ = -kz2 £ f£ / u^                                           (2-22)

      /3  = constant

     Below the thermocline a constant  K  was specified  for Lake Ontario.  In
Lake Washington,  Equation (2-21)  and (2-22) were applied throughout- the
depth.   In Lake  Washington bottom  shear was important  for mixing as opposed
to  deeper Lake Ontario  where  surface wind shear dominated  the mixing
process.

     Several  other  formulations  for  E  and K  have been developed which are
not based on  the  Munk and Anderson  equations.  For example, Blumberg (1977),
in his laterally  averaged model  of  the Potomac River  Estuary,  employed an
expression for K which uses a  ratio  of Ri to a critical Ri to relate K to
stabil ity, where:
                                    25

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                    Kv = Klz2(¥l2|"l'1-^-^'                    (2-23)
where K..  is  a  turbulence constant which must be determined by calibration,
and Ri   is  the  critical Richardson number, which is  the  value of Ri at which
mixing  ceases  due  to strong stratification.  Blumberg also related  E   to K
through the  following  formulation:

                      E  = K  (1 + Ri)     for 0 <  Ri < Ri          (2-24a)
                       V    V                            t*
                          EV = KV = 0      for Ri > Ric             (2-24b)

     Using  the  above  formulations,  Blumberg  obtained  reasonably  good
comparisons  for salinity distributions in the Potomac River.

     Simons  (1973)  based  his formulation for K  for  Lake  Ontario on the
results  of  dye diffusion experiments performed by  Kullenberg j?t al_. (1973)
where K  is  expressed  as:

                          K  = C     |    |                           (2-25)
where C  =  an  empirical constant, (2~8)10~
      W  =  wind  speed, length/time
      N  =  Brunt-Vaisala frequency, ^ — »  time"
      an                            " ^Z      -I
      sp- =  vertical shear of the current,  time
      OL

Simons also assumed that the vertical eddy viscosity coefficient was  based
on a similar relationship.

     The above formulation is a result of  experiments performed  in  fjords,
coastal  and open sea areas, as well as from Lake  Ontario,  and is generally
valid for expressing the vertical mixing in  the upper 20 m for  persistent
winds  above 4-5 m/sec.  The lower value of  the  numerical  constant refers to
the lake data  and the higher value to the  oceanic data.
                                   26

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     For  low  and  varying wind speeds  Equation (2-25) will not  be  valid
(Murthy  and Okubo, 1975).   In these cases  the internal  mixing is considered
to be governed by local  processes, i.e., the  energy source is the  kinetic
energy fluctuations.   Kullenberg (as  reported by Murthy and Okubo (1975))
proposed  the following relation for weak local winds:
       10      10    10
where q L  =  V/ + V/
               x     y

      V' ,V'  =  velocity fluctuations in the  x and  y directions,
       A   y
              respectively,  length/time

Equation  (2-26) is representative  of  the vertical  mixing both  above  and
below the thermocline under  conditions of low wind speeds.
     Tetra Tech  (1975) has  used  the  following empirical expressions  for
     utation of  the vertical eddy thermal  diffusiv
dimensional hydrodynamic simulation of Lake  Ontario.
computation  of  the  vertical  eddy thermal diffusivity, K  , in their three-
                                                                  (2'27)
where p  = density  of fresh  water at 4°C,  mass/volume
                                              2
      TS  = surface wind stress, mass/(length-time ).

     Lake  systems  that are  represented geometrically as  a  series  of
completely mixed horizontal slices  consider  advective and  dispersive
transport processes to occur in the  vertical  direction alone.  Baca and
Arnett (1976), in their one-dimensional hydrothermal lake model,  proposed
the following expression for determining the one-dimensional  vertical
dispersion coefficient:
                      Kv =  al + a2 Vw d-'                          (2-28)

                                    27

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                                              p
where K     = vertical dispersion coefficient, m /sec
      z     = depth, m
      Vw     = wind speed, m/sec
      d     = depth of thermocline, m
                                  2
      a,,a?  = empirical constants, m /sec and m respectively

     The following table of values  (Table 2-2) for a,  and a2,  as  given by
Baca and  Arnett (1976), were obtained  from previous model applications.
          TABLE 2-2.  VALUES FOR EMPIRICAL COEFFICIENTS a1 and
         Lake
               Max.
Description   Depth (m)
  •j
(m /sec)
(m)
American Falls
Lake Washington
Lake Mendota
Lake Wingra
Long Lake
well-mixed
stratified
stratified
well-mixed
linearly
stratified
18
65
24
5
54
1 x 10"5
1 x 10'6
5 x 10"7
5 x 10"5
5 x 10"6
1 x 10"4
1 x 10"5
5 x 10"5
2 x 10"4
5 x 10"5

     The vertical eddy viscosity and eddy diffusivity concepts continue  to
be practical  and  are a popular means for simplifications of the momentum and
mass conservation equations.  As pointed out  by Sheng and Butler (1982)  and
McCutcheon (1983), however, a wide variety exists  among the various forms of
the vertical  turbulence  stability functions  determined empirically  by
various  investigators, and suggest that the appropriate stability function
is dependent  on the type  of numerical  scheme used and the  nature of  the
water body under  study.  The wide variation in formulations is, in part,  due
to the attempt to fit empirical functions determined under  specific field
conditions  to  a wider  range of water body types and  internal mixing
phenomena. Due to the possibility of  applying an empirical  relationship
                                    28

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beyond its valid  limits, site-specific testing of formulations for E   and  K
will probably be  required in most model  applications.

     The  above discussion has concentrated  on the eddy diffusion concept  on
which many models are based.  However, an  alternative to  this approach  is
the  mixed layer concept which has  been successfully applied by numerous
investigators to predict  the  vertical temperature regime  of lakes and
reservoirs.   As summarized by Harleman (1982), the mixed layer or integral
energy concept involves the following:  the  turbulent kinetic  energy (TKE)
generated by the  surface wind stress is  transported downward and acts  to mix
the upper water column  layer.   At the  interface between  the upper mixed
layer and the lower  quiescent layer, the remaining TKE, plus any that  may  be
locally generated by  interfacial shear  (minus dissipation  effects),  is
transferred into potential energy by entraining quiescent fluid from below
the  interface into the mixed layer.  This  entrainment, in  addition  to any
vertical  advective  flows, determines the  thickness of the mixed layer.  TKE
is  also produced by convective currents  which  occur during  periods of
cooling, and can  contribute to the mixing  process.  Also,  the total vertical
heat  balance due to surface  heat flux and  internal absorption must be
considered in evaluating  the  vertical density distribution and potential
energy of the water  column.   A discussion  of the mixed layer model approach
can  be  found in Harleman (1982), French  (1983) and Ford  and Stefan  (1980).
Models based on  this approach  include those  by Stefan  and  Ford (1980),
Hurley-Octavio et _§]_. (1977), Imberger et  aj_. (1977) and CE-QUAL-R1 (1982).

2.3.3  Horizontal Eddy Diffusive Transport

     Generally,  horizontal eddy diffusivity is several orders of magnitude
greater than the  vertical eddy diffusivity (see Figure 2-4).  The Journal  of
the Fisheries Research Board  of Canada  (Lam and Jacquet, 1976) reported a
range of values for  the  horizontal diffusivity in lakes  from 10  to 10
  p
cm /sec.   Unlike diffusive transport in  open-channel type flows, diffusion
in open water,  such  as in lakes  and oceanic  regimes, cannot  be effectively
related  to the mean flow characteristics (Watanabe §t aj_., 1984).   Oceanic
or lake turbulence represents a   spectrum of different eddies resulting  from

                                   29

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the breakdown  of large-scale  circulations in shore zones  and  by wind and
wave  induced circulations.  Attempts to analyze  this phenomenon  have
demonstrated that the horizontal  diffusive  transport,  D,  depends on the
length scale L  of the phenomenon.  The most widely used formula  is the four-
thirds power  law:

                              Dh  =  ADL4/3                           (2-29)

where AD  is  the dissipation  parameter  (of  the order  .005,  with Dh in
cm2/sec).   The  length scale L is loosely defined depending  on the nature of
the diffusion  phenomenon.  For  a  waste discharge in the ocean,  for example,
L  is often estimated  based on the diffuser  length, which  is  typically the
order of  a kilometer.  Another example  is  to estimate L based on the length
of the tidal  excursion in estuaries  or  coastal  areas.  When  using Equation
(2-29)  to estimate  the  diffusion  coefficient in two or  three-dimensional
numerical models, the length  scale is often taken as the size  of  the
horizontal grid spacing,  since this  approximates the minimum scale of eddies
which can  be  reproduced in the model.

     Useful summaries of  lake and ocean  diffusion data are  given by Yudelson
(1967), Okubo (1968)  and  Osmidov (1968).   Okubo  and Osmidov  (1970)  have
graphed the  empirical relationship between the horizontal eddy diffusivity
and the length  scale, as  shown in Figure 2-5.   According to Figure 2-5:

                Dh^2 x 10"3 L4/3  for  L <  105cm

                Dh~104            for  105  < L  < 5 x 105 cm

                Dh = 10"3  L4/3      for  L >  5 x  105 cm                 (2-30)
                  2
where  Dh  is  in cm /sec and L in cm. Based on  these empirical observations,
it is seen that the dissipation parameter of the four-thirds  law decreases
at larger  length scales.

     A comprehensive  collection of diffusion data  in the ocean was presented
by Okubo (1971), who  proposed as best fit to all the data the relation:
                                   30

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                     = 0.01L
                            1.15
    for 10  < L < 10
                                                      cm
                               (2-31)
which  is graphed  in Figure 2-6.   According to Christodoulou et aj_.  (1976),
the four-thirds law seems theoretically  and experimentally  acceptable  for
expressing the horizontal  eddy diffusivity in large lakes and in the ocean,
providing the length scales of  interest  are not of the order of the size  of
the energy containing eddies.   In  addition, the four-thirds law is not fully
acceptable near the shore,  due  to  the  shoreline and bottom interference.

     Two  examples  of the  use  of Equation (2-29) in lake models are  in  Lam
and Jacquet (1976)  and Lick et  aj_.  (1976).  Lam  and Jacquet  obtained the
following formulation  for the  horizontal eddy diffusivity for lakes,  based
on experimental  results:
                  109

                  108-

                  107-
               o  106-
               0)
               CO
              CN
               e  io5-
               o
               si
               21  104'

                  103<

                  102'

                  10 •
                     10s
10'
10C
                                 LENGTH,cm
            Figure  2-5.  Dependence of the horizontal  diffusion
                        coefficient on the scale of the phenom-
                        enon (after Okubo and Osmidov (1970)).
                                    31

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            10M
         o
         0)
         CO
E
o
            10
              c I
              5-l
            A North Sea, 1964
            €> North Sea, 1962
            D New York Bight
            • Off Cape Kennedy
            O Off California
            + Banana River
            x Other
    103


Figure 2-6.
                         104
                          io5       io6
                          LENGTH, cm
107
IO8
                        Okubo's diffusion data and 4/3 power lines
                        (after Okubo (1971)).
                                   = .0056L
                                           1.3   *
                                                            (2-32)
                                          2
where D,  = horizontal eddy diffusivity,  cm /sec
      L  = length scale of grid,  cm

As reported by Lam and Jacquet,  for a  grid   size  larger than 20  km, the
                                                     fi    ?
diffusivity is expected to be essentially constant  (10  cm /sec).

     Lick  (1976)  used a  similar formulation after Osmidov (1968), Stommel
(1949), Orlob  (1959),  Okubo  (1971) and Csanady (1973):
                                     32

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                              Dh  = a E1/3 L4/3                      (2-33)

where a =  constant of proportionality, of the order 0.1
      E =  rate of energy dissipation per unit mass
                                         n      r   o
Observations by  Lick  indicated values of 10  to 10  cm /sec for D,  for  the
overall  circulation  in the Great  Lakes with smaller values  indicated in  the
near-shore regions.

     The above relationships  can be used as a general  guide to evaluate  the
horizontal  diffusivities in  a numerical model, where the grid size may be
regarded as  the  approximate length scale of diffusion.  However, as pointed
out  by Murthy and Okubo  (1977):   (1)  the  data  upon which these empirical
relations  are obtained do not represent diffusion  under  severe weather
conditions,  and thus may include  a bias towards relatively mild conditions;
(2)  the  horizontal diffusivity  can  vary (depending primarily upon the
environmental  conditions)  by  an order of magnitude  for the same length scale
of diffusion;  (3) the definition of the length scale  of  diffusion for  the
horizontal  diffusivity  is  somewhat  arbitrary;  and  (4)  the horizontal
diffusivity  varies by an order of magnitude between  the  upper and lower
layers of  oceans  and deep  lakes.   Thus, to  develop  reliable three-
dimensional  models the scale  and stability dependence  of eddy diffusivities
and  the  large variability of the magnitude of the eddy diffusivity with
depth and  environmental factors (wind, waves, inflows, etc.) must somehow be
incorporated into the models.

     The formulations  for horizontal eddy diffusivity discussed above  are
generally  representative of empirical (physical)  diffusion behavior and  are
most compatible  with  a three-dimensional approach.   As  previously discussed,
horizontal  dispersion  is  the  "effective diffusion"  that  occurs  in two-
dimensional  mass  transport equations  that have  been integrated over  the
depth.  Thus  the horizontal dispersion must account for both horizontal  eddy
diffusivity due to horizontal turbulence  and  concentration gradients, as
well  as the  effective spreading  caused by velocity  and concentration
variations over  the vertical.  In  addition, any  simplifications  in  the

                                    33

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velocity field used in  modeling must also be accounted  for in the dispersion
coefficients.  The less detailed the flow field is  modeled,  the larger the
dispersion  coefficient  needs to be to  provide for the spreading that would
occur  under  the  actual  circulation (Christodoulou  and Pearce,  1975).
Therefore,  the dispersion  coefficients are characteristic not only of the
flow conditions to be  simulated, but more significantly  of the way the
process  is  modeled.   Hence these coefficients  are  model-dependent and
difficult to  quantify in  any general,  theoretical manner.  For example, many
two-dimensional   models use  a constant dispersion  coefficient over the
whole model domain as well as over time despite the fact that dispersion
changes  both  spatially and temporally as the circulation features change.
An  example  of a  model  that uses constant dispersion coefficients  is
Chri stodoul ou et al_. (1976).

     One two-dimensional model  which  utilizes  variable  dispersion
coefficients (velocity  dependent)  in time and space  is the finite difference
model by Taylor  and Pagenkopf (1981).   They utilize Elder's  (1959)
relationship for  anisotropic  flow where  the dispersion of a  substance  is
proportional to the friction  velocity,  u*,  and  the water depth, h, as
follows:
                             Dr  =  5.9 u*h                       (2-34)

                             Dn  =  0.2 u^h                       (2-35)

                                                          p
where D   = dispersion  coefficient along the flow axis, length /time
      D   = dispersion  coefficient  normal to  the flow  axis,
                 2
           length /time
      u*   =  V8  I U I  ' length/time
      f   = Darcy-Weisbach friction factor, dimensionless
      I "*"!
      IUI  = absolute  value of mean velocity  along flow  axis,
           length/time
     The  above relationship is incorporated into  the  two  dimensional  mass
conservation equation resulting in an  anisotropic mixing  process which
calculates a dispersion coefficient at each time step  and node as a function

                                   34

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of  the  instantaneous flow conditions.  The  expressions used for  the
dispersion coefficients in the model  are as follows:
                  Dxx =      (     + q)  (5'9 - 5'7 Sl
                  Dxy = 11.4 \     (qx2 + qy2) sin & cos 6             (2-37)
                  Dyy =      (q   +  q)  (5'9 ' 5'7 cos^            (2'38)
where D  ,D Y..,D    = dispersion coefficients
       •*•*  *y yy       _-.
      e           = tan"  (q /q )
                            j  *
      q           = flow in x direction
      q           = flow in y direction

     The above model has  been successfully tested  agai  nst dye diffusion
experiments in Flushing Bay, New York, and in Community Harbor, Sau di  Arabia
(Pagenkopf and Taylor (1985); Taylor  and Pagenkopf  (1981)).

     A two-dimensional, finite element water quality model was developed  by
Chen jet _al_. (1979), based  on the  earlier model  by Chri stodoulou et a! .
(1976).   They provided  for flow-dependent anisotropic  dispersion
coefficients  by  using the following relationships:
                          D  = ^V.4  + .-**                         (2-39)
                           x    ul/6    -x                               ;
                                n
                          Dy -

       *      *                                   **       **
where -~  and  ;  ar-e user-defined  constants as are e    and  £  ,  the latter
       x      y                                   x        y
being  provided  for additional  dispersion effects such as wind and marine
traffic.
     Whether the  two-dimensional model  in  question  utilizes  constant  or
flow-dependent dispersion coefficients,  the dispersion mechanism is usually
somewhat dependent on  factors  typically  beyond user control,  such  as
numerical  i nstabi 1 i'ti es  and grid sire  averaging effects.   It  is therefore

-------
stressed that any application of a two-dimensional  water quality model  be
verified  either through  site-specific salinity or dye tracer data.
Naturally, when performing field tracer experiments the time and length
scales  of the field phenomenon should  be compatible with  the time and length
scales  to be represented in the model.  For example, a  dye study  lasting
only a few hours  is  not  valid for verification  of a  model using a daily
computational  time step.   Similarly, a dye study confined to a small portion
of a large lake or estuary will not allow for verification of the model  over
the entire system.

2.3.4  Longitudinal Dispersive Transport in Estuaries

     As previously discussed, longitudinal dispersion  is the "effective
diffusion" that occurs in  one-dimensional mass transport  equations that  have
been integrated over the cross sectional area perpendicular to flow.   This
one-dimensional  approach to modeling has often been applied to tidal and
nontidal rivers, and to estuaries.

     The  magnitude  of  the  one-dimensional  dispersion coefficient  in
estuaries and tidal rivers is determined in  part by the time saale  over
which  the simulation is  performed.   The time scale specifies the interval
over which quantities  that generally change instantaneously, such  as tidal
current, are averaged. For  shorter time scales the simulated hydrodynamics
and therefore water quality relationships are resolved in greater detail and
hence, in such  models,  smaller dispersion coefficients are needed than in
those which, for example,  average hydrodynamics over a tidal cycle.

     The  magnitude of the dispersion coefficient can  also be expected to
change as a function of  location within an  estuary.   Since  the  one-
dimensional dispersion coefficient is  the result of spatial  averaging over a
cross section  perpendicular to flow, the greater the  deviation  between
actual  velocity and the  area-averaged velocity, and between  actual
constituent concentrations  and area-averaged concentrations, the  larger
will be the dispersion coefficient. These deviations are usually  largest
near  the mouths of  estuaries due  to density gradients set up  by the

                                  36

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interface  between fresh and saline water.  Strong tidal  currents may also
result  in  large dispersion coefficients.

     Because of the time scale  and  location dependency  of the dispersion
coefficient,  it  is convenient to divide the discussion of dispersion into
time varying and tidally averaged time expressions,  and  then  to subdivide
these  according  to estuarine  location, i.e, the salinity intrusion region
and the freshwater tidal  region.   The salinity intrusion region is that
portion of  the estuary where  a longitudinal  salinity gradient exists.  The
location of  the line of demarcation between the salinity intrusion region
and  the freshwater tidal region varies throughout the tidal cycle,  and also
depends on the volume of freshwater discharge.  It should also be noted that
the  freshwater tidal region  can  contain saline water, if the water is  of
uniform density throughout the  region  (TRACOR, 1971).  There is at present
no  analytical method for  predicting dispersion in the salinity intrusion
region  of  estuaries.'  However,  because of the presence  of a  conservative
constituent  (salinity), empirical measurements are easily performed.   In the
freshwater tidal region, analytical expressions have  been  developed, while
empirical measurements become  more difficult  due to  the  lack of a naturally
occurring  conservative tracer.   Empirical measurements can alternatively  be
based,  however, on dye release  experiments.

2.3.4.1 Time  Varying Longitudinal Dispersion

     A  model  which  is  not averaged over the  tidal cycle is more capable  of
representing the mixing  phenomena since it represents  the  time varying
advection in  greater detail.  However, the averaging effects of  spatial
velocity gradients  (shear) and  density gradients must still  be accounted
for.   The specification of longitudinal dispersion  coefficients is  closely
associated with the type of mathematical techniques used  in a  given model.
Most of the  model developments  for one-dimensional  representation  of
estuaries  has occurred  in  the early 1970's, and the most prominent
techniques are summarized below.
                                    37

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     The  "link-node" or network model developed originally by WRE (1972)  and
commonly  known as the Dynamic  Estuary Model  (DEM) used  the basic work of
Feigner  and  Harris (1970) to describe the numerical  dispersion in  the
constant  density region of an  estuary:

                          DL  = Cl E1/3Le4/3                         (2-41)

                                                    2
where D.  =  longitudinal dispersion coefficient, length /time
      E  =  rate of energy dissipation per unit  mass
      L  =  mean size of eddies participating  i'n the mixing process
      C-,  =  function of relative channel roughness

      For computational purposes, Feigner used  the following simplification:

                          DL  = 0.042 |u| R                         (2-42)

where R   = hydraulic radius,  ft
      |u|  = absolute value of  velocity, ft/sec

     There exists  no corresponding  formulation  for the longitudinal
dispersion  coefficient in the salinity intrusion regions of estuaries.
Rather, a careful calibration  procedure is required using available salinity
data to prescribe the appropriate dispersion  coefficients.  Obviously, this
approach  somewhat  restricts the predictive  nature of  such models since a
substantial  amount of empirical data  is  necessary  for proper  model
appl ication.

     Similar  versions of  the  DEM exist in one form  or  another.  Not  all
versions,  however, include  the option for specification of longitudinal
dispersion.  This stems from the fact that considerable numerical dispersion
occurs in the  DEM  from the first order, explicit,  finite difference
treatment of  the advective transport terms.  Feigner and  Harris (1970) gave
some comparisons of different weightings of  the first order differencing in
terms of  trade-offs between numerical mixing, accuracy, and stability.  Work
on this problem has been done  by Bella and Grenney (1970)  and a numerical

                                   38

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estimate'of this dispersion  can be given by the following  equation:
                        num
\ \(l-2v) Ax -  VAt                      (2-43)
where v  represents  the  weighting coefficient assigned  to the concentrations
of two adjacent nodes.

     This equation shows that the  numerical dispersion  is a function  of
Ax, At,  and the velocity, V, which is a function of  location and time.   This
equation is useful for estimating the magnitude  of numerical dispersion.  It
illustrates the lack of control that the modeler has over this phenomena  in
the DEM.

     Daily and Harleman  (1972) developed a network water quality model  for
estuaries  which  uses a finite element numerical technique.  The hydraulics
are coupled to the salinity  through the density-gradient terms in the manner
formulated by Thatcher and Harleman (1972). The  high accuracy finite element
Galerkin weighted residuals technique is relatively free of artificial
numerical dispersion.  The longitudinal dispersion formulation combines both
the vertical  shear  effect and the  vertical density-induced circulation
effect through the following expression:

                                      0
                          D(x,t) = K|^|+ m DT                       (2-44)
                                     d^      T

where D(x,t) = temporally and spatially varying  dispersion coefficient,
               ft2/sec.
      §      = s/s where s(x,t)  is  the  spatial   and  temporal
               distribution of salinity, ppm
      s       = ocean salinity, ppm
      8       = x/L
      L       = length of estuary, ft (to head of tide)
                                                   25/6
      DT     = Taylor's  dispersion coefficient in ft /sec = 77 u nRh
      u       = u(x,t) tidal velocity,  ft/sec
                                   39

-------
      n      = Manning's friction coefficient
      R,     = hydraulic radius, ft.
                                              2
      K      = estuary dispersion parameter in ft /sec =  u L/1000
      u      = maximum ocean velocity at the ocean entrance, ft/sec
      m      =a  multiplying factor for  bends  and  channel
              irregularities

     One-dimensional, time varying  modeling using this  expression has been
performed for several  estuaries, a recent example being an  application
(Thatcher and Harleman,  1978) to the Delaware  Estuary wherein the time-
varying  calculations  were made for a  period'of an  entire year in order  to
provide  a model  for testing different water management policies.

     For real time simulations in the constant density region of estuaries
and tidal rivers, the following expression has been proposed  (TRACOR, 1971):

                         D,  = 100 n U   RU5/6                      (2-45)
                          L          max  H                         v

where D.   = longitudinal  dispersion  coefficient  in the  constant
                             2
            density  region, ft /sec
      n    = Manning's roughness coefficient, ft
      Um,« = maximum  tidal velocity,  ft/sec
      ffla X
      RU  = hydraulic radius, ft.

     The determination of real time dispersion coefficients  in the salinity
intrusion region  requires  field data on salinity distribution.  Once the
field data  have  been  collected,  the  magnitudes of  the dispersion
coefficients can  be  found  by fitting the solution of the salinity mass
transport equation to the observed data.   As reported in  TRACOR (1971), this
technique has been  applied to the Rotterdam Waterway, an estuary of almost
uniform  depth and width.  The longitudinal dispersion coefficient was  found
to be  a function of x,  the distance measured  from the mouth (ft),  as
follows:
                                   40

-------
                       DL  =   13000  (l - f )                         (2-46)
where D.  = real  time longitudinal dispersion  coefficient in salinity
       L                      2
           intrusion region, ft /sec
      L  = length of entire tidal region  of  the  estuary.

                                                      2               2
     At the estuary mouth, D.  was found  to be  13,000 ft /sec  or 40 mi /day
          72
(1.2  x  10  cm /sec) by using the technique  described above.  Under the same
conditions in a constant  density  region,  Equation (2-38)  predicts D. =
      2252
175 ft /sec, or  0.5 mi /day (1.6 x 10  cm /sec).  This illustrates  the large
difference that  can be expected between  the  real time dispersion coefficient
in the  salinity intrusion region of an  estuary and in the constant density
region.  For more detailed discussions of real time longitudinal  dispersion
in estuaries, see Holley et al . (1970) and Fischer et al .  (1979).

2.3.4.2  Steady  State Longitudinal Dispersion

     For  tidal ly  averaged or net nontidal  flow simulations,  the dispersion
coefficients must somehow include the effects  of oscillatory tidal mixing
which  has been averaged out of the hydrodynamics representation.   No known
general analytical  expressions exist  for this coefficient.   Hence,  it is
cautioned and emphasized that steady-state dispersion coefficients must be
determined based on observed data, or based  on empirical  equations  having
parameters that are determined from observed data.  This limitation exists
for both the constant density and salinity intrusion regions of the estuary.

     In their one-dimensional  tidally averaged estuary model,  Johanson
et jfl_. (1977) used  an empirical expression, comprised of  three principal
components (tidal  mixing,  salinity gradient,  and net freshwater advective
flow) for the dispersion coefficient.  The relative location  in an  estuary
where  each of these factors is significant,  and their relative magnitudes,
are shown in Figure 2-7.
                                   41

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           Salinity Gradient Mixing
    MOUTH

  Figure 2-7.
                                                      HEAD
Factors contributing to tidally averaged dispersion
coefficients in the estuarine environment (modified
after Zison et al., 1977).
    The expression used is:
                                                                      (2-47)
where DL  = tidally averaged dispersion coefficient, ft /sec
      Cj  = tidally-induced mixing coefficient (dimensionless)
      y   = tidally averaged depth, ft
      |u| = tidally averaged absolute value of velocity, ft/sec
      
-------
     The first term  on  the right side of Equation'(2-47) represents mixing
brought about  by the oscillatory  flows associated with  the  ebbing and
flooding  of  the  tide.  The second  term represents additional  mixing when
longitudinal  salinity gradients  are present.   It  is noted that, in practice
the above  formulation requires careful calibration using field salinity data
due to the high empirical dependency of this  relationship.

     One common  method  of experimentally determining the tidally  averaged
dispersion  coefficient is  by  the  "fraction of freshwater method,"  as
explained  by  Officer  (1976). The expression  is:

                          D =    Rs    =  rc(f-l) t                  (2-48)
                           L   A(ds/dx)   A(df/dx)                  {     !
                                                   2
where D. = tidally averaged dispersion coefficient, ft /sec
      s = mean salinity at a particular location averaged over depth,
           mg/1
                                               2
      A = cross-sectional  area  normal to flow, ft
      R = total  river runoff flow rate, cfs
      f = freshwater fraction = —jj—, unitless
      a = normal ocean salinity of  the coastal water into which  the
           estuary empties, mg/1
      x = distance along estuary axis, ft.

D.  can be  calculated at any location within  the  estuary if the river
flow,  cross-sectional  area,  and salinity or freshwater fraction
distributions are known.
     The above method has certain pitfalls which  are  pointed out  by  Ward and
Fischer (1971) in their  analysis of such an application  to the Delaware
Estuary.   They point  out that  the  use of  a  dispersion coefficient
relationship, i.e., a  functional relationship of dispersion to  distance,
which  is  also  directly related to the measured  upstream freshwater inflow.
neglects entirely the basic response of the waterbody  to variations in
freshwater  inflow.   Ward  and Fischer show,  for  example, that it  may take  a
period  of  months  for the  estuary  to adjust to a short  period  change in
                                   43

-------
 freshwater discharge and that any dispersion coefficient relationship based
 on a simple correlation analyses may be  seriously in error.

     Hydroscience  (1971) has collected values of tidally averaged  dispersion
 coefficients for numerous  estuaries, and these values  are  shown in
 Table 2-3.

     In his book,  Officer (1976) reviews studies  performed  in  a  number of
 estuaries throughout the  world.  He discusses the dispersion  coefficients
 which have been determined, and a summary of values for  these estuaries is
 contained in Table 2-4.   Many values  were developed using the fraction of
 freshwater method  just discussed.  Additional  values for the longitudinal
 dispersion coefficient have been summarized in Fischer et a_l_. (1979).

 2.3.4.3  The Lagrangian Method

     The models discussed in previous sections of this chapter have  all  been
 based on the Eulerian concept of assigning velocities and concentrations to
 fixed  points on a spatial  grid.  As  previously discussed, the  fixed  grid
 approach tends to  introduce a fictitious  "numerical" dispersion into the
 mass  transport solution since the length scale of the diffusion  process is
 somewhat artificially imposed depending  on the grid detail.   To  avoid such  a
 problem,  an alternative approach termed the Lagrangian method has been  used
 by Fischer (1972), Wallis (1974), and Spaulding and Ravish (1984)  for models
 of  estuaries and tidal waters.  Briefly, the Lagrangian method establishes
 marked volumes of  water, distributed along the channel axis, which are moved
 along  the channel at the mean flow velocity.  Numerical diffusion is almost
 entirely eliminated,  since there  is no allocation of  concentrations to
 specific  grid points; rather,  the "grid"  is a set  of moving points  which
represent the centers of  the  marked  volumes.   Longitudinal dispersion
between marked  volumes can  be set according to  appropriate empirical or
theoretical  diffusion behavior (Fischer ert _al_.,  1979).   The  Lagrangian
method  has  been primarily  applied to  channelized  estuaries  such  as  the
Suisun Marsh (Fischer,  1977)  and  Bolinas Lagoon (Fischer,  1972), and more
recently  has been  extended by  Spaulding and Ravish  (1984) to simulate
particulate transport in  three dimensions.
                                    44

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TABLE 2-3.  TIDALLY AVERAGED DISPERSION COEFFICIENTS FOR SELECTED ESTUARIES
                         (from Hydroscience, 1971)
Estuary
Delaware River
Hudson River (NY)
East River (NY)
Cooper River (SC)
Savannah River (GA, SC)
Lower Raritan River (NJ)
South River (NJ)
Houston Ship Channel (TX)
Cape Fear River (NC)
Potomac River (VA)
Compton Creek (NJ)
Wapplnger and
Flshkin Creek (NY)
Freshwater
Inflow
(cfs)
2,500
5,000
0
10,000
7,000
150
23
900
1,000
550
10
2
Low Flow
Net Nontldal
Velocity (fps)
Head - Mouth
0.12-1.000
0.037
0.0
0.25
0.7-0.17
0.047-0.029
0.01
0.05
0.48-0.03
0.006-0.003
0.10-0.013
0.004-0.001
Dispersion
Coefficient
(mlVday)*
5
20
10
30
10-20
5
5
27
2-10
1-10
1
0.5-1
(ft2/sec)
1610
6450
3230
9680
3230-6450
1610
1610
8710
645-3230
320-3230
320
160-320
V
*1 m12/day = 322.67 ft2/sec.
2.3.5  Dispersive Transport in Rivers

2.3.5.1  Introduction

     Dispersive transport in rivers is typically,  but not  always, modeled
using a one-dimensional equation such as:
dc +  uac
9t     <9x
where  C  = concentration of solute, mass/length
       U  = cross-sectional averaged velocity, length/time
                                                       2
       D,  = longitudinal dispersion coefficient, length /time
       x  = longitudinal coordinate, length
       t  = time
                                     45
                                                                      (2-49)

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      TABLE  2-4.   TIDALLY AVERAGED  DISPERSION  COEFFICIENTS
                          (FROM  OFFICER,  1976)
     Estuary
    Dispersion
Coefficient  Range
    (ft2/sec)
                                                           Comments
San Francisco Bay, CA
   Southern Arm
   Northern Arm
Hudson River, NY
Narrows of Mercey,  UK     1,430-4,000
Potomac River, MD
     65-650
Severn Estuary,  UK
Tay Estuary,  UK
Thames  Estuary,  UK
Yaquina Estuary
                   Measurements were made at slack
  200-2,000        water over a period of one to a
  500-20,000       few days.  The fraction of
                   freshwater method was used.
                   Measurements were taken over
                   three tidal cycles at 25 loca-
                   tions.

4,800-16,000       The dispersion coefficient was
                   derived by assuming D. to be
                   constant for the reach studied,
                   and that it varied only with flow.
                   A good relationship resulted be-
                   tween D.  and flow, substantiating
                   the assbraption.

                   The fraction of freshwater method
                   was used by taking mean values of
                   salinity over  a tidal cycle at
                   different cross sections.

                   The dispersion coefficient was
                   found to be a function of dis-
                   tance below the Chain Bridge.
                   Both salinity distribution studies
                   (using the fraction of freshwater
                   method) and dye release studies
                   were used to determine D. .

                   Bowden recalculated D,  values
                   originally determined by Stommel,
                   who had used the fraction of
                   freshwater method.  Bowden in-
                   cluded the freshwater inflows from
                   tributaries, which produced the
                   larger estimates of D. .

  530-1,600        The fraction of freshwater method
                   was used.  At a given location, D.
                   was found to vary with freshwater
                   inflow rate.

    3,640           Calculations were performed using
 (high  flow)        the fraction of freshwater method,
  600-1000          between 10 and 30 miles below
 (low flow)         London Bridge.

  650-9,200        The dispersion coefficients for
 (high  flow)        high flow conditions were substan-
  140-1,060        tially higher than for low flow
 (low flow)         conditions, at the same locations.
                   The fraction of freshwater method
                   was used.
     75-750
                                    46

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     Because of the difficulty of  accurately solving Equation  (2-49)
numerically, some  researchers  (e.g., Jobson, 1980a; Jobson and Rathbun,
1985)   have chosen a Lagrangian approach, where the  coordinate  system is
allowed to move  with  the local  stream velocity.   Using  this  approach,
Equation (2-49)  become:

                          ^L = 9_ /D  9
                          dt  9£ ( L 9
             t
where £ =  x- J* Udr
           o

The numerically troublesome  advective term does not appear  in Equation (2-
50).   In  general ,  the equation  can be solved more  easily and with more
accuracy than Equation  (2-49).

     A second method  used  to simulate dispersive  transport in rivers is to
consider lateral mixing in addition to  longitudinal  mixing.  A typical  form
of the two-dimensional  equation is:

                   9L  ,   i  \ 9C    9 /  9C\  ,  9  i    9C\             /o n \
                   di  + u(y) ft " ^ (Sc w} + ey (ey 9^             (2^l]

where  u(y)  = depth  averaged velocity  of water, which is a function  of
             y,  and  is  no  longer the  cross-sectional  averaged
             velocity, length/time
            = depth  averaged  longitudinal  diffusion coefficient,
       x           2
             length /time
       e     = depth averaged lateral  diffusion coefficient,
       y           2
             length /time
       y     = lateral  coordinate,  length

Note that  longitudinal  dispersion  coefficient, DL,  in  Equation (2-49) is not
the same  as the longitudinal diffusion  coefficient, e  , in Equation
                                                   A
Typically, D»E.
                                   47

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2.3.5.2  Longitudinal Dispersion in Rivers

     Fischer (1966,  1967a, 1967b,  1968)  has  performed much of the earlier
research on  longitudinal dispersion in natural  channels.  Prior to  Fischer,
Taylor  (1954) studied dispersion in straight  pipes and Elder (1959) studied
dispersion in an infinitely wide open channel.  More recently Fischer crt al .
(1979)  and  Elhadi  ejt al_.  (1984) have  provided a comprehensive review of
dispersion processes.

     Researchers have  shown that  Equation  (2-49) is valid only after some
initial  mixing length, often called the Taylor  length or convective  period.
While  the convective period  has been  a  topic  of active  research in the
literature (e.g., Fischer, 1967a and b; McQuivey  and Keefer, 1976a; Chatwin,
1980),  this concept  is not embodied in one-dimensional" water quality models
in general  use.

     Table 2-5  summarizes references on stream dispersion.  • The  references
include information  from  at least one of the following  areas:

     •    methods to  predict D.  , typically for model applications
     t    methods to  measure DL from field data
     •    data  summaries of dispersion coefficients
     t    approaches used to  simulate dispersion  in,a non-Fickian
          manner.

Bansal  (1971),  Elhadi and Davar (1976), Elhadi jet jK  (1984)  also provide
reviews of stream  dispersion.

     To date, the predictive capabilities of expressions for  dispersion
coefficients have not been thoroughly tested.   However, it  is known  that the
Taylor  (1954) or Elder  (1959) formulas do not accurately predict  dispersion
coefficients for natural  streams.   Glover (1964) found that  dispersion
coefficients in natural streams were likely to be 10 to 40 times  higher than
predicted by the Taylor or Elder equations.  The  lateral variation  in stream
velocity is  the primary reason  for the increased dispersion not  accounted
for by Taylor and Elder.  Fischer (1967a) quantified the contribution of the
                                    48

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  TABLE 2-5.   REFERENCES  RELATED TO LONGITUDINAL  DISPERSION
       Reference
                Comments
Taylor (1954)

Elder (1959)


Glover (1964)

Krenkel (1960)




Parker (1961)


Fischer (1967a, 1967b)
Elhadi and Davar (1976)



Fischer (1968)



Bansal (1971)






Godfrey and Frederick (1970)
Thackston (1966)
D.  =10.1R u*;  pipe flow.

D.  = 5.93Hu*;  lateral  velocity  variation
     not considered.

D,  = SOORu*;  natural  streams.

DL   G^H1'2^0'3; two-dimensional channel.

(E = USg)
DL   14.3R
         ;  open channel  flow.


        ; concentration  variances
                                            are measured after an initial  period.
                                            Long tails may introduce some  error.
DL =— /  q'(y)dz/
                                             A  o

                                                        /d(y)
                                                        (U(y,z)-u)dz
                                                     o

                                       This formula considers the effects  of
                                       lateral velocity changes.
                                                  2

                                       DL=-fdT
                                                                          q'(y)dy.
D.  = Q.3u'l~ -^- ;  a simplification of the

integral equation above

Fischer also discusses another method for
determining D.  called the  routing procedure.

Reviewed many methods to predict D.  .  Found
D,/(Hu*) is not a constant as reported by
many researchers.

Field measurements of D,  were made  in
the Green and Duwamish Rivers.

    
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                          TABLE  2-5.    (continued)
       Reference
                                                       Comments
Thackston and Krenkel  (1967)
Miller and Richardson (1974)
McQuivey and Keefer (1974)
    The limitations of dispersion  equations
    which do not consider lateral  velocity
    variations are discussed.   Site specific
    measurements of D.  are recommended.

    In laboratory experiments,  D.  varied from
    0.6 ft /sec to 66 ftVsec.

    Dispersion coefficient data were reviewed,
    including hydraulic data,  for  17 rivers.
                                                  ir
                                       D, = 0.66 ^.
                                                  3
                                                    '
McQuivey and Keefer (1976b)
Liu (1977)
                                            0.058
    Dispersion  tests  performed  in  the
    Mississippi  River are summarized.
Fischer (1975)





Hays et _al..  (1966)




Thackston and Schelle (1970)


Day (1975)
Day and Wood (1976)
Liu and Cheng (1980)
                                        B *• 0.18/VqRsV'5
                                                  I   U/
                                        Summary of D. values also reported.
    D,
                                          _ O.OlluV
    Liu (1977)  shows this  is  a special  case  of
    his formula when /3= 0.011.

    Several  conceptual  models of  mass exchange
    with dead zones  are presented and the
    Fickian  Equation is modified  to include  mass
    transfer to and  from dead zones.
Application of Hays et ^1.
model to TVA stream (Tata.
                               (1966)  dead zone
    Longitudinal  dispersion of fluid  particles
    in small  mountain streams  1n  New  Zealand was
    investigated.   It was shown that  the
    dispersion coefficient increased  with
    distance  and  never approached an  asymptotic
    value.

    Longitudinal  dispersion of fluid  particles
    in the Missouri River and  in  a small moun-
    tain stream was Investigated.  The dis-
    persing particles were shown  to behave
    differently from the Taylor type  model.   A
    method to predict dispersion  was  developed.

    A non-Fickian model 1s presented  to predict
    stream dispersion.

(continued)
                                         50

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                           TABLE 2-5.   (continued)
       Reference
                  Comments
Sabol and Nordin (1978)
Valentine and Wood (1977)
Valentine and Wood (1979)
Rutherford, Taylor, Davies (1980)
Beltaos (1980a)
  A modified model  of stream dispersion is
  presented that includes the effects of
  storage along the bed and banks.

  Effects of dead zones on stream dispersion
  are addressed

  Experimental  results are provided  to show
  how dead zones modify longitudinal  dis-
  persion.

  A hybrid method is discussed to predict
  dispersion in the Waikato River, New
  Zealand.

  Dispersion processes in streams are
  reviewed and  it is shown that many
  experimental  results do not comply  with
  Fickian dispersion theory.   A non-Fickian
  dispersion model  is proposed.
Beltaos (1982)


Bajraktarevic - Dobran (1982)



Beer and Young (1983)



Jobson (1980a)
Jobson (1985) and
McBride and Rutherford (1984)
Jobson and Rathbun (1985)
  Dispersion in  steep  mountain
  streams is examined.

  Fischer's  methods  are  successfully  applied
  to predict dispersion  in mountainous
  streams.

  Methods are developed  to predict  dispersion
  in rivers  including  the effects of  dead
  zones,  using a (j.n.m) model.

  The Fickian Equation is solved with a
  Lagrangian scheme  to avoid  lumping  numerical
  dispersion with actual physical dispersion.
  See Jobson (1980b).

  Determined that D. and coefficients for
  nonconservative water  quality constituents
  could be determined  simultaneously  during
  calibration.   D. determined by this method
  is in good agreement with literature values
  (Jobson) or match  D, values determined from
  dye studies (McBride and Rutherford).

  Numerical  dispersion minimized with a
  Lagrangian routing procedure that provides
  more consistent estimates of D. than the
  method of  moments  for  pool  and riffle
  streams.   Applying this procedure to peak
  dye concentrations yielded  D. to  within 10X

  of estimates based on  the entire
  concentration-time curves.

(continued)
                                         51

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                           TABLE  2-5.    (continued)
Footnotes:
   A        =  cross-sectional area
   b        =  channel width
   £        =  wave  velocity
   d(y)      -  depth of water at y
   E        =  rate  of energy dissipation per unit mass of fluid
   E        =  lateral turbulent mixing coefficient
   H        =  stream depth
   K        =  regional dispersion factor
   1          lateral distance from  location of maximum velocity
    2
   a        -  variance of distance - concentration curves
    ?    ?
   °t2'  °tl =  variance °f time concentration curves
   ty, "L    =  mean  times of passage
   p        =  mass  density of water
   Q        =  discharge at steady base flow
   q'(y)      integral of velocity deviation on depth
   R        =  hydraulic radius
   Rp       -  pipe  radius
   S        -  slope of energy gradient at  steady base flow
   U        =  mean  velocity of flow  in reach
    i
   u        =  deviation of velocity  from cross-sectional mean
   U        =  mean  velocity of flow  at sampling point
   u*       =  shear velocity
   ft        -  coefficient of viscosity of  water
   W        =  channel width at steady base flow
                                           52

-------
lateral  velocity variation on stream dispersion.

     A number of the formulas  in  Table 2-5 are  of  the type DL/(U*H)  =
constant.  However, several researchers, including Bansal  (1971), Elhadi  and
Davar (1976), and Beltaos (1978a) have shown that the  ratio DL/(U*H) is not
a constant.   Figure 2-8  shows  this ratio can  vary by several orders  of
magnitude.

     Two widely used methods  of predicting the longitudinal dispersion
coefficients  were developed by  Liu  (1977) and Fischer (1975) and are shown
in Table 2-5.  Liu showed that  Fischer's method is identical to  his  own
when j3 = 0.011.

     Although numerous researchers (e.g.,  Sabol and Nordin,  1978) have shown
how to  include the effects of dead zones on  dispersive transport, this
refinement does  not yet appear to be in general use in  water quality models
today.   In fact,  some water quality models do not include dispersion at all
(at least physical dispersion; numerical dispersion  may be  present,
depending on the solution technique  used).

     Dispersion can  be neglected in certain  circumstances with  very little
effect  on the  predicted concentration  distributions.  Thomann  (1973), Li
 (1972), and Ruthven  (1971)  have  investigated  the influence of  dispersion.
Ruthven gave a particularly simple expression  for a pollutant  which decays
at  a rate k.  If

                             kD    1
                             -T < -b =  -04
                             u

then the concentration profile will  be affected  by no more than 10  percent
if dispersion is ignored.   Consider, for  example, a decaying  pollutant with
                                                        2
k  = 0.5/day in a stream where U  = 1  fps  and D,  = 500 ft  /sec.  The ratio
     p                                       L
kD,/U =.003, which indicates that dispersion can  be ignored.   This guideline
assumes that the pollutant  is being continuously released and  conditions  are
at steady state.   The basic  presumption is  that  if  the  concentration
gradient is  small enough, the dispersive transport is also small, and
                                   53

-------
  o Godfrey and Frederick (1970)
  A Glover (1964), rectangular flume
  A Glover (1964), triangular flume
  D Glover (1964),South  Platte River
  • Glover (1964), Mohawk River
  • Yotsukura et. al.(1970), Missouri  River
  • Fischer, Sacramento  River (see Sooky,1969)
  v Fischer (1968),Green-Duwamish  River
  + Fischer (1967),trapezoidal flume
T Smooth .meandering flume
$ Rough, meandering  flume1
» Smooth,meandering flume
* Thackston and Schnelle (1969)
° Hou and Christensen (1976)
  Width/radius of curvature -0.28
  Width/radius of curvature -0.14
10,000 q
 1,000 -
  100 -
    10 -
                         10                100
                            WIDTH/DEPTH
              1000
 Figure  2-8.  Dispersion coefficients  in streams (Beltaos,  1978a),
                                      54

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perhaps negligible.   On  the other hand when  pollutants are  spilled,
concentration  gradients are large and  dispersion is not  negligible.

     Thomann  (1973)  investigated the importance of longitudinal dispersion
in rivers that received time variable  waste loadings, and  therefore produced
concentration gradients  in  the rivers.  His results showed that for small
rivers, dispersion may be important when the waste loads vary with periods
of 7 days  or  less.  For large rivers, dispersion was found to be important
whenever the waste load was time-variable.

2.3.5.3  Lateral  Dispersion in Rivers

     Although  two-dimensional water quality models are less widely used  in
rivers  than one-dimensional  models, lateral mixing has  been the topic  of
considerable research.  Models that simulate lateral  mixing are particularly
useful  in  wide rivers where the one dimensional approach may not  be
applicable.  Vertical mixing is rarely simulated in river  modeling because
the  time required for vertical mixing is usually very rapid compared  to the
time required  for lateral mixing.   Thermal plumes are an exception.

     An example of a model that simulates lateral  mixing  in  rivers is the
RIVMIX  model  of  Krishnappan  and Lau (1982).  The  model  is  particularly
useful  for  delineating mixing  zones or regulating  the rate  of pollutant
discharge  so  that concentrations outside of the mixing  zones are limited  to
allowable values.

     When lateral and longitudinal  mixing are  both  simulated,  the x and  y
coordinates are  generally assumed to continuously change to be oriented  in
the longitudinal  and transverse directions.   Although   Equation (2-51)
should  rigorously contain  metric factors (Fukuoka and Sayre, 1973)  to
account for  these continuous changes,  modelers typically assume the metric
factors are  unity.

     Lateral  mixing  coefficients  are usually presented  in  one  of the
following two  forms:

                                   55

-------
                                 y                                 (2-52)
or                                     2
                                Dy=£f                           (2-53)

                                             2
where  e    = lateral mixing coefficient, length /time
       y                                   52
       D    = lateral diffusion factor, length /time
       H    = water depth, length
       a,jS = coefficients that vary  from river to river
       u+   = friction velocity, length/time
                              3
       Q    = stream flow, length /time
       W    = width of river, length
D  and e  are related by, the following formula:
 J      J
                             Dy = HUmx£y                            (2-54)

where m  = average metric value in x-  direction (~1)
       A

Equation (2-52) is generally the most widely used of the  two formulas.
Equation (2-53) is  used  when the two-dimensional convective-diffusion
equation is  expressed in terms of cumulative discharge (Yotsukura and Cobb,
1972).

     Table 2-6  summarizes studies of transverse  mixing in streams.  Data
from  the literature are  summarized in Tables 2-7 through 2-9.   Table 2-9
contains values of (3 for use in Equation (2-53).

     Elhadi et  al .  (1984) have recently  provided a detailed review  of
lateral  mixing in  rivers.  They concluded that lateral  mixing  coefficients
can be predicted with accuracy only in relatively straight  channels.
                                   56

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    TABLE  2-6.   SUMMARY  OF  STUDIES  OF  TRANSVERSE  MIXING  IN  STREAMS
            Reference
                                                                       Comments
Okoye (1970)


Prych (1970)


Yotsukura, Fischer, Sayre (1970)


Yotsukura and Cobb  (1972)



Hoi ley (1975)
Hoi ley and Abraham  (1973)


Yotsukura and Sayre (1976)


Shen (1978)


Lau and Krishnappan (1981)



Somlyody (1982)



Gowda (1978)

Mescal and Warnock  (1978)


Benedict (1978)

Henry and Foree  (1979)


Beltaos (1980)



Cotton and West  (1980)


Hoi ley and Nerat  (1983)


Demetracopoulous  and Stefan (1983)



Webel  and Schatzmann (1984)
This  study presented  a detailed analysis  of  laboratory experiments
of lateral mixing.

This  study detailed  the effects of density  differences on lateral
mixing.

A  lateral dispersion  coefficient of 1.3 ft /sec was determined  for
the Missouri  River.

Studies  of  lateral  mixing  were performed on  the  South River,
Atrisco Feeder  Canal,  Bernardo Conveyance  Channel, and the Missouri
River.

A two-dimensional model of contaminant  transport  in rivers was
developed and applied to the  Missouri and  Clinch Rivers,  p  was
experimentally  determined using                             •*
                                                                        dx
Transverse dispersion measurements  were made in the Waal  and  Ussel
Rivers, Holland.   The change of moments method was used.

Transverse cumulative discharge was used as an independent  variable
replacing transverse distance in the 2-D mass transport equation.

The approach of Yotsukura and Sayre (1976) was extended to  include
transient mixing.

Field data for transverse mixing coefficients were  summarized.  A
further  extension of the approach  of Yotsukura and Sayre was made.
Values of e /(u^H) were found to depend on depth/width  ratios.

Tracer  studies  were performed in five streams to predict lateral
mixing coefficients.  A numerical model  used in the study was an
extension of the work of Yotsukura  and Sayre (1976).

Transverse mixing coefficients were measured in the Grand River.

A  study  of lateral  mixing 1n  the Ottawa River produced  the
expression S  = 0.043HU.

This study reviewed various mixing  expressions.

An approximate method of two-dimensional  dispersion modeling  was
presented.

Transverse mixing  characteristics of  three rivers  1n Alberta,
Canada were documented by  tracer tests  for open water  and  ice
covered flow conditions.

Rhodamine WT dye  was used  to  determine  the transverse diffusion
coefficient on a straight reach  of  an open channel.

Inclusion  of secondary mixing as part  of a lateral diffusion
coefficient was concluded to have a limited physical basis.

Transverse mixing  was studied in wide  and shallow  rivers using
heated discharge as a tracer.   A modified method  of  moments  was
developed to compute transverse  mixing coefficients.

An experimental study was conducted to Investigate variations 1n
transverse mixing  coefficients 1n straight, rectangular channels.
E-/(u*H)  was found to be constant.
E  = lateral  mixing coefficient

U  = cross-sectional average velocity

ff  = variance of  concentration in y-direct1on

u4 » shear velocity

H  = depth
                                                  57

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          TABLE  2-7.    TRANSVERSE MIXING  COEFFICIENTS  IN NATURAL  STREAMS  AND  CHANNELS
                                                 (FROM  BELTAOS,  1978a)
   Source
      Channel
      and
      Description
                                                    W
                                                    (m)
                                                             W
                  U
                (ra/s)

                   /(Hu*)
                          Comments
 Glover 1964
 Yotsukura
 et _aJK, 1970

 Yotsukura and
 Cobb, 1972

 Sayre and Yeh,
 1973
 Engmann and
 Kellerhais,
 1974
 Meyer, 1977
 Krlshnappan &
 Lau, 1977
Beltaos, 1978b
                      Columbia River
Missouri River,  two mild
alternating bends

South River, few mild
bends

Missouri River,  sinuous,
severe bends
Lesser Slave River,  ir-
regular, almost contorted
meander, no bars;  sinu-
osity = 2.0
Mobile River,  mostly
straight,  one  mild  curve

Meandering laboratory
flume with "equilibrium
bed".  Planview sinu-
soidal.  Meander wave-
length^ irW=1.88m
Athabasca River below Fort
McMurray, straight with
occasional islands, bars;
s1nous1ty=l.O
 305     100


 183    68.7


18.2    46.2


 234    59.1




43.0    17.0





 430    87.2
 .30    10.5
 .30    15.9
 .30     7.6
 .30    10.2
 .30     9.0
 .30    11.6
 .30    10.0
 373
         170
1.35


1.74


 .21


1.98




 .65





 .30
 .26
 .27
 .31
 .30
 .28
 .23
 .32

 .95
.034


.014


.284


.015




.045





.028
.162
.105
.163
.208
.271
.156
.101

.028
 .74         Test results and analysis
             approximate

 .60         Flow distribution available at only
             two cross  sections

 .30         Analysis by streamtube method
3.30         Analysis by numerical and
             analytical methods. Periodical
             variation of E  detected;
             average value indicated here

.33          Effects of transverse advection
             lumped together with transverse
             dispersion. Reanalysis of ice
             covered data' by streamtube method
             gave e /Ru*   .16

7.20         Steady-state condition unlikely
             Evaluation of Ey by a numerical
             simulation method.   Use of constant
             Cyqave more consistent results
             than laterally variable values of
                                                                                      .75         Slug-injection tests; analysis  by
                                                                                                  streamtube method applied to dosage
                                                                                                  (see  also Beltaos 1975)
Beltaos, 1978b
Beltaos, 1978b
Beltaos
(unpublished)
Beltaos
(unpublished)
Athabasca River  below
Athabasca,  Irregular
meanders with  occa-
sional bars,  islands;
sinuosity=1.2

Beaver River  near Cold
Lake, regular  meanders,
point bars and large
dunes, sinuosity=1.3

North Saskatchewan River
below Edmonton,  nearly
straight,  few, very mild
bends with occasional
bars, islands; sinuo-
sity=1.0

Bow River at Calgary,
sinuous with frequent
islands;  mid-channel bars
diagonal  bars, sinu-
osity^. 1
 320     156
                                                  42.7     44.6
 213     137
 104     104
                                                                     .86
                                                                     .50
                 .58
                 1.05
                                                                             .067      .41
                                                                            .062     1.0
                         .152      .25
                          .143     .61
                                                                                                  Steady-state concentration tests.
                                                                                                  Analysis by stream-tube method.
                                              By steady-state concentration and
                                              slug-injection tests.   Analysis
                                              by streamtube and numerical
                                              methods respectively
A    amplitude of meanders
f    fraction factor
R    hydraulic radius
U    cross-sectionally averaged velocity
W  = width
H    depth
EV   lateral mixing coefficient
                                                               58

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TABLE 2-8.  SUMMARY OF FIELD DATA FOR TRANSVERSE DISPERSION COEFFICIENTS
                      (LAU AND KRISHNAPPEN, 1981)
Width,
Data Source in meters
Yotsukura and Cobb (1972)
Missouri River near
Blair
Yotsukura and Cobb (1972)
South River
Yotsukura and Cobb (1972)
Aristo Feeder Canal
Yotsukura and Cobb (1972)
Bernado Conveyance
Channel
Beltaos (1978a), Athabasca
below Fort McMurray
Beltaos (1978a), Athabasca
River below Athabasca
Beltaos (1978a), North
Saskatchewan River
below Edmonton
Beltaos (1978b), Bow River
at Calgary
Beltaos (1978b), Beaver
River near Cold Lake
Sayre and Yeh (1975)
Missouri River below
Cooper Generation
Station
Lau and Krishanppan (1977)
Grand River below
Kitchener


183.0

18.3

18.3


20.1

373.0

320.0


213.0

104.0

42.7



234.0


59.2
Average velocity
in meters
W/H per second


66.7

46.2

27.3


28.7

170.0

156.0


137.0

104.0

44.6



59.1


117.0


1.74

0.18

0.67


1.25

0.95

0.86


0.58

1.05

0.50



1.98


0.35
Shear Velocity
1n meters
per second


0.073

0.040

0.062


0.061

0.056

0.079


0.080

0.139

0.044



0.085


0.069
Dispersion Coefficient,
Friction £y, 1n meters squared
factor per second £y/u*W ey/utH


0.014

0.220

0.069


0.020

0.028

0.067


0.152

0.143

0.062



0.015


0.314


0

0

0


0

0

0


0

0

0



1


0


.101

.0046

.0093


.013

.092

.066


.031

.085

.042



.110


.009


7.5 x

6.3 x

8.2 x


10.6 x

4.4 x

2.6 x


1.8 K

5.9 x

22.4 x



55.8 x


2.2 x

•5
10'3
_Q
10 J
0
10 3

0
10 3
-^
10 J
•1
10 3


ID'3
•5
10 3
o
10'3


•3
10 3


10'3


0.50

0.29

0.22


0.30

0.75

0.41


0.25

0.61

1.00



3.30


0.26
Sinuosity
S


1.1

1.0a

1.0a


1.0a

1.0a

1.2


1.0a

1.1

1.3



2.1


1.1

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 TABLE 2-9.   SUMMARY OF NONDIMENSIONAL  DIFFUSION FACTORS  IN NATURAL STREAMS
                                 (FROM GOWDA, 1984)



Source of data
Hamdy and Klnkead
(1979) St. Clair River

Glover (1964) Columbia
River near
Rlchland
Hoi ley and Abrahan
(1973)Haal River
Yotsukura and Cobb
(1972) Missouri River
near Blair
Beltaos (1980b) Athabasca
River below Fort
McMurray
Beltaos (1980b) Athabasca
River below
Athabasca


Holly and Abrahan
(1973) Ijssel River

Beltaos (1980b) Beaver
River near Cold Lake



Yotsukura and Cobb
(1972) Bernardo Conve-
yance Channel
Gowda (1980) Grand
River below Waterloo

Yotsukura and Cobb
(1972) Atrlsco Feeder
Canal near Bernallllo


Yotsukura and Cobb
(1972) South River
near the Town of
Wayresboro
Gowda (1980) Boyne
River below Al listen
Notes:
D W
*••*
Discharge,
1n cubic Mean
meters width, 1n
Salient features per second meters
12.0 km straight 6,800.00 819.3
stretch with
an Island
0.11 km stretch 1,235.30 304.8
with a gradual
S-curve
10.0 km straight 1,027.75 266.1
stretch
10.0 km stretch 965.60 183.0
with mild alter-
nating curve
17.6 km stretch 776.00 373.0
with occasional
bars and Islands
17.0 km stretch 566.00 320.0
with Irregular
meanders, occa-
sional bars and
Islands
8.6 km stretch 269.75 69.5
with three al-
ternating bends
1.5 km stretch 20.5 42.7
with regular
meanders, point
bars and large
dunes
2.0 km straight 17.75 20.1
stretch

3.4 km stretch 12.54 57.3
with two alter-
nating curves
2.0 km straight 7.42 18.3
stretch with a
channel of nearly
uniform cross-
section
0.4 km stretch 1.53 18.2
with a few very
slight bends

0.2 km straight 0.82 8.85
stretch


	 Mean
Mean velocity Nond1mens1onal
depth, 1n In meters diffusion
meters per second factor, /3
10.00 0.83 5.9 x 10 "4


3.00 1.35 4.7 x 10'4


4.70 0.82 5.3 x 10"4

2.74 1.74 6.6 x 10"4


2.20 0.95 7.8 x 10'4


2.05 0.86 8.4 x 10"4




4.00 0.97 23.0 x 10"4


0.96 0.50 41.0 x 10"4




0.70 1.25 81.0 x ID"4


0.56 0.39 10.0 x 10'4


0.67 0.67 13.0 x 10"4




0.38 0.21 25.0 x 10'4



0.43 0.22 25.0 x 10"4


°y ' ^ Vy

W  channel width
Q - flow rate
H = depth
U * velocity
mx » average value of matrix (=1) 1n x- direction
                                            60

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2.3.6  Summary

     The previous sections have  provided a brief review on the treatment  of
dispersive  transport in water  quality  models.   This  has included  a
discussion  of  vertical dispersion  in lakes and estuaries, and horizontal
(lateral  and longitudinal)  dispersion in lakes, estuaries,  and rivers.   It
is readily seen that a wide variety of numerical  formulations for dispersion
exist in  the literature.  Formulations for dispersion  coefficients tend  to
be model-dependent and are all  based to some extent on general  lack of a
complete  understanding of  the highly  complex turbulence  induced mixing
processes which  exist in  natural water bodies.   In  all cases, due to this
model  and empirical  dependence,  it is -desirable to include a  careful
calibration and/or verification  exercise using  on-site field data for any
water quality modeling application.

2.4  SURFACE HEAT BUDGET

     The total  heat budget  for a  water body includes the effects of inflows
(rivers,  discharges), outflows,  heat generated by  chemical-biological
reactions, heat exchange with the stream bed, and  atmospheric heat exchange
at the water surface.  In all practicality, however,  the  dominant process
controlling the  heat budget is  the atmospheric heat  exchange, which is the
focus  of the following paragraphs.   In  addition, however,  it  is  also
important to  include the  proper boundary conditions for advective exchange
(e.g., rivers, thermal discharges,  or tidal flows)  when the relative source
temperature and  rate of advective  exchange is  great enough to affect the
temperature  distribution of the water body.

     The transfer of energy which occurs  at  the air-water  interface  is
generally handled in one of two  ways in river, lake,  and estuary models.   A
simplified approach is to input temperature values directly and avoid a more
complete  formulation of  the energy transfer phenomena.  This approach  is
most often applied to those aquatic systems  where the temperature  can  be
readily measured.  Alternatively, and quite conveniently, the various energy
transfer phenomena which occur  at the air-water interface can be considered
in a heat budget  formulation.
                                   61

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     In a complete atmospheric heat budget  formulation, the  net  external
heat  flux, H, is most  often formulated as  an  algebraic sum  of several
component energy  fluxes  (e.g., Baca and Arnett,  1976; U.S. Army  Corps of
Engineers, 1974; Thomann  et aj_.,  1975; Edinger and Buchak, 1978; Ryan and
Harleman, 1973; TVA, 1972).  A typical  expression is given as:
                 H =
where  H     =  net surface heat flux
       iQ    =  shortwave  radiation  incident  to water surface,
               30 to 300 kcal/m 2/hr
                                                           2
       tQ    =  reflected short wave  radiation, 5 to 25 kcal/m /hr
       4-Q    =  incoming long wave radiation from the atmosphere, 225 to
               360  Kcal/m2/hr
                                                          2
       +Q    =  reflected long wave radiation, 5 to 15 kcal/m /hr
         ar
       fQ,    =  back  radiation emitted  by  the  body  of water,
               220 to 345 kcal/m2/hr
                                                             2
       •t-Q    =  energy utilized by evaporation, 25 to 900 kcal/m /hr

       |Q_    =  energy convected to or  from the body of water, -35 to 50
                    2
               kcal/m /hr at the surface

       NOTE:  The magnitudes  are typical  for middle latitudes of the
             United States.  The arrows indicate if  energy is coming
             into the system (+), out of the system (t),  or both ($).

     These  flux components can be calculated within  the models from  semi-
theoretical  relations, empirical equations, and basic meteorological data.
Depending on  the algebraic formulation used for the net heat flux  term and
the  particular empirical expressions chosen for each component, all or some
of the following meteorological data may be required:  atmospheric pressure,
cloud  cover, wind  speed and  direction, wet and dry bulb air  temperatures,
dew point temperature, short wave solar radiation,  relative  humidity,  water
temperature,  latitude, and longitude.

     Estimation of the various heat flux components has been the subject of
many theoretical and experimental  studies in the late 1960's and early
                                    62

-------
1970's.   Most  of  the  derived  equations rely  heavily on  empirical
coefficients.   These formulations  have been reviewed extensively by the
Tennessee Valley Authority (1972), Ryan and Harleman (1973), Edinger «rt  aK
(1974),  and Paily ^t jjK  (1974).   A summary of  the  most commonly  used
formulations in water quality models  is given in the following sections.

2.4.1  Measurement Units
     The measurement units  in  surface heat transfer  calculations do not
follow any consistent units  system.  For heat flux,  the English system  units
          2                                                      2
are BTU/ft /day.  In the metric system, the units are either Kcal/m /hr  or
      2
watt/m   (1 watt =  1 joule/sec).  The Langley (abbreviated Ly), equal  to 1
      2
cal/cm ,  also persists in usage.  The following  conversions are useful  in
this section:
  1 BTU/ftVday
  1 watt/m2
  1 Ly/day
  1 kcal/m2/hr
  1 kilopascal
  1 mb
  1 mm Hg
  1 in Hg
= 0.131 watt/m
= 7.61 BTU/ft2/day
= 0.483 watt/m2
=1.16 watt/m2
= 10 mb
= 0.1 kilopascal
= 1.3 mb
= 33.0 mb
0.271 Ly/day
2.07 Ly/day
3.69 BTU/ft2/day
2.40 Ly/day
7.69 mm Hg
0.769 mm Hg
0.13 kilopascal
25.4 mm Hg
= 0.113  kcal/rrr/hr
= 0.86 kcal/m2/hr
= 0.42 kcal/m2/hr
= 8.85 BTU/ft2/day
= 0.303  in Hg
= 0.03 in Hg
= 0.039  in Hg
= 3.3 kilopascal
2.4.2  Net  short wave Solar Radiation, Q
                                      sn
     Net short wave solar radiation  is the difference  between the incident
and reflected  solar radiations  (Qs  -  Qsr).  Techniques are available  and
described in the aforementioned  references to estimate  these fluxes as  a
function  of meteorological data.  However, in order  to  account for  the
reflection, scattering, and absorption incurred by the  radiation through
interaction with  gases, water  vapor,  clouds,  and dust particles, a great
deal of  empiricism is involved  and  the necessary  data  are relatively
extensive if precision is desired.
                                   63

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     One of the most common simplified formulations for net  short wave  solar
radiation (Anderson,  1954; Ryan and Harleman,  1973) is  expressed as:

                    Qsn = Qs - Qsr = 0.94 Qsc  (1-0.65C2)              (2-56)

                                             2
where  Q   = clear  sky solar radiation, kcal/m /hr
        j \+
       C   = fraction of sky covered by clouds

As  reported by Shanahan (1984), Equation (2-56)  is an  approximation in that
it  assumes average  reflectance at the water surface  and employs clear sky
solar radiation.   In certain  circumstances  atmospheric attenuation
mechanisms are much  greater than normal, even  under  cloudless conditions.
For such situations, the more complex formulae  described by TVA (1972) are
required.

     A number of methods are  available for  estimating  the clear sky  solar
radiation.  TVA  (1972)  presents  a  formula for  Q   as a function  of the
                                                  O v*
geographical  location, time of year, and hour of the day.   Thackston (1974)
and Thompson (1975)  report methods for calculating daily average values of
solar  radiation as  a function of  latitude, longitude,  month, and sky cover.
Hamon jjt jjl_. (1954)  have graphed the daily average insolation as a function
of  latitude, day of year and percent of possible  hours  of sunshine,  and is
given in Figure 2-9.

     Lombardo  (1972)  represents the  net short wave solar  radiation,.Q
(langleys/day),  with  the following expression:

                              Qsn = (1-R) Qs                         (2-57)

where Qs   =  short wave radiation at the surface (langleys/day)
       R   =  reflectivity of water = 0.03, or alternately:
       R   =  AaB  (A,B  given below in Table 2-10)
          =  sun's altitude in degrees
                                    64

-------
                 3000
CTl

tn
                 2500
 >


o
\

»»
u.
\



m

 c
 o
'£


T)


oc
o
0)

i
(A
             JS
             O
                 2000
                 1600
                 1000
                  BOO
                     0 10  20 30 10 20 28 10 20 30 10 20 30 10 20 30 10 20 3O 10 20 30 10 20 30 10 20 30 10 20 30 10 20 30 10 20 30


                       Jan     F«b    Mar     Apr    May    Jun     Jul     Aug    Sep    Oct    Nov     Dec
                  Figure  2-9.   Clear sky solar  radiation  according  to Hamon, Weiss and Wilson (1954)

-------
     TABLE 2-10.  VALUES FOR  SHORT WAVE RADIATION  COEFFICIENTS A AND B
                             (LOMBARDO, 1972)

Cloudiness
A
B
Clear
1.18
-0.77
Scattered
2.20
-0.97
Broken
0.95
-0.75
Overcast
0.35
-0.45

     The WQRRS model  by  the U.S.  Army Corps  of Engineers (1974)  considers
the net short wave solar radiation  rate (Qs - Qsr) as  a  function of sun
angle,  cloudiness,  and the level of particulates  in the atmosphere.  Chen
and Orlob,  as reported by Lombardo  (1973),  determine the  net  short wave
solar radiation by considering absorption and scattering in the atmosphere.

     A final  important note on  calculation of the net  short  wave solar
radiation  regards  the effects of shading from trees and banks primarily on
stream systems or rivers with steep banks. Shading  can significantly reduce
the  incoming  solar radiation to the  water surface, resulting  in~ water
temperatures much lower than  those occurring  in unobstructed areas.  Jobson
and Keefer (1979) present a  method to account  for the reduction  of incoming
solar radiation by prescribing geometric relations of vertical  obstruction
heights and  stream  widths for  each  subreach  of their  model of the
Chattahoochee River.

2.4.3  Net  Atmospheric Radiation, Q
     The atmospheric  radiation is characterized  by much longer wavelengths
than solar  radiation since the major  emitting elements  are  water vapor,
carbon  dioxide,  and ozone.  The approach generally adopted to compute this
flux involves  the  empirical determination  of  an overall  atmospheric
emissivity and the use of the Stephan-Boltzman law (Ryan  and  Harleman,
1973).   The formula  by Swinbank  (1963)  has been  adopted  by many
investigators for use in various water quality models (e.g., U.S. Army Corps
of Engineers, 1974;  Chen and Orlob, 1975;  Brocard  and Harleman,  1976).  This
                                   66

-------
formula  was believed to give reliable values of the atmospheric radiation
within a probable error to  +_5  percent.  Swinbank's formula is:

           Qan =  Qa - Q,v,  =1-16 x 10"13 U + 0.17C2) (Ta +460)6      (2-58)
            an     a    ar
                                                      2
where Q   = net long wave atmospheric radiation, BTU/ft /day
       C  = cloud cover,  fraction
       T  = dry bulb air  temperature, °F
        a

A recent investigation by  Hatfield jrt al. (1983) has found that the formula
by Brunt (1932) gives more  accurate  results over  a range of latitudes  of
26°13'N  to 47°45'N and an elevation  range of -30m to + 3,342m.   Brunt's
formula is:

             Qari = 2.05xlO~8(l+0.17C2)(T +460) 4( 1+0.149 v^)           (2-59)
              an                       a                 £.
                                                      2
where ()   = net long wave atmospheric radiation, BTU/ft /day
       an
      e~  = the air vapor pressure 2 meters above the water surface, mm
            Hg
      T   = air temperature 2  meters above the water surface,  °F
       a

2.4.4  Long Wave Back Radiation, Q.

     The long  wave back radiation from  the  water  surface  is usually the
largest of all  the fluxes  in  the  heat  budget  (Ryan and Harleman, 1973).
Since the emissivity of a water surface (0.97)  is known with good precision,
this flux can be determined with accuracy  as a function of the water surface
temperature:

                              Qbr = 0.97 <7T$4                        (2-60)

                                           2
where  Qbr = long wave back radiation, cal/m /sec
       T   = surface water  temperature, °K
       o   = Stefan-Boltzman constant =1.357 x 10"8, cal/m2/sec/°K4
                                    67

-------
     The  U.S.  Army  Corps of  Engineers (1974) uses the  following
linearization of Equation (2-60) to express the  back radiation  emitted by
the water  body:

                           Qbr =  73.6 + 1.17 T                       (2-61)

where  T = water temperature, C

     In the range of 0° to 30°C, this  linear function has a maximum error of
less than  2.1 percent relative to  Equation (2-60).

2.4.5  Evaporative Heat Flux, Q

     Evaporative heat  loss occurs as  a  result of the change  of state of
water from a liquid to vapor, requiring sacrifice of the latent  heat of
vapori zati.on.   The basic  formulation  used in all heat budget formulations
(e.g., Ryan and Harleman, 1973; U.S. Army Corps of Engineers,  1974; Chen and
Orlob, 1975; Lombardo,  1972) is:

                               Qe=PLwE                            <2-62)
                                              p
where  Q   = heat loss due to evaporation, kcal/m /sec
                             3
       p   = fluid density, kg/m
       LW  = latent heat of vaporization, kcal/kg
or     L,  = 597 - 0.57 T
       w               s
       E   = evaporation rate, m/sec
       T   = surface water temperature, °C

      The  general expression for evaporation from a natural water surface  is
 usually written as:

                           E =  (a + bW) (es - ea)                     (2-63)

 where a,b = empirical coefficients
                                   58

-------
       W   = wind  speed  at  some specified elevation  above water
            surface,  m/sec
       es  = saturation  vapor  pressure  at the surface  water
            temperature, mb
       e   = vapor pressure of the overlying  atmosphere,  mb

      Various  approaches have  been  used to evaluate the above expression.
In a very simplified approach, the empirical  coefficient,  a, has often  been
                                           -9          -9
taken  to be zero, while  b ranges from 1  x 10   to 5 x 10    (U.S. Army Corps
of Engineers, 1974).  The value of e  is  a nonlinear function of the surface
water  temperature.  However e  can  be estimated in a piecewise  linear
fashion as follows:
                             es = a.  + /3n. Ts                       (2-64)

where  a-,/3. = empirical coefficients  with  values  as given  in
              Table 2-11.
       T     = surface water temperature,  C
              TABLE 2-11.  VALUES FOR EMPIRICAL COEFFICIENTS

Temperature Range, C
0-1
5-10
10-15
15-20
20-25
25-30
30-35
35-40
ai
6.05
5.10
2.65
-2.04
-9.94
-22.29
-40.63
-66.90
01
0.522
0.710
0.954
1.265
1.659
2.151
2.761
3.511

     A more convenient formula for the  saturation vapor pressure, e  ,  is
presented by Thackston (1974) as follows:

                  es  = exp [l7.62 -  9501/(T$ + 460)]                 (2-65)
                                   69

-------
where e  = saturation vapor pressure at the surface water temperature,
           in  Hg
      T  = water temperature,  °F

The standard error of prediction of Equation (2-55)  is  reported by Thackston
(1974) to be 0.00335.

     A large  number  of  evaporation formula  exist for  a  natural  water
surface,  as demonstrated in Table 2-12 (Ryan and Harleman, 1973).  Detailed
comparisons of these formulae by  the above  authors  showed  that the
discrepancies between these formulae were not significant.  Both Ryan and
Harleman  (1973),  and TVA  (1968) recommend the use  of  the Lake  Hefner
evaporation formula developed by Marciano and  Harbeck  (1954), which has the
best data base, and has been shown to perform satisfactorily for other water
bodies.   The Lake Hefner formula is written as:
                            Qe = 17 W2 (es - e2)                     (2-66)
                                              2
where  Q  =  heat loss due to evaporation, BTU/ft /day
       W2  =  wind speed at 2  meters above surface,  mph
       e  =  saturated vapor pressure at the surface  water temperature,
            mm Hg
       e^  =  vapor pressure at 2 meters above surface, mm Hg

It is important to note that the Lake Hefner formula  was developed for lakes
and  may not  be  universally valid  for streams or open  channels  due  to
physical blockage of the wind by trees, banks,  etc.;  and due to differences
in the surface  turbulence which  affects the liquid  film aspects  of
evaporation  (McCutcheon, 1982).  Jobson developed a modified evaporation
formula which was  used in  temperature  modeling of the San Diego Aqueduct
(Jobson, 1980) and the Chattahoochee River (Jobson and Keefer, 1981).  This
formula is written as:

                   E = 3.01 + 1.13 W (ec - e_)                      (2-67)
                                      S    a
                                   70

-------
                                 TABLE 2-12.   EVAPORATION FORMULA FOR  LAKES AND  RESERVOIRS
                                                   (RYAN AND  HARLEMAN, 1973)
Name
Lake
Hefner
Kohler
Zaykov
Meyer
•^j

Morton
Rohwer

Formula in
Original Form
E=6.25-10~4W8(es-e8)
E=.00304W4(es-e2)
E=[,15+.108W2](es-e2)
E=10{l+.lW8)(es-e8)

E=(30CH-50W)(es-ea)/p
E=.77l[l.465-.0186B]x
[.44+.118W](es-ea)
where B=atmos. press.
Units*
cm/3 hr
knots
mb
in. /day
miles/day
in. Hg
mm/ day
m/s
mb
in. /month
mph
in. Hg

i n . /month
mph
in. Hg
in. /day
mph
in. Hg

Observation
Levels
Sm-wind
Bm-e,
a
4m-wind
2m-e,
a
2m-wind
2m- e,
a
25 ft-wind
25 ft-e,
a

8m-wind
2m- e
a
0.5-1 ft-wind
1 inch-e,
a

Time
Increments
3 hrs
Day
Day

Monthly

Monthly
Daily

Water Body
Lake Hefner
Oklahoma
2587 acres
Lake Hefner
Oklahoma
2587 acres
Ponds and
small reservoirs
Small lakes
and reservoirs

Class A pan
Pans
85 ft
diameter tank
1300 acre
Reservoir
Formula at sea-level
Meas. Ht. Spec. Units
BTU/ft2/day mph, mm Hq
12.4W8(es-e8)
17.2W2(es-e2)
15.9W4(es-e2)
17.5W2(es-e2)
(43+14W2)(es-e2)
(73+7.3W3)(es-e8)
(80+10W2)(es-e2)

(73.5-H2.2Wg)(es-e2)
(73.5+14.7W2(es-e2)
(67+10W2)(es-e2)

Remarks
Good agreement with Lake
Mead, Lake Eucumbene,
Russian Lakes.
Essentially the same as
the Lake Hefner Formula.
Based on Russian
experience. Recommended
by Shulyakovskiy
e is obtained daily from
mean morning and evening
measurements of T , R...
Increase constant! by 10% if
average of maximum and
minimum used.
Data from meteorological
stations. Measurement
heights assumed.
Extensive pan measurements
using several types of pans.
Correlated with tank
reservoir data:

*For each formula, the units are for evaporation rate, wind speed,  and vapor pressure.

-------
 where E    is in mm/day
      W  = wind speed at  some specified elevation above the  water
           surface, m/sec
      e  = vapor  pressure at the same  elevation  as the wind,
       a
           kilopascals
      e  = saturation vapor pressure at  the water surface temperature,
           kilopascals

 It  is noted that the wind speed function of Equation (2-67) was  reduced by
 30  percent during calibration of the temperature model for the Chattahoochee
 River (McCutcheon,  1982).  The original  Equation  (2-67) was  developed for
 the San  Diego Aqueduct which represented substantially different  climactic
 and exposure conditions than for the Chattahoochee River.  McCutcheon  (1982)
 notes  that the wind speed function is  a catchall term that must compensate
 for a number of difficulties which include, in part:

     •    Numerical dispersion in  some models.

     •    Inaccuracies in the measurement  and/or calculation of wind
          speed, solar and long-wave radiation, air temperature, cloud
          cover,  and relative humidity.

     •    Effects of wind  direction, fetch, channel width, sinuosity,
          bank  and tree height.

     •    Effects of  depth, turbulence, and  lateral  velocity
          distribution.

     •    Stability of the air moving over the stream.

2.4.6  Convective Heat Flux,  Q

     Convective heat  is  transferred  between air and water by  conduction and
transported  away from  (or toward)  the  air-water interface by convection
                                   72

-------
associated with  the moving air mass.  The convective  heat flux is related to
the evaporative  heat flux, Q , through the Bowen  ratio:
R =3|= (6.19  x  10"4) p
                                              Ts-Ta
                                              es -  ea
(2-68)
where  R  =  Bowen  Ratio
       p  =  atmospheric pressure, mb
       T  =  dry bulb  air temperature, °C
        a
       T  =  surface water temperature,  C
       e  =  saturation vapor pressure at the surface water temperature,
            mb
       e, =  vapor  pressure of the overlying atmosphere, mb
        a
     The above  formulation  is  used in the surface  heat transfer budget of
several  models (e.g.,  U.S.  Army Corps  of Engineers,  1974; Brocard  and
Harleman, 1976).

2.4.7  Equilibrium  Temperature and Linearization

     The preceding paragraphs present methods  for  estimating  the magnitudes
of the  various components  of heat  transfer  through  the  water surface.
Several  of these  components are nonlinear functions  of the surface water
temperature,  T .  Thus,  they  are most appropriately used  in transient  water
quality  simulations where the need to predict temperature variations is on
the time scale of minutes or  hours.  However, for  long  term water  quality
simulations  or  for steady state simulations, it  is more  economical to use a
linearized  approach to heat transfer.   As developed by Edinger  and  Geyer
(1965),  and reported by  Ryan  and Harleman (1973), this approach involves two
concepts, that of equilibrium temperature, T£,  and  surface heat exchange, K,
where H  can now  be  written as:

                              H = K (Ts - TE)                        (2-69)
                                    73

-------
     The equilibrium temperature, TE,  is defined as that  water surface
 temperature which, for a given set  of meteorological conditions,  causes the
 surface  heat  flux H, to equal zero.  The surface heat  exchange coefficient,
 K, is defined  to give the incremental change of net heat exchange induced by
 an  incremental  change of water  surface temperature.  It varies with the
 surface temperature  and thus  should be recalculated as  the water  temperature
 changes.

 2.4.7.1  Equilibrium temperature, Tr-

     The equilibrium temperature Tr is the temperature  toward  which every
 water body  at  the site will  tend,  and is useful  because  i1^ is dependent
 solely upon meteorological  variables  at a given  site.  A water body at a
 surface temperature, T , less than  TF, will have a net  heat input  and  thus
                     W             L.
 will tend  to  increase its  temperature.  The opposite is true  if T  > TF.
                                                                  W    L.
 Thus, the equilibrium temperature embodies all the external  influences  upon
 ambient temperatures.

     Certain  formulations  for the equilibrium  temperature  have  been
 developed  which  require an  iterative or trial and error solution approach
 (Ryan and Harleman, 1973).  An approximate formula for  obtaining  Tr has been
 developed  by Brady ^t al.  (1969) which has  been  shown to yield  fairly
 accurate  results:

                    TF =	^	+ T,                 (2-70)
                     L    23 + f(W) (0+ .255)     a

where  Qgn   =  net short wave  solar  radiation, BTU/ft2/day
       T     =  dew point temperature of air, °F
       f(w) = empirical wind  speed relationship
           = 17W2 (based on  Lake Hefner data), BTU/ft2/day/mm Hg
       fB   = proportional i ty  factor  which is  a fuirction  of
             temperature,  mm Hg/°F
       W~   = wind speed at 2 meters above surface,  mph
                                    74

-------
The expression  for /3 is written as:

                            /3= .255 -  .0085 T* + .000204 T*2        (2-71)

where
                              T* =  \ 

2.4.7.2  Surface  Heat Exchange Coefficient, K

     The surface  heat exchange coefficient, K, relates the net heat transfer
rate to changes in water surface temperature.  An expression for  K developed
by Brady et a]_. (1969), (and reported by Ryan and Harleman,  1973) is:

                       K = 23 + (13   + .255) 17W,                     (2-73)
                                 W           L.

where W? = wind speed at 2 meters, mph

and  ft  is evaluated at T  based on  Equation (2-62):
      W                 W

                       /3w = .255 -  .0085 TW + .000204 T2             (2-74)

     Charts  giving  K  as  a function of water surface temperature and wind
speed are given by Ryan and Stolzenbach  (1972), assuming an  average relative
humidity of 75  percent.  Shanahan (1984) presents a calculation procedure to
determine T£ and  K from average meteorological data.

2.4.8  Heat Exchange with the Stream Bed

     For most lakes, estuaries, and  deep rivers,  the thermal  flux  through
the  bottom is  insignificant.   However, as reported by Jobson (1980) and
Jobson and Keefer (1979),  the bed conduction  term  may be  significant in
determining the diurnal  variation of temperatures in water bodies  with
depths  of 10 ft (3m) or  less.   Jobson (1977)  presents  a  procedure for
accounting for bed  conduction  which does not require temperature
measurements within the  bed.   Rather, the procedure estimates  the heat

                                    75

-------
exchange  based on the gross thermal  properties of the  bed,  including the
thermal  diffusivity and heat storage capacity.  The inclusion of this method
improved  dynamic temperature simulation on the San Diego Aqueduct and the

Chattahoochee River.


2.4.9  Summary


     The previous  section  has  presented  a brief summary  of  the most

frequently  used formulations for surface heat exchange  in numerical water

quality models.  These formulations are widely used and have been  shown to

work quite  well within the  normal range of meteorological and  surface water

conditions,  provided a reasonably  complete data  base  is  available on
meteorological  conditions  at the site of interest.  Meteorological data

requirements include atmospheric  pressure, cloud cover,  and at  a  known
surface elevation: wind speed and direction, relative humidity, and wet and

dry bulb air temperatures.   Shanahan  (1984) presents a useful summary of
meteorological data requirements for surface heat exchange computations.


2.5  REFERENCES

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Quality Modeling of Deep Reservoirs, J.  Water Pollution Control Federation,
Vol. 48, No. 1.

Anderson, E.R.    1954.   Energy  Budget  Studies,  Part  of Water  Loss
Investigations  - Lake Hefner Studies.  USGS Prof. Paper 269.

Baca, R.G. and  R.C. Arnett.  1976.  A Limnological Model for Eutrophic  Lakes
and  Impoundments, Battelle Inc., Pacific Northwest Laboratories,  Richland,
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Bajraktarevic-Dobran, H.   1982.  Dispersion in Mountainous Natural Streams.
Journal  of the Environmental Engineering Division, ASCE.   Vol.  108, No. EE3,
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Bansal,  M.K.  1971.  Dispersion in Natural Streams.  Journal  of Hydraulics
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Beer, T.  and P.C. Young.  1983.  Longitudinal Dispersion  in Natural Streams.
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Bella,  D.A.  and  W.J. Grenney. 1970.  Finite-Difference Convection  Errors.
Journal of  the Sanitary Engineering Division,  ASCE,  Vol.  96,  No.  SA6
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                                   76

-------
Beltaos,  S.   1978a.  Mixing  Processes  in Natural Streams.   In:  Transport
Processes  and  River Modeling Workshop.  Canada Center for Inland Water.

Beltaos,  S.   19785.  Transverse Mixing  in Natural Streams,  Transportation
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Beltaos, S.   1978c.  An Interpretation  of  Longitudinal  Dispersion  Data in
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Beltaos,  S.   1980a.  Longitudinal Dispersion  in Rivers.   Journal of the
Hydraulics Division, ASCE.  Vol.  106,  No.  HY1, pp. 151-172.

Beltaos, S.   1980b.  Transverse Mixing  Tests in Natural  Streams.  Journal of
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Beltaos,  S.   1982.  Dispersion in Tumbling Flow.  Journal of  the Hydraulics
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Benedict, B.A.   1978.  Review of Toxic Spill Modeling, Department of Civil
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Bird, R.B.,  W.E.  Stewart, and E.N.  Lightfoot.  1960.   transport Phenomena.
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Blumberg, A.F.   1977.   Numerical Model of  Estuarine Circulation, ASCE,
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Blumberg,  A.F. and G.L. Mellor.  1978.  A Coastal Ocean Numerical  Model.
Submitted to the  Proceedings of the Symposium on  "Mathematical Modelling of
Estuarine  Physics,"  Springer-Verl ag.

Brady,  O.K., W.L. Graves, and J.C. Geyer.  1969.  Surface Heat Exchange at
Power Plant  Cooling Lakes,  Cooling Water Studies for Edison  Electric
Institute, Report  No. 5, John Hopkins University,  November 1969.

Brocard, D.N. and D.R.F.  Harleman.   1976.   One-Dimensional Temperature
Predictions  in  Unsteady  Flows.  Journal of  the  Hydraulics  Division, ASCE,
No. HY3, Proc: Paper 11982, March, 1976.

Brunt,  D.  1932.  Notes on Radiation in  the  Atmosphere.  Quarterly Journal
of the Royal  Meteorological Society, Vol.  58,  pp.  389-418.

CE-QUAL-R1.   1982.  A  Numerical One-Dimensional Model of  Reservoir Water
Quality.  User's Manual.  U.S. Army Corps  of Engineers,  Waterways Experiment
Station,  Environmental  and  Water Quality Operational  Studies,  Instruction
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Chatwin, P.C. 1980.  Presentation of Longitudinal  Dispersion Data.   Journal
of the Hydraulics  Division, ASCE. Vol.  106, No.  HY1, pp. 71-83.

                                    77

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Chen,  C.W.  and G.T.  Orlob.   1972.   Ecologic  simulation for Aquatic
Environments.  WRE, Inc., Walnut Creek.   Final Rep.  to OWRR, December  1972,
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Chen, C.W.  and  G.T.  Orlob.   1975.   Ecologic  Simulation for  Aquatic
Environments,  In:   Systems  Analysis and Simulation in Ecology, Vol.  3,
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Chen, C.W.  and J. Wells.  1975.  Boise  River Water  Quality-Ecological  Model
for Urban  Planning Study, Tetra Tech technical report prepared by U.S.  Army
Engineering  District,  Walla Walla, Wash., Idaho Water Resources Board, and
Idaho Dept.  of Environmental and Community Services.

Chen,  H.S.,  Lukens,  R.J  , and  C.S.  Fang.   1979.  A Two-Dimensional
Hydrodynamic  and Biogeochemical Water Quality Model  and Its Application  to
the Lower  James River.   Special Report No. 183 in Applied  Marine Science and
Ocean Engineering, Virginia Institute of Marine Science, Gloucester Pt., VA.

Chri stodoulou, G.C.  and B.R. Pearce.  1975.  Mathematical  Modeling Relevant
to the  Glass  Bead Study. R.M. Parsons Lab., MIT, Cambridge, Massachusetts.

Christodoulou,  G.C., Connor, J.J. and B.R. Pearce. 1976.  Mathematical
Modeling of  Dispersion in Stratified Waters.  R.M. Parsons  Laboratory,  MIT,
Technical  Report No.  219.

Cooperative  Instream  Flow Service Group.   1981.  Description and Application
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                                    87

-------
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                                   89

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                                Chapter 3
                             DISSOLVED OXYGEN

3.1  DISSOLVED OXYGEN SATURATION

3.1.1  Introduction

     Dissolved oxygen saturation,  commonly symbolized as  C  and expressed in
mg/1 , is  a  basic parameter used  in a great many water quality models.  Since
dissolved oxygen predictions  are  often primary reasons for developing  water
quality models, accurate values  for C  are needed.

     Table  3-1 illustrates  the equations  used to calculate  saturation
dissolved  oxygen  values in  a  number of water  quality models.  The most
frequently  used equation is  the  polynomial equation developed by  Elmore  and
Hayes  (1960)  for  distilled  water (Equation (3-1) in Table 3-1).  In this
equation, neither pressure nor salinity effects are considered (pressure is
assumed to  be  1 atm and salinity  is 0  ppt).

     Effects of pressure on  saturation values  are expressed as  a  ratio of
site pressure  to  sea level  (Equation (3-5)) or as a function of elevation
(Equation (3-6)).  Effects of salinity (relevant  to estuaries and  oceanic
systems)  are considered in the last two model equations (Equations  (3-7) and
(3-8)).  When  used in fresh water  applications, the sections of  the
equations in which the saline term appears reduce to zero and have no effect
on the  dissolved oxygen saturation. Every saturation equation,  whether or
not  modified  to  include non-standard pressure or salinity,  evaluates
dissolved oxygen saturation  as a  function of temperature.
                                   90

-------
TABLE 3-1.  METHODS USED BY SELECTED MODELS TO PREDICT DISSOLVED OXYGEN SATURATION
Equation
Number
3-1
3-1
3-1
3-1
3-2
3-3
3-4
3-5
3-5
3-6
3-7
3-8
Model Name
(or Description)
Limnological Model
for Eutrophic Lakes
and Impoundments
EXPLORE-1
Level Ill-Receive
Water Quality Model
for Large Lakes:
Part 2: Lake Erie
WRECEV
QUAL-II
CE-QUAL-R1
One Dimensional Steady
State Stream Water
Quality Model
HSPF (Release 7.0)
DOSAG and DOSAG3
Pearl Harbor Version
of Dynamic Estuary
Model (DEM)
RECEIV-II
Model
Reference
Baca and Arnett,
1976
Battelle, 1973
Medina, 1979
Di Toro and
Connolly, 1980
Johnson and
Duke, 1976
Roesner, et al.,
1981
U.S. Army COE,
1982
Bauer, et al.,
1979
Imhoff, et al.,
1981
Duke and Masch,
1973
Genet et al.,
1974
Raytheon Co. ,
1974, and
Weiss, 1970
Equation or Method for Dissolved Oxygen
Saturation C (mg/1)
Cs = 14.652 - (0.41022 T) + (0.007991 T2) - (7.7774xlO~5 T3)
T = °C
Same as above
Same as above
Same as above
Cs = 14.62 - 0.3898 T + 0.006969 T2 - 5.897xlO"5 T3
T =°C
Cs = 24.89-0.4259 T + 0.003734 T2 - 1.328xlO~5 T3
T = °F
C = (14 6)e'~(°'027767 " °-00027 T + 0.000002 T2) T)
C = (14. 652-. 41022 T + 0.007910 T2 -7.7774xlO~5 T3) (BP/29.92)
T = °C
BP = Barometric pressure (in.Hg)
Same as above
(14.62 - (0.3898 T) + (0.006969 T2) - (5.897xlO*5 T3))
[l.O - (6.97xlO'6 E)]5'167
T = °C
E = Elevation, ft.
Cs = 14.5532 - .38217 T + .0054258 T2-CL(1.665xlO"4-5.866xlO"6T + 9.796xlO"8 T2)
T = °C
CL = Chloride concentration (ppm)
Cc - 1.4277 exp[-173.492 + 24963. 39/T + 143.3483 ln(T/100.) ,
s -0.218492 T + S(-0. 033096 + 0.00014259 T - 0.00000017 r)]
T = °K = °C + 273.15
S = Salinity (ppt)

-------
3.1.2  Dissolved  Oxygen Saturation As Determined by the APHA

     The APHA (1985)  presents a tabulation of oxygen solubility  in water as
a function of both  chlorinity and water temperature (see Table 3-2).   This
table is the work of  Benson and Krause  (1984)  who collected the data and
developed  the equations  for conditions in which the water  was  in  contact
with water  saturated  air at standard pressure (1.000 atm).

     Since  chlorinity is related to salinity,  and salinity is  more  often
measured than chlorinity, the relationship between the two quantities is of
interest.  The relationship, expressed here three  ways, is:

      Salinity (ppt or O/OQ) = 0.03 + 0.001805 Chlorinity  (mg/1)      (3-9a)
or
      Salinity (ppt or 0/OQ) = 5.572 x 10"4(SC)  +  2.02 x 10"9(SC)2    (3-9b)

where SC =  specific conductance in micromhos/cm

or
      Salinity =  1.80655  (chlorinity as ppt)                          (3-9c)

where chlorinity  and  salinity are  as defined in the footnote to  Table 3-2.

      Equation (3-9b)  is from USGS (1981) and Equation (3-9c) is  from APHA
(1985).

     The APHA (1985)  recommends that the concentration of  oxygen in water
(at  different temperatures and salinity) at equilibrium with water saturated
air  be calculated using the equation below (Benson and Krause, 1984):

         In Cs = -139.34411 + (1.575701 x 105/T)                      (3-10)
                  -(6.642308 x 107/T2) + (1.243800 x 1010/T3)
                  -(8.621949 x 10U/T4)
                  -Chl[(3.1929 x 10"2) - (1.9428 x 10/T)
                     + (3.8673 x 103/T2)]

                                     92

-------
             TABLE  3-2.   SOLUBILITY OF  OXYGEN  IN  WATER  EXPOSED
                 TO  WATER-SATURATED  AIR  AT  1.000  ATMOSPHERIC
                                  PRESSURE  (APHA,  1985)
Tanp.
1n°C
ChloHnity. ppt
0.0 5,0 10.0 15.0 20.0 25.0
Dissolved Oxygen, mq/1
Difference
per 0.1 ppt
ChloHnity
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0.
20.0
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0
29.0
30.0
31.0
32.0
33.0
34.0
35.0
36.0
37.0
38.0
39.0
40.0
14.621
14.216
13.829
13.460
13.107
12.770
12.447
12.139
11.843
11.559
11.288
11.027
10.777
10.537
10.306
10.084
9.870
9.665
9.467
9.276
9.092
8.915
8.743
8.578
8.418
8.263
8.113
7.968
7.827
7.691
7.559
7.430
7.305
7.183
7.065
6.950
6.837
6.727
6.620
6.515
6.412
13.728
13.356
13.000
12.660
12.335
12.024
11.727
11.442
11.169
10.907
10.656
10.415
10.183
9.961
9.747
9.541
9.344
9.153
8.969
8.792
8.621
8.456
8.297
8.143
7.994
7.850
7.711
"7.575
7.444
7.317
7.194
7.073
6.957
6.843
6.732
6.624
6.519
6.416
6.316
6.217
6.121
12.888
12.545
12.218
11.906
11.607
11.320
11.046
10.783
10.531
10.290
10.058
9.835
9.621
9.416
9.218
9.027
8.844
8.667
8.497
8.333
8.174
8.021
7.873
7.730
7.591
7.457
7.327
7.201
7.079
6.961
6.845
6.733
6.624
6.518
6.415
6.314
6.215
6.119
6.025
5.932
5.842
12.097
11.783
11.483
11.195
10.920
10.656
10.404
10.162
9.930
9.707
9.493.
9.287
9.089
8.899
8.716
8.540
8.370
8.207
8.049
7.896
7.749
7.607
7.470
7.337
7.208
7.083
6.962
6.845
6.731
6.621
6.513
6.409
6.307
6.208
6.111
6.017
5.925
5.835
5.747
5.660
5.576
11.355
11.066
10.790
10.526
10.273
10.031
9.799
9.576
9.362
9.156
8.959
8.769
8.586
8.411
8.242
8.079
7.922
7.770
7.624
7.483
7.346
7.214
7.087
6.963
6.844
6.728
6.615
6.506
6.400
6.297
6.197
6.100
6.005
5.912
5.822
5.734
5.648
5.564
5.481
5.400
5.321
10.657
10.392
10.139
9.897
9.664
9.441
9.228
9.023
8.826
8.636
8.454
8.279
8.111
7.949
7.792
7.642
7.496
7.356
7.221
7.090
6.964
6.842
6.723
6.609
6.498
6.390
6.285
6.184
6.085
5.990
5.896
5.806
5.717
5.631
5.546
5.464
5.384
5.305
5.228
5.152
5.078
0.016
0.015
0.015
0.014
0.014
0.013
0.013
0.012
0.012
0.012
0.011
0.011
0.011
0.010
0.010
0.010
0.009
0.009
0.009
0.009
0.009
0.008
0.008
0.008
0.008
0.007
0.007
0.007
0.007
0.007
0.007
0.006
0.006
0.006
0.006
0.006
0.006
0.006
0.006
0.005
0.005
DEFINITION OF SALINITY

Although  salinity has been traditionally defined as the total solids  in water after all  carbonates
have been converted to oxides, all bromide and iodide have been replaced by chloride, and all
organic matter has been oxidized, the new scale used to define salinity 1s based on the  electrical
conductivity of seawater relative to a specified solution of KC1 and Had (UNESCO, 1981).  The scale
is dimensionless and the traditional dimensions of parts per thousand (I.e., mg/g  of solution)  no
longer applies.


DEFINITION OF CHLORINITY

Chlorinity 1s now defined in relation to salinity as.follows:

     Salinity- 1.80655 (ChloHnity)

Although chlorinity is not equivalent  to chloride concentration,  the factor for translating a
chloride  determination in seawater to include bromide, for example, is only 1.0045 based on the
molecular weights and the relative amounts of the two ions.  Therefore, for practical  purposes,
chloride  (in mg/g of solution) is nearly equal to  chlorinity in seawater.  For wastewater, a
knowledge of the ions responsible for the solution's electrical conductivity 1s necessary to correct
for the  ions impact on oxygen solubility and use  of the  tabular  value  or the equation  is
Inappropriate unless the relative composition of the wastewater is'Similar to seawater.
                                             93

-------
where C   = equilibrium  oxygen concentration,  mg/1 , at  1.000  atm
           (standard pressure)
         = temperature  (°K)  = °C + 273.150 and  °C  is  within 0.0 to
T

Chi  =  chlorinity within  0.0 to 28.0, ppt
           40.0°C
     Table 3-2 replaces the older  table of previous  APHA Standard Methods
editions.  The USGS  (1981) has replaced older tables based on calculations
of Whipple and Whipple (1911)  with tables generated from  an equation by
Weiss (1970) (Equation  3-8).

     The  APHA (1985) recommends  that saturation  dissolved oxygen
concentration at non-standard pressure be calculated  using the following
equation:
                    r  = r P
                    s    s
                             (l-Pwv/P)
                                                             (3-11)
where C,
      P
      P
 wv

In P.

6
T
         WV
= equilibrium oxygen concentration  at non-standard
  pressure, mg/1
= equilibrium oxygen concentration at 1.000 atm, mg/1
= pressure, atm,  and is  within 0.000 to  2.000 atm
= partial pressure  of  water vapor, atm, which may  be
  computed
= 11.8571- (3840.70/Tk)  -  (216961/Tk2)
= temperature in °K
= 0.000975 - (1.426 x 10~5TJ + (6.436 x 10~8T 2)
                o
= temperature in  C
      The expressions  for P   and 6 are  also from APHA (1985).
     For altitudes less than approximately 4000 feet the bracketed quantity
is very  nearly  1  and at  these altitudes multiplying C  by P(atm)  alone
                                     i                 S                i
results in a good approximation of C  .  A more accurate calculation of C
                                  94

-------
can be made by using  Table  3-3.   The  quantity in  brackets from Equation
(3-11)  is  tabulated  for temperatures  between  0-40°C and for pressures from
1.1  to 0.5 atm  (Benson and  Krause,  1980).   As an approximation of  the
influence  of  altitude, C   decreases  about  7 percent  per 2,000 feet of
elevation  increase.
     TABLE  3-3  VALUES FOR  THE BRACKETED  QUANTITY SHOWN IN EQUATION  3-11
         TO BE USED WITH  THE  CORRESPONDING TEMPERATURES AND PRESSURES
                            (BENSON  AND KRAUSE,  1980)



T(°C)

1.1

1.0

0.9
P atm
0.8

0.7

0.6

0.5

0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
1.0005
1 .0007
1.0010
1.0015
1.0021
1.0029
1.0039
1.0053
1.0071
1.0000
1.0000
1.0000
1.0000
1.0000
1.0000
1.0000
1.0000
1.0000
0.9994
0.9991
0.9987
0.9982
0.9974
0.9965
0.9952
(0.9935)
(0.9913
0.9987
0.9980
0.9971
0.9959
0.9942
0.9921
(0.9892)
(0.9854)
(0.9805)
0.9977
0.9966
0.9950
0.9929
(0.9901)
(0.9864)
(0.9814)
(0.9750)
[0.9665]
0.9963
0.9946
0.9922
(0.9889)
(0.9845)
(0.9787)
[0.9711]
[0.9610]
[0.9479]
0.9944
0.9918
0.9882
(0.9833)
[0.9767]
[0.9680]
[0.9566]
[0.9415]
[0.9217]

      Explanation of Interpolation Procedure:

      Linear  interpolation in P and T will introduce an error <0.02% in the upper and left
      sections of table.   Interpolation using numbers in parentheses will  lead to errors
      <0.05%.  With  the  numbers  in brackets, interpolation errors become larger.  Either
      temperature or presssure may be interpolated first, as illustrated for T - 3.00 C  and
      P = 0.67 atm by the  two arrays shown below.
           Temperature Interpolated First            Pressure Interpolated First
            0.7      0.67      0.6                 0.7      0.67      0.6
0
3
5
0
0
0
.9977
.99704
.9956

0.9965
answer
0.
0.
0.
9963
99528
9946
0
3
5
0
0
.9977
.9966
0
0
0
.99728
.9965,
.99600
0.9963
answer
0.9946
                                        95

-------
     Earlier  the  APHA (1980) calculated  the effects of barometric  pressure
on dissolved oxygen saturation as:
                                     ' P  - P.
                             "s   "s
C  = C  f      WV
 This is equivalent to  Equation (3-11) when 6=0.

 3.1.3  Comparison of Methods

     Table 3-4 compares  the dissolved oxygen  saturation values for Equations
 (3-1)  through  (3-8)  and  APHA (1971) against  the values in Table 3-2 from
 the APHA (1985), Equation  (3-10).  The comparisons are performed at 0.0 mg/1
 salinity and sea  level.   When the values  from the equations are compared
                                                              o *
 with the APHA (1985) values within the temperature range  10-30 C  and  the
 maximum differences  examined, four "groups^"  of differences appear.  Values
 from Equation (3-8) are  in the group that shows  the least difference  from
 APHA  (1985):   0.03 mg/1  higher than the APHA  (1985) predictions.   Values
 from Equations (3-2),  (3-4), (3-6) and APHA (1971) are in  the second  group
 with  differences  of  .07  to  .11 mg/1  higher than APHA (1985).  Values from
 Equations (3-1), (3-3) and (3-5) are in the third group with differences  of
 .11 to  .13 mg/1  lower  than APHA (1985).  Equation (3-7) produced differences
 that comprise the fourth group with some  values >0.4 mg/1  higher than  APHA
 (1985).  Generally,  the  maximum differences  with each equation occur at
 higher temperatures,  when dissolved  oxygen depletion may contribute  to
 serious water quality  problems.

     In Table 3-5 Equations  (3-7),  (3-8), (3-13) and APHA (1971)  (those
 including  salinity factors)  are evaluated  at a chloride concentration of
 20,000 mg/1  at 1 atm pressure and compared to  APHA (1985)  values.
* Typically,  the  temperature range  in which most freshwater  water  quality
  analyses  take place.

                                    96

-------
TABLE 3-4.   COMPARISON OF DISSOLVED  OXYGEN  SATURATION  VALUES  FROM TEN
            EQUATIONS AT 0.0  mg/1  SALINITY  AND  1  ATM PRESSURE

Temperatur
°C
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0
29.0
30.0
31.0
32.0
33.0
34.0
35.0
36.0
37.0
38.0
39.0
40.0
e
(3-1)
14.652
14.250
13.863
13.491
13.134
12.791
12.462
12.145
11.842
11.551
11.271
11.003
10.746
10.499
10.262
10.034
9.816
9.606
9.404
9.209
9.022
8.841
8.667
8.498
8.334
8.176
8.021
7.871
7.723
7.579
7.437
7.298
7.159
7.022
6.885
6.749
6.612
6.474
6.335
6.194
6.051
Equation Number From Table
(3-2)
14.620
14.237
13.868
13.512
13.169
12.838
12.519
12.213
11.917
11.633
11.360
11.097
10.844
10.601
10.367
10.142
9.926
9.718
9.518
9.3251
9.140
8.961
8.789
8.624
8.464
8.309
8.160
8.015
7.875
7.739
7.606
7.477
7.350
7.227
7.105
6.986
6.868
6.751
6.635
6.520
6.404
(3-3)
14.650
14.248
13.861
13.490
13.133
12.790
12.460
12.144
11.841
11.550
11.270
11.002
10.744
10.497
10.260
10.033
9.814
9.604
9.401
9.207
9.019
8.838
8.664
8.495
8.331
8.172
8.017
7.866
7.719
7.574
7.432
7.292
7.154
7.016
6.880
6.743
6.606
6.468
6.329
6.188
6.045
(3-4)
14.600
14.204
13.826
13.465
13.120
12.790
12.475
12.173
11.883
11.606
11.340
11.085
10.840
10.605
10.378
10.161
9.951
9.749
9.555
9.367
9.186
9.011
8.842
8.679
8.521
8.367
8.219
8.075
7.935
7.800
7.668
7.539
7.414
7.293
7.174
7.058
6.945
6.834
6.726
6.620
6.517
(3-5)
14.652
14.250
13.863
13.491
13.134
12.791
12.462
12.145
11.842
11.551
11.271
11.003
10.746
10.499
10.262
10.034
9.816
9.606
9.404
9.209
9.022
8.841
8.667
8.498
8.334
8.176
8.021
7.871
7.723
7.579
7.437
7.298
7.159
7.022
6.885
6.749
6.612
6.474
6.335
6.194
6.051
3-1
(3-6)
14.620
14.237
13.868
13.512
13.169
12.838
12.519
12.213
11.917
11.633
11.360
11.097
10.844
10.601
10.367
10.142
9.926
9.718
9.518
9.325
9.140
8.961
8.789
8.624
8.464
8.309
8.160
8.015
7.875
7.739
7.606
7.477
7.350
7.227
7.105
6.986
6.868
6.751
6.635
6.520
6.404

(3-7)
14.553
14.176
13.811
13.456
13.111
12.778
12.456
12.144
11.843
11.553
11.274
11.006
10.748
10.502
10.266
10.041
9.827
9.624
9.432
9.251
9.080
8.920
8.772
8.634
8.506
8.390
8.285
8.190
8.106
8.033
7.971
7.920
7.880
7.850
7.832
7.824
7.827
7.841
7.866
7.901
7.948

(3-8)
14.591
14.188
13.803
13.435
13.084
12.748
12.426
12.118
11.823
11.540
11.268
11.008
10.758
10.517
10.286
10.064
9.850
9.644
9.446
9.254
9.070
8.891
8.720
8.554
8.393
8.238
8.088
7.943
7.802
7.666
7.533
7.405
7.281
7.161
7.043
6.930
6.819
6.711
6.606
6.505
6.405
APHA
(1971)
14.6
14.2
13.8
13.5
13.1
12.8
12.5
12.2
11.9
11.6
11.3
11.1
10.8
10.6
10.4
10.2
10.0
9.7
9.5
9.4
9.2
9.0
8.8
8.7
8.5
8.4
8.2
8.1
7.9
7.8
7.6
7.5
7.4
7.3
7.2
7.1
-
-
_
-

APHA(1985)
3-10
14.621
14.216
13.829
13.460
13.107
12.770
12.447
12.139
11.843
11.559
11.288
11.027
10.777
10.537
10.306
10.084
9.870
9.665
9.467
9.276
9.092
8.915
8.743
8.578
8.418
8.263
8.113
7.968
7.827
7.691
7.559
7.430
7.305
7.183
7.065
6.950
6.837
6.727
6.620
6.315
6.412
     Equation (3-13)  is based  on  the  data  of  Green  and Carritt  (1967).  From
their data Hyer j3t aj_.  (1971)  developed  an expression  relating  C   to both
temperature and salinity.
                       GS is given by:
                  = 14.6244 - 0.367134T + 0.0044972r
                    0.0966S + 0.00205ST + 0.0002739S'
                                 97
                                                                      (3-13)

-------
TABLE 3-5.   COMPARISON  OF DISSOLVED  OXYGEN  SATURATION  VALUES  FROM
        SELECTED EQUATIONS AT A CHLORIDE  CONCENTRATION OF
        20,000 mg/1  (36.1 ppt SALINITY) AND 1  ATM  PRESSURE

Temperature
°C
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0
29.0
30.0
31.0
32.0
33.0
34.0
35.0
36.0
37.0
38.0
39.0
40.0
Equation
(3-7)
11.215
10.953
10.699
10.452
10.212
9.978
9.752
9.532
9.320
9.114
8.915
8.723
8.538
8.360
8.189
8.025
7.868
7.718
7.574
7.438
7.308
7.186
7.070
6.961
6.859
6.764
6.676
6.595
6.521
6.454
6.394
6.340
6.294
6.254
6.221
6.196
6.177
6.165
6.160
6.162
6.171
Number from
(3-8)
11.400
11.105
10.823
10.553
10.295
10.048
9.811
9.585
9.367
9.158
8.958
8.765
8.580
8.402
8.231
8.067
7.908
7.755
7.607
7.465
7.327
7.194
7.066
6.942
6.822
6.594
6.594
6.485
6.379
6.277
6.177
6.081
5.987
5.896
5.808
5.722
5.638
5.557
5.477
5.400
5.325
Table 3-1
(3-13)
11.492
11.203
10.924
10.653
10.391
10.139
9.895
9.661
9.435
9.218
9.011
8.812
8.623
8.442
8.270
8.108
7.954
7.809
7.674
7.547
7.429
7.321
7.221
7.130
7.049
6.976
6.912
6.857
6.812
6.775
6.747
6.729
6.719
6.718
6.726
6.743
6.770
6.805
6.849
6.902
6.965
APHA
(1971)
11.3
11.0
10.8
10.5
10.3
10.0
9.8
9.6
9.4
9.2
9.0
8.8
8.6
8.5
8.3
8.1
8.0
7.8
7.7
7.6
7.4
7.3
7.1
7.0
6.9
6.7
6.6
6.5
6.4
6.3
6.1

_
^
—
_
_
_
_
_
-
APHA (1985)
(3-10)
11.354
11.067
10.790
10.527
10.273
10.031
9.801
9.575
9.362
9.156
8.957
8.769
8.586
8.411
8.241
8.077
7.922
7.770
7.624
7.482
7.347
7.215
7.087
6.964
6.844
6.727
6.616
6.507
6.401
6.297
6.197
6.100
6.005
5.912
5.822
5.734
5.648
5.564
5.481
5.400
5.322
                               98

-------
where T =  temperature,   C
      S =  salinity, ppt.

      The  values were compared over  a temperature  range  of 5-30  C.
Equation  (3-8),  as before, agreed closely-with APHA (1985)  throughout the
5-30°C temperature range with a maximum  difference of .022 mg/1  less  than
APHA  (1985).   Equation  (3-7) had differences of  .08 less than  and .04 mg/1
greater than APHA (1985)  from 5-25°C  and  near .2 mg/1 higher  than  APHA
(1985)  at  30°C.   The  values from the  APHA (1971) (reported  to the nearest
tenth mg/1)  had a maximum  difference range of 0 to .1 mg/1 higher  than  APHA
(1985)  and  the fourth equation, Equation (3-13), varied the  most from APHA
(1985)  with differences  in the range  of  approximately .03 to 0.5  mg/1
higher.

3.1.4  Methods  of Measurement

      Elmore  and Hayes  (1960)  have  summarized  the work of numerous
researchers  who have measured dissolved  oxygen  saturation.  According  to
Elmore and  Hayes,  Fox in 1909 used a gasometric technique  in which a known
volume of  pure oxygen was exposed to  a known  volume  of water.   After
equilibrium had  been  established the  volume of oxygen  above the water was
determined,  and the solubility calculated assuming air contained 20.90
percent oxygen.

      From Fox's expression, Whipple and Whipple (1911) converted their
results from milliliters  per liter to parts  per million.   These results were
tabularized, circulated and used as standards by water agencies for years,
and  are only  now being gradually replaced with tables  developed from more
elaborate  equations.

      Benson and Krause  (1984) determined the solubility of oxygen in fresh
and seawater over a temperature of 0-60°C using  an equilibrator  different
from the Jacobsen Worthington-type  equilibrator  used in previous
investigations.  They felt the new  apparatus  minimized  the  uncertainties
associated  with  methods  involving thin films of liquids  (Benson, et al.,

                                   99

-------
1979).   The  dissolved gas values were  determined with  use  of a mercury
manometric  system.   The resulting  data  and equations  were compared to
previous sets of values  from Carpenter (1966), Green (1965), and Murray and
Riley  (1969).   The   APHA (1985) subsequently adopted the Benson and  Krause
concentrations as tabulated in. Table 3-2.  In  earlier work  involving fresh
water  only  (Benson  and Krause, 1980)  the  new concentration values were
recommended  by Mortimer  (1981) for use in fresh  water systems.

      To date there  is  no "standard method"  recommended by APHA to measure
saturated dissolved oxygen.  The laboratory methods noted in the preceeding
paragraphs  are  sophisticated methods  developed and/or modified for each
research effort  and are  not conducive to simplier laboratory  environments
nor are they adaptable for field use.

      Calibration of popular dissolved oxygen probes is  carried out under
saturation conditions by methods recommended  by  the instrument  manufacturers
in conjunction with a table such as Table 3-2.   The values  obtained may be
verified with  one of the several  wet  chemistry iodometric methods (or
"Winkler" titrations) (APHA, 1985).

3.1.5  Summary

      Notable differences exist  among the results obtained by  various
methods  used to determine saturated dissolved oxygen values under specified
conditions of temperature, salinity and pressure.  These  discrepancies may
be as  high  as  11  percent for high  saline  conditions  (Table 3-5).  Under
conditions of zero salinity observed  differences are generally less than
2 percent (Table 3-4).  The accuracy of the Elmore and Hayes expression, one
of the  most frequently used formulas,  rapidly deteriorates  at  water
temperatures exceeding 25°C.  The  algorithm, Equation  (3-8), used  in ttte
RECEIV-II model  (Weiss,  1970 and USGS, 1981)  matches the APHA (1985) data
better than  any formula  reviewed, for both saline and freshwater conditions.
The  algorithm, Equation  (3-10),  presented in  APHA  (1985)  and its
corresponding  table of saturation  values,  Table 3-2,  are based on  latest
research and provide the most accurate values of Cg to  date.   Knowing the

                                   100

-------
possible sources  of  error using any other  particular formulation for C
permits  the user to decide whether  they  are  significant  in  a  particular
study.

3.2  REAERATION

3.2.1  Introduction

      Reaeration  is the process of oxygen exchange  between the atmosphere
and a water body in  contact with the atmosphere.   Typically, the net
transfer of  oxygen  is from  the  atmosphere and  into the  water,  since
dissolved  oxygen levels in most  natural waters  are below saturation.
However, when photosynthesis produces supersaturated  dissolved oxygen
 levels, the net transfer is back into the atmosphere.

      The reaeration  process is modeled as the product  of a  mass-transfer
coefficient multiplied  by  the difference between dissolved  oxygen saturation
and the  actual dissolved oxygen concentration, that  is:

                              Fc =  kL(Cs-C)                         (3-14)

 where F  = flux of dissolved oxygen across the water surface, mass/
           area/time
      C  = dissolved  oxygen concentration, mass/volume
      C  = saturation dissolved oxygen concentration, mass/volume
      k. = surface transfer coefficient,  length/time

      For  practically all  river  modeling applications  and  for
 vertically mixed  estuaries a depth  averaged flux (F'),  is  used:

                           F1 = — = —  (^c~^'                      H
                            c   H    H    s                         ^

where H  = water depth,-length
                                   101

-------
     In  Equation 3-15 the surface transfer rate  and depth  are  typically
combined  into  a single term,  called the reaeration rate  coefficient or
reaeration coefficient,  denoted  in the  literature by k0 or k :
                                                    (-     a

                                      kL
                                 k2 = £-                             (3-16)

3.2.2  Reaeration in Rivers

3.2.2.1  Overview

     Rivers have been the focus  of the  majority of reaeration  research in
natural  waters.   Some of the equations that have been developed  for  rivers
have been successfully applied to estuaries, and is indicative  of the lack
of estuarine reaeration research.

     Table 3-6  summarizes reaeration  coefficient expressions  (k~ values) for
rivers.   All  formulas for reaeration  in Table 3-6 are depth averaged values
and  are  in units of I/day.   The table  also shows the units required for the
parameters in each formula,  and  when  possible the range of  conditions used
in the  development of the  formulas.  All values of k^ are base  e, and are
referenced to 20 C, unless otherwise  noted.  Although base e values are used
directly in most modeling  formulations,  in the earlier days of  reaeration
research, k~ values were often expressed  in  base 10.  The relationship
between base e  and base 10 reaeration  coefficients is:

                k?      = In (10)k?        = 2.303 k?                 (3-17)
                 base e           base 10           base 10

     Stream  reaeration research began  in earnest in the late 1950's,  and
continues today.  The formulas  that are  shown in Table 3-6 are  based on
theory,  empiricism, or  a  combination of the two.   In  the  late 1960's  the
radioactive tracer method was introduced  by Tsivoglou  and  Wallace (1972).
The  tracer method, or a modification of  it, forms the basis for much  pf  the
research being  conducted on reaeration today.
                                    102

-------
                             TABLE 3-6.  REAERATION COEFFICIENTS  FOR  RIVERS AND STREAMS
o
CO
Author(s) k2, base e(l/day at 20°C)
O'Connor and Dobbins (1958) 12.9U°'5
H1'5
Churchill et al. (1962) 11.6U0'969
H1.673
Owens etiL- <1964) 21.7U°'67
Owens .et.aK (1964) 23. 3U^'73
langbeln and Durum (1967) 7.6U
^753
Isaacs and Gaudy (1968) 8.62U
Parkhurst and Poraeroy (1972) 48. 4(1+0. 17F2)(SU)3/8
H
AA0-85
Negulescu and Rojanskl (1969) 10-9(ff)
Thackston and Krenkel (1969) 24.9(l+F°-5)u*
H
Lau (1972b) 2515/lilj^
Units
U-fps
H-feet
U-fps
H-feet
U-fps
H-feet
U-fps
H-feet
U-fps
H-feet
U-fps
H-feet
U-m/s
S-m/m
H-meters
U-fps
H-feet
u.-fps
H-feet
U*-fps
H-feet
Applicability
Moderately deep to deep channels; 1-
-------
                 TABLE 3-6.   (continued)
Author(s)
Krenkel and Orlob (1962)
Krenkel and Orlob (1962)
Padden and Gloyna (1971)
Cadwallader and
McDonnell (1969)
Bansal (1973)
Bennett and Rathbun (1972)
Dobbins (1964)
Ice and Brown (1978)
McCutcheon and Jennings (1982)
k2> base e(l/day at 20°C)
234(US>'408
8.4 D^"321
H2'32
6.9U0-703
336(US)°'5
H
4.67U0'6
H1'4
1Q6U0.413S0.273
H1.408
20.2U0'607
H1'689
117(l+F2(US)°-375)cot|r4.10(US)°-125l
(0.9+F)U5H L (0.9+F)°'5J
37H2/3S1/2U7/V/2
Q2/3
[ / a I 24 \ * 1
'ln L1'2 V(30.48H)2/ J
T
Units
U-fps
S-ft/ft
H-feet
0, -ft2/m1n
H=feet
U-fps
H-feet
U-fps
S-ft/ft
H-feet
U-fps
H-feet
U-fps
S-ft/ft
H-feet
U-fps
H-feet
S-ft/ft
H-feet
S-ft/ft
U-fps
q-ft3/sec
H-feet _ ,„
a=1.42 (1.1)T'ZO
T °r
Applicability
Based on I1 wide flume data. 0.08'< H<0.2'
Experiments performed 1n a 1' wide flume by deoxygenatlng
the water. Other similar formulas are also reoorted. The
flume dispersion coefficient, OL, was below the range
expected 1n natural systems.
Regression analysis performed on data where 9. 82^28. 8/day.
Based on multlvarlate analysis of reaeratlon data.
Based on reanalysls of reaeratlon data 1n numerous rivers.
These two equations are based on a reanalysls of historical
data, with the second equation being al most as good a
predictor as the first, but not having the slope term.
Theory combined with measurements 1n natural streams, and
flume data of Krenkel and. Orlob (1963).
Based on data collected 1n several small Oregon streams.
Based on the Velz method (1970) and replaces the Iterative
technique. The expressions for the mix Internal I are basec
  0.0016 + 0.0005 H    H<2.26 ft
0.0097 ln(H) - 0.0052  H>2.26 ft
                            (continued)

-------
                                                         TABLE 3-6.    (continued)
Author(s)
Long (1984)
Foree (1976)
Foree (1977)
k2. base e( I/day at 20°C)
1.923U0'273
H0.894
0.30+0.19S1/Z at 25°C
• 0.888 (O.eS+O^S1'15^0-25 at 25°C
for 0.05 < q < 1
Units
U -meters/ sec
H-meters
S-feet/mile
S-feet/mile
q-cfs/ml2
Applicability
Known as the 'Texas* equation. Based on data collected on
streams in Texas.
Radioactive tracer technique used on small streams in
Kentucky. 0l

                                •  0.42 (0.63+0.4S1'15)  at 25°C

                                    for   q<0.05
en
Tsivoglou and Wallace (1972)


Tslvoglou and Neal  (1976)
0.054 -    at 25°C


•  0.11  /-^JJ

   f or 1 < Q < 10 cf s

.  0.054

   for 25 < Q < 3000 cf s
                               Ah-feet
                                 t-days

                               Ah-feet
                                 t-days
Based on sunmary of radioactive  tracer applications
to 5 rivers.

Based on data collected on 24 different streams using
radioactive tracer method.
Grant (1976)
Grant (1978)
O.OoY-^}
          at 25°C
at 25°C
                               Ah-feet
                                 t-days
                                Ah-feet
                                 t-days
                                                            Based  on data from 10 small  streams in Wisconsin  using
                                                            radioactive tracer techniques:
                                                              2.1  < k,<55/day
                                                              1.2  i S<:<70 ft/mile
                                                              0.3  < Q < 37 cfs
Based on radioactive tracer data  developed on Rock River.
Wisconsin and Illinois:
  0.01< k,S0.8/day
  0.25
-------
                                                                   TABLE  3-6.    (continued)
o
CTi
Author(s)
SMndala and Truax (1980)
k2, base e(l/day at 20°C)
• O.OS/-^ at 25°C
for Q < 10 cf s
• 0.06^ at 25°C
for 10 < Q < 280 cfs
Units
Ah-feet
t-days
Applicability

Based on statistical analysis of reaeratlon coefficients
for rivers 1n 7 states, where the radioactive tracer Method
was used to find the reaeratlon rates.
          Eloubaldy and Plate  (1972)

          Haltingly (1977)

          Gulliver and Stefan  (1981)

          Frexes et a].. (1984)
Wind effects  analyzed.  See text for discussion.

Wind effects  analyzed.  See text for discussion.

Wind effects  analyzed.

Wind effects  analyzed.
          Definitions of Symbols:
          DL = longitudinal  dispersion coefficient
          f  * Froude number
                  U
               (gh)0'5
          g  * acceleration  due to gravity
          Ah = change 1n stream bed elevation between two  points
          q  « stream discharge divided by drainage area
          R  » hydraulic radius
          S  • slope
          t  * travel time between two points where Ah measured
          U  » stream velocity  ,
          u* « shear velocity -  VgRS
          W  = width

-------
3.2.2.2  Reviews of Stream Reaeration

     Over  the past decade, several  researchers have reviewed  reaeration
formulas,  and  have  tried to evaluate the performance of the formulas.  One
of the earlier reviews,  Bennett  and  Rathbun (1972), is  also an excellent
source for  reaeration  theory.  They  describe the theories behind  various
conceptual  models of reaeration  (including film, renewal, penetration, film-
penetration,  and two-film theory models),  semi-empirical models,  and
empirical  models.  They  also discuss methods to determine  the  reaeration
coefficient that  include dissolved oxygen balances in natural streams,
dissolved  oxygen  balances in  recircu1ating flumes,  the distributed
equilibrium technique (where sodium  sulfite is  usually added to the water to
deoxygenate it), and the radioactive tracer technique.

     Table 3-7 summarizes the Bennett  and Rathbun  review in  addition to
other studies  that have  compared  reaeration coefficients.  The  studies
conclude  that no single  formula  is best for all  rivers.  For one  set  of data
one formula may be best, while for another set  of data  another formula  may
appear to  be best.

     Figure 3-1 compares 13 reaeration coefficient expressions for  a range
of depths  (from  Bennett  and Rathbun, 1972).  The figure illustrates the
variability between predictions for a velocity of 1.0 fps and slope of
0.0001.   The range of differences between predicted values  spans one to two
orders of  magnitude.  The formulas  agree  with each other  best  within  the
depth range of 1 to 10 feet, typical of many rivers.

     Figure 3-2 compares calculated  and observed reaeration  coefficients for
the  formulas  of  Dobbins  (1965) and Parkhurst and Pomeroy (1972). These
formula were found by Wilson and MacLeod  (1974) to best fit the observed
data.  Notice  that the  spread of  data  is slightly less than one order of
magnitude.

     The  data of Wilson  and  Macleod also  show that  the  depth - velocity
model of Bennet and Rathbun (1972) does not fit the  experimental  data nearly

                                   107

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                  TABLE 3-7.   SUMMARY OF  STUDIES  WHICH  REVIEWED
                            STREAM  REAERATION  COEFFICIENTS
      •- •                         Bennett and Rathbun  (1972)
 •  Thirteen equations  were evaluated.
 •  The standard error of the  estimate was  used as a measure  of the  difference between
   predicted values and  data.
 t  The equation which  provided the best fit to their original data set was Krenkel  (1960).
 •  The equations which best fit the entire range of data were:  O'Connor and Dobbins (1958),
   Dobbins (1965),  Thackston and Krenkel (1969).
 •  Of the thirteen  equations the  Churchill e_t al.  (1962) formula  provided the  best fit to
   natural stream data.
 t  The Bennett and  Rathbun formula, developed from the data evaluated during their review,
   provided a smaller  standard error for natural streams than the other 13 equations.
 •  There was a significant difference between  predictions  from equations derived from flume
   data and equations  derived from natural stream  data.
 •  The expected root-mean-square error from different measurement  techniques is:  15 percent
   using  the radioactive tracer technique;  65 percent  using the dissolved oxygen mass balance,
   and 115 percent  using the disturbed equilibrium  method.
                                         Lau  (1972b)
 •  Both'conceptual  and empirical  models were reviewed.
 •  Conclusions reported were similar to those  of Bennett and Rathbun.
 •  It was found that no completely satisfactory method exists to predict reaeration.
                                  Wilson and  MacLeod (1974)
 •  Nearly 400 data  points were used in the analysis.
 •  Sixteen equations were reviewed.
 t  The standard error  of estimate and graphical results were both  used  in error analysis.
 •  It was  concluded that equations which use  only depth and velocity are not accurate over the
   entire range of  data investigated.
 •  The methods of  Dobbins (1965)  and Parkhurst  and Pomeroy (1972) gave the best fits to the
   data investigated.
                                       Rathbun (1977)
 •  Nineteen equations were reviewed.
•  Equation  predictions were compared against  radioactive tracer  measurements on 5 rivers
   (Chattahoochee,  Jackson,  Flint,  South,  Patuxent).
t  The best  equations in terms of the smallest standard error estimates was Tsivoglou- Wallace
   t   1   |?'05?8)?  Parkhur>st-Pomeroy (1972)  (0.0818),  Padden-Gloyna (1971) (0.0712) and  Owens

•  No one  formula was best for all  five rivers.
                                             108

-------
                                TABLE 3-7.   (continued)
                                  Rathbun and Grant (1978)

•  Compared  the  radioactive and modified tracer techniques for  Black Earth Creek and Madison
   Effluent  Channel  1n Wisconsin.

•  Differences  1n Black Earth Creek were -9% to 4% in one reach and 16% to 32% on another reach
   attributable  to  Increased wind during the latter part of the test.

•  Unsteady  flow during the Madison Effluent Channel tests led  to differences of as much  as  25
   to 58% 1n one case and -5% to 3% in another.


                                  Shlndala and Truax  (1980)

•  Reaeration  measurements  for streams  in  Mississippi, Wisconsin, Texas,  Georgia,  North
   Carolina, Kentucky, and New York were made using the radioactive tracer technique.

•  The energy  dissipation model  resulted  in the best correlation for reaeration coefficient
   prediction for  small streams. The following escape  coefficients (defined as the coefficients

   of ^r in  energy  dissipation models for reaeration coefficients) were recommended:

       0.0802/ft  .for Q  <10   cfs
       0.0597/ft  ,for 10 < Q < 280 cfs

                                   NCASI Bulletin (1982b)

•  Six reaeration formulas  were  compared  against measurements made using radioactive tracer
   techniques and  hydrocarbon tracer techniques for a  reach of  the Ouachita River, Arkansas.

t  The hydrocarbon tracer technique produced reaeration rates  higher than both the radioactive
   tracer and empirical formulas.

•  The O'Connor -  Dobbins  (1958) equation was chosen as the best empirical equation.

                                   Kwasnik and Feng (1979)

•  Thirteen reaeration formulas  were reviewed and compared against values measured using the
   modified  tracer  technique for two streams in Massachusetts.

•  The equations  of Tsivoglou-Wallace  (1972) and Bennett-Rathbun (1972)  gave the closest
   predictions  to  the field values.

•  The study indicates that results using the modified tracer technique are reproducible.

                                 Grant and Skavroneck  (1980)

•  Four  modified  tracer methods  and 20 predictive equations  were compared against the
   radioactive  tracer methods for 3 small streams in Wisconsin.

•  Compared  to  the  radioactive tracer method the errors in the modified tracer techniques were:

      11% for the propane-area method
      18% for the propane-peak method
      21% for the ethylene-peak method
      26% for the ethylene-area method

•  Compared  to  the  radioactive tracer method, the equations with the smallest errors were:

      18% for Ts1voglou-Neal (1976)
      21% for Negulescu-Rojanski (1969)
      23% for Padden-Gloyna (1971)
      29% for Thackston-Krenkel (1969)
      32% for Bansal  (1973)



                                            109

-------
                                 TABLE  3-7.   (continued)
                                 House and Skavroneck   (1981)

   •  Reaeration coefficients were determined on two creeks 1n Wisconsin using the propane   area
      modified tracer  technique and compared against 20 predictive formulas.

   •  The top five predictive formulas were:

         Tsivoglou - Neal (1976), 34% mean error
         Foree (1977), 35% mean error
         Cadwallader and McDonnell (1969),  45X, mean error
         Isaacs-Gaudy  (1968), 45X, mean error
         Langbein-Durum (1967),  495!, mean error.

                                      Zison  et al_. (1978)

   •  Thirteen reaeration formulas were reviewed, but none were compared  against historical data.

   •  Covar's method (1976) was discussed which shows how stream reaeration can be  simulated  by
      using three formulas  (O'Connor-Dobbins (1958),  Churchill et al_. (1962),  and Owens et &]_.
      (1964)), each applicable in a different depth and velocity regime.

                                    Yotsukura et al_. (1983)

   •  Developed a steady injection method to avoid uncertainty in dispersion corrections.

   •  Determined reproducibility to be 4%.

   •  Found negligible effect of wind where stream banks  are high.

                           Ohio Environmental Protection Agency (1983)

   t  Eighteen reaeration coefficient equations were compared against data collected  in  28  Ohio
      streams.

   •  The streams were divided into four groups based on  slope and velocity.  The best  predictive
      equations for each group are shown below:
Group Slope (ft/mile)
1 <3
2 3-10
3 3-10
4 >10
Flow (cfs)
All data
<30
>30
All data
Preferred Equation
Negelescu-Royanski (1969)
Krenkel-Orlob (1962)
Parkhurst-Pomeroy (1972)
Thackston-Krenkel (1969)
Parkhurst-Pomeroy (1972)
Tsivoglou-Neal (1976)
as  well   (see   Figure  3-3).     This  was  the formula which Bennett and  Rathbun

(1972) found produced the smallest  error of  the formulas they reviewed.


      Figure  3-4 shows the three reaeration  formulas found  by Rathbun (1977)

to  best  predict  observed  values  for  the Chattahoochee,  Jackson,  Flint,

                                            110

-------
  1000
   100-
    10-
>-
<
      1-
UJ
o
o
ce:
LU
<
UJ
    0.1-
   0.01-
 0.001
                                                  Mean Velocity=1.0 feet per second
                                                            Slope =.0.0001

                                                     Range of Experimental Data

                                                  —,.	___________—,
                                                                  Equation
                                                                Identification
                                                                        -1
Key:

  1
  2
  3
  4
  5
  6
  7
  8
  9
 10
 11
 12
 13
Dobbins (1965)
Krenkel (I960)
Thackston (1966)
Negulescu and Rojansk! (1969)
Thackston (1966)
Fortescue and Pearson (1967)
O'Connor and Dobbins  (1956)
O'Connor and Dobbins  (1956)
Issacs and Gaudy (1968)
Owens et al. (1964)
Isaacs ancTGaudy (1968)
Churchill et al. (1962)
Owens et aTT TT964)
                                                NOTE:  References  repeated in  the key
                                                indicate that the  authors developed
                                                more than one formula for reaeration
                                                rate.
      0.01                 0.1                   1                  10                  100
                                           DEPTH, IN FEET
   Figure 3-1.   Predicted  reaeration coefficients  as a  function  of depth  from
                   thirteen predictive  equations (from Bennett  and  Rathbun,  1972)

                                            111

-------
  1000
Q"
LU

   100-
o   10-
LU
O
LU
DC
LU
<
LU
DC
     1 -
z
Q   0.1-
                0.01
      0.01      0.1       1        10      100     1000

       REAERATION COEFFICIENT OBSERVED, DAY'1
1
Q
LU
   1000'
z
UJ

o
U.
LL
LU
O
O
DC
LU
<
LU
DC
   100-
o    10-
                  1 -
   0.01
               I

              0.1
                   0.01     0.1       1        10      100      1000

                     REAERATION COEFFICIENT OBSERVED, DAY"1

                                       (b)

Figure 3-2.  Comparisons of  predicted  and observed reaeration coefficients
             for the  formula of Dobbins  (1965) (a) and Parkhurst-Pomeroy

             (1972)  (b).

                                     112

-------
South,  and Patuxent Rivers.  The range  of reaeration coefficients  analyzed
here is considerably smaller than analyzed  by Wilson and  Macleod.  The
Tsivoglou  - Wallace method  is  noticeably better than either  the Padden-
Gloyna or Parkhurst-Pomeroy methods.   However, the Tsivoglou-Wallace method
was originally developed using this  data set, so  it is not surprising that
the fit is  best.

     Figure 3-5 shows the energy dissipation  model of Shindala and Truax
(1980)  applied to streams  with flow rates  less  than 280 cfs.   They found
that the best fit  to the data was achieved when  the flow  rate was  divided
into two groups:   less than 10 cfs and greater than 10 cfs.

     Covar (1976), as  discussed by Zison _et  _al_. (1978) found that  the
research of O'Connor-Dobbins (1958), Churchill et _al_.  (1962), and Owens  et
al. (1964) could be used jointly to  predict stream reaeration coefficients
             1000
           C  0.01
                0.01     0.1      1        10      100     1000
                 REAERATION COEFFICIENT OBSERVED, DAY''
      Figure 3-3.  Formula of  Bennett and Rathbun (1972)  compared
                  against observed reaeration coefficients.
                                  113

-------
 for a range of depth and velocity combinations.   Figure 3-6  shows  the data
 points collected by each investigator  and  the regions Covar choose  to  divide
 the  applicable  formulas.   Figure 3-7  shows  the plots  of  reaeration
 prediction.  Note that the predictions approximately match at the boundaries
 of each  region.
         9.6
      z
      IU
      f  7.2H
      UJ
      O
      o
      UJ
      fi
      a.
      S
      _
                  2.4      4.8     7.2      9.6    0      2.4     4.8
                            EXPERIMENTAL REAERATION COEFFICIENT, DAY'1
                         (a)                                 (b)
                                              7.2
96
                      I
                        9.6
                      UJ
                      i 7-2-
                      LL
                      UJ
                      O
                      o
                      2 4.8 H
UJ

-------
          40
                 DATA FOR FLOWRATES
                 BETWEEN 10.0 AND 280.0 CFS
                           120      180     240     300     360     420
                          ENERGY DISSIPATION.SU (FEET/DAY)
                                        (a)
                                                            460
         50
                DATA FOR FLOWRATES
                LESS THAN 10.0 CFS
                           160
                      240
320
400
480
560
640
Figure 3-5.
              ENERGY DISSIPATION, SU (FEET/DAY)
                           (b)

Reaeration coefficient  versus  energy dissipation  (a)  for  flow  rates
between 10 and 280 cfs  and (b)  for flow rates  less  than 10  cfs.
(Note:   Curves for predicted reaeation  coefficients are forced
through the origin).
                        115

-------
3.2.2.3  Measurement Techniques

     Methods  to determine reaeration rates based  on instream  data include
the dissolved  oxygen  balance, deoxygenation by sodium sulfite, productivity
measurements,  and  tracer techniques (both radioactive tracers and hydocarbon
tracers).   Today,  use  of tracers  is the most widely accepted method.
Productivity  measurements are sometimes used, but because of their indirect
approach  could be subject  to considerable error.  Some of these methods are
discussed in  Kelly et  a/L (1975), Hornberger  and Kelly  (1975), and Waldon
(1983).  Only the  tracer methods are discussed here.
          Q.
          UJ
          0
              50
              40
              30
              20-
              10
               8
               6
               4
               3
              .6-
              .4-
              .3-
                A O'Connor-Dobbins
                o Churchill,et.al.
                D Owens,et.aj.
                         A
                .1
                            A
                            A
 A
A
                                 DA
                                D
                             D  DD
                                  D
                                         "A" Line
                                               •"B"Line
                    .2   .3  A   .6  .8  1       23456
                           VELOCITY, ft./sec.
Figure 3-6.   Field data considered by three different investigations.
                                    116

-------
     The tracer method which appears  to produce the most accurate  results is
the radioactive tracer technique developed and reported by Tsivoglou et^ al.
(1965), Tsivoglou (1967), Tsivoglou ei_ a]_. (1968), Tsivoglou  and Wallace
(1972),  and Tsivoglou and  Neal  (1976).   The method  involves  the
instantaneous  and simultaneous release of three tracers:  krypton-85,
tritium, and  a  fluorescent  dye.   The fluorescent dye indicates when to
sample the invisible  radioactive  tracers  and provides  travel time
information  as  well.  The tritium  acts as a  surrogate for dispersion:  the
           t
           LU
           Q
                .3-
                  • ^^^z
                  .1      .2   .3 A   .6 .8  1       2   3456
                              VELOCITY, ft./sec.
    Figure  3-7.  Reaeration coefficient (I/day) vs. depth and velocity
                using the  suggested method of Covar (1976).
                                   117

-------
tritiated water disperses in  the  same manner as the  natural  water.  The
krypton-85  is  lost to the atmosphere in a constant, known ratio compared
with dissolved oxygen.  The  formula used is:
                                 = exp (-kkpt)                      (3-18)
       /C.  \
where   7^-    = concentration ratios of  krypton and tritium at
       \°tr/A,B
                 locations A  and B when the dye peaks  at each location
       t       = travel time  between A and B
       k.       = atmospheric  exchange rate of krypton

           kkr
     Since -r^- = 0.83±0.04, the dissolved oxygen reaeration rate, k?, can be
           K2
found directly from k.   .  The  ratio 0.83 was found in  the laboratory and has
not been proven to be constant for all conditions.

     Wilhelms (1980)  has applied the radioactive tracer technique to flow
through a hydraulic model.  The results compared favorably with results from
disturbed-equilibrium tests.

     Because  of the costs and  potential hazards of using this method,  other
tracer techniques have been developed which do not use radioactive tracers.
These methods have been discussed by Rathbun .et _al_. (1975),  R,athbun ^t al.
(1978),  Rathbun  and Grant (1978),  Kwasnik and  Feng (1979), Bauer et jTL
(1979), Rathbun (1979), Jobson and Rathbun (undated),  Grant and Skavroneck
(1980),  House  and Skavroneck  (1981), Rainwater and  Holley  (1984), Wilcock
(1984a). and Wilcock (1984b).   Not all researchers agree on the accuracy to
the  modified  tracer techniques.   Kwasnik  and Feng  (1979), Grant and
Skavroneck (1980), House and Skavroneck (1981)  all  reported successful
applications of the method.  However, NCASI  (1982b)  reported  that the
hydrocarbon  tracer technique  produced  results higher  than  both  the
radioactive  tracer and  empirical methods.  The application was on a  large

                                   113

-------
sluggish  stream.   Rainwater  and Holley (1984)  have  investigated  two
assumptions  of  the  hydrocarbon tracer technique (constant  ratios between
mass transfer  coefficients and negligible absorptive losses) and found  both
assumptions  to  be valid for that particular  study.

     The modified  tracer  techniques use a hydrocarbon gas  tracer and a
fluorescent dye (e.g., rhodamine-WT)  as  the  dispersion-dilution  tracer.
Sometimes two different tracer gases (e.g.,  ethylene and propane)  can be
used simultaneously to yield two estimates  of reaeration rate.   Two  methods
can be  used:  the peak concentration method  and the total weight  method.

     Using the  total-weight method the  exchange rate of the  tracer with the
atmosphere,  k  is computed as follows:
                                                                    (3-19)
where AU and Ad =  areas under the gas  concentration-versus-time curves
                  at  the  upstream and  downstream ends  of  the reach,
                  respectively, and
      Q  and Q. =  stream discharge at  each  end of the reach.

      The reaeration  coefficient k? is computed as:

                                                                   (3-20a)


                                                                   (3-20b)


Recently Wilcox (1984a, b) has proposed  methyl chloride as a  gas tracer.  At
20°C,

                             kT
                       k2 = "757  ' for meth^1 chloride             (3-20c)

                                   119
kT
.87
\c
kT
[.72
, ethylene


, propane


-------
The  methyl  chloride  transfer coefficient  kT  was found to  exhibit a
temperature  dependence.

     The peak concentration method  is  similar in form to the radioactive
tracer equation:
                                                                   (3-21)
where k-r          = the base  e desorption coefficient for the tracer
                    gas;
      t.-t        = the time of travel  between the peak concentrations;

      CT and Cn    = the  peak  concentrations of the  tracer gas  and
                    rhodamine-WT dye,  respectively
      (Ap) ., (AD)  = area  under dye versus time curve downstream  and
                    uptream, respectively

      More  recently Yotsukura et_ al.  (1983) have conducted tests to  assess
the feasibility  of a steady-state propane gas  tracer method  as a  means of
estimating  reaeration coefficients.   The  tests were conducted on Cowaselon
Creek, New York.  It was concluded that the steady state method, which also
includes  an instantaneous injection of dye tracer, is feasible and  provides
a reliable method of determining the reaeration coefficient.

3.2.2.4  Special Influences on Reaeration

      In addition to  hydraulic variables which typically appear  in the
expressions in Table 3-6,  the reaeration coefficient can be influenced by
certain special  factors which include:

      •  surfactants
      •  suspended particles
                                    120

-------
      •  wind
      •  hydraulic  structures, and
      •  water temperature

     While  surfactants, suspended solids,  and wind can influence reaeration
in rivers,  in practice the  effects of  these  factors are rarely if ever
included in  water quality models.   Discussion  of  the  influence  of
surfactants  is given in Zison et a±.  (1978), Poon and Campbell (1967),  and
Tsivoglou  and Wallace  (1972).   The influence of  suspended solids  is
discussed by  Holley (1975)  and Alonso et _§]_. (1975).

3.2.2.4.1   Wind Effects

     While  wind effects are typically not  included in reaeration predictions
in rivers,  there  is evidence that at high  wind speeds, the reaeration rates
can be  significantly increased.  These effects are occasionally alluded to
in the literature when experimental measurements are abnormally high.

     Eloubaidy and Plate (1972)  performed experiments  in  the wind-wave
facility at  Colorado State  University.  They arrived at the  following
expression  for the  surface transfer coefficient, k, , in feet per day:

                                   cu*  h  u*
                              k,  =    s    c                         (3-22)
                                      v
where C  = a constant of proportionality
                                          2
      v  = kinematic viscosity of water,  m /sec
      U* = surface shear velocity due to  wind, m/sec = 0.0185  Vw
        s
      V,, = wind  speed, m/sec
                                            I	
      IL = water shear velocity defined as y9nSr » m/sec
       •x                                   v   v*
      h  •= normal  depth (i.e., depth with uniform flow), m
      Sc  = pressure-adjusted channel slope, unitless, SQ +
      P  = mass  density of water, kg/m
                                       2
      g  = gravitational constant, m/sec
      S   = slope of energy gradient (channel slope for uniform flow),
            unitless

                                    121

-------
                                                                     o
        4^-  = air pressure  gradient in the longitudinal  direction, kg/m -
        QX       n
              sec
       From  their  experiments Eloubaidy and  Plate found that C = .0027.

     The variables comprising Equation 3-22  are readily obtainable, with the
exception of the pressure gradient.   The authors determined that an error on
the  order  of 2 percent  was obtained  in  k2 (= k^/h)  by neglecting  the
pressure gradient.

     A summary of  the conditions under which Equation 3-22 was developed is:

          channel  slope:   .00043,  .001
          air velocity:    22, 30,  38 fps for  each slope
          discharge:       0.79, 0.83, 0.91  cfs at 0.001 slope
                          0.58, 0.63, 0.75  cfs at 0.0043 slope
          water depth:     0.385 feet

     Note the extremely  high wind  velocities used in  the experiments
(greater than 22 fps).  Hence the validity of  the approach to lesser wind
speeds typically encountered in  the  natural  environment has not been
demonstrated.

     Mattingly (1977)  also performed laboratory studies of the effects of
wind on channel reaeration.  He obtained  this  empirical expression:
                              - 1 =  0.2395 V  1'643                   (3-23)
                            o              w

where k2    = reaeration coefficient  under windy conditions, I/day
      (k2)Q = reaeration coefficient  without wind, I/day
      VM    = wind velocity in meters  per second  in  the free stream
             above the boundary layer  near the water surface
                                   122

-------
     A  plot  of  the experimental data  is  shown  in Figure 3-8.  Note  the
importance  of  wind  induced reaeration at moderate to high wind speeds.
Further discussion of the effects of wind are found in Gulliver and Stefan
(1981)  and Frexes et  al_. (1984).

     Because wind effects  are  typically  neglected  in  river  and  stream
reaeration  modeling,  this approach is equivalent to assuming a zero wind
velocity.  For  many water  quality model ing  applications,  such  as  wasteload
allocation,  this  approach  is reasonable.
             100-
              10—
          JC

           CN
                                              D
                                        WATER VELOCITY
                                          O = 18.0 cm/sec
                                          A= 9.0 cm/sec
                                          D = 4.5cm/sec
                              i   i   i  I       i
                                      10
                             WIND SPEED, m/sec
100
     Figure 3-8.  Ratio of reaeration coefficient under windy conditions
                 to reaeration coefficient without wind, as a function
                 of wind speed (based on laboratory studies).
                                  123

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3.2.2.4.2  Small Dams

     On many rivers  and  streams small to moderate sized  dams  are present.
Dams can influence reaeration  by  changing the dissolved oxygen deficit from
1 to 3 mg/1  (typically)  in  a very short reach of  the river.  Table 3-8
summarizes various predictive  equations that have been used to simulate the
effects of  small dams. Avery and Novak (1978) discuss limitations of these
equations  and aspects of oxygen transfer at hydraulic structures.

     Butts and Evans  (1983)  have reviewed various approaches  that predict
the effects  of small dams  on channel  reaeration and  further collected  field
data on 54  small  dams located  in  Illinois to determine their reaeration
characteristics.  They identified 9  classes of  structures, and quantified
the aeration coefficient b for use in the following  formula:

                  C -C
              r = r^- = 1 + 0.38abh (1 - O.llh)  (1  + 0.046T)        (3-24)
                    "
where a = water quality factor  (0.65 for grossly polluted streams;  1.8 for
         clean streams)
      b = weir dam aeration coefficient
      h = static head loss in meters
      T = water temperature, °C

     Figure 3-9 shows the general  structural classification  and the  aeration
coefficient, b, for each class.

     The present review  does  not  include influences of large dams,
artificial reaeration, or other hydraulic structures.  Cain  and Wood (1981)
discuss aeration  over Aviemore  Dam, 40 m (130 ft) in height, Banks et _al_.
(1983)  and NCASI  (1969) discuss effects of  artificial reaeration, and
Wilhelms _et  aK  (1981),  Wilhelms (1980),  and Wilhelms  and  Smith (1981)
further discuss  reaeration  related to hydraulic structures.
                                  124

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        TABLE  3-8.  EQUATIONS THAT PREDICT  THE EFFECTS OF SMALL DAMS
                              ON STREAM REAERATION
Reference
Gameson (1957)
Gameson et a±. (1958)
Jarvis (1970)
Holler (1971)
Holler (1971)
Department of the
Environment (1973)
Department of the
Environment (1973)
Nakasome (1975)
Foree (1976)

r =
r -
r!5
r20
r20
r =
r =
log
r =
Predictive Equation
l+0.5abh
l+0.11ab(l+0.046T)h
= 1.05 h°'434
=1+0. 91h
- 1+0. 21h
l+0.69h(l-0.11h)(l+0.0464T)
l+0.38abh(l-0.11h)(l+0.046T)
, \ n AC-7C1.1-28 0.62 ,0.439
e(r20) = 0.0675h q d
exp(O.lbh)
Units
h,
h,
h,
h,
h,
h,
h,
d,
q,
h,
in
in
in
in
in
in
in
h,
in
in
meters
feet
meters
meters
meters
meters
meters
in meters
m2/hr
feet
Source
field
model
model
model
survey



prototype
model
model
model
field



survey

Symbols:  r-,-
               Cs-Cu
             = dissolved oxygen saturation
        C , C . = concentration of dissolved oxygen upstream and downstream of dam,
        u      respectively
        a     = measure of water quality (0.65 for grossly polluted; 1.8 for clear)
        b     = function of weir type
        h     - water level difference
        d     = tailwater depth below weir
        q     = specific discharge.
        T     = water temperature, °C
3.2.2.4.3  Temperature  Effects on  Reaeration

      The influence of temperature  on reaeration is  typically  simulated  using
the  following  type of temperature  dependence:
                           k2(T)=k2(200C)0'

where  T = water temperature, °C
       B = temperature adjustment factor

                                       125
                                                                              (3-25)

-------
      Table  3-9 summarizes  values of  0 from  the  literature.  Typically values

of  1.022 to 1.024  are used in  most modeling applications.


      Schneiter and Grenney (1983) developed a different approach  to simulate

temperature corrections  over  the  ranges 4°C to  30°C.   Their  approach

effectively allows 0  to  vary  as  a function  of temperature.  However,  the

approach is not widely  used.
                                                 Head Loss Structure
                               I                                               I
                           Dan or Heirs                                          Rock Barriers
                 I                           I
             Sharp Crested                    Broad Crested
       Vertical Face       Sloping Face   Round Crest	    	Flat Crest	
     ||      (Straight)  (Curved Sloping Face)     II
    Gates       Heir                         Sloping Face             Vertical Face


                                       Curved  Straight        Straight      Step
                                                               Irregular   Regular

                                        Reference Hunter


                                          5432
               Reference                  Dam Type
                Numbers                    (2)
                  1          Flat  broad-crested regular step           0.70
                  2          Flat  broad-crested irregular step          0.80
                  3          Flat  broad-crested vertical face           0.80
                  4          Flat  broad-crested straight slope face     0.90
                  5          Flat  broad-crested curved face            0.75
                  6          Round broad-crested curved face           0.60
                  7          Sharp-crested  straight slope face          1.05
                  8          Sharp-crested"vertical face               0.80
                  9          Sluice gates with submerged discharge      0.05
             Figure 3-9.  Division of  head  loss structures by  dam type.


                                           126

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           TABLE 3-9.  REPORTED VALUES OF TEMPERATURE  COEFFICIENT
  Temperature
  Coefficient, 6	Reference	

     1.047             Streeter, et al.  (1926)
     1.0241            Elmore and West (1961)
     1.0226            Elmore and West (1961)
     1.020             Downing and Truesdale (1955)
     1.024             Downing and Truesdale (1955)
     1.016             Dowining and Truesdale (1955)
     1.016             Streeter (1926)
     1.018             Truesdale and Van Dyke (1958)
     1.015             Truesdale and Van Dyke (1958)
     1.008             Truesdale and Van Dyke (1958)
     1.024             Churchill ^t _al_ (1962)
     1.022             Tsivoglou (1967)
     1.024             Committee on Sanitary Engineering  Research  (1960)
3.2.2.5  Sources  of  Data

     Many sources of stream  reaeration rates exist in the literature.
Table  3-10 summarizes  a number of the major sources.  Many state agencies
are also repositories  of  reaeration data.

3.2.3  Reaeration in Lakes

     Simulation of reaeration  in  lakes is normally accomplished using  the
surface  transfer coefficient kL  rather than the depth averaged k2-   Most
often in lake simulations the  surface transfer coefficient kL is assumed to
be a function of wind  speed.
                                    127

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                 TABLE 3-10.   SOURCES OF STREAM  REAERATION  DATA
          Source
                         Contents
Owens et  al., (1964)




O'Connor  and Dobbins  (1958)


Churchill et al. (1962)



Tsivoglou and Wallace  (1972)



Bennett and Rathbun (1972)




Foree (1976)



Grant (1976)


Grant (1978)


Zison et  al. (1978)


Kwasnik and Feng (1979)


Grant and Skavroneck  (1980)

House and Skavroneck  (1981)

Shindala and Truax  (1980)




Terry et ah (1984)




Bauer et  al. (1979)





Goddard (1980)
Reaeration  coefficients using  disturbed equilibrium
technique for six rivers in  England (Ivel, Lark, Derwent,
Black Beck,  Saint Sunday's  Beck, Yewdale Beck),  and
associated hydraulic data.

Reaeration  data for  Clarion  River,  Brandywine Creek,
Illinois River, Ohio River,  and Tennessee  River.

Reaeration data  using  dissolved oxygen  balance downstream
from deep impoundments  for Clinch River, Holston River,
French Broad  River,  Watauga  River, Hiwassee River.

Hydraulic  properties  and radioactive  tracer measured
reaeration coefficients  for  Flint, South,  Patuxent,  Jackson,
and Chattahoochee Rivers.

Summaries  of data  from Churchill  et al_., (1962),  Owens et
al., (1964),  Gameson ert  al. (1958),  O'Connor and Dobbins
TT958), Tsivoglou et 71.,  (1967,1968),  Negulescu and
Rojanski (1969), ThackTEonU966), Krenkel  (I960).

Radioactive  tracer measurements and reaeration hydraulic
characteristics for  small  streams in Kentucky,  and
reaeration measurements  for  small dams in  Kentucky.

Reaeration measurements  and  hydraulic  characteristics for 10
small streams in Wisconsin.

Reaeration measurements  and  hydraulic characteristics for
Rock River, Wisconsin.

Summary of  reaeration  coefficients  and hydraulic
characteristics for  rivers throughout  the  United States.

Reaeration data  using  the  modified tracer technique on
selected streams in  Massachusetts.

Reaeration data from three small  streams 1n Wisconsin.

Reaeration data for  two  small streams  1n Wisconsin.

Radioactive tracer measurements of  reaeration  rates and
escape  coefficients, plus  hydraulic data,  for rivers in
Mississippi,  Wisconsin, Texas,  Georgia, North  Carolina,
Kentucky and New York.

Hydrocarbon tracer measurements of k,  and  hydraulic  data for
Spring  Creek, Osage Creek, and Illinois River, Arkansas.
Bennett-Rathbun (1972) best  fit  all three streams.  Eight
equations  were tested.

Hydrocarbon tracer measurements of k- and  hydraulic data for
the Yampa River, Colorado best matcned the Tsivoglou  Neal
and Thackston and Krenkel energy dissipation type equations.
Lau's  equation was extremely error prone.   Nineteen
equations were tested.

Hydrocarbon tracer  measurements of k- and hydraulic  data
from  the Arkansas  River 1n Coloradcr were used to test 19
equations.   The  best fitting  equations were  those by
Dobbins,  Padden  and  Gloyna,  Langbein and Durum,  and
Parkhurst and Pomeroy.
                                           128

-------
                          TABLE 3-10.   (continued)
          Source
                      Contents
 Hren (1983)
 Rathbun et al_. (1975)
 NCASI (1982c)
 farkhurst and Pomeroy (1972)
 Ice and Brown (1978)
 Ohio Environmental Protection
 Agency (1983)
 Long (1984)
Radioactive tracer measurements for the North Fork Licking
River, Ohio.

Hydrocarbon tracer measurements for West Hobolochitts Creek,
Mississippi.

Radioactive tracer measurements for Ouachita River,
Arkansas, and Dugdemona River, Louisiana.

Reaeration coefficients were determined by a deoxygenation
method in 12 sewers  in the  Los Angeles County Sanitation
District.

Reaeration coefficients were determined using sodium sulfite
to deoxygenate the water in  small streams in Oregon.

Reaeration coefficients were determined for 28 different
streams in Ohio using predominantly the modified tracer
technique, and in one case the radioactive tracer technique.

Reaeration coefficients, hydraulic data, and time of travel
data collected on 18 streams in Texas.
     Since many  lakes are not vertically  well-mixed,  multiple layers  are

often  used  to simulate dissolved  oxygen dynamics.  Atmospheric reaeration

occurs only through the  surface  layer,  and  then  dissolved oxygen is

dispersed  and  advected to layers  lower in  the water body.


     Table 3-11  summarizes various methods that have  been used to simulate

reaeration  in  lakes.   With the exception of the  method  of Di Toro and

Connolly  (1980),  all formulas  include  a wind  speed  term.   Di  Toro and

Connolly applied a constant  surface  transfer coefficient  to  Lake Erie.  They

found  that the surface layer of the  lake remained near saturation  so that

the  value of  k,  used was not  important as long  as it  was  sufficiently  high

to maintain  saturated dissolved oxygen levels in  the  surface layer.
     All  the  surface  transfer coefficients shown  in  Table 3-11 should  be

viewed  as  empirical;  the researchers  have  simply  hypothesized that the

suggested  formulas are adequate to simulate reaeration.   The coefficients  (a

and  b)  are  of  limited  validity, and  should  be treated as  calibration

parameters.   O'Connor  (1983)  has analyzed from  a more  theoretical point  of

view the effects of wind  on  the surface transfer  coefficient.

                                      129

-------
           TABLE  3-11  .   REAERATION  COEFFICIENTS FOR LAKES
Author(s)
                                         Surface Transfer Rate, k,  (m/day)
Di Toro and Connolly  (1980)
Chen et al.,  (1976)
Banks (1975)
Baca and Arnett  (1976)
Smith (1978)
Liss (1973)



Downing and  Truesdale (1955)


Kanwisher (1963)


Broecker et  a]_.  (1978)


Yu et _al_. (1977)


Broecker and Peng (1974)
                                  2.0
                                               86400D
                             D

                             V
                                           (200-605.5 m/sec
                             kL   a  +  bV
                             a    0.005 - 0.01 m/day
                             b  =  10"6 - 10"5 m"1
                             V  =  wind speed, m/day
                             kL    a + br
                             a  =  0.64 m/day
                             b  -  0.128 secV^ay
                             V  =  wind speed, m/s
                             kL    0.156 V
                             k     0.0269V
           ,0.63
           1.9
V <4.1  m/sec
V > 4.1  m/sec
                             V    wind speed, m/sec

                             kL  = 0.0276V2'0
                             V   = wind speed, m/sec

                             kL   0.0432V2
                             V   = wind speed, m/sec
                             kL   0.864V
                             V   = wind speed, m/sec

                             kL  - 0.319V
                             V    wind speed, m/sec
                             kL  = 0.0449V
                             V   - wind speed, m/sec
                                    130

-------
                        TABLE 3-11.   (Cont'd)
             Author(s)                   Surface Transfer Rate, k. (m/day)

      Weiler (1975)                    k,_ » 0.398   V <1.6 m/sec
                                    kL = 0.155V2 V >1.6 m/sec
                                    V  = wind speed, m/sec

      Notes:
      1.  Elevation of wind speed measurements is not always reported.
      2.  a and b are empirically determined.

     Some  limited research has  addressed  the  influence  of  rainfall  on
reaeration (Banks _et _al_.,  1984; Banks and Herrera, 1977).   Rainfall effects
are more of theoretical  interest rather of practical concern.

3.2.4  Reaeration  in Estuaries

     The  present  state of reaeration simulation in estuaries combines
concepts used in river and lake approaches.  Very little original research
on estuarine reaeration has been completed to date.

     Table 3-12 summarizes different formulations that have  been used  to
predict  reaeration in estuaries.   The different approaches include both  kL
(surface  transfer) and k,, (depth  averaged)  reaeration terms.  In some
models,  k? can be specified (e.g.,  Genet  et ^1_.,  1974 and MacDonald  and
Weismann,  1977).  O'Connor et _§]..  (1981) specified the surface transfer rate
to be 1 m/day in  their two-layered  model of  the New York Bight.   One of  the
more widely used  approaches is  the  O'Connor  (1960) formula,  which has
subsequently  been  modified  to  include  wind speed terms  (Thomann  and
Fitzpatrick, 1982).

     Few field studies have  been  performed for  the purpose of directly
measuring reaeration  in estuaries.   Baumgartner _et _al_., (1970) used Krypton-
85 to measure the range of reaeration  in the  Yaquina River Estuary. However,
no predictive formulas were developed.
                                   131

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                 TABLE 3-12.   REAERATION  COEFFICIENTS FOR ESTUARIES
            Reference
                                                      Reaeration Rate
   O'Connor (1960)
                                      (DLU0)
                                           1/2
                                        H
     372
             (I/day)
                                 U  = mean tidal velocity over a complete
                                     cycle,  m/day
                                 D,  - molecular diffusivity of oxygen, m /day
                                 H  - average depth, m
   Genet et _§!_., (1974)            kg  = user specified

   O'Connor et a],.,  (1981)         kL  = 1 m/day

   MacDonald and Weisman (1977)     k,  * user specified
   Harleman et al_.,  (1977)
                                            V°-6HW,
= 10.86
(I/day)
                                 V  = tidal velocity, ft/sec
                                 H  = depth, ft
                                 WT = top width, ft
                                 A  = cross-sectional area, ft
   Thomann  and Fitzpatrick (1982)   k2 = ȣ! + 1^81 (0.728W0'5 - 0.317W + 0.0372W2)    (I/day)
                                 V  - depth averaged velocity, fps
                                 H  - depth, ft
                                 W  = wind speed, m/sec
   Ozturk  (1979)
                                     4.56V
                                          4/3
                                        H
             (I/day)
                                 V  - mean tidal  velocity, m/sec
                                 H  * mean depth, m
   aThe coefficient  10.86 1s the recommended value, but can be changed as  discussed by Harleman
    et al.  (1977).
      Tsivoglou  (1980)  has discussed the application of  radioactive tracer
techniques  to  small  estuaries within  the  Chesapeake  Bay.   Special  discussion
was  given  to the Ware River Est.uary.
                                           132

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3.2.5  Summary

     The most common method of  simulating reaeration in rivers is  to  use the
depth averaged k~ approach, while in lakes the  surface transfer  rate k,  is
typically  used.   In estuaries either  k~ or  k,  is used, depending on the
importance  of stratification.   Very little research on reaeration has  been
done  in either  lakes or  estuaries.   In lakes, reaeration is  typically
specified  to  be  a  constant or to be  a function of wind speed.   Little
information  is  available on  how to select  parameters  in  the  wind speed
functions.  Site specific calibration of the. parameters may be required.

     In contrast to  lakes and estuaries much research has been conducted on
reaeration in rivers.  Thirty-one formulas were  shown earlier in  Table 3-6.
The formulas have been developed based on hydraulic parameters, most often
depth  and  velocity.  Consequently, the variables in reaeration expressions
are generally not of concern in distinguishing among the utility  of the
formulas.   One  exception is  formulas that contain longitudinal  dispersion
coefficients, which  are difficult to quantify.

     Considerable  evidence shows  that  reaeration  formulas  are most
applicable over  the range of variables for which they were  developed, and
outside of  that range, errors  might  be quite large.  This  suggests  that
reaeration rates  developed from laboratory flume data' may be quite  limited
for natural stream applications.  Some research supports  this supposition
(Bennett and Rathbun, 1972).

     Previous reviews of stream reaeration (see Table 3-7)  have  shown  that
no one  formula  is  best under  all conditions,  and depending on the data set
used, the range of the reaeration  coefficients in the data set,  and the
error  measurement  selected,  the  "best" formula may change.  Some of the
reaeration rate  expressions  which  have been judged "best" during  past
reviews are:

     •    The O'Connor  and Dobbins  (1958), Dobbins  (1964), and
          Thackston and Krenkel  (1969) formulas best fit the  entire
          range of data reviewed by Bennett and Rathbun (1972).
                                   133

-------
     t    The  Churchill  et !]_.  (1962) formula provided the best fit to
         natural stream  data  in the Bennett and Rathbun review.

     •    The  methads of  Dobbins (1964)  and Parkhurst and  Pomeroy
         (1972) gave the best fits to the data reviewed by Wilson and
         MacLeod (1974).

     0    The Tsivoglou-Wallace  and Parkhurst-Pomeroy methods were best
         in the review by Rathbun (1977).

     •    The  energy dissipation model produced the best correlation
         for  small streams based  on  the study of Shindala and Truax
         (1980).

     From  previous reviews, one of the more  popular  and more  accurate
methods  for reaeration rates  prediction is the energy dissipation method of
Tsivoglou.  The method requires  knowledge of the escape  coefficient, which
appears  to  depend on streamflow.  Typical values of the  escape coefficient
are 0.08/ft for flow rates less than  10 cfs,  and  0.06/ft for flow rates
between  10  and 280 cfs.

     The method of Covar  (1976),  which combines the O'Connor-Dobbins,
Churchill et _§]_., and Owens et _§_]_., formulas, has merit  in that it  attempts
to  limit the  use of the three formulas to within the  depth-velocity range
for which they were developed.   However, for  relatively small and  shallow
streams, the  method of Owens  et_ j/L, tends to overestimate reaeration, so
that the energy  dissipation method, which appears to perform well  in small
streams, could be used to supplement  the method.

     The radioactive  tracer method appears to be the  best method  for
measuring  stream reaeration coefficients.  Even so, the coefficients that
are predicted  are valid only for the  particular flow condition existing at
the time of sampling.  Thus  to completely characterize the range of values
of the  reaeration coefficient  would require numerous sampling events or use
of an acceptable predictive equation.

                                   134

-------
     Sampling methods which require indirect  knowledge of parameters  that
are difficult to quantify should be avoided.  The gas tracer method has been
used with  at  least partial  success, but  applications do not yet  appear
widespread.  When stream reaeration rates are being measured the wind should
be light  or calm; otherwise wind effects can produce atypical reaeration
rates.

     In deep,  slowly moving  backwater regions  of rivers reaeration  can
either be simulated using a  river formula or lake formula.  The O'Connor-
Dobbins method  is probably  the most appropriate stream formula to  use,
although for very slowly moving backwater regions the predicted reaeration
coefficient can be between 0.01 to 0.05/day, which is below the range of  k2
values  used in the development  of the formula.  If a lake reaeration formula
is used,  the reaeration rate  coefficient can exceed the range predicted
using  the O'Connor-Dobbins formula.  Under these conditions, wind and not
depth and velocity can control  the rate of reaeration.

3.3  CARBONACEOUS DEOXYGENATION

3.3.1  Introduction

     Biochemical oxygen demand (BOD) is the utilization of  dissolved  oxygen
by  aquatic microbes to metabolize organic matter, oxidize  reduced nitrogen,
and oxidize reduced mineral species such as ferrous iron.   The term  BOD  is
also applied  to  the substrate itself.  Concentrations of reduced minerals in
waste streams are usually inconsequential,  and so BOD is  commonly divided
into  two  fractions: that exerted by carbonaceous -matter (CBOD) and that
exerted by nitrogenous matter  (NBOD).  In domestic wastewaters, CBOD  is
typically exerted before NBOD, giving rise to the well-known two-stage BOD
curve (although the processes can be simultaneous in natural systems and
certain  industrial effluents).  Because wastewaters are potentially high in
BOD, and because dissolved  oxygen concentration is used as a principal
determinant  of  the health of an aquatic system,  BOD is a widely applied
measure  of aquatic pollution.   This section  discusses dissolved  and
                                   135

-------
suspended CBOD;  Section  3.4 deals with NBOD  and Section 3.5 treats  benthic
oxygen  demand or sediment  oxygen demand (SOD).  All are related processes.

     Figure 3-10 shows the major sources  and sinks of carbonaceous BOD  in
natural waters.  Anthropogenic inputs  include point sources  and nonpoint
sources such  as  urban  runoff and feedlot runoff.   Autochthonous  sources
derived from the aquatic biota (particularly algae) can be important  in  some
systems.   Also,  re-entrainment of oxygen-demanding material from  benthic
deposits may occur.   Removal of CBOD from the  water column  occurs through
sedimentation, microbial degradation and  the sorption to or uptake by the
benthic flora.  Some components of BOD may also volatilize  from the water
column.  Carbonaceous material which has settled or been sorbed becomes  part
of the  benthic oxygen demand.

     It is important that the  analyst distinguish in the modeling  process
between both the sources of BOD and the instream removal mechamisms.   Waste
load allocation decisions based upon models  which consider CBOD as a
"lumped" quantity may not  accurately  or fairly  assess the  water quality
impact  of  the point sources.

     Efforts  to  characterize CBOD  kinetics have  focused  chiefly  on
water-column decay processes,  and that is the major  emphasis  of  this
section.   A  general expression for BOD decay is:

              BOD + BACTERIA + 02 + GROWTH FACTORS  (NUTRIENTS)
                     —+-  C02 + H20 + MORE BACTERIA + ENERGY

3.3.2  Water Quality Modeling Needs

     Nearly  all water quality models characterize CBOD  decay with first
order kinetics represented by:
                                   136

-------
where  L   = ultimate  CBOD, mg/1
       k ,  = first order rate coefficient, I/day,  base e
       t   = time, days

This equation when coupled with  stream dissolved oxygen  kinetics becomes the
classic Streeter-Phelps equation:
                      D =
                            kdl
 -k .t
e  d   -e
                 kf
+ D  e
   o
                                                  (3-27)
       POINT AND NON-POINT
         SOURCE INPUTS
                        AUTOCHTHONOUS SOURCES
                Dead invertebrates,   Fecal     Algal Exudates
                algae,fish .microbes   Pellets
                            CARBONACEOUS BOD
                                 DISSOLVED AND
                                  SUSPENDED
                                                            SCOURING AND LEACHING
                                                            FROM BENTHIC DEPOSITS
         MICROBIAL
         DEGRADATION
      SETTLING FROM
      WATER COLUMN
                     ADSORPTION/ABSORPTION BY
                        BENTHIC BIOTA
           Figure 3-10.
Sources  and sinks  of  carbonaceous  BOD in the
aquatic  environment.
                                       137

-------
where D  =  dissolved oxygen deficit,  mg/1
      k?  =  stream reaeration rate,  I/day, base e
      D  =  initial stream deficit,  mg/1

This equation  in principle is similar in nearly all state-of-the-art water
qua!ity models.

     In using this  representation  of  BOD/DO for waste  load allocation
modeling, the  analyst  may require measurement or estimation of three
independent factors which include:

      (a)   the magnitude  of ultimate CBOD  of the  point sources and the
          resulting  instream spatial distribution,
      (b)   the magnitude  and spatial distribution of  the  instream CBOD
          removal  rate, and
      (c)   the ratio  of  point source  ultimate CBOD  to 5-day CBOD (if
          compliance is to be based upon CBOD,-).

      It  is important to note  that the water quality model is based upon
ultimate CBOD and not CBODr.  Some models  internally convert from 5 day  to
ultimate using an  assumed  ratio.  In the  case of the QUAL-II model  (NCASI,
1982a), this ratio is 1.46 and is not user  specified.  This assumption has
significant implications  to  water quality modeling because  recent experience
has  shown that this  ratio is both wasteload and receiving water specific.
Ultimate to 5 day  ratios as high  as  30  have been reported for some paper
industry wastewaters (NCASI,  1982d).  Since first  order kinetics are assumed
in  most  models,  the ultimate to 5 day ratio is not independent of the decay
rate,  k,.  Consequently,  analysts  should  be certain  that the river  water
ultimate to 5 day BOD is  not as-signed independently of the  rate, k ,.

3.3.3  Nomenclature

      Since microbial  degradation is not the only process contributing to the
observed depletion of CBOD in a water  body (see  Figure  3-10),  laboratory
rates of carbonacous deoxygenation must  be distinguished from those which
                                   138

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occur in the  field.   The following terms are used herein to maintain these
distinctions:

     k-|  = laboratory-derived CBOD  decay rate,
     k^  = CBOD decay rate in natural waters
     ks  = CBOD settling rate
     kR  = overall rate of CBOD  removal from water column

By these definitions,

                               kR = kd + ks                         (3-28)

                               kd ^ kp typically                   (3-29)

     Note that uptake/sorption by the benthic biota  is not explicitly dealt
with.   In  practice, the effects of  instream deoxygenation  and benthic
biological  CBOD  removal are  difficult  to distinguish.  Thus reported  k.
values may incorporate both  processes.  Unless otherwise specified, all  rate
coefficients discussed in  this  section are corrected to 20 C, are to the
base e,  and are in units of  inverse days.

3.3.4 Factors Affecting CBOD Removal

     A number of factors are known to influence the  rate  at  which CBOD  is
removed  from the water column.  Chief  among these are water temperature,
hydraulic  factors,  stream  geometry  and the nature of  the carbonaceous
material.   The  influence  of these  factors has been  described by  both
theoretical and empirical formulations.

     Like all biochemical  processes, CBOD decay occurs at  a  rate which
increases  with  increasing  temperature  up to the  point where  protein
denaturation begins.   This temperature dependence  is generally formulated
for a limited range of temperature as:
                                                                   (3-30)

                                  139

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where kT  = rate constant at temperature  T
      k^g = rate constant at 20°C
      0   = an empirical  coefficient.
     This formulation is based on the Arrhenius  equation  which  incorporates
the  energy of activation of the overall  decay reaction.   Arrhenius  proposed
the relationship:

                              d  Ink  _ _   E                             /,  -n
                                dT   -  -2                            <331>

where T = absolute temperature,  °K
      R = universal  gas  constant
      E = activation energy of the  reaction
      k = rate constant

Integrating Equation (3-31)  results  in

                               k    -E 
                            ln   =                                    (3"32)
where T  = arbitarily chosen  reference  temperature, °K
      k  = rate constant at temperature T
Equation (3-32)  can be  rewritten  as
    -E (T-T V
exp  p T  T° )                      (3-33)
                                     /-MT^

                                    VToT
Equations (3-30)  and (3-33)  are  identical  if  6  is  defined  as

                          0 = exp  (p^r)                             (3-34)
Note  that whether T-TQ is in  units  of  °C  or °K  is  of  no  concern.  Thus  6,
which is assumed to  be  independent  of  temperature  in  Equation  (3-30),  really
has some slight temperature dependence.
                                    140

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     Table 3-13 shows  values of 6 which have  been  used for CBOD decay.  The
value  1.047 is very  widely used and corresponds  to an energy of activation
of 7900 calories per mole measured by Fair _et aj_.  (1968).  There are  limits
to the applicability of this approach because  the activation energy is not
actually constant.  Studies by Schroepfer _et  _a]_.  (1964)  indicate that the
value  of 1.047 for 6 is valid between 20°C  and 30°C, but higher values are
appropriate at  lower temperatures.  Fair _et aJL  (1968) suggest 6 values of
1.11 and 1.15  for 10°C  and  5°C, respectively.   Few water quality models
incorporate a varying  temperature dependence for CBOD degradation.  Some
impose temperature limits, generally 5-30°C, outside of which the reaction
is considered not  to occur.   The model  SSAM-IV  (Grenney  and Kraszewski,
1981) adjusts the  BOD  decay rate for temperature via the expression:

                               kT =   rk2Q                            (3-35)

 wnere  r =    0.1393 exp (0.174(1-2))
           0.9  + 0.1 exp (0.174(1-2))

This  is equivalent to  varying  the value  of 6 with temperature.

     The 1.047 value originated from  the  work  of  Phelps  and  Theriault
(Phelps, 1927,  Theriault, 1927).   The  6  value of 1.047 was an  average value
obtained from  three  separate studies  with a reported standard deviation of
0.005.   Moore noted in 1941 that  the  correlation of the CBOD decay  rate with
temperature using the Arrenhius model was  not  strong,  since correlation
coefficients of 0.56 to 0.78 were obtained (Moore, 1941).

     Water  turbulence  is hypothesized  to influence the rate  of BOD  depletion
in a  receiving  water in several  ways.   It influences kg by controlling such
processes  as scour and  sedimentation. Increased  turbulence may  enhance
contact between BOD  and the  benthic  biological community.   It  also
influences the carbonacous  deoxygenation rate,  so that  laboratory  samples
which are agitated during incubation yield higher  k-j values than  quiescent
samples (see Morrissette  and  Mavinic,  1978, for example).  This  confounds
the use of  k, values from static  laboratory tests  in place  of field values

                                    141

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                                 TABLE 3-13
              VALUES OF  THE TEMPERATURE COMPENSATION COEFFICIENT
                      USED FOR  CARBONACEOUS BOD DECAY
   0, TemperatureTemperature
   Correction Factor	Limits (°C)	Reference
      1.047
      1.05
                     Chen(l970)
                     Harleman et al_.  (1977)
                     Medina (1979)
                     Genet _et _al_.  (1974)
                     Bauer et _§]_.  (1979)
                     ORB (1983)
                     Bedford et  a]_.  (1983)
                     Thomahn and Fitzpatrick  (1982)
                     Velz (1984)
                     Roesner _et  al_.  (1981)

                     Crim and Lovelace  (1973)
                     Rich (1973)
      1.03-1.06
      1.075
      1.024
(0-5)-(30-35)
Smith (1978)
Imhoff et al.  (1981)
Metropolitan  Washington Area
Council  of Governments  (1982)
      1.02-1.06
                     Baca and Arnett  (1976)
                     Baca et  al.  (1973)
      1.04

      1.05-1.15
5-30
                     Di  Toro  and  Connolly  (1980)
Fair et al_.  (1968)
of kd.   To  more closely duplicate  natural conditions, some investigators
used stirring  during  laboratory incubations (NCASI, 1982a).   This particular
experiment showed  nj3  effect  of  stirring  on  the reaction kinetics.
                                    142

-------
     Adjustment factors based on stream characteristics   have also been used
 in  BOD calculations.  Bosko (1966)  expressed  kd  in  terms of k] for streams
 by  the expression:

                             kd = k1  + n(V/D)                         (3-36)

 where V = stream velocity,  length/time
      D = stream depth, length
      n = coefficient of bed activity,  dimensionless

     The  coefficient of bed activity is a step function  of  stream gradient;
 values  are  given  in Table 3-14.  This expression has  been used  in  a  version
 of  QUAL-II  applied to rivers in New England (ORB,  1983; Van Benschoten and
 Walker, 1984; Walker, 1983), by Terry et aj_.  (1984)  on  the  Illinois  River,
 Arkansas, and by Chen and Goh (1981).

    TABLE 3-14.  COEFFICIENT OF BED ACTIVITY AS  A FUNCTION OF STREAM SLOPE
                             (from BOSKO, 1966)
                    Stream
                  Slope  (ft/mi)
                       2.5                             .1
                       5.0                             .15
                      10.0                             .25
                      25.0                             .4
                      50.0                             .6
      Stream hydraulic  factors may also account for differences between the
deoxygenation rate k. and  the overall BOD removal rate kR.   Table 3-15  shows
examples of such  differences in six U.S. rivers.   Higher values of kR are
attributable to settling of particulate BOD.  Bhargava (1983)  observed  rapid
settling of particulate BOD just  downstream from sewage  outfalls in two

                                   143

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Indian  rivers,  where kR was several  times greater than farther downstream.
He modeled  this effect by  considering the  BOD to  be composed  of two
fractions, using the expression:

                                      Vc
                           Lt =  4(1- ^t) +  L2exp(-kdt)             (3-37)

where L.  = BOD remaining at downstream travel  time t
       U
      L,  = portion of original BOD  removed by  settling
      L2 = portion of original BOD  subject to  in-stream degradation
      V   = settling velocity of particulate BOD
      D   = average stream depth
          TABLE  3-15.  DEOXYGENATION RATES  FOR  SELECTED U.S. RIVERS
                      (ECKENFELDER AND O'CONNOR, 1961)

River
Elk
Hudson
Wabash
Willamette
Clinton
Tittabawassee
Flow
(cfs)
5
620
2800
3800
33
__
Temp.
(°C)
12
22
25
22
--
__
BOD5
(mg/1)
52
13
14
4
—
__
*
kd 1
(day *)
3.0
0.15
0.3
0.2
.14-. 13
0.05
*
kR ,
(day'1)
3.0
1.7
0.75
1.0
2.5
0.5
*
 Note:   These  data are over 20 years old.   It is likely  that advances  in
        waste  treatment have altered the  BOD  kinetics in these waterways.
      Some  modelers distinguish between  benthic and  water-column  CBOD
removal,  and assign rate coefficients to  each  type.  For example, the sum of
                                   144

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settling and benthic biological CBOD uptake  is widely portrayed  as  a first-
order process (Baca  and Arnett, 1976; Grenney and Kraszewski,  1981;  Duke and
Masch, 1973;  Orlob,  1974):

                               --(k   +  k)L                      (3-38)
where k . = water-column deoxygenation rate
      ko = total  removal rate to the benthos by settling and sorption

     The settling rate alone may be derived  from the particle  settling
velocity and mean depth of the water column:

                              k  =  —                              (3-39)
                               s   D

The  effects  of scour are  often incorporated  into the benthic  removal
coefficient k,.  This may be done implicitly, or  by calculating k^  as  the
sum of  two first-order coefficients having opposite sign  (Bauer et al . ,
1979).   Scour of benthic BOD  is also treated  as  a zero-order  process
(e.g.,  Baca _et _a]_. , 1973):

                              aL =  -kDL + L                         (3-40)
                              et     R     a

where L  = rate of BOD re-entrainment by scour,  mg/(l-day).
       a

      The nature of the oxygen-demanding material  also affects the  rate of
its removal  from a receiving water.  Particulate BOD, while it  may be
susceptable to settling, is  more refractory than  soluble BOD.   Also  two
waters  having the same ultimate BOD may show very different BOD depletion
profiles.   For in-stream BOD arising from a wastewater inflow, the degree of
treatment of the wastewater is important.  In general, the higher the degree
of treatment,  the greater the degree of waste stabilization, and the lower
the deoxygenation rate will be.   Fair ^t a]_. (1968)  cite deoxygenation rates
of 0.39,  0.35 and 0.12-0.23  per day for raw wastewater, primary  and
secondary effluent, respectively.
                                    145

-------
      Martone  (1976)  observed  a similar  trend  with paper  industry
wastewaters.   Following biological  treatment, rates as low as 0.02 per day,
base e were observed.  This low rate was  attributed to the refractory  humic
material  remaining  in the wastewater.  Similar  low rates were also noted  in
receiving streams  (NCASI, 1982a).

      The U.S. Environmental Protection Agency (1983), using the data  of
Hydroscience (1971)  and Wright-McDonnell  (1979)  has derived  a relationship
between  stream depth and CBOD removal.   This  is shown in Figure 3-11.   Note
that the predicted decay rate corresponds  to  the  sum of  water column and
benthic deoxygenation.  Should SOD data be  available, modelers are cautioned
when  using this  figure to  avoid double  counting  of SOD  in the  oxygen
balance.

      To this  point, depletion of  dissolved oxygen caused by CBOD decay has
been implicitly considered to depend only on the concentration of substrate,
i.e., CBOD.  However, at low dissolved oxygen  concentrations, oxygen may  be
limiting  to  the reaction.   Provision  for  this "oxygen  inhibition"  is
incorporated into many water quality models as discussed below.

      Autochthonous sources may be a major  influence on BOD dynamics.   In
lakes, carbon  fixed  by phytoplankton may  become  the  predominant source  of
CBOD.   Investigators have  dealt with the input of autochthonous CBOD  in
several ways.   Modeling Onondaga Lake in  New York, Freedman et_ al . (1980)
considered the biological contribution to  water-column CBOD to be equivalent
to the mass rate of  phytoplankton  production of  organic material.  Baca and
Arnett  (1976) considered the death rates of phytoplankton and zooplankton
separately.  These affected BOD according  to the expression:
                               = -kd  L +  a  (FpP + FzZ)               (3-41)

where a  =  stoichiometric coefficient, mg02/mgC
      FZ  =  death rate of zooplankton from  fish predation, I/day
      F  =  death rate of phytoplankton from  zooplankton grazing,  I/day

                                   146

-------
      P  = phytoplankton concentration, mg-C/1

      Z  = zooplankton concentration, mg-C/1




      A Potomac Estuary Model  by Thomann and Fitzpatrick (1982) considers

the "non-predatory" death  rate of  phytoplankton to augment water-column

CBOD:
                                                                      (3-42)
         10
          5 -
     1

     QC
     LU
     OL
         0.5 -
         0.1 -
                                                   KEY
• Hydroscience Data (1971)

o Wright-McDonnell Data(1979)
           0.3   0.5      1     1.5
   5      10


DEPTH (feet)
                     50    100
           'NOTE: kd includes a

                  Benthic Deoxygenation

                  Component



     Figure 3-11.   Deoxygenation  coefficient  (k^)  as  a  function of depth



                                    147

-------
where k,p   = death  rate of phytoplankton other than  from grazing,
             I/days
      P     = phytoplankton carbon, mg/1
      BOD ,-  = ratio  of ultimate to  5-day CBOD,  taken  as 1.85 for
         uo
             phytoplankton

3.3.5  Predictive Expressions for Deoxygenation

     The carbonaceous deoxygenation rate is determined in two general ways.
Most investigators base  their  measures of kd  on  the results  of field or
laboratory  experiments that  monitor dissolved oxygen or ultimate CBOD. In
stream modeling, this traditional approach has  recently been augmented by
efforts to quantify k, as a function  of hydraulic parameters.

     It is important to note that these correlations  relied  upon  published
values  of k .  (such  as Figure 3-11).  No distinction was  made  as to how k.
was obtained; and in these  correlations, observed instream values  have equal
weight with  measured laboratory values.  Thus, considerable ambiguity exists
in the  published  literature  with regard to the meaning of  k  , and  the
resulting correlation may be of limited value.

     Bansal  (1975) attempted to predict deoxygenation rates based  on  the
Reynolds  number and the Froude number.   This approach was found to have
limited applicability (Novotny and  Krenkel,  1975).   More commonly,  k. is
found  as  a  function of flow rate, hydraulic radius or average stream depth.
Wright and McDonnell (1979)  utilized  data from 36 stream reaches in the U.S.
to derive the expression:
                                =  (10.3)Q~°'49                      (3-43)
where Q =  flow rate, ft /sec
     They found that above flow  rates of about  800 ft3/sec,  kd  is not a
function of  flow rate.  The  lower limit of  the applicability of this
expression is  approximately 10 ft3/sec.  Below this flow rate,  deoxygenation

                                  148

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rates  were  noted  to consistently  fall  in the range  2.5-3.5 per  day,
independent of streamflow.  For this same range  of flowrates (between 10 and
800 cfs),  an expression  based on channel  wetted perimeter was also found
successful  in predicting k.:

                             kd = 39.6P~°'84                        (3-44)

where P = wetted  perimeter, feet

     The  deoxygenation  rate coefficient  has also  been  expressed as  an
exponential function  of stream depth (Hydroscience, 1971; Medina, 1979)  and
hydraulic radius  (Grenney  and Kraszewski, 1981).

     Regardless of how carbonaceous deoxygenation rate  coefficients  are
derived,  they are widely applied in  only  two  ways:  first-order decay and
simultaneous  first-order decay.  In the latter case, the CBOD is partitioned
into more  than one  fraction; each fraction is degraded at a specific  rate
according to  first-order kinetics.  The first-order approximation for  CBOD
decay has been widely criticized, and multi-order or logarithmic models  have
been used by individual investigators (see Hunter, 1977 for a review).

     Martone  (1976),  in a  study of BOD  kinetic models, observed that first
order  kinetics did  not  universally  describe  observed BOD data.  In  a few
cases,  a two-stage carbonaceous BOD model resulted in  a  better statistical
fit  (McKeown et^ aj_., 1981).  The Wisconsin  Department of Natural Resources
included this alternative  formulation in its  QUAL-III model (Wisconsin  DNR,
1979).   However,  no  alternative formulation  has  been shown to be universally
superior,  and oxygen-sag computations are comparatively easily performed for
first-order decay.  Hence, this is the  pre-eminent model in use today.
     Table 3-16  shows  the expressions  used by water  quality modelers  to
describe the consumption  of oxygen as a function  of water column CBOD decay.
Note that nonoxidative processes such  as  settling, where  CBOD is  removed
from  or added to the water  column, do  not contribute to dissolved oxygen

                                    149

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        TABLE  3-16.    EXPRESSIONS  FOR  CARBONACEOUS  OXYGEN  DEMAND
                           USED  IN  WATER  QUALITY  MODELS
Depletion Rate of Dissolved
Oxygen  by CBOD Decay, |^                        Model and Reference


-k L                             MIT-DNM (Harleman et ah, 1977)
                                 Dynamic Estuary Model (DEM)  (Genet et^K, 1974)
                                 EXPLORE-I  (Baca et a±., 1973)
                                 USGS river modelTBauer et _aj.., 1979)
                                 HSPF (Inhoff  et a\_., 19817
                                 DOSAS3 (Duke  and Masch, 1973)
                                 DIURNAL (Deb  and Bowers. 1983)
                                 QUAL-II (Roesner et al., 1981)
                                 O'Connor et al. (T58TT*


                                 Lake Erie Model* (Di Toro and Connolly, 1980)
                                 Potomac Estuary Model (PEM)  (Thomann and Fitzpatrick, 1982)


                                 Level Ill-Receiving (Medina, 1979)

                                 Wright and McDonnell (1979)
                                 Rinaldi (1979)


                                 Bedford et al. (1983)
-k.L  . - k,L . .                   WQRRS (Smith,  1978)
  1 so1    i aet                  CE-QUAL-R1*  (Corps of Engineers, 1982)
                                 Chen et _§!.* (1974)

-kl (depth, D> 2.44m) 1          RECEIV-II   (Raytheon, 1974)
  °                   I          WRECEV (Johnson  and Duke, 1976)
       -0.434
 -Cj(Rh C2)L                      SSAM-IV (Grenney  and Kraszewski, 1981)

 -k^L                           Freedman e^ _§]_. (1980)
*"L" represents  a fraction of organic carbon,  soluble and/or detrital, rather than CBOD.

Definition of symbols:

  kd          field CBOD oxidation rate
  L           carbonaceous BOD concentration
  Oj          concentration of dissolved oxygen
  kn          half-saturation constant for oxygen
    2
  a,b,Cj,C2   empirically-determined coefficients
  D           water depth
  Q           stream flow rate
  k,, k,      oxidation rates for two CBOD fractions
  I...        soluble CBOD (or. dissolved organic carbon)

  Ldet        particulate CBOD (particulate organic carbon)
  Rh          steam hydraulic radius
  .           nonlinear 0« inhibition coefficient
                                             150

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depletion,  and  are not included  in the expressions.   In  cases where k .  is
                                                                    d
calculated  within the model  using a hydraulic expression, that expression  is
included  in  the table.  As shown,  the  rate expressions  do not include
temperature  correction coefficients.   Some of  the models listed (starred
references) do  not treat CBOD per  se, but organic carbon  or  carbonaceous
detritus.  The effect of  low  dissolved oxygen  concentration is generally
handled through  a Michaelis-Menten formulation.  A representative value  of
kQ2,  the  half-saturation coefficient for oxygen  uptake, is 0.5 mg/1.  Some
models  partition  oxygen-demanding  matter into soluble  and particulate
fractions, with different rate coefficients.   In  limnological models, the
particulate or  detrital fraction may  be determined   as  a  function of the
death  of  phytoplankton and  zooplankton, with no  additional particulate CBOD
present.

3.3.6  Values of Kinetic Coefficients

     Table  3-17  is a compilation of deoxygenation  rate coefficients and the
methods by which  they were determined.  Unless otherwise specified, the
coefficient is  kd.  In some  cases, investigators reported kR values as such;
in other  cases, rates reported as deoxygenation  were actually observations
of total removal (kn) and they are cited as such.  Most of the  data are from
rivers, although some lake and estuary values have been reported.   The range
of values  reported as in-stream  deoxygenation rates is wide, spanning more
than two orders  of magnitude.

3.3.7  Measurement of Ultimate BOD Decay Rate

     In laboratory studies using BOD bottles, BOD exertion is found  as the
difference between  sample and control  dissolved oxygen depletion.
Respirometry  studies  and reaerated  stirred-reactor  studies involve
essentially continuous monitoring of  oxygen usage.  The results of these
laboratory  experiments  produce  cumulative oxygen  demand-vs-time
relationships.

     A number of methods have  been  used to derive  k-,  from  these curves.
Among these are:
                                  151

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TABLE 3-17-   VALUES OF KINETIC COEFFICIENTS FOR DECAY
                       OF CARBONACEOUS BOD
kd
Location (I/days 9 20 C, base e)
Potomac Estuary 1977
1978
Willamette River, OR
Chattahoochee River, GA
Ganga River, India
Yamuna River, India
S. Fork,
Shenandoah River
Merrimack River, Mass
Gray's Creek, Loulsana

Onondaga Lake, New York

Yampa River, Colorado

Skravad River, Denmark

Seneca Creek

Kansas (6 rivers)
Michigan (3 rivers)
Truckee River, Nevada
Virginia (3 rivers)
N. Branch, Potamac, WV
South Carolina (3 rivers)
New York (2 rivers)
New Jersey (3 rivers)
Houston Ship Channel, TX
Cape Fear R. Estuary, NC
Holston River, Tenn

New York Bight
White River, Arkansas

N. Fork Kings River, CA
Lake Washington, WA
Ouachita River, Arkansas


36 U.S. river reaches
plus laboratory flume
San Francisco Bay
Estuary
Boise River, ID
W. Fork, Trinity
River, TX
0.14 ± 0.023
0.16 ± 0.05
0.1-0.3
0.16
3.5-5.6 (kp)
1.4 K
0.4(kR)

0.01-0.1
1.44 (kR)
K
0.10

0.40

0.15
0.90 (kR)
0.008

0.02-0.60
0.56-3.37
0.36-0.96
0.30-1.25
0.4
0.3-0.35
0.125-0.4
0.2-0.23
0.25
0.23
0.4-1.5

0.05-0.25
0.004-0.66 (k.,)

0.2
0.2
0.15
0.17 (kR)
0.02 (k")

0.08-4.24
0.2

0.75
0.06-0.30

Method of
Determining
Coefficient
field study



field study

field study

field study
model
calibration
model
cal ibration
model
calibration
field study



various
methods








model
calibration

laboratory
study


calibration
laboratory
study
field studies



laboratory
study
Reference
US EPA (1979a)
US EPA (1979b)
Baca et a±. (1973)
Bauer et .al.. (1979)
Bhargava (1983)

Deb and Bowers (1983)

Camp (1965)
Crane and Malone (1982)

Freedman et aK (1980)

Grenney and Kraszewskl (1981)

Hvitved-Jacobsen (1982)

Metropolitan Washington
Council of Governments (1982)
Reported by Bansal (1975)









Novotny and Krenkel (1975)

O'Connor et 3\_. (1981)
Terry et al_. (1983)

Tetra Tech (1976)
Chen and Orlob (1975)
Hydrosdence (1979)
NCASI (1982a)

Wright and McDonnell (1979)
Chen (1970)

Chen and Wells (1975)
Jennings et ^1- (1982)

                       152

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                            TABLE 3-17.   (Cont'd)
Location
Mil lamette River, OR
Arkansas River, CO
k!l
(I/days 0 20°C, base e)
0.07-0.14
1.5
Method of
Determining
Coefficient
lab and field
field study
Reference
McCutcheon (1983)
      Lower Sacramento          0.41
      River, CA
      Delaware River Estuary      0.31
      Wappinger Creek           0.31
      Estuary, NY
      Potomac Estuary           0.16,0.21
      Speed River, Ontario        1.0
field study
          Hydroscience (1972)
Thomann and Fitzpatrick (1982)
Gowda (1983)
     1.  The linear least-squares technique of Reed and Theriault
     2.  Thomas' graphical slope method
     3.  The moment method of Moore (1941)
     4.  Orford and Ingram1s logarithmic method
     5.  Rhame's two-point method
     6.  Nemerow's general laboratory method  (graphical)
     7.  The daily difference method of Tsivoglou (1958)
     8.  The rapid ratio method of Sheehy (1960)
     9.  Nonlinear regression method of NCASI (1982d).

The first six methods are discussed by Nemerow (1974).  Gaudy et_ _al_.  (1967)
review and compare a number of calculation methods.  Some of the techniques
assume a particular kinetic model for the data,  while others do not.   The
linear least-squares method  can be  used with a first or second-order BOD
dependency, with  somewhat  different  calculations.  Orford and  Ingram1s
method assumes that cumulative BOD  exertion varies with the logarithm  of
elapsed time,  and no limiting value is approached.  The nonlinear regression
technique has  the  advantage  of flexibility in evaluating alternative BOD
models.

     Barnwell  (1980)  developed  a nonlinear least-squares technique for
fitting laboratory CBOD  progressions.   It is  based upon  the first-order
decay  model,  and is suitable for implementation on programmable calculators
or microcomputers.  It allows computation of confidence  contours  for the
estimates of k, and ultimate CBOD.  The nonlinear regression technique  also

                                     153

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provides  estimates of the  confidence contours.   Further discussion  of BOD
measurement  techniques are contained  in  Stover and McCartney  (1984) and
Stamer et al_. (1983).

     Estimates of  the length  of time  necessary to evaluate the BOD
parameters  have  been provided by Berthouex  and Hunter (1971).    They
determined,  using  statistical arguments,  that  this length of time is a
function  of  the anticipated  decay rate,  k-,.   The time computed  from 4/k,  is
suggested as the maximum value.  Barnwell  (1980)  and NCASI (1982d) have
shown that the estimate of the confidence contours is directly related  to
the  length of time  the BOD  experiment was conducted.   As the length of time
increases, the confidence contours get smaller.

     In field estimation of deoxygenation  rates, water samples from along
the  stream reach are collected, and  their  ultimate  CBOD values are
determined  in the  laboratory.   Graphical methods  are then used to find the
CBOD decay rate.  These techniques are based  on a  mass balance for  BOD  in
the  stream.  Note  that if unfiltered  water  samples are used, the rate
calculated is k^,  not k..   It may be that  the two rates are essentially
equivalent.  An  unvarying  profile of  suspended solids  along the reach may
indicate  the validity of these measurements to estimate k..  Alternatively,
filtered samples may be  incubated, and the  contribution  of particulate
matter to BOD assumed to be  insignificant.

     The  calculation methods  described herein are  based upon simplified
forms of  the BOD mass-balance equations.  The user  should assess carefully
whether  the necessary simplifying assumptions can reasonably be applied to
the study system.

     One  simple and commonly  used  technique is  for streams influenced by
continuous point sources.   The stream reach  under study should  have  a
relatively constant cross  section,  constant flow  rate,  and a single  point-
source BOD loading.   The BOD concentration  downstream from the source  is
given by:
                                  154

-------
                                         -v
                             L = LQexp  \ 	  J                     (3-45)

where X  = distance downstream from source,  length
      L  = BOD  concentration immediately downstream from source,  at
           X =  0, mass/volume
      V  = average stream velocity, length/time

     A graph  of  the logarithm  of BOD concentration versus  distance
downstream should  show a straight-line relationship with a slope  of  -kR/V if
decay  is first order.  Sometimes  the slope may be more steep  for the first
few miles below a point source,  where settling  of  BOD as well as decay is
occurring  (Deb and  Bower,  1983).   The  slope may be found graphically or by
linear  regression.  Figure 3-12  is  an example of this type of computation.
If the slope is determined by regression, the natural  log of BOD should be
regressed on distance.  If the slope is  found graphically from  a semi-log
plot,  it  must  be  multiplied by 2.3 (to  convert from base-10 to  base-e)  for
model applications.

     The  same   approach is possible for tidally influenced  rivers,  as
discussed in Zison ^t ^1_. (1978).   However, the tidally  averaged  dispersion
coefficient is required as an  additional piece of information and will  add
some degree of  uncertainty to the predicted kd value.

3.3.8  Summary  and Recommendations

     Although its shortcomings have been  widely discussed, the first-order
model  is  still the  common  method for  simulating  instream CBOD kinetics.
Relative  ease of computation,  a long history of use  and the  absence of
alternative formulations which are superior over a range of conditions  are
probably  responsible for this precedent.

     In estimating k.,  there is increasing use of various stream hydraulic
parameters.  Estimates based  on  flow  rate seem to be most successful,

                                   155

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    15
=•  10-
 O)
 E
Q
o
CO
O
5-

4-


3-



2-
       u
                                  V-4 mi/day

                                  KR--Slope xV
                                     -2.3(0.6)
                                     -1.4/day
                                   Slope =2.3 pft

                                        -0.6/mile
                                  8
                                       MILE
10
12
   Point Source
14
  Figure 3-12.  Example computation of kR based on BOD measurements
               of stream water.
                                156

-------
although  stream geometric parameters  such  as hydraulic radius  and  depth are
also used.   The use of  hydraulic characteristics for kd  prediction has
limits,  since  deoxygenation is independent  of flow rate at  both high  and low
flow.   These predictive equations should  be used with caution.

     To assess CBOD  fluxes based on  site-specific data,  it is essential to
have some  familiarity with the water body  under  study.  A  reconnaissance
survey  can  help  elucidate the possible  importance of CBOD sedimentation or
resuspension,  as well as the magnitude  of aquatic biological  processes.  The
survey  is  also an opportunity to assess what assumptions  can  reasonably be
made about the system to simplify calculations.

     For those river waters  and effluents  which  contain  significant
concentrations of NBOD, the  analyst must  consider an appropriate  procedure
for the separation of NBOD from CBOD in the ultimate BOD test.  Currently,
two  techniques are used which include:  the  use of nitrification inhibitors
such as TCMP and  others, and the  monitoring  of nitrogen  series with time
during  the test  to define the NBOD.   There  is currently no consensus  as to
which technique is best.  Nitrification  inhibitors have  been observed to
have an  unpredictable inhibition effect  on the CBOD  kinetics as well
(Martone,  1976).   For  large modeling projects,  the monitoring of  nitrogen
species in the BOD bottle tests can create  significant additional laboratory
expense.  Though  likely to be more expensive, the  latter technique  provides
more  information  regarding the CBOD and  NBOD kinetics and  is recommended by
NCASI (1982b).

     The  investigator  should  exercise  caution in using deoxygenation
coefficients obtained for other water bodies.  The wide range  of values in
Table  3-17 indicates substantial variation in rate estimation and  reporting
procedures.   Unfortunately, many  investigators  automatically equate k^  or kR
with k.,  and do  not fully  consider the different meanings of these rates.
Some report k. and kR values without stating  whether these  apply  to total
BOD or CBOD, are temperature-corrected, are to base e or base 10, etc.
                                  157

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     One way to  handle these uncertainities is to  conduct sensitivity
analyses  of  model  predictions.   Such  analyses are beyond the scope of many
projects;  however, results are available for many widely-used models either
in the  model documentation or in the final reports of large-scale projects.
Examples of sensitivity analyses  for deoxygenation rate  coefficients  are
Crane and Malone  (1982), Thomann  and Fitzpatrick (1982) and NCASI (1982a).

     In  addition, it is possible  to quantitatively evaluate the uncertainly
associated with  an estimated coefficient.  Barnwell's (1980)  and NCASI's
(1982b)  calculation techniques allow computation of confidence limits for an
estimated k,  value.  Jaffe and Parker  (1984)  provide  a  procedure  for
estimating the uncertainty of kd  values as  influenced by the field sampling
scheme.   Chadderton et_ aj_.  (1982)  evaluate the relative contributions to
uncertainty of the parameters of  the Streeter-Phelps equation.

3.4  NITROGENOUS  BIOCHEMICAL OXYGEN DEMAND

3.4.1  Introduction

     The transformation of reduced forms  of nitrogen to more oxidized  forms
(nitrification)  consumes oxygen.  Although nitrification  is also a nutrient
transformation process,  this section addresses the oxygen consumption
aspects,  since numerous  models simulate nitrogenous  biochemical oxygen
demand (NBOD) without  detailing nitrogen  transformations.

     Nitrification  is  a two-stage process.  The first  stage is the oxidation
of ammonia to nitrite  by Nitrosomononas bacteria:

                      NH* +  1.5 02—»-NO~  + H20 +  2H+                 (3-46)

                   (14 gm)   (48 gm)

Stoichiometrically  48/14 or 3.43 gm of oxygen  are consumed for each gram of
ammonia-nitrogen  oxidized to nitrite-nitrogen.  During  the second  stage of
nitrification Nitrobacter bacteria oxidize nitrite to  nitrate:
                                   153

-------
                      NO;; + 1/2  02—a-NO^                           (3-47)

                   (14 gm) (16 gm)

Stoichiometrically 16/14  =  1.14  gm  of oxygen  are  consumed per gram  of
nitrite-nitrogen oxidized.  If the  two  reactions are  combined, the complete
oxidation of  ammonia can be represented  by:

                       NH* + 2 02—*-NO~ + H20 + 2H+               (3-48)

                    (14 gm) (64 gm)

As  expected,  64/14 = 4.57  gm of oxygen  are  required for the  complete
oxidation of  one gram of ammonia.

     In  the  reactions above, the  organic-nitrogen  form does  not  appear,
since organic-nitrogen  is  hydrolyzed to ammonia,  and does not consume oxygen
in the process.  However,  organic nitrogen  will  eventually contribute to the
NBOD, as the following  equation shows:
                      NBOD
= 4.57 (NQ + NX) + 1.14 N2                (3-49)
where N~ = organic-nitrogen concentration,  mass/volume
      N, = ammonia-nitrogen concentration,  mass/volume
      N2 = nitrite-nitrogen concentration,  mass/volume

     The  stoichiometric coefficients  of 3.43, 1.14,  and  4.57 in the
equations above are  actually somewhat  higher than  the  total  oxygen
requirements because  of  cell synthesis.   Some  researchers (e.g.,  Wezernak
and Gannon, 1967 and Adams and Eckenfelder, 1977) have suggested that the
three coefficients  be  reduced to 3.22,  1.11,  and  4.33, respectively.

3.4.2  Modeling  Approaches

     Modelers use both  the two-stage and one-stage approach to simulate NBOD
decay, as shown  by Table 3-18.  First  order kinetics is  the  predominant
                                   159

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   method  used to  simulate  the  process.   Oxygen  limitation is used by some
   modelers (e.g., O'Connor ^t _§_]_.,  1981; Thomann  and Fitzpatrick, 1982;  and
   Bedford _et aj.., 1983).

        Relatively few modelers  explicitly simulate the effects of  benthic
   nitrification  (exceptions are  Williams and Lewis,  1984 and Mills, 1976).
   The models of Williams  and Lewis, and Mills were  developed  for relatively
   shallow streams where bottom  effects could be important.   Of these two, only
   Mills looks at the details of  oxygen and nitrogen transfer  from the  water
   column  into an  attached nitrifying biofilm.  Several  studies (Kreutzberger
   and Francisco, 1977; Koltz, 1982) have confirmed  that  nitrifying bacteria
   can  thrive in the beds  of shallow  streams, and that,  in the streams they
   investigated, nitrification occurred primarily  in the  bed,  and not  in  the
   water  column.   Denitrification  has been shown to occur  in stream sediments
      TABLE 3-18.  EXPRESSIONS  FOR NITROGENOUS BIOCHEMICAL  OXIDATION RATES
                   USED  IN A  VARIETY OF WATER QUALITY MODELS
Expression for Nitrogenous Oxidation
	Rate. eDO/at	
                Model and/or Reference
   - a  k   N. - a  k  N,
     1  n.   1   2  n,  2
  -knLn
WQRRS (Smith, 1978)
Bauer et _aj_.  (1979)
QUAL-II  (Roesner et jH., 1981)
SSAM IV  (Grenney and Kraszewski,  1981)
CE-QUAL-R1 (U.S. Army COE, 1982)
RECEIV II (Raytheon, 1974)
NCASI (1982d)
Baca and Arnett (1976)
MIT Transient Water Quality Model (Harleman et al., 1977)
DOSAG3 (Duke  and Masch, 1973)
HSPF (Imhoff  et al., 1981)
Genet _et a]_.  (1974)

DIURNAL  (Deb  and Bowers, 1983)
Gowda (1983)
EXPLORE-1 (Baca et al., 1973)
Bauer et al.  (1979)
Di Toro and Matystik, 1980
                                        160

-------
                                  TABLE  3-18.   (Cont'd)
Expression for Nitrogenous Oxidation
	Rate. gDO/at	
                                         Model  and/or Reference
  - a- k
     3  n °2 + Knit
N,
                                          O'Connor ^t _§]_. (1981)
                                          Thomann and Fitzpatrick (1982)
   " a3 a4 Q Q  + K	 Nl
     J  4   U2    nit  L

Time Shifted First Order (time  delayed)
Lagged First Order (nonoxidative step
followed by an oxidative step)

Benthic Nitrification:

   - a, S  (zero order kinetics)
   - Jc (Monod kinetics)
                                         Bedford  et &\_.  (1983)


                                         NCASI (1982d)
                                         NCASI (1982d)
                       Williams and Lewis (1984)
                       Bauer ^t _al. (1979)

                       Mills (1976)
Definition of Symbols:
    k
                             dissolved oxygen concentration
                             half-saturation constant
                             zero order benthlc nitrification rate
                             benthic oxygen flux rate by nitrifying
                             organisms growing in an attached
                             biofllm
          amnonla to nitrite oxidation rate
          nitrite to nitrate oxidation rate
          NBOD decay rate
          3.43, typically
          1.14, typically
          4.57, typically
       b   unspecified
          N0~ -N
          nitrogenous BOD
 as well  (Wyer and  Hill,  1984).   Denitrification  is discussed  in  more detail
 in Chapter  5.

      The most straightforward  method  of including  the effects of  organic
 nitrogen on the  potential depletion  of dissolved oxygen is  to  simulate the
 conversion  of organic nitrogen  to ammonium  nitrogen (a rate of O.I/day  is
 typically  used).   The  increased ammonia concentration is then  available  to
 exert  an oxygen  demand.   However,  it  is not clear  that  all the models  in
                                            161

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    Table 3-18  simulate the organic nitrogen to ammonia conversion.  Some models
    appear to combine ammonia and organic nitrogen together into a single term.

         While  first order kinetics is the most popular approach for simulating
    nitrification in natural systems, Monod and zero-order kinetics are often
    used  to  simulate  nitrification in wastewater treatment processes (Hall and
    Murphy,  1980;  Charley  _et _al_. ,  1980;  Rittmann and  McCarty,  1978).
    'Figure 3-13 shows  how nitrification is simulated using Monod kinetics. "At
    the high level  of  reduced nitrogen compounds found  in  wastewater,
    nitrification  can  proceed at its maximum rate, and thus is zero order
    (independent of substrate concentration).  At  lower reduced nitrogen
    concentrations,  first order kinetics are applicable.
      Vmax
LU
fe
cc
o
5
£  O.SVmax
£
                                                       ZERO ORDER
               FIRST
              ORDER
                      Kc
                         REDUCED NITROGEN CONCENTRATION
      Figure 3-13.
Effect of Reduced Nitrogen Concentration on Nitrification
Rate  as Reported by Borchardt  (1966).
                                     162

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     Several  researchers (e.g.,  Wi Id _et _§_]_. , 1971;  Kiff, 1972; Huang  and
Hopson,  1974)  have established concentration ranges of ammonia nitrogen when
zero order  kinetics appear to be followed.  The  range is quite wide,  from
1.6 mg/1 to  673 mg/1.  Concentrations  of ammonia-nitrogen in natural waters
can exceed  the lower end of the  scale reported,  and indicate that zero order
or Monod kinetics may be  appropriate in these  circumstances (e.g., see
Wilber et _al.. ,  1979).

3.4.3  Factors That Affect Nitrification

     Table 3-19 summaries studies that  have  investigated factors that
influence  the rate of nitrification.  The factors include pH, temperature,
ammonia and nitrite concentrations,  dissolved oxygen,  suspended solids,  and
organic and  inorganic compounds.  Sharma and  Ahlert (1977) also prpvide a
review of previous studies.

     Many  of  the  studies  have been carried out in controlled environments,
and not in  natural  waters.  Also, the concentration of organic  substances
which have inhibitory effects on nitrification  are often,  but  not  always,
well  above  1  mg/1  (Wood _et al  . ,  (1981)),  so  that the  compounds  are not
likely to be  inhibitory in  natural  waters.

     Modelers  typically consider  only the  temperature  effect  on
nitrification, although  a few do model  dissolved oxygen limitations (see
Table 3-18).   Other inhibitory or  stimulatory effects  are assumed to be
included  in   the  "reference" rate (typically at 20°C) measured  or otherwise
selected for the modeling  applications.

     Researchers  have found that within the temperature range of  10°C to
30°C temperature effects can be simulated by the following expression:

                                        T-20                         f 3-501
                                                                    (6 buj
where k on = nitrification rate coefficient  at  20°C
       n^U
      0    = temperature  correction factor

                                   163-

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                                   TABLE  3-19.    SUMMARY  OF FACTORS  THAT  INFLUENCE NITRIFICATION
                         Reference
                                                     Factors  Investigated
                                                       Comments
                    Sharma and Ahlert (1977)
Temperature,  pH, Nitrogen
Concentrations, Dissolved
Oxygen, Organic Compounds
In reviews  of  previous studies  found:  12 studies for dissolved
oxygen,  15  studies  for pH,  14 studies for the effect of ammonia
levels  on  nitrification,  11 studies of effects of nitrate levels
on nitrification, 34 studies on substances that are required  or
stimulate  nitrification; 47 studies  on substances that inhibit
nitrification.
                    Stenstrom and Poduska  (1980)
                   Wild, Sawyer, and McMahon (1971)
Dissolved Oxygen
pH, Temperature, Ammonla-
nltrogen
01
                   Kholdebarin and Oertli (1977a)     pH, Ammonia-nitrogen
                    Kholdebarin and OertH  (1977b)     Suspended Solids
                   Bridle, CHmenhage, Stelzlg
                   (1979)
                   Qulnlan (1980)
                   Hood, Hurley,  Matthews  (1981)
                   Hockenbury and Grady  (1977)
pH, Temperature, Amnonla-
nitrogen,  Copper
Temperature
Organic Compounds
Organic Compounds
In this  literature review of the  effects of dissolved oxygen
concentrations on nitrification, the lowest concentration where
nitrification  occurred is approximately 0.3 mg/1.  However, the
dissolved oxygen level required for no oxygen inhibition varied to
as high  as 4.0  mg/1, while other researchers found only 0.5 mg/1
1s required.

Studies  were  conducted in a  pilot nitrification  unit  receiving
trickling filter  effluent.  Ammonia  nitrogen did not  Inhibit
nitrification at concentrations less than 60 mg/1.  Optimum pH for
nitrification was  found to be 8.4.   The rate af nitrification
Increased with temperature in  the range 5 C to 30 C.

For water samples collected from the Whitewater River, California,
the optimum pH  for nitrification of ammonia and nitrite was 8.5.
Nitrite  oxidation was stimulated  by the  addition  of 3  mg/1
ammonium.

In water  from the Whitewater River in California, suspended solids
were  found to have  a stimulatory  effect on nitrification,
presumably caused by the physical support provided by the sol Ids.

In batch  reactors ammonia nitrification was not inhibited for TKN
levels up to 340 mg/1.  The optimum pH for nitrification was 8.5.
The nitrification rate Increased approximately 2.5 fold for  each
10 C  Increase.   Copper concentrations of 3000 mg/1  produced no
adverse effect; concentrations of 6000 mg/1 were Inhibitory.

Temperature for optimal ammonia and nitrite oxidation was found to
depend on nitrogen concentrations.   At low nitrogen concentra-
tions  the optimum temperatures were 35.4 C for ammonia oxidation
and 15.4°C for nitrite oxidation.

Laboratory studies were conducted  using filtered liquor  from
return activated  sludge.  Approximately 20 compounds were tested
in concentrations from 10 to 330 mg/1.   Approximately half the
compounds  had no Inhibitory effects.

This study reviewed previous work  on the influence of organic
compounds on nitrification.   Additionally, they found that many
compounds  did not Inhibit nitrification at concentrations as  high
as 100 mg/1, while other compounds  inhibited nitrification at
concentrations less than 1  mg/1.

-------
     Values  of  the temperature correction factor are reported in  Table 3-20.
Temperature  correction values are slightly  higher for ammonia oxidation than
for nitrite  oxidation.  The mean temperature  correction values  are 1.0850
for  ammonia oxidation and  1.0586 for nitrite oxidation.   Many models use
temperature  correction factors slightly lower than these values.   Typically
modelers use  only  one  temperature  correction  coefficient,  and do not
distinguish between temperature corrections  for  ammonia  and  nitrite
oxidation.   Example of  temperature  correction  factors used  in  selected
models are:

     •    1.05, EXPLORE-1 (Baca etaK, 1973)
     0    1.065,  MIT  Nitrogen model (Harleman _et _a_L, 1977)
     •    1.08, New York  Bight model  (O'Connor _et a/L, 1981)
     •    1.047,  QUAL-II  (Roesner  et _al_.,  1981),  USGS Steady State Model
          (Bauer  et _al_.,  1979)
     •    1.045,  Potomac  Estuary Model  (Thomann and Fitzpatrick,  1982)
                                TABLE 3-20
            TEMPERATURE  CORRECTION FACTOR, 6, FOR  NITRIFICATION


        Reference          Ammonia Oxidation         Nitrite Oxidation
Stratton (1966); Stratton and
McCarty (1967)
Knowles et _aj_. (1965)
Buswell et _al_. (1957)
Wild _et _al_. (1971)
Bridle et _aj_. (1979)
Sharma and Ahlert (1977)
Laudelout and Van Tichelen (1960)
Mean
1.0876
1.0997
1.0757
1.0548
1.1030
1.069
-
1.0850
1.0576
1.0608
-
-
-
1.0470
1.0689
1.0586
                                  165

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     •     1.02-1.03, WQRRS (Smith,  1978)
     •     1.08, Lake Erie model (Di  Toro  and Connolly, 1980)

     While Equation (3-44) can provide adequate temperature correction up to
approximately 30°C, beyond  this temperature the nitrification rate  is
inhibited  by the high temperature, so the  relationship  no  longer  holds.
Figure  3-14 illustrates the effect of  temperature on nitrification and shows
that the rate rapidly decreases at temperatures beyond 30 C.
                     100
90-

80-

70

60

50-
                  o
                  b
                  UJ
                  CC
                  li.
                  O
                  Z   40
                  111
                  o
                  IT
                  UJ   30
                      20-
                      10-
                           10    20   30   40   50
                                 TEMPERATURE,°C
                           60   70
    Figure 3-14.   Effect of Temperature on Nitrification as Reported
                  by  Borchardt (1966).
     The influence of pH on rates  of  nitrification is also quite important.
If pH is outside of the range  7.0  to  9.8,  significant  reduction  in
nitrification  rates can occur.   Table  3-19  indicated that the optimal  pH for
nitrification is approximately 8.5  and  at  pH  values below about 6.0,
nitrification  is not expected  to occur.  Figure 3-15 shows the effect of pH
                                    166

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on ammonia and nitrite oxidation.  A more  thorough  review of  pH effects is
contained in Sharma and Ahlert  (1977).
     Effects of  solid  surfaces have frequently  been documented  as  being
important for nitrification  (e.g.,  Kholdebarin  and Oertli, 1977).  The
following section  discusses  this  effect  more fully through a number  of case
studies.
  UJ
  cc
  2
  ID
  2
  X
  <
  LU
  O
  DC
  UJ
  CL
      100
90-
80-
70-
60-
50-
40-
30-
20-
10-
 0
        6.0
               LLJ
               £
               cc
               5
               D
               2
               X
              UJ
              O
              QC
              UJ
              0.
                  70
8.0
ph
9.0
10.0
                       (a) AMMONIA OXIDATION (Wild et.al.,1971)
            100
             90-
             80-
             70-
             60-
             50-
             40-
             30-
             20-
             10-
             0
                     0  5.5 6.0 6.5 7.0 7.5 8.0 8.5  9.0 9.5 10.0 10.5
                                       Ph
                        (b) NITRITE OXIDATION (Myerhof,l9l6)
              Figure  3-15.   pH  Dependence of Nitrification.
                                    167

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3.4.4  Case  Studies and Nitrification  Rates

     Table 3-21 summaries case studies  of  nitrification in natural waters.
These studies  are  intended to show how various researchers  have determined
nitrification rates in natural  waters,  some of the complications that can
occur in  doing so, and what the rates  are.

     Except for Slayton and Trovato (1978, 1979) all "the case studies are
for streams  or rivers.  Note the high  variability in  nitrification" rates
from study to  study.  For rivers,  documented first order nitrification rates
varied from  0.0/day to 9.0/day.  For the  two Potomac estuary studies,  the
nitrification rates were fairly small and  constant (0.1 to 0.14/day).   The
nitrification  rate was often determined  from  plots of TKN  or NBOD versus
distance  or travel time.   Figure 3-16  shows an example.  A number of the
studies (e.g.,  Koltz (1982) and Ruane  and Krenkel  (1978))  emphasized  that
algal  uptake  of ammonia  can  be  an important transformation and should be
accounted for  in the rate determination.   The increase  of  nitrate nitrogen
can  be monitored, as well  as the decrease  in  ammonia nitrogen for more
conclusive evidence that nitrification is occurring.  Bingham ejt a±.  (1984)
show how  the nitrification rate constant  is  changed in  a QUAL-II application
when algae is  simulated compared to when  algae is not simulated.

     Several of the case studies have  enumerated nitrifying bacteria present
in the water column and in the sediments  (e.g., Kreutzberger and Francisco
(1977)).   Far more nitrifying organisms are  typically present  in  the
sediments than in  the water column.  Case studies on the  following rivers
have reached the same conclusion:

     t    Kanawha  River, West Virginia (U.S. EPA, 1975)
     •    Tame and Trent Rivers, England  (Curtis et ^1_., 1975)
     •    North Buffalo Creek, North Carolina  (Williams and Lewis, 1984)
     •    Willamette River, Oregon (Rinella  et_ _al_., 1981)
     t    Chattahoochee River, Georgia (Jobson, undated)
                                   16C

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                               TABLE  3-21.   CASE  STUDIES OF NITRIFICATION  IN NATURAL WATERS
          Reference
Study Area
                                           Purpose of Study
   Reported
Nitrification Rates
Methods of Determining
Nitrification Rates
                                                                                                                     Comments
en
Uezernak and Gannon
(1968)
Stratton and HcCarty
(1969)
Blain (1969)

Gowda (1983)






Curtis (1983)





Deb and Bowers
(1983)


Deb, Klafter-Snyder,
and Richards (1983)




Ruane and Krenkel (1978)




Koltz (1982)




Clinton River,
Michigan, a
shallow stream
with velocities
of 1-2 fps

Speed River,
Canada, a
relatively
shallow river
with velocities
from 0.3 to
1.5 fps
Still River,
Connecticut




South Fork of
Shenandoah River


Leatherwood,
Creek, Arkansas




Holston River,
Tennessee



Iowa and Cedar
Rivers, Iowa



To mathematically
model nitrifica-
tion 1n a stream
(This was one of
the earlier
modeling attempts)
To determine the
affects of nitrifica-
tion on dissolved oxygen
levels within the river



To determine the fate
of ammonia in the
river by simulating
oxidative and non-
oxidative transforma-
tions
To simulate the
dissolved oxygen of the
river using the
DIURNAL model
To simulate the
dissolved oxygen
dynamics of a small
surface-active stream
for wasteload allocation
purposes
To examine the various
nitrogen transformations
that occur 1n the river


To determine the
locations and rates
of nitrification down-
stream from two waste-
water treatment plants
ammonia oxidation:
3.1-6.2/day
nitrite oxidation:
4.3-6.6/day


0.2-4.41/day






0.0-0.4/day





0.2-1.25/day



1.1-7. I/day





0.15-0.3/day




0.5-9.0/day



(continued)
Measurements of
ammonia, nitrite, and
nitrate at three
locations within the
stream

Plots of TKN versus
travel time





Comparison of total
ammonia decrease to
nitrate increase



Plots of NBOD versus
travel time


Plots of TKN versus
travel time




Rate of ammonia
reduction and rate
of nitrate increase


Rate of ammonia
reduction and rate
of nitrate increase


The nitrogen balance developed
Indicated that nitrification was
primary mechanism responsible for
observed nitrogen transformations.


NBOD predicted to be much
more important on the dissolved
oxygen deficit than CBOD.




















The complexity of the nitrogen
cycle 1n the Holston River is
discussed Including the effects
of ammonia transformations other
than caused by nitrification.
Algal assimilation of ammonia
appeared to be an important
transformation process. Labora-
tory rates of nitrification varied
from 0.02-0.35/day.

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                                                                   TABLE  3-21.    (continued)
              Reference
   Study Area
                                                     Purpose of Study
                                                                                 Reported
                                                                              Nitrification Rates
                                               Methods of Determining
                                               Nitrification Rates
                                                                                                                                             Comments
Kreutzberger and
Francisco (1977)
Morgan Creek,
Ruin Creek, and
Little L1ck
Creek; three
shallow streams
In North Carolina
To determine the
distributions of
nitrifying organisms,
and to examine the
nitrogen transformation
occurring in the streams
Counts of nitrifying organisms
were enumerated in the water
column and in the top 1 cm of
sediments. The populations were
much larger in the sediments,
which indicated that nitrifica-
was occurring predominantly in
the sediments and not In water
column.
        Cirello et aK  (1979)
o
        Finstein and
        Matulewich (1974)
Passaic River,
New Jersey
Passaic River,
New Jersey
To determine whether
nitrification was  a
significant process in
the Passaic River
To determine the
distribution of
nitrifying bacteria
In the river
                                                  There were high ammonia  nitrogen
                                                  concentrations in the river with
                                                  relatively little nitrification
                                                  occurring.  The potential  for
                                                  nitrification appeared  high, and
                                                  was expected to be exerted if
                                                  water quality within the river
                                                  improved.

                                                  Nitrifying bacteria were found to
                                                  be from 21 to 140,000 times more
                                                  abundant  voluraetrically  in sedi-
                                                  ments than in the water  column.
         SI ayton and Trovato
         (1978. 1979)
Potomac Estuary
To determine factors
important in the
oxygen balance within
the estuary
0.10-0.14/day
Thomas Graphical
Method

-------
  O)
 CD
      4.0
      3.0-
      2.0-
      1.0
     0.9-
     0.8
     0.5
                                Kn"1.25/day
                               Kn=0.2/day
         0           0.5

             Figure 3-16.
       1.0           1.5
   TIME OF TRAVEL,DAYS
2.0
2.5
Nitrogenous  biochemical oxygen demand
versus travel  time in Shenandoah River
(Deb and  Bowers, 1983).
     Additional  nitrification rates are shown in  Table 3-22.  Bansal (1976)
has documented nitrification rates in numerous rivers  throughout the  United
States,  and developed a method to  predict nitrification rate based  on
hydraulic data.   His method has been criticized by Gujer  (1977) and  Brosman
(1977) and is not reported.

     Relatively few nitrification rates were found for  lakes or estuaries.
The few  data in  Table  3-22  for lakes  and estuaries are generally in the
range O.I/day to  0.5/day.
                                    171

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                 TABLE 3-22.   SUMMARY OF NITRIFICATION RATES
River
Grand River,
Michigan
Clinton River,
Michigan
Truckee River,
Nevada
South Chickamaugo Creek,
Tennessee
Oostanaula Creek,
Tennessee
Town Branch,
Alabama
Chattahoochee River,
Georgia
Willamette River,
Oregon
Flint River,
Michigan
Upper Mohawk River,
New York
Lower Mohawk River,
New York
Bange Canal near
Upper Mohawk River,
New York
Ohio River
Big Blue River,
Nebraska
Delaware River
Estuary
Willamette River,
Oregon
Ouachlta River,
Arkansas and Louisiana
Potomac Estuary
Lake Huron and
Saginaw Bay
New York Bight
Maximum
3.9
15.8
4.0
2.4
1.9
0.8
—
--
0.7
2.5
0.3
0.3
0.25
0.25
0.25
0.54
—
~
—
~
~~
Average
2.6
5.7
1.9
1.9
—
—
0.7
0.44
—
1.4
0.25
0.3
0.25
0.25
0.11
0.3
0.75*
1.05**
0.1*
0.5**
0.09-0.13
0.20
0.025
Minimum
1.9
2.2
0.4
—
1.1
0.1
--
—
0.4
0.1
0.25
0.3
0.25
0.25
0.03
0.09
~
—
--
~
•~
Reference
Courchaine (1968)
Wezernak and Gannon (1968)
O'Connell and Thomas (1965)
Tennessee Valley Authority
Ruane and Krenkel (1978)
Tennessee Valley Authority
Ruane and Krenkel (1978)
Tennessee Valley Authority
Ruane and Krenkel (1978)
Stamer et al_. (1979)
Rinellaet al_. (1981)
Bansal (1976)
Bansal (1976)
Bansal (1976)
Bansal (1976)
Bansal (1976)
Bansal (1976)
Bansal (1976)
Alvarez-Montalvo, et aT_.
undated
NCASI (1982c)
Thomann and Fltzpatrick, 1982
D1 Toro and Matystik, 1980
O'Connor et _§],. 1981
Note:  Nitrification rates are 1n units of I/day.
   *  Ammonia Oxidation
   **  Nitrite Oxidation
                                         172

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3.4.5  Summary

     Typically modelers  simulate nitrification  by first order  kinetics,
either the single stage or two stage  approach.  Most nitrification  rate data
have been collected in streams and rivers,  where the rates  can  be quite
variable  due to bottom effects.   Instream rates can differ  significantly
from  laboratory or bottle  rates.   However,  for large bodies  of  water
(typically lakes or estuaries)  the relative  importance  of  the  bottom is
diminished,  and nitrification  rates  tend to  approach  bottle  rates.
Available data  suggest nitrification  rates between 0.1 to 0.3/day  are often
appropriate for  large lakes,  large  rivers, or estuaries.

     In flowing  waters, instream nitrification rates are  often determined
based on TKN  versus travel time.   Care should be taken that  the assumptions
of the  approach are met, and that  processes that transform nitrogen other
than nitrification  are assessed (i.e.,  the other components  of  the  nitrogen
cycle).

     Because  benthic nitrification  can be important in small streams, it is
important not  to "doubly count"  oxygen sinks in modeling  applications.  A
component of  the sediment oxygen  demand would include benthic nitrification,
so the  two processes need  to be  accounted for in a mutually  exclusive way
for modeling  applications.

     Very  few studies  actually try  to measure populations  of  nitrifiers in
natural  systems.  This, however,  is the most  conclusive method to confirm
that nitrification  is occurring.

3.5  SEDIMENT OXYGEN  DEMAND  (SOD)

3.5.1  Concept  of SOD

     Oxygen demand by benthic  sediments and  organisms  can represent  a large
fraction  of oxygen consumption in surface  waters.  Benthal deposits at  any
given location in an  aquatic  system are the  result  of  the transportation  and

                                   173

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deposition of organic material.  The material may be  from a source outside
the system such as leaf litter or wastewater particulate  BOD (allochthonous
material), or it may be  generated inside the system as occurs with plant
growth (autochthonous material).  In either case,  such organic matter  can
exert  a high oxygen demand under some circumstances.   In addition to oxygen
demand caused by decay  of  organic matter,  resident invertebrates  can
generate significant  oxygen  demand through  respiration (Walker  and
Snodgrass, 1984).  The importance of this process to water quality modeling
is reflected  in  a  recent symposium (Hatcher and Hicks, 1984).  This same
symposium also reviewed measurement techniques and a concensus favoring j_n
situ measurement was reached.

     It is generally agreed (e.g., Martin and  Bella, 1971) that the organic
matter oxygen demand is influenced by two different phenomena.  The first is
the rate  at which oxygen  diffuses  into the bottom sediments and is then
consumed.  The  second is essentially the rate  at which  reduced organic
substances are  conveyed  into the water column,  and are  then oxidized.
Traditional measurement techniques, whether they are performed jm situ or in
the laboratory, do not differentiate between the two processes but measure,
either directly or  indirectly, the gross oxygen uptake.  Hence, in modeling
dissolved oxygen,  a single  term in the dissolved oxygen  mass  balance
formulation is  normally  used for both  processes.  If  the two phenomena  are
modeled separately  (e.g., see Di Toro, 1984),  then  additional modeling
complexity is necessary.

     The process is  usually referred to as sediment  oxygen demand  (SOD)
because of the  typical  mode of measurement:   enclosing the sediments in  a
chamber and measuring the  change in  dissolved  oxygen concentration at
several time  increments.  This technique is  used  in  the laboratory or
                                                          2
in situ.  The oxygen utilized per unit  area and  time  (gO^/m -day)  is  the
SOD.  The technique measures oxygen  consumption by all of the processes
enclosed in the chamber:  chemical reactions,  bacterially mediated  redox
reactions,  and  respiration by higher organisms (e.g.,  benthic  worms,
insects, and molluscs).   Background  water  column respiration  is then
subtracted from this rate to compute the  component  due solely  to  the

                                    174

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sediment interface.   SOD  is usually  assumed to encompass  the  flux of
dissolved constituents  such as DO to sediment and reduced chemicals to the
water column.   However, solid particle flux as  BOD or  sediment entrainment
or settling is modeled  separately.

     The major factors  affecting SOD are:  temperature, oxygen concentration
at the sediment water interface (available oxygen), makeup of the biological
community, organic  and  physical characteristics of the  sediment, current
velocity over the  sediments, and chemistry of  the interstitial water.   Each
of these factors is a resultant of  other  interacting processes occurring
elsewhere in  the  aquatic  system.   For  example, temperature and available
oxygen can be  changed as  a result of transport  and biochemical  processes in
the  water column  or system boundaries.  Temperature  and oxygen are usually
modeled explicitly,  and can be used as input variables to  the SOD process
equations.  Another important linkage is  that  the biological community  will
change with the water quality (e.g., oxygen and nutrient concentrations)  and
productivity  of the system.   The organic characteristics will change  over
the  long term  due to settling of organic  matter (detritus, fecal matter,
phytoplankton) and its  subsequent  degradation and/or burial by continued
sedimentation.  The biological community and the organic  and physical
characteristics of the  bottom sediments  are usually treated as a composite
characteristic of the particular system.   Recently,  techniques have been
developed for  investigating these factors; however, the usual technique is
to measure the SOD  directly rather than the underlying factors  that control
the  processes  of SOD.

     At least  two major factors affecting  SOD are usual ly'neglected in SOD
modeling.   Current velocity is often neglected despite the fact that it  has
a  major effect on  the  diffusive gradient  of oxygen beginning just below  the
sediment-water  interface.   Most measurement techniques provide mixing,by
internal  mixing or  by recirculating or flow-through systems to  minimize the
effect  of concentration gradients.  However,  the velocity of such systems
may be insufficient (WlYlttemore,  1984a)  or may  be so vigorous as to cause
scour and resuspension.   Interstitial water chemistry affects substrates  for
biochemical  and non-biochemical  oxidation-reduction reactions and their

                                    175

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reaction  rates.  This factor is also usually neglected in SOD measurements
and kinetic formulations.

3.5.2  Kinetics

     The generalized  equation for sediment oxygen demand is:
                         = f(d1sso1ved oxygen,
               at      n
                            temperature, organisms, substrate)        (3-51)

where H   = water depth, m
                                                      2
      SOD = sediment  oxygen demand (as measured), gO?/m -day
      t   = time
      C   = oxygen concentration in the overlying water, mg/1

3.5.2.1  Dissolved Oxygen

     The benthic oxygen consumption has been hypothesized to  depend on  the
dissolved oxygen  concentration in the overlying waters (e.g.,  Edwards  and
Rolley, 1965;  McDonnell and Hall, 1969):

                                SOD = a Cb                           (3-52)

where a,b = empirically determined constants

In the McDonnell and  Hall (1969) study, b was found to be 0.30 and a to vary
from 0.09 to 0.16,  primarily as a function of  the population  density of
benthic invertebrates.

     Lam j2t jil_. (1984)  use  a Michael is-Menten  relationship to express  the
effects  of oxygen on SOD:

                            dc -  ks  AS    c
                                    176

-------
                                                        2
where k   = rate constant for SOD in Lake Erie,  0.1  g 0-,/m -day
       s                          2                  L
      A_  = area of  the sediment, m
                                   3
      V   = volume of water layer, m
      Kn  = oxygen half saturation constant (1.4 mg/1)
       U2
      C   = oxygen concentration, mg/1

     Walker and Snodgrass (1984) divided SOD in  Hamilton Bay in Lake Ontario
into  two fractions:  chemical-microbial (CSOD)  and biological (BSOD).   The
chemical fraction was defined as a first-order function of oxygen:

                            CSOD = kt(T) C                          (3-54)

where k^(T) = temperature-adjusted rate constant for biochemical  SOD,
              I/day

The biological  fraction was estimated  to  be  20-40 percent  due  to
macroinvertebrates in Hamilton Bay sediments but still followed a Michael is-
Menten relationship:
                          BSOD = u(T) .,   x r                        (3-55)
where u(T)  = temperature-adjusted rate constant for biological  SOD
                                                                   2
             (obtained  by measurement:  range  =  0.58 to 5.52  g  Op/m -
             day) ,  I/day
      Kn   = oxygen half-saturation constant (1.4  mg/1)
It is  interesting to  note  the similarity between  the two estimates of Kn
                                                                        U2
(Lam e^al_. ,  1984;  Walker and Snodgrass,  1984).

     The  direct  effects  of dissolved oxygen on  the  rate constant are
generally neglected except in a few models.  For example,  in the HSPF  model
(Johansen j?t jil_. ,  1981), dissolved oxygen concentration affects the rate of
sediment oxygen  utilization exponentially:

                                    177

-------
                        dC
                        f - - r                                  <3-56'
                                                     2
where kT =  the temperature adjusted  rate constant, mg/m -day

3.5.2.2  Temperature

      Temperature effects on SOD  are most  commonly modeled using the
van't Hoff  form of the Arrhenius  relationship:

                                                                   (3-57)

where kT = the rate at ambient temperature T
      k-p = the rate at a reference  temperature (usually Tr=20  C)
      6  = the  temperature  coefficient  for adjusting  the rate
            (Table 3-23)

Although  this  form  of the  relationship  is  the  most common  and  gives
equivalent results  to the  Arrhenius equation, it  is not preferred  in
standard nomenclature (Grau et_ _al_.,  1982).

     The exceptions  to use  of Equation  (3-57)  are RECEIV-II  (Raytheon,
1974),  HSPF (Johanson et _al_.,  1981), and SSAM-IV  (Grenney and Kraszewski,
1981).  RECEIV-II apparently does not  provide a temperature correction  for
the SOD  rate  coefficient although  other  rate coefficients  in  the model  are
adjusted according to Equation  (3-57)  with  6= 1.047  for CBOD.  HSPF  uses a
linear function for adjusting the SOD  for  temperature:

                             kT  = 0.05 Twk2Q                        (3-58)
where kj  =  the temperature adjusted coefficient
      k2g  =  the rate constant at  20°C

      TW  =  water temperature, °C



                                    178

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TABLE 3-23.  SOME  TYPICAL  VALUES OF THE TEMPERATURE COEFFICIENT
    FOR SOD RATE COEFFICIENTS USED IN WATER QUALITY MODELS

Model
DOSAG-3
QUAL-II
Vermont QUALII
Lake Erie Model
WASP
WASP
LAKECO
WQRRS
ESTECO
DEM
EAM
EAM
USGS-Steady
AQUA- IV
EXPLORE- I
Laboratory/Field Studies
e
1.047
1.047
1.047
1.08
1.08
1.1
1.02
1.02-1.04
1.02-1.04
1.04
1.02
1.047
1.065
1.02-1.09
1.05
1.040-1.130
Q10(20°C)*
1.58
1.58
1.58
2.16
2.16
2.59
1.22
1.22-1.48
1.22-1.48
1.48
1.22
1.58
1.88
1.22
1.63
1.5-3.4
Reference
Duke & Masch (1973)
Roesner e_t aK (1977)
JRB (1983)
Di Toro & Connolly (1980)
Thomann & Fitzpatrick (1982)
O'Connor e_t a_K (1981)
Chen & Orlob (1972, 1975)
Smith (1978)
Brandes (1976)
Genet e_t ^L (1974)
Bowie ejt al_. (1980)
Tetra Tech (1980), Porcella ejt al.. (1983)
Bauer et ai- (1979)
Baca & Arnett (1976)
Baca et ai. (1973)
Zisone_t al. (1978); Whittemore (1984b)

* Q10(20°C) = ratio of
at
                   =6
                     10

-------
     Grenney and Kraszewski  (1981) used a modification  of  the Thornton  and
Lessem (1978)  equation for SSAM-IV to provide,  essentially, a continuously
variable  adjustment coefficient  (0)  for the rate constants in biological
processes.  The equation adjusts over a temperature  range of 5 to 30°C which
is similar to using Equation (3-51) with a variable  6 coefficient:

                                K, ey
-------
Additional  field experience and the use of divers to place the respirometers
should measurably  improve these results.

3.5.2.3  Biological Effects on SOD

     The biological  component  is  usually neglected  when modeling  SOD,
because of  the  complexity of  modeling  benthic microorganisms and
macroinvertebrates.  The spatial and seasonal variability  in  SOD caused by
sediment  biological processes and communities results in variation in SOD
that modelers appear to account for by varying the temperature coefficient.
Some  investigators have attempted to incorporate this variation  directly in
the model  (Grenney and Kraszewski, 1981), or have suggested that the value
of  the  temperature coefficient changes with season (e.g., Bradshaw  et al.,
1984) or with location downstream (e.g., Mancini ^t ail_. ,1984) . Other models
(LAKECO, ESTECO, WQRRS, EAM) incorporate a  benthic organisms compartment and
may be able to evaluate the effects of benthos on SOD directly.   However, no
verification studies have  been discovered that  demonstrate this  to be a
useful technique.

3.5.2.4  Substrate Variability

     The process describing  the substrate utilized is where most  models
differ  (Table 3-24).  In  the first water quality models that  were widely
used  (DOSAG-3,  QUAL-II),  the decay of substrate  is  assumed  to balance
continued  settling resulting in a steady-state sediment concentration of
oxygen-demanding substrate.  The resulting equation is:
                                                                    (3'60)
                                                      p
where k-p = temperature adjusted rate constant SOD, gO^/m -day
      H  = mean  water depth, m

As shown in Table  3-24, most models have  followed this approach.
                                    181

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                           TABLE  3-24.   MODEL FORMULATIONS COMMONLY  USED  IN SOD  COMPUTATIONS
Formulation
k/A
k/H
Units
k,mg00/m day
2
A.ni
2
k .mgO-Xm day
Description
SOD rate normalized
by bottom area
SOD rate normalized
Model (Reference)
DOSAG-3 (Duke & Masch, 1973)
QUAL-II (Roesner e_t aU (1977)
Vermont QUAL-II (JRB, 1983)
IICCC Ctn=.^w ID*, .or- 0+ 5,1 1Q7QA
                                     H>m                                                 AQUA-IV (Baca & Arnett,  1976)
                                                                                         WASP  (O'Connor et aK  1981)
                                                                                         RECEIV-II (RaytTieon,  1974)
                                                                                         OEM  (Genet e_t a_K 1974)
                                                                                         HSPF  (Johanson  et aK  1981)

r§            a k SED            a,mgO,/mg Sed             Conversion  factor              LAKECO* (Chen & Orlob,  1972,  1975)

                                    kj/day                   Decay rate                  W™* 
-------
     Substrate  has  been  incorporated directly into ESTECO, LAKECO, WQRRS,
EAM,  and EXPLORE-I.  Different  settling rates of  oxygen-demanding  organic
materials  can lead  to different  amounts  of  sediment materials,  and
consequently different SOD rates  calculated according to:

                             ^ = -  a k SED                         (3-61)

where a   =  stoichiometric conversion  factor relating oxygen to organic
            sediment, mg CL/mg  sediment
      k   =  sediment decay rate constant, I/day
      SED =  sediment substrate  that is  subject to  decay

In .EXPLORE-I, only carbonaceous BOD is simulated  as the  substrate  (SED),
which  in  turn  is  affected by scour  or settling  from the water column.   In
the other models, all of the nutrient elements (C,  N,  P)  are transformed
according to a first-order reaction  (k SED) but sediment oxygen demand is
exerted only by carbon.   Values  of the conversion  factor for sedimented
organic carbon to 0?  lie  in  the range of  1.2  to  2.0 mgO^/mg sediment.
Nitrogen decays  to ammonium and is released to  the overlying waters  where
nitrification  can take place  (see Section 3.4).  Other  nutrients also enter
the overlying waters as a result  of similar transformations.

     In some versions of the WASP model (Di Toro and  Connolly, 1980; Thomann
and Fitzpatrick, 1982), the oxygen-demanding materials in  the sediment  are
divided  into multiple compartments.   First, the decay processes of sediment
organic matter  generate concentrations of CBOD  and NBOD  constituents  in
interstitial  waters.   Then both CBOD and NBOD are released to the water
column where they subsequently  decay  in the appropriate compartments.   In
addition  to CBOD  release, oxygen utilization in the interstitial water is
computed as  oxygen equivalents, and diffusion into the  interstitial  water
compartment is determined.  If  oxidation in excess  of  the amount available
from  diffusion occurs, these excess "oxygen equivalents" continue  to
represent a potential demand on the dissolved  oxygen system.  Finally, a
deep oxygen  demand has been hypothesized in an  attempt  to  account  for  the
measured  oxygen demand.  These concepts are described Di Toro and Connolly,

                                    183

-------
1980.  More recently,  Di  Toro (1984) has provided an additional  correction
to SOD from denitrification of nitrate,  although he suggests  that this
correction is usually  negligible.

3.5.3  Measurement Techniques

     Essentially three types of  measurement techniques have been used  to
estimate SOD rates:  model calibration to estimate  SOD,  in  situ measurements
using respiration chambers, and  laboratory respiration  chamber measurement
using cores  or dredged  samples.   However, all three methods have severe
disadvantages  and the uncertainty of calculating SOD rates  is so great that
the  simple  formulations  in the  model equations  (Table 3-24) are very
appealing to model users.  Unfortunately, these simple  formulations will  not
result in credible models with good  predictive capability when single values
are used for rates and coefficients.

     It would  be expected that considerable spatial and temporal variation
would occur  in  SOD.  Spatially,  the  bed sediments of streams,  lakes ,  and
estuaries  vary in  their physical  and chemical characteristics, rates of
deposition,  and other factors.   For example, a  stream may have .fine
sediments  in  low velocity  areas  and coarse cobble  or  boulders in steep
gradient-high  velocity reaches.  Depth  and velocity  can vary significantly
in any  one  cross-section.  Reservoirs  have deposition  zones near inlets  and
at dam structures.  Estuaries like  streams and  lakes vary considerably in
substrate  type and water  velocity but are  influenced by the salinity
gradient and  an added factor of coagulation  and rapid settling in zones
where fresh  and saline waters mix.

     Another  source  of  variation  is  temperature.  Temperature  varies
seasonally  but that is  accounted  for in use of  the  van't Hoff or similar
relationships.  However, temperature and season both  cause a shift  in
benthic  community composition.   Macroinvertebrate populations, especially
emergent insects, change dramatically with life  stage.   Also,  it would be
expected that  considerable variation  in microbial  community characteristics
would occur  in  response to temperature  changes.

                                   184

-------
     These spatial  and  seasonal characteristics suggest  that a large number
of SOD measurements  would be required to estimate  and  obtain sufficient
variation in rate coefficients.  This  has led to the development of in  situ
                     •>                                            •--  •———
and laboratory methods  for measuring SOD that  will be  site-specific and
seasonal  for SOD.   SOD mapping strategies  may be necessary.   Ideally,
in situ  methods would provide the best approach, but considerable variation
in results occurs because of problems associated with field  sampling:

     t    Horizontal and longitudinal non-homogeneity of  stream bottom
          materials.   Areas  of cobble, soft sediments,  logs,  and
          bedrock,  increase the cost of measurement  because more
          samples are needed.   Soft, flocculent sediments are very
          difficult to evaluate with in situ methods.  In some streams,
          an  inaccurate characterization of reach-averaged  SOD will be
          obtained.

     •    Difficulties  in placement of respiration  chamber.   For
          example, obtaining a complete seal in  cobbled  and  bouldered
          areas or where significant interaction with the ground water
          system  occurs  is essentially impossible.

     •    Mixing in the  respiration  chamber  may not  be  modeled
          correctly nor simulate  natural  conditions  and this  is
          reflected in  the wide variance in results from measurements.
          For example,  the Institute of Paper  Chemistry  reported  on a
          comparison  of  5 j_n s i tu  samplers of two  basic types
          (recirculating and internally mixed) and found  the  results to
          be  markedly different (Parker,  1977).

     Laboratory measurements  suffer  from  similar problems.  They would
appear  to work reasonably well for  aquatic systems of relatively uniform
sediment  characteristics, but heterogeneous  sediments  often  lead  to
measurement variability.
                                    135

-------
     Some practices  improve laboratory measurement:  correcting  of  results
for  varying sediment  depth is usually  unnecessary when  depths exceed
5-10 cm; undisturbed core samples are  preferred  over dredge  samples even
though they are more costly to collect; storage of samples and  acclimation
of samples to laboratory temperatures  is discouraged because  of potential
changes in benthos or substrate; divers may help to improve precision.

     In regard to the effect of variability in oxygen-demanding  materials,
there  appears to be no strong relationship between SOD  and various measures
of organic matter (NCASI, 1978),  but this may have  been due to  inaccurate
measurement  techniques.   Improper mixing (i.e,  velocity too  high or too
low), inadequate oxygen supp-ly,  storage or  improper pretreatment  of  samples
in the  laboratory,  and inappropriate laboratory temperatures  may lead to
errors that prevent  the derivation of SOD/substrate relationships.  However,
Gardiner  _et  al.  (1984), using  a  laboratory chamber, showed that SOD was
related to chemical  oxygen  demand (COD) of  the sediments   in Green Bay,  a
large  gulf in  the  northwest  corner  of Lake Michigan,  according to the
following  equation:

                       SOD =  7.66 COD/(156.5  +  COD)                 (3-62)

As further evidence,  the higher  SOD values  coincided  with areas of summer
dissolved  oxygen depletion  in  Green Bay.

     Given the many sources of  measurement error,  it is  not  surprising  that
Whittemore (1984b)  was  unable  to  correlate  literature  SOD  values  obtained in
                                                                  o
simultaneous  field and  laboratory measurements.   He obtained a low r   value
of 0.58.   But  even more significant,  the  j_n situ  SOD  values  were
consistently  higher than laboratory derived  values  at  low  SOD concentrations
and the reverse observed at high SOD concentrations.  This  systematic  error
indicates  the need  for better  methods of  estimating SOD as  well  as
developing a  better understanding of the component  SOD mechanisms.

     The model calibration approach  to estimating  SOD  is essentially a
determination of the SOD rate  by calibration  subject  to the constraint of a

                                   186

-------
reasonable range of SOD values.   Thomann (1972) used  literature SOD rates
and modeling experience to suggest  SOD  ranges for certain environments
(Table 3-25).  The model  approach  (e.g.,  Terry and  Morris,  1984; Draper
^t jj_.,  1984),  by itself,  contains considerable variance because there are
uncertainties  in the  other processes  (reaeration,  nitrification,
respiration,  photosynthesis, flow) as well as the  considerable spatial and
temporal  variation expected  in most aquatic environments.  Lam ert _al_.  (1984)
suggest  that variation  in dissolved oxygen  load to  Lake Erie owing to

           TABLE 3-25.  AVERAGE VALUES OF OXYGEN UPTAKE RATES OF
                   RIVER BOTTOMS (AFTER THOMANN, 1972)

o
Uptake (g 02/m -day)
Bottom Type and Location
Sphaerotilus - (10 gm dry wt/m)
Municipal Sewage Sludge-
Outfall Vicinity
Municipal Sewage Sludge-
"Aged" Downstream of Outfall
Estuarine mud
Sandy bottom
Mineral soils
9
Range
-
2-10.0
1-2
1-2
0.2-1.0
0.05-0.1
20°C
Average
7
4
1.5
1.5
0.5
0.07

hydrologic fluctuations could  easily mask the effects of SOD on water  column
oxygen.

3.5.4  Summary

     There is a diversity of modeling and measurement techniques  used for
predicting oxygen consumption  by  sediments.  This diversity reflects the
need  for better  process descriptions  and measurement techniques.   Simple
zero-order model  formulations  have  been used, but first-order multi-
component reactions with a separate benthic organism component may be  needed
to accurately model sediment oxygen demand (SOD).
                                    187

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     Consequently,  it is suggested  that modelers  use  site-specific  SOD
rates.  In situ  methods such as described  in Whittemore (1984a)  and Markert
_et  al .  (1983) are more useful and credible than laboratory methods  at this
time.

     As an  aid  to estimating SOD  rates  and establishing reasonable ranges
for calibration,  the SOD literature values in  Tables 3-26,  3-27,  and 3-28
are  presented for rivers  and streams, lakes and reservoirs,  and  estuaries
and marine environments, respectively.  These should be considered only  as
order of magnitude estimates.

3.6  PHOTOSYNTHESIS AND RESPIRATION

3.6.1  Introduction

     Photosynthetic  oxygen production (P)  and respiration  (R)  can  be
important sources and sinks  of  dissolved oxygen in natural waters.  Many
models  simulate these processes directly in  terms of algal growth  and
respiration.   For example, net  algal growth is simulated  with the  QUAL-II
model (Roesner j5t  jj_. , 1981) using:

                                            )A                      (3-63)
where A = algal concentration,  mass/volume
      M = specific growth rate  of algae, I/time
      P = algal respiration rate, I/time
      a = algal settling rate,  I/time

     The net algal oxygen  production minus  consumption is  simulated by
QUAL-II as:

                                                                    (3-64)

where C  = dissolved oxygen concentration, mass/volume
                                   188

-------
        al  ~ oxygen  production  per unit  of  algal  mass,  mass  oxygen/mass
               algae
        a,,  = oxygen  uptake per  unit  of  algal  mass,  mass  oxygen/mass algae


The  stoichiometric  coefficients a.,   and  a. relate  algal  growth  and  death to
oxygen  production  and consumption.   Tables  3-29  and 3-30  summarize values of
these coefficients  used  in  different models.
               TABLE  3-26.   MEASURED  VALUES OF SEDIMENT  OXYGEN  DEMAND
                                      IN  RIVERS AND  STREAMS
SOD, g02/m  day
                            Environment
                                 Experimental  Conditions
                                                                                               References
0.022-0.92
0.09±0.02 (312"C
0.15±0.04 (6>20°C
0.20+0.03 (P28°C
0.29±0.07  (?36°C
0.18+0.05 (912"C
0.55±0.22 (@20"C
0.60±0.28 (I?28"C)
0.87+0.23 ((?36°C)

3.2-5.7
0.52-3.6
2-33


0.9-14.1


<0.1-1.4(@20°C)



0.27-9.8



0.10-5.30
(920°C)


1.1-12.8



0.3-1.4


0.20-1.2


1.7-6.0


1.5-9.8


4.6-44.
Upper Wisconsin River


Eastern U.S.  River



Southeastern  U.S. River
                       Fresh shredded tree bark
                       Aged shredded tree bark
Four eastern U.S.  rivers
downstream of paper mill
discharges
Eastern U.S.  river
downstream of paper
mill discharge

Northern Illinois rivers
(N = 89 stations)
Six  stations in
eastern Michigan rivers
New Jersey rivers
(10 stations)
Swedish rivers


Swedish rivers


Spring Creek, PA
74 samples from
from 21 English rivers

Streams
60-hour laboratory core incubation,
periodic mixing, 4°C, dark

45 day incubation of
0.6 liters sediment in
3.85 liters BOD
dilution water, light
10-liter incubations  in
aged  tap water, room
temperature, light

In-situ chamber
respTrometers, 22-27°C, light,
stirred at varying rates;
open-ended tunnel  respirometer,
in-situ. 22-27°C,  dark

In-situ respirometer
stirred at various rates
9-16  C, dark, 6 =  1.08

In-situ respirometry, dark,
T"=~5°~- 31°C
time   l>s-3 hours
       respirometry  1n
stirred chambers, 15-27 hours
dark,  19-25°C, 6 = 1.08

In-situ respirometer, dark,
30 minutes-8 hours, stirred.
Temperature unknown

In-situ respirometer, light,
stirred, 0-10°

Laboratory Incubations,
stirred, dark, 5-10°C

Laboratory incubators 1n
dark,  stirred, 20 C

Laboratory incubation of
cores; 15DC

Oxygen mass balance
Sullivan et^ a\_. (1978)


NCASI  (1981)
NCASI (1971)



NCASI (1978)





NCASI (1979)



Butts & Evans (1978)



Chiaro & Burke (1980)



Hunter e_t a]_. (1973)



Edberg & Hofsten (1973)


Edberg & Hofsten (1973)


McDonnell & Hall (1969)


Rolley & Owens (1967)


James (1974)
                                                     189

-------
                 TABLE  3-27.   MEASURED VALUES OF SEDIMENT  OXYGEN  DEMAND
                                      IN  LAKES AND RESERVOIRS
SOD, g02/m  day
                            Environment
                               Experimental Conditions
                                                                                           References
1-7

0-2.2



0.4-2.6


0.21-1.5
5.5 (31-32.5°C)
5.1 (22.5-25.6°C
2.1 (13.2-16.1°C

0.84-3.3

0.4-3.6
0.40-0.45
0.27

0.12-0.22


0.47-0.92



0.72-8.40

0.6-3.6


1.7-8.9



0.17-0.5


0.54-0.71


0.3-1.0

0.076-0.48


0.004-0.012
Green Bay, Lake Michigan

Fish culture ponds



Swedish lakes


Swedish lakes


Horseshoe Lake, IL



Lake Apopka, FL

Lake Apopka, FL



Hyrum Reservoir, UT
Lake Powell

Shagawa Lake


Swedish Lakes



Lakes

Hamilton Harbor,
Lake Ontario

Lake Mohegan, NY



Swedish lakes


Swedish lakes


Lake Hartwell, SC

Marion Lake, BC


Lake Superior
Lab incubation in darkness, 20 C

In situ respirometry with 100-cm
long plexiglass columns (dark pvc),
over 47 days. Temperature unknown

In situ resplrometer. light
stirred", 5-18

Laboratory incubations,
stirred, dark, 10-13°C

In situ respirometry, dark,.
stirred about 1 hour
Laboratory incubation of
cores at room temperature,
2-3 hours, light.  No stirring.
Laboratory flow-through system
(closed, 100 1 volume)

3-phase microcosms,
25DC, dark

In-situ chambers (1m ), at
7-inrTdepths; 12-14 C (est.)

Laboratory measurement with
undisturbed cores;  used in situ
temperatures

Oxygen mass balance

In situ chambers, 11-16°C
Measurement based on mass
balance, continuous flow
lab chamber, 22-32 C

In situ & laboratory measurements,
winter temperatures

Laboratory Incubation of
undisturbed cores, 8 C

Laboratory chambers, 18°C

Laboratory incubation of
undisturbed cores, no mixing,  15°C

Laboratory incubation of
undisturbed cores, 4UC
Gardiner et al_.  (1984)

Shapiro S Zur (1981)



Edberg & Hofsten (1973)


Edberg 4 Hofsten (1973)


Butts & Evans (1979)



Bel anger (1981)





Medine et aK (1980)


Sonzogni  et al_.  (1977)


Graneli  (1977)



James (1974)

Polak &  Haffner  (1978)


Fillos (1977)



Edberg (1977)


Andersen  (1977)


Brewer e_t al_. (1977)

Hargrave  (1969)


Glass &  Podolski (1975)
        In  addition to algal  respiration,  respiration  from  zooplankton  and
 nekton can  contribute  to  oxygen  depletion,  and  would  be  included in  Equation

 (3-64),  along with  additional  equations  to  describe their growth and  death.
 Models that  simulate algae and zooplankton  (such  as those in  Tables  3-29 and

 3-30)  are discussed in detail  in  Chapters 6  and  7  of  this  report.    This
 section  describes  methods to  predict P-R without  simulating  algal  growth  or

 respiration.   The methods  pertain  largely  to  streams  and  rivers,   and  are
 useful in that  they simplify  the  modeling approach.

                                               190

-------
     It should  be mentioned that some water  quality models  do not simulate
photosynthesis and algal respiration.  This approach  is valid where P=0 and
R=0.   Other  models simulate only daily average photosynthetic  oxygen
production  ("P) and daily  average respiration  (R).   If, on a daily average
basis,  P-R — 0,  these models would predict  little effect of algal activity on
dissolved oxygen.   However, if P and R are both  large numbers, then actual
dissolved oxygen  levels will be higher  during the day  and  lower at  night
than predicted  by the models.

3.6.2  Methods

     Table 3-31  summarizes the methods  reviewed to  predict photosynthetic
oxygen  production and respiration without  simulating  algal  growth.   The
methods  consist of either  single station methods or two-station methods.
Odum (1956) appears to be one of the first researchers to use this approach.
          TABLE 3-28.  MEASURED VALUES  OF SEDIMENT OXYGEN DEMAND
                      IN ESTUARIES  AND  MARINE SYSTEMS

SOD, g02/m day Environment
0.10±0.03 (@12°C) A North Carolinian estuary
0.20±0.05
0.22±0.09
0.37±0.15
2.32±0.16

1.88±0.018
0.14-0.68
(320 C)
028°C)
@36°C)
Buzzards Bay near raw
sevage outfall
Buzzards Bay control
5°C) Puget Sound
Experimental Conditions
45 day incubation of 0.6 liters
sediment in 3.85 liters BOD dilution
water, light

In-situ dark respirometers, stirred,
1^3 days. Temperature unknown

Laboratory incubations
References
NCASI (1981)



Smith e^aK (1973)


Pamatmat et al. (1973)
0.20-0.76 (10"C) sediment cores
0.30-1.52 (15°C)
0.05-0.10

1.25-3.9

0.02-0.49

0.9-3.0

0.4-0.71
0-10.7

0.3-3.0
San Diego Trough
(deep marine sediments)
Yaquina River estuary,
Oregon
Eastern tropical Pacific

The Baltic Sea

The Baltic Sea
Delaware Estuary
(22 stations)
Fresh & brackish waters,
In-situ respirometry for 5-13
hours, 4°C, light
Dark laboratory incubators,
stirred, 20°C
Shipboard incubations, 15°C
stirred, dark
In-situ light respirometer,
stirred, 10°C
Laboratory incubations, stirred,
dark, 10°C
In-situ dark respirometry,
13-14°C
In-situ respirometry, 0-18°C
Smith (1974)

Martin & Bella (1971)

Pamatmat (1971)

Edberg & Hofsten (1973)

Edberg & Hofsten (1973)
Albert (1983)

Edberg & Hofsten (1973)
               Sweden
Laboratory cores, 5-13 C
                                   191

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                  TABLE 3-29.   OXYGEN  PRODUCED PER  MASS OF  ALGAE
          Model
           Value
                                                       Reference
DOSAG3


QUAL-II


WASP

WASP


WASP

LAKE ECO

WQRRS

AQUA-IV

ESTECO

EAM

EAM

EAM

DEM
          Vermont-
          QUAL-II
                         1.4 - 1.
                         1.4   1.
                                         °
                  2
                                  mg algae (D.W. )
               mg  Op
          mg algae (D.W.)
                              2.67 mg 02/mg C

                              2.66 mg 02/mg C
                             .133 mg 02/mg  Chi-a

                              2.67 mg 02/mg C

                          1.6 mg 02/mg algae (D.W.)

                          1.6 mg 02/mg algae (D.W.)

                            1.6 - 2.66 mg 02/mg C

                         1.6 - 1.8 mg 02/mg algae (D.W.)

                         1.24 mg 02/mg algae (D.W.)

                         1.6 mg 02/mg algae (D.W.)

                         1.24mg • 02/mg algae (D.W.)

                         1.6 mg 02/mg algae (D.W.)
Duke & Masch (1973)


Roesner et al_.  (1977)


Di Toro & Connolly (1980)

O'Connor et al_. (1981)
O'Connor et al_. (1981)

Thomann & Fitzpatrick  (1982)

Chen & Orlob (1975)

Smith (1978)

Baca & Arnett  (1976)

Brandes (1976)

Porcella et. a].. (1983)

Bowie et a]_.  (1980)

Tetra Tech (1980)

Feigner & Harris (1970)
1.4   1.8 mg  02/mg algae (D.W.)      JRB (1983)
          Note:
             D.W.   dry weight
Both numerical  and  analytical  techniques  have  since been developed.   The
light-dark  bottle  technique and  benthic chamber method are  also  included in
the  table.

      As shown in Table 3-31, O'Connell  and  Thomas  (1965)   applied  a total
derivative  approach  for  P-R calculation, and compared the  results against  a
                                           192

-------
second procedure  using  a submerged  algal  chamber.   Respiration was  corrected
for  oxygen  consumption  by bacterial  oxidation.   Figure 3-17  compares the  two
methods for a station on the  Truckee River,  and  shows  good  agreement.

      O'Connor  and Di  Toro  (1970)  use  a half  cycle  sine wave or  a Fourier
series to find  the time  varying photosynthetic oxygen  production  rate.   In
                   TABLE  3-30.   OXYGEN CONSUMED  PER MASS  OF  ALGAE
        Model
         DOSAG 3

         QUAL-II

         WASP

         WASP

         WASP



         LAKE ECO

         WQRRS

         AQUA-IV

         ESTECO

         EAM

         EAM

         EAM

         DEM
         Vermont
         QUAL-II
            Value
                                                                  Reference
 1.6 - 2.3 mg 02/mg algae (D.W.)

 1.6 - 2.3 mg 02/mg algae (D.W.)

        1.87 mg 02/mg C

        2.0 mg 02/mg C

        2.0 mg 02/mg C
      .10 mg 02/mg Chl-a^

   1.6 mg 02/mg algae (D.W.)

 1.6   2.0 mg 02/mg algae (D.W.)

     1.6  2.66 mg 02/mg C

1.6 - 1.8 mg 02/mg algae (D.W.)

   .95 mg 02/mg algae (D.W.)

   1.6 mg 02/mg algae (D.W.)

   .95 mg 02/mg algae (D.W.)

   1.6 mg 02/mg algae (D.W.)


1.6 - 2.3 mg 02/mg algae (D.W.)
Duke  & Masch (1973)

Roesner et al_.  (1977)

Di  Toro & Connolly (1980)

Thomann & Fitzpatrick  (1982)

O'Connor e_t aj_. (1981)
O'Connor et a1_. (1981)

Chen  & Orlob (1975)

Smith (1978)

Baca  & Arnett (1976)

Brandes (1976)

Porcella et £]_. (1983)

Bowie et_ a]_. (1980)

Tetra Tech (1980)

Feigner & Harris (1970)


JRB (1983)
           This  is multiplied by an oxygen  limitation factor,
           saturation constant equal to 0.1 mg/1.
                                                            0,
                                        2   , where  K is a half-
         Note:
           D.W.  = dry weight
                                          193

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                          TABLE  3-31.   SUMMARY  OF  METHODS TO PREDICT  PHOTOSYNTHETIC  OXYGEN PRODUCTION
                                      AND  RESPIRATION WITHOUT  SIMULATING ALGAL GROWTH AND  DEATH
             Source
                                          Equations
                                                                         Symbols
                                                                                                                        Comments
      Odum (1956)
                           see comments
D'Connell  and Thomas (1965)    P  - R = Q + U |£ - k,(C -C) +
                                  9\.    Of,   C  5
                                                                 knN
UD
                                                                  see comments
                                                                  U  =  stream velocity
                                                                  k- =  reaeratlon rate

                                                                  C  =  dissolved oxygen
                                                                  Cs =  dissolved oxygen  saturation

                                                                  k1 =  CBOD decay rate

                                                                  L  =  CBOD
                                                                  k  =•  nitrification rate
                                                                   n
                                                                  N  =  NBOD
                              1.  Photosynthetic oxygen production  was based
                                  on  a graphical procedure.  Either  two
                                  stations or single station approaches
                                  could  be  used.   A method was also
                                  presented to find the  reaeratlon
                                  coefficient.

                              1.  P-R was found in two Independent  ways.   In
                                  the first, all terms in the dissolved
                                  oxygen mass-balance were found
                                  independently and then P-R was found as
                                  the only remaining term in the oxygen
                                  balance.   In the second  method, an algal
                                  chamber was placed on the  river bed.

                              2.  The two methods gave comparable results.

                              3.  The approach was  used on the Truckee
                                  River, where attached algae were  abundant.
O'Connor and Oi Toro (1970)    Half cycle sine wave:
                                      {-
                                      \p
                           p-/ni    (p    s/s      s
                               I 0 when  t$ + p < t <  t  + 1

                           Fourier series extension:


                           P =

                           where
                               bn = cos  (ni7p)
    = rate  of  photosynthetic
      oxygen  production,
      mg/(l-day)

n(x)=max1mum   rate   of
      photosynthetic  oxygen
      production, mg/(l-day)

    » time  of  day when source
      begins

    » fraction of  day when
      source is active
                                                                       (continued)
                                                                                                        1.  This approach  is  found In DIURNAL,  a
                                                                                                           stream model developed by O'Connor  and
                                                                                                           D1 Toro.

                                                                                                        2.  The approach is potentially applicable to
                                                                                                           any vertically mixed water body.

                                                                                                        3.  The method of Erdmann (1979a) was used to
                                                                                                           evaluate  P  and  R  for  a  wasteload
                                                                                                           allocation application on the Shenondoah
                                                                                                           River  (Deb  and Bowers,  1983) and  on
                                                                                                           Leatherwood  Creek, Arkansas (Deb et al..
                                                                                                           1983).

                                                                                                        4.  O'Connor and Di Toro (1970) applied the
                                                                                                           method to the Grand, Clinton, and  Flint
                                                                                                           rivers in Michigan, the Truckee River in
                                                                                                           Nevada,  and the  Ivel  River in Great
                                                                                                           Britain.   They used a trial and  error
                                                                                                           procedure to  determine Pm,  ts, P and R to
                                                                                                           best fit observed  diurnally varying
                                                                                                           dissolved oxygen data.

-------
                                                                  TABLE  3-31.    (continued)
               Source
                                              Equations
                                                 Symbols
                                                                                                                                  Comments
       Kelly, Hornberger, Cosby
         (1975)
                                    P - R
        Hornberger and  Kelly (1972)
tn
                                         A  = unknown coefficients          1.

                                         w « 2 77/48

                                         The An are determined based on    2.
                                         measurements of  dissolved oxygen
                                         at either one of two locations
                                         1n a stream.  They are chosen to    3.
                                         give a  "best  fit" between
                                         predicted and observed dissolved
                                         oxygen values.
                                              dissolved
                                              concentration
                                                                                                    oxygen
                                                                               U  - stream velocity

                                                                               k, = reaeratlon rate

                                                                               G  =• dissolved oxygen saturation
                                     A 48-hour cycle was  used so that values  at
                                     the beginning and  end of a  day are not
                                     constrained to be Identical.

                                     R 1s total respiration,  Including both
                                     algal  respiration and bacterial decay.

                                     The single  station  analysis can be used
                                     when the dissolved oxygen concentrations
                                     at the  upstream  and downstream stations
                                     are approximately the same.

                                     Three methods were examined to predict
                                     P-R:   a finite difference method,  an
                                     analytical  solution assuming P-R remains
                                     constant  over the time  Interval,  and a
                                     second  analytical  method assuming P-R
                                     varies  linearly over a time step.

                                     The analytical methods were preferred over
                                     the numerical  approach  from a conceptual
                                     point  of  view,  and because  time  steps
                                     smaller than the residence time through
                                     the stream reach  could be used.
        Erdmann  (1979a)
P - R -  k2(cs-c) -

where:
C   =•  concentration of dissolved
 nm   oxygen  at  station m and
      time n
                                     Dt
          C2rCll+C22~C12   C12~C11+C22 C21)U  = t 1 m e  of  sample  at
                                                downstream station

                                           :,  = time of sample at upstream
                                            1    station
                                                                                t   * travel time  between two
                                                                                r    stations
                                                                                k-   = reaeratlon  rate

                                                                                C   ^dissolved  oxygen
                                                                                 s    saturation

                                                                                C   = dissolved oxygen

                                                                           (continued)
Respiration  1s first computed at  night
when P  =  0.  Then P 1s computed during the
day using known R.

The method was applied to Charles River,
Massachusetts.

R 1s total oxygen consumption rate by both
algae and bacteria.

-------
                                                               TABLE  3-31.   (continued)

Source
Erdmann (1979b)
Equations
F- (ACu+ACd)
D + D .
R - k, ( „ ) + (AC +
Symbols
P = d a i 1 y average
photosynthesis


Comments
1. The method is a simplification of Erdmann
(1979a) and is used to predict dally
average values of P-R from data at two
stations .
10
cr>
                                                                           4Cu.4Cd
                     respiration

                     reaeration rate

                     travel time between
                     two stations

                     diurnal  range  of
                     dissolved oxygen at
                     upstream stations

                     dally   average
                     dissolved oxygen
                     deficit at upstream
                     and  downstream
                     stations

                    •dally   average
                     d1s s o 1 ved  oxygen
                     concentratlon at
                     upstream  and
                     downstream stations
                                                                                                            2.  The method was  applied to the Charles
                                                                                                               River, Massachusetts.

                                                                                                            3.  Some Important assumptions  Include
                                                                                                               constant  temperature and symmetrical
                                                                                                               diurnal curves.
       Gulliver, Mattke, Stefan
         (1982)
kzlcs-c)
U  =  stream velocity              1.

k, =  reaeration rate

C  =  dissolved oxygen

C  «  dissolved oxygen saturation   2.

0,  =  longitudinal disperson
     coefficient

                                3.
                                                                          (continued)
A finite difference computer model  DORM
was  used to route dissolved oxygen changes
between two stations  and includes  the
effects  of temperature variations  and
dissolved oxygen levels on respiration.

The model  was applied to experimental
stream reaches  in  the  U.S.  EPA's
Monticello Ecological Research Station,
Minnesota.

For the channels analyzed, 1t was found
that affects of longitudinal dispersion
were negligible.  However the results were
sensitive to reaeration, residence time
between the two  stations, and temperature
dependent processes (saturation  and
respiration rates).

-------
                                                        TABLE  3-31.    (continued)
       Source
                                     Equations
                                                Symbols
                                                                                                                        Comments
U.S.  EPA (1983)
light and dark bottle technique
U.S. EPA (1983)
benthic  chamber
1.  Light and dark bottles are suspended at
   various  depths in water and dissolved
   oxygen measurements are made at regular
   Intervals to  determine P-R.

2.  This method suffers  from  numerous
   limitations which include:

      •  only photosynthetic activity of algae
        1n water  column is measured
      *  the estimate of R includes algal and
        bacterial  respiration
      •  the P-R is a point estimate, rather
        than representative of a  reach.

1.   P-R  of attached  algae 1s measured  using  a
    clear benthic chamber and a covered (dark)
    chamber.

-------
their applications,  they used  a trial and error procedure to determine P-R
that best  fit  diurnally varying dissolved oxygen  data.   In the Deb  and
Bowers  (1983) application of  the same method,  Erdmann's approach (1979a)  was
used to evaluate  P-R.   The method  of Erdmann combines  all terms which
contribute  to  deoxygenation  (algal respiration,  CBOD decay and NBOD decay)
into a  single respiration term.  To find algal respiration,  CBOD and NBOD
are subtracted from total community respiration.

     Kelly et jfL, (1975),  also  shown in Table 3-31,  use  a  Fourier series,
but  with a 48 hour period.   The  coefficients A   are not true Fourier
coefficients but are based on a best fit between predicted and observed
dissolved  oxygen values.   Cohen  and Church (1981)  have more recently applied
these methods  to measure  productivity of algae in  cultures open to  the
atmosphere.
           +1.5
           +1.0
           +0.5
        £    0
        o>
        E
        cr
-0.5
            -1.0
            -1.5
             0000
                 i  i  i  i  i  i   i  i  i  i  i  i  i  i  i  i  i  i   i  i  i  i  i
          0400     0800    1200    1600
                      TIME OF DAY
2000
2400
        FINITE DIFFERENCE DATA
        ALGAE CHAMBER DATA
         Figure  3-17.
           Diurnal  variation of (P-R)  in  Truckee River near
           Station  2B  (O'Connell and Thomas,  1965).
                                  198

-------
     Erdmann (1979a,  19795)  has developed methods  to  predict time-varying
P-R  values and daily average values.  In the time varying  case the concept
of the Stokes total  time  derivative is used (see Figure 3-18).  The  total
derivative is the  sum of the time  derivative (dC/dt)  and the advective
derivative (U<9C/<9x).   The time derivative is evaluated  as  the average of two
times, and the advective  derivative is the average  between two stations.
        Figure 3-18.   Concept of Stokes total  time  derivative.  Here
                      DC/Dt = 0.43 mg Ci'h (from  Erdmann, 1979a).
     Gulliver _et _§]_.,  (1982)  provide  a  literature review  of the various
methods  used to predict P-R in streams.   They  also developed a computerized
model to determine P-R that includes dispersion.  However, they found that
effects  of dispersion were  negligible  for  their applications.  Several
applications of diurnal curve analyses not reported in Table 3-31 include
the  work  of Schurr and Ruchts (1977) who used a single station method to
predict monthly average P-R values, and the work of Simonsen and Harremoes
(1978) who used a two station approach to  predict P-R on a river in Denmark.
                                    199

-------
     The final two methods shown  in Table 3-31  are the light-dark  bottle
method  and  the  benthic chamber  method.  These methods measure  P-R of algae
in the water column (light-dark  bottles) and  of  attached algae  (benthic
chamber).   The  methods  provide single point  estimates that may  not be
representative of the water body  as  a whole.

     Some models simulate daily average  photosynthetic  oxygen production
rather than  time-varing production.  Erdmann (1979b) shows that, the daily
average photosynthesis oxygen products rates, P, can be approximated  by:

                         P" = 2ADO  (mg/i/nr)                         (3_65)
                              24

where ADO =  daily maximum dissolved  oxygen concentration minus daily
            minimum dissolved oxygen concentration, mg/1

This  approximation appears  to be  valid only for reaeration rates less than
0.2/day (Manhattan College, 1983).

     A second method of estimating  P is to integrate a sinusoidal curve that
represents the instantaneous  photosynthetic oxygen production rate.   The
result is:

                                -   2 Pmp
                                P  = -^r-                           (3-66)

where Pm = maximum  daily photosynthetic  oxygen  production rate,
          mg/l/day
      p  = fraction of day  when algae are producing oxygen,  decimal
          fraction

     The U.S. EPA (1983)  describes  a third method to estimate daily  average
production based on light-dark bottle measurements:
                                                                    (3-67)
                          COS (rrtj/f) - COS(n-t2f)

                                   200

-------
where P   = observed average  production rate between times t~ and t,
      AT  = (t2 - t^/24
      f   = number of hours  in day when oxygen  is  being produced
     Relationships  between photosynthet i c oxygen production  and
chlorophyll-a  have been developed  by a number of researchers.   While a
detailed  review  of these methods is outside  of the scope of this  section,
several of  the more commonly used  formulations  are summarized  here.
Megard jrt  al .  (1979)  developed the following expression for daily average
photosynthetic oxygen production:
                                                                   (3-68)
where I   =  light intensity at the water surface
      I   =  light intensity at depth z
      C,  =  chlorophyll-a concentration
       a
      £c  =  specific attenuation of light by chlorophyll-a
      EW  =  specific attenuation of  light by all causes other than
           chlorophyll-a
      Pm  =  maximum daily photosynthetic oxygen production  rate,
           mg/l/day

     Demetracopoulos and Stefan (1983) modified  this expression  to predict
hourly photosynthetic oxygen production,  and  used the expression in  a model
of the Mississippi  River.

     In experiments on the Sacramento-San Joaquin Estuary,  Bailey (1970)
correlated the  daily photosynthetic oxygen  production rate to  a number of
factors.  The resulting expression was:

                                T0.677
                  P   = 3.16 C  ^-i	+ 0.16T  -  0.56H               (3-69)
                   av        a   k
                                    201

-------
where P
      I
      k,
      T
      H
      C
av
average dally gross photosynthetic rate, mg/l-day
mean daily solar intensity, cal/sq.cm-day
light extinction coefficient, I/meter
mean temperature,  C
mean water depth, m
mean chlorophyll, mg/1
     Finally, simple relationships between chlorophyll-a  and, Pm  have been
proposed  (U.S.  EPA,  1983).   Figure 3-19  shows how Pm/Ca ratios are
           a
           O
        1.0

        0.9

        0.8

        0.7

        0.6

        0.5

        0.4

        0.3

        0.2

        0.1

         0-
                     Probable Range
                         \ „,--'"
                                                           Carbon
                                                             Ca
                                                           65
                                                           50
                                                           35
                                                  No nutrient limitation
                                    T
                                       T
                     10
                         12
                            14
                                16   18   20  22  24

                                WATER TEMPERATURE (°C)
                                            1	1	1	1—
                                            26  28  30  32
       Figure 3-19.  Algal productivity and chlorophyll relationships
                     for streams (U.S. EPA, 1983).
influenced by water temperature and algal carbon/Ca ratios.   For  a  typical
water  temperature (20°C) and a typical carbon/Ca ratio (50), Pm/Ca = 0.25.
However, this ratio is likely to vary between  0.1 to 0.6  for the  range of
conditions present in streams.
                                     202

-------
3.6.3  Data

     Table 3-32 summarizes  data  reviewed on photosynthetic oxygen production
and respiration.  Respiration  is  sometimes reported  as  total community
respiration and at other times  as  algal respiration.  As shown by the data,
photosynthetic oxygen production can be quite variable,  both over distance
and time.  In the Havelse  River, for example,  average photosynthetic oxygen
                                            o
production rates varied from 0.2 to 25.9 g/(m -day).   One of the primary
reasons for the variability was  because solar radiation  intensity changed  by
more than  an order of magnitude  between measurement  periods.

3.6.4  Summary

     Most water quality models that simulate photosynthetic  oxygen
production and  algal respiration  simulate algal  growth and respiration.
Stoichiometric coefficients are  used to convert growth  and respiration  to
oxygen  production and consumption.   Tables  3-29  and  3-30 summarize these
coefficients.

     Some river water  quality models use the approach that photosynthetic
oxygen production and respiration can be modeled without  the  necessity  of
simulating algal activity.   Rather, some type of  curve,  such as a sine curve
or more generally a Fourier series, is  used instead,  where  certain
parameters must be delineated to characterize the curve.

     Typically instream dissolved oxygen measurements at  two  stations are
used to generate P-R data.   Either finite difference or  continuous solutions
to dissolved oxygen mass  balance  equations are used.   Mhile light-dark
bottles or benthic chambers can  in principal  be used  to find the required
information, these approaches  are  limited in a number of ways.  The two
station methods are better in that  they  provide an  integrated estimate of
algal activity.

     However, two station methods should also be used  cautiously.  In a
sense, the methods  are  curve fitting techniques:  they are  used  to fit a

                                   203

-------
curve  based on dissolved  oxygen variation  between two  stations.  Typically
other rate  constants  such as  reaeration  rates,  carbonaceous BOD decay,
nitrogenous BOD  decay  are needed to fit  the curves.   Thus errors  in  these
coefficients are propagated into P-R calculations.  Also  care  should  be
taken  if results  are extrapolated  to other situations  (e.g., different
temperatures,  different  solar  intensities,  and different nutrient  loadings).
      TABLE 3-32.   PHOTOSYNTHETIC OXYGEN PRODUCTION AND RESPIRATION RATES IN  RIVERS
Reference
O'Connor and Di Toro (1970)
O'Connor and Di Toro (1970)
O'Connor and Di Toro (1970)
O'Connor and Di Toro (1970)
O'Connor and Di Toro (1970)
Thomas and O'Connell (1966)
Thomas and O'Connell (1977)
T Pm
River °C g/m -day
Grand, Michigan 28 12.7 37.6
Clinton, Michigan 21 13.2 22.9
Truckee, Nevada 28 12.9 26.
Ivel , Great Britain 16 24.
Flint, Michigan 28 4. 40.
North Carolina Streams
Laboratory Streams
Pav R
2 2
g/m -day g/m -day
4.4 13.0 9.3 12. 7a
4.2 7.3 9.3a
4.8 9.6 3.6 6.2a
9.0 4.6a
1.3 18. 4. 20a
9.8 21. 5b
3.4 4.0 2.4 2.9b
 Erdmann (1979a,b)

 Deb and Bowers (1983)
Charles, Massachusetts   19-25
Shenandoah, Virginia
                                           23
                                                4.8  17.
  Algal respiration only
  Total community respiration
  Measurements were made over the
                                      0.0   12.
0.0  36.l
0.9  5.9°
Kelly
Kelly
Kelly
Kelly
Kelly
Kelly
et
et
1*
et
et
et
Simonsen
Gul 1 iver
li-
al.
al_.
al_.
al-
ll-
and
ejt
(1975)
(1975)
(1975)
(1975)
(1975)
(1975)
Harremoes (1978)
al_. (1982)
Baker,
Virginia
Rappahannock, Virginia
S. Fork
Rivanna
South,
Mechums
Havelse
Rivanna, Virginia
, Virginia
Virginia
, Virginia
, Denmark
Experimental Channels 9-24 5. 45.
0.
6
2
2
45
.1
.1
.3
2.0
1
0.2
1.5
.3
25. 9C
14.8
1.
7,
3.
5.
5.
2.
4.8
2.6
.9
.3
,4
.4
,3
,6


b
b
b
b
b
b
22.
10.






9b
,7b
                         period of one year, and solar radiation varied by more than a factor of 10.
                                        204

-------
In cases where diurnal  water temperature changes are  great, diurnal  curve

analyses  should include temperature correction effects.


     All  of  the  approaches reviewed  in Table  3-31  have apparently  been

successfully  applied.   However,  no comprehensive comparison of the
approaches  against  the  same  data set  were found.   In  cases  where  a

significant  amount of  data is available  for analysis,  a computerized

approach  such as Kelly jrt  aj_.  (1975) or Gulliver et _al_.  (1982) appears  to  be

better than  trial  and error  procedures.   The method that has been most

rigorously tested is the  DORM model of  Gulliver et al_.  (1982).  Also  these
methods  can  be used when the distance between  stream stations is great,
because the models do not  assume that P-R remains constant over the travel

time between  the stations.


     Under  the  appropriate conditions the  simpler  approach of Erdmann
(1979a,b) can be used.  One restriction on using approaches where P-R  is

assumed  constant  over the time increment  is that the travel time between
stations must be  short  (i.e.,  1 to 3 hours)  so  that the  constant P-R

assumption is not violated.


3.7  REFERENCES

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High Strength Ammonia Wastewaters,  Journal of Water Pollution  Control
Federation,  Vol. 49, No. 3, March, pp. 413-421.  Albert, R.C.   1983.  Report
of Findings,  Delaware Estuary  Sediment Oxygen Demand Study.   Delaware  River
Basin Commission.  West Trenton,  New Jersey.

Albert, R.C.   1983.  Report of Findings,  Delaware Estuary Sediment Oxygen
Demand Study.  Delaware River  Basin Commission.   West Trenton, New  Jersey.

Alonso,  C.V., J.R. McHenry, and  J.C.S.  Hong. 1975.  The  Influence  of
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Alvarez-Montalvo,  A.,  R.A.  Ferrara,  and D.R.F.  Harleman.   Undated.
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Andersen, J.M.  1977.  Importance of  the Denitrification Process for the
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-------
Between Sediments and Fresh Waters.   Proceedings  of an Internati ona'i
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Bacon, R.G.,  W.W. Waddel, C.R.  Cole,  A.  Brandstetter, and  D.B. Cearlock.
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Banks, R.B. 1975.  Some Features  of Wind Action on Shallow Lakes, ASCE,  J.
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                                   206

-------
Bansal, M.K.   1975.  Deoxygenation in Natural  Streams.   Water Resources
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Bauer, D.P., R.E. Rathbun,  H.W.  Lowham.   1979.  Travel  Time, Unit-
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                                    207

-------
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                                    226

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                                     227

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                                    228

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                                    229

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                                    230

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                                 Chapter 4
                             pH AND ALKALINITY
4.1  INTRODUCTION
     The subjects of  pH  and alkalinity are becoming  increasingly important
as society  begins to deal  with acidic precipitation.   New  models developed
to analyze  effects of alternative controls on inputs of acidity to sensitive
aquatic environments use alkalinity as  a state variable,  then predict pH
from alkalinity  (Gherini _et _§_]_., 1984).  Earlier models did not contain  many
of the  processes  that affect pH,  and their predictive  capability was
adequate for  some,  but not  all, environments (e.g. Henriksen, 1979).   More
elaborate models now exist which take into account  a more  complete picture
of the  constituents that  comprise  alkalinity in the dilute systems that are
at risk from acidic precipitation (organic acids, other non-carbonate  weak
acids,  etc.)  and which compute other source-sinks  of  alkalinity and factors
that affect pH (Chen^t aj_.,  1984).

4.2  CARBONATE ALKALINITY  SYSTEM

     The carbonate system is of great importance in lakes, rivers,  and
estuaries.  Carbonate chemistry  of  natural waters has been described in
detail elsewhere (Stumm and Morgan, 1970, 1981;  Trussell and  Thomas, 1971;
Park,  1969; Butler,  1982; Chen and Orlob, 1972, 1975).  The carbon dioxide
                                           p
(CO,,) - bicarbonate (HCOl)  - carbonate (CO-  ) equilibrium is the major
buffer  system in  aquatic environments.  This  equilibrium directly affects
the pH,  which  in turn can  affect the biological  and chemical constituents of
the  system.   For example,  it may become necessary to simulate pH  and
alkalinity in order  to compute the  toxicant, un-ionized  ammonia   (see
Chapter  5),  or to determine  available concentrations of  metals
(e.g., Gherini et _al_., 1984).
                                    231

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     Since algae  use  carbon  dioxide  as  a carbon  source  during
photosynthesis, this is a nutrient which can reduce the  growth rate when
alkalinity is  low and other nutrients  are high (Goldman, ^t _al_., 1972).
Most models include a carbonate system representation which  calculates the
total inorganic  carbon (TIC)  as  the sum of  bicarbonate,  carbonate, and
carbon dioxide.  Carbon dioxide is  assumed to be produced by  respiration and
consumed  by algal  growth.  The major  source is  atmospheric exchange.

     The  major chemical species considered  to constitute  alkalinity are
dissolved  carbon dioxide, bicarbonate,  and carbonate ion,  together with the
hydrogen and  hydroxyl ions.  Mass balance equations assume  that ionic
equilibrium exists  and calculate carbon inputs  and outputs from a  pool of
total inorganic carbon  (TIC).  Conversions between different  carbon forms
are  based  on  stoichiometric equivalents.   The carbon dioxide form is
involved  in most of the important processes,  including surface  reaeration,
respiration, excretion, algal uptake, and organic  decay reactions.  However,
dissolved carbon dioxide combines with water to form carbonic  acid,  which,
in turn, dissociates  to bicarbonate ion, carbonate ion,  and  hydrogen ion.
Since the dissociation  reactions occur very  rapidly in comparison  to the
other biological  and chemical processes, dissolved carbon is modeled as the
                      2-
sum of CO,.,  + HCC>   +  C0_ , and is referred  to as total  inorganic  carbon
(TIC).

     Dissolved inorganic carbon is  derived  from several sources.   These
include  surface  reaeration; respiration by  fish,  zooplankton, benthic
animals,  and algae; soluble excretion by fish,  zooplankton,  and benthic
animals; and the  decay of organic  matter in the form of detritus, sediment,
and sewage  BOD.  Dissolved carbon is  removed  by assimilation  during algal
photosynthesis.

     Conceptually, the  mass balance equation  defining these relationships
for the EAM model  (Tetra Tech, 1980)  is  expressed  as follows:
                                   232

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                                                           ^      A
                                                         sed)  I  sed
1=1  j=l \
n_^  /
         • Zr • •  C.
                                 zoo) +  "f^  (aV  Ari'  Calg)
                \  (zooi ' Zdexi ' Czoo) +  (ben) (Bdex)  (Cben)
             +   BOD   KBOD  CBOD
                 ^   '  \    / \
             +   /Rrn  \ /CO     - CO \  /Area)                        (4-1)
                 \ LU2/ V   sat     V  \     /

             =  detritus  decay + sediment decay + fish  respiration
                + benthic  animal respiration + zooplankton  respiration
                + algal respiration + fish excretion +  zooplankton excretion
                + benthic  animal excretion - algal assimilation
                + BOD  decay + surface reaeration.

      Although Equation (4-1) is a  substantially complete picture of TIC
dynamics in  an aquatic system, most models do not contain the  same degree of
complexity.   However,  whether multi-compartmented or few compartments, the
general  aspects of  the process are modeled similarly.   Also,  the  inputs and
outputs can  be based on C0? with suitable stoichiometric conversions (e.g.,
Di Toro and  Connolly,  1980) rather than TIC.

      Surface reaeration  of CO^ from atmospheric sources  is  done  in a way
similar  to  oxygen  (Section 3.2).  However, only minimal  effort  to measure

                                    233

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C02 reaeration is necessary  and  literature values have  been used  (Emerson,
1975; Liss, 1973).   Reaeration occurs only at the surface  of the water body,
and is a function of the  carbon  dioxide saturation  level.  The saturation
concentration is  a  function of the water temperature  as  it affects the
Henry's law constant (KH) for computing COp  .:

                            C02sat  = KH  PC02                          (4-2)

where pC02  is the partial  pressure of  C02 in  the atmosphere (generally
0.00033 atmospheres  is used) and
              KH =
                          2385.73  -  14.0184 + 0.0152642 TK
                             T
K                           J          (4-3)
where MCQ   = 44,000 mg/mole,  C02
      TK    = temperature in K = 273.15 + °C
      KM    = Henry's law constant,  mg/(liter-atm)

     After computing  the total inorganic carbon  according to  the mass
balance in  Equation (4-1),  the dissolved carbon  dioxide concentration  is
calculated using relationships derived from the  equilibrium constants of the
dissociation reactions.  The reactions involved  are:

                     H2C03^± HCO~  + H+            KI                (4-4)

                     HCO~;=±C03  +  H+              K2                (4-5)

                     H00=± H+ +  OH"               K                 (4-6)
                      f. ^                           w

where the  equilibrium constants are defined as
                             KI =[_n^3JL" J                          (4_7)

                                   [H2C°3]

-------
                                                                     (4-8)
                                 [HCO-]

                                = [H+] [OH']                          (4-9)
The equilibrium constants K^ K2, and KW vary with temperature according to
the following relationships  (Tetra Tech, 1979):

                [l4.8435 - 0.032786 TK -  (3404.71/TK)]
         Kx  =  10                                                    (4-10)

                [6.498 - 0.02379 TK - (2902.39/TK)1
         K2  =  10                                                    (4-11)

                ["35.3944 - 0.00835 TK - (5242. 4/TK  - 11.826 log (TK)J
         Kw  =  10                                                    (4-12)

     In a carbonate system,  the alkalinity (alk) is calculated according to
the mass balance equation:
      alk  =  alkalinity = |~HCO~]  + 2 [cOg]  +   [oH'J  -  [H+]         (4-13)
     Other processes can affect alkalinity in  aquatic systems.  Addition of
acids and  nitrification reduce alkalinity,  and uptake of  nitrate by algae
increases  alkalinity.  Because of the magnitude of the ammonia concentration
in waters  receiving municipal effluents,  nitrification can affect alkalinity
substantially,  generating  2  equivalents  of  acid (H  )  per  equivalent of
ammonia oxidized  (see Section 3.4).   Similarly  in eutrophic waters, nitrate
uptake can  increase  alkalinity  by the production  of approximately 1
equivalent of  base (OH") per equivalent of  nitrate taken up by plant cells.
These  corrections would  be of consequence  in  low alkalinity waters  (less
than 200^eq/l),  and would be applied to  Equation (4-13).

     Once  the  total inorganic carbon  and alkalinity have been determined
using the  mass balance equations (4-1, 4-13),  the hydrogen ion concentration
                                    235

-------
 can be calculated by trial  and error solution of the following relationship:
 After  [H ]is determined,  it is substituted into the expression for CO,,,
 which  can then be solved  directly for the dissolved COp concentration:

                                                                   (4-15)
                           Ki   K-l •  l\n
                        1  + — +
                          V]   [H+l2

     Not  all models compute inorganic carbon species or pH.  Generally these
computations  have been made primarily in lake systems where they are of
significance  in  acid precipitation  or are used  for additional  model
verification  as in  Di  Toro  and Connolly (1930).   In  all cases,  the
formulations are based on  the  above derivations, although  the computation
details may differ  from  model to model.  Water  quality models that contain
the COp, alkalinity, pH formulations  include those discussed  in  the
following references:

            Smith, 1978                   WQRRS
            Thomann et jfl_. , 1974           LAKE-3
            Di Toro and Connolly, 1980     Lake  Erie Model
            Scavia,  £t _al_. , 1976           Lake  Ontario Model
            Tetra Tech, 1980               EAM
            WES, 1982                     CE-QUAL-R1

4.3  EXTENDED ALKALINITY APPROACH

4.3.1   Definition of Extended  Alkalinity

      The mass balance equation (4-13) has ignored  several H -ion acceptors,
and is appropriate in many  instances.  In very  low  alkalinity waters,
                                   236

-------
however, the  concentration of  these neglected  H  -ion acceptors  can  be
significantly large.  The  neglected H -ion  acceptors include  organic
substances  with carboxyl and phenolic  hydroxyl groups,  for example:
         R-COO" +
                         R-COOH  (organic acids)
                                                                   (4-16)
and the monomeric aluminum species  and their complexes,  for  example,
                           A1
                                  3+
      and
                                                                   (4-17)
          Al-R
                        A1
                               3+
                                                                    (4-18)
An extended alkalinity relationship would  include the alkalinity  associated
with  water itself, the carbonate system, the monomeric aluminum  system and
its organic complexes, and dissolved organic  acid  anions.  The  dissolved
organic  carbon alkalinity  can  be represented by a triprotic  (H^R-i) and/or
monoprotic (HR, ) model organic acid with fixed dissociation constants  and a
fixed number of  acid-base functional groups  per unit mass  of carbon
( eq/mgC).  The components of the total alkalinity,  as represented by the
H -ion acceptors, are given below:
Alk = AlkH  0  + Alkc + AlkR  + AlkR   + AlkA1
      water  carbonate   organic
              system      acids
                                         aluminum system
                                                                   (4-19)
where
AlkH n  =  [OH"]  - [H+]
                                                                   (4-20)
Alkc    =  [HCO~]
Alk
                            3[R3']

                              237
                                                                    (4-21)

                                                                    (4-22)

-------
     AlkR    = [R-
     AlkA1   = [A1(OH)2+] + 2[Al(OH)p.+ 3[A1(OH)°] + 4[A1(OH)']      (4-24)

     AlkA1.Q - 3[A1  Rj + [A1R2+] +  2[Al(R2)+] + 3[A1(R2)3]           (4-25)

     An  alternative  representation of  solution-phase alkalinity, which is
mathematically equivalent to the above is given as follows,
                   Alk=  2k ZkNk = ICB - 2CA                       (4-26)

where SCD = the sum of the base cations

                                            K+]  +  [wj]          (4-27)

      2C. = the sum of the strong acid anions

          = 2 [so42'] +  [NO-]  +  [cr]                            (4-28)

     The derivation is based on the  mass balance equation and the  solution
electroneutral ity  condition.   Figure (4-1) shows the  equivalence  for
lakes in the State of  Washington.

4.3.2 Modeling Extended Alkalinity

     The concept of extended alkalinity  has  been incorporated in a model
called PHCALC.   This  model  was developed primarily  for the ILWAS model
(Tetra  Tech,  1983),  and  was  later modified into an  interactive FORTRAN
program  to compute any one of the following options:  pH,  alkalinity, total
inorganic carbon  (TIC)  and  "solution equilibration".   The solution
equilibration approach  is  similar to the approach  for pH,  except that
alkalinity can  be  adjusted for gibbsite precipitation or dissolution.
Table 4-1 shows the  list of required parameters for any given option.

     All the  concentrations on the  left-hand-side  of  Equations  (4-20)
through  (4-25)  can be expressed in  terms of ionization  fractions  and
                                   238

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   320
                   KEY:
                    LAKES IN STATE
                    OF WASHINGTON
   -40
      -40
         120     180    200    240
REPORTED ALKALINITY (/ieq/D
280    320
       Figure 4-1.  [£CR-SO. ] plotted against reported alkalinity
                    (from Gherini  et al_.,  1984).
temperature-dependent  dissociation constants.   Fluoride  and  sulfate
concentrations are required for the determination of their  complexations
with aluminum.

4.3.3  Equilibrium Constants and Solubility Products
     The equilibrium  constants  used in PHCALC are  obtained  by first
expressing a thermodynamic temperature dependence for  a  related  constant,
1C,:
         239

-------
TABLE 4-1.   OPTIONS  AND THEIR REQUIRED INPUT PARAMETERS FOR PHCALC

Options*            	Parameters Required to be Specified	
  pH                Alk, TIC or EQp Aly, OACp OAC2, F, S042", T

  Alk               pH, TIC or EQp Aly or EQ2, OACp OAC2, F, S042", T

  TIC               pH, Alk, A1T, or EQ2, OACp OAC2, F, S042", T

  EQ                Alk, TIC or EQp Aly, EQ2, OACp OAC2, F, S042", T

Definition  of Parameters:
Alk          alkalinity
TIC          total  inorganic  carbon
EQ           equilibration  of a  solution with A1(OH)_
A1-,          total  aluminum
OAC,         total  organic  acid  (1)
OAC2         total  organic  acid  (2)
F            fluoride concentration
   p_
SO,          sulfate concentration
T            temperature, °C
EQ,          ratio  of  TIC  to air-equilibrated TIC (specified  for  open
             system)
EQ2          -log (Ksp) for A1(OH)3 mineral or one of the following minerals
             for the equilibration with gibbsite

             AG - amorphous gibbsite          (pKsD = 31-19)
             MG - microcrystalline gibbsite   (pKg  = 32.64)
             NG - natural gibbsite            (pK$  = 33.22)
             SG - synthetic gibbsite          (pK$  = 33.88)
*0ptions are the parameters  to  be  computed
                                   240

-------
                Iog10 K.  =  a + y + cT + dlog1QT
                                                           (4-29)
     The  constants a,  b,  c  and d are given as  follows
 w
       6.0875
       545.56
            -17052
            -4470.99   -0.01706
          0.12675
   d       Reference
   0       Stumm & Morgan,  1981

-215.21    Loewenthal  & Marais,
          1978
       -6.498
            2902.39    0.02379
                                  Loewenthal & Marais,
                                  1978
K
 'H
-14.0184
2385.73    0.0152642
   0
Stumm &  Morgan, 1981
       K  , K,, and.Kp are dimensionless while  KM  is in moles liter"  atm~ .
KM has to be multiplied by RT to convert to a dimensionless form.  R  is the
universal  gas constant and T is the absolute temperature  in  degrees  Kelvin
in the range of 273 K to 313 K.

       The solubility products used in the equilibration with  gibbsite were
shown earlier in Table 4-1.

4.4   SUMMARY

      Two  approaches have  been presented for the relationship  of  total
inorganic carbon, alkalinity and pH.   For waters with low dissolved organic
carbon (with little color) and high  alkalinity (al k2l200^eq/l) ,  the
conventional alkalinity definition  is  recommended.  For waters  with high
dissolved organic  carbon and waters with  alk  <200 ^ieq/1  where  the
alkalinities  contributed  by aluminum  and  organic acids are  no  longer
negligible, the  extended  alkalinity approach is  recommended.   The
equivalence between  the  expression Alk = SC_ - 2C.  and  the  extended
alkalinity definition provides a convenient tool  in alkalinity  evaluation.
                                   241

-------
4.5  REFERENCES

Butler, J.N.   1982.   Carbon Dioxide Equilibria  and  their Applications.
Addison-Wesley Pub.  London. 259 p.

Chen,  C.W.,  and  G.T.  Orlob.  1972.  Ecological  Simulation for Aquatic
Environments, Report to Office of Water Resources Research OWRR C-2044,
Water Resources Engineers  Inc., Walnut  Creek, California.

Chen,  C.W.,  and  G.T.  Orlob.  1975.   Ecologic  Simulation of  Aquatic
Environments.  Systems  Analysis and Simulation  in Ecology, Vol. 3, B.C.
Patten, (ed.).  Academic Press, New York, N.Y. pp.  476-588.

Chen,  C.W.,  S.A. Gherini,  J.D.  Dean, R.J.M. Hudson,  and  R.A. Goldstein.
1984.  Development and  Calibration of the Integrated  Lake-Watershed
Acidification Study Model.  In Modeling of Total Acid Precipitation Impacts.
J.L.  Schnoor  (Ed.),  Butterworth, Boston, Mass.

Di Toro, D.M., and J.P.  Connolly.  1980.  Mathematical  Models of Water
Quality in Large Lakes  Part 2:  Lake  Erie, EPA-600/3-80-065, U.S.
Environmental Protection Agency, Duluth, Minnesota.

Emerson, S.   1975.   Gas  Exchange Rates in Small  Canadian Shield  Lakes.
Limnol. Oceanogr.  20:754-761.

Gherini, S.A., C.W.  Chen,  L. Mok,  R.A.  Goldstein, R.J.M.  Hudson, and G.F.
Davis.  1984.   The ILWAS Model: Formulation and Application.   In  the
Integrated Lake-Watershed  Acidification Study.  4:  Summary of Major Results.
EPRI  EA-3221.  p.  7-1 to 7-46.

Goldman, J.C., D.B.  Porcella, E.J. Middlebrooke, and D.F.  Toerien.   1972.
Review Paper:  The Effect  of Carbon  on Algal  Growth:   Its  Relationship to
Eutrophication.  Water  Res. 6:637-679.

Henriksen, A.  1979.  A Simple approach For Identifying and Measuring
Acidification in Freshwater.  Nature, 278, 542.

Liss, P.S.   1973.  Processes of Gas Exchange Across an Air-Water Interface.
Deep-Sea Res. 20:  221-238.

Loewenthal, R.E., and  G.V.R. Marais.   1978.  Carbonate Chemistry of Aquatic
Systems:  Theory and Application.   Volume 1.  Ann Arbor Science, Michigan.

Parks, P.K.  1969.  Oceanic C0? System:   An Evaluation of Ten Methods of
Investigation: 179-186.          c

Scavia, D.,  B.J. Eadie,  and A.  Robertson.  1976.   An Ecological Model  for
Lake  Ontario Model Formulation, Calibration, and Preliminary Evaluation.
NOAA  Technical Report ERL  371-GLERL 12.  NOAA.  Boulder Colorado.   63 p.

Smith,  D.I.  1978.  WQRRS, Generalized  Computer Program for River-Reservoir
Systems.  User's Manual  401-100, 100A:  U.S. Army Corps of Engineers,
Hydrologic Engineering  Center (HEC), Davis, California.  210  pp.

                                  242

-------
Snoeyink, V.L.,  and D.  Jenkins.  1980.   Water Chemistry.   New York.  John
Wiley & Sons.

Stumm,  W.,  and  J.J. Morgan.  1970.  Aquatic Chemistry.  (New York: Wiley-
Interscience).

Stumm,  W.,  and  J.J. Morgan.  1981.  Aquattc Chemistry, 2nd Ed., Wiley, New
York.

Tetra Tech,  Inc.  1979.   Methodology for  Evaluation of Multiple Power Plant
Cooling System  Effects, Volume II:  Technical  Basis for Computations.
Electric Power Research Institute, Report  EPRI EA-1111.

Tetra Tech,  Inc.  1980.  Methodology for Evaluation of.Multiple Power Plant
Cooling System  Effects, Volume V.  Methodology Appl ication to Prototype-
Cayuga Lake.  Electric Power  Research Institute, Report EPRI  EA-1111.

Tetra Tech,  Inc.  1983.   The Integrated Lake-Watershed Acidification Study,
Volume 1:  Model Principles  and Application  Procedures.   Electric Power
Research Institute.  Report EPRI EA-3221.

Thomann, R.V.,  D.M. Di  Toro, R.P. Winfield,  and D.J. O'Connor.  1975.
Mathematical  Modeling of Phytoplankton  in  Lake Ontario.   I. Model
Development  and Application.  EPA-660/3-75-005.  USEPA, Corvallis,  Oregon,
97330.  177  p.

Trussell, R.R.,  and J.F. Thomas.  1971.  A  Discussion  of the Chemical
Character of Water Mixtures.  J. American  Water Works Assoc.  63(1), 49.
                                   243

-------
                               Chapter  5
                               NUTRIENTS
5.1  INTRODUCTION
     Certain  elements  are referred to  as  nutrients because they  are
essential to the life processes of aquatic organisms.  The major nutrients
of concern  are  carbon,  nitrogen, phosphorus,  and silicon.  Silicon is
important only  for  diatoms,  one of the major  components of the algal
community.  Other micronutrients such as iron, manganese, sulphur, zinc,
copper,  cobalt, and molybdenum are also  important.   However, these  latter
nutrients are  not considered in water quality models because they  are
required only in trace amounts and they  are  usually present in quantities
adequate to meet the  biochemical requirements of the organisms.

     Nutrients are important in water  quality modeling for several reasons.
For example, nutrient dynamics  are critical components of eutrophication
models since nutrient availablility is usually the main factor controlling
algal blooms.   Algal  growth  is  typically limited by either phosphorus or
nitrogen, with the exception of diatoms which  are  often silicon Limited.
Some blue-green  algae can  fix nitrogen and  are  therefore not limited by
nitrogen.  Carbon is  usually available in excess although in some cases it
may also be limiting.   Carbon is also  important because of  its role in the
pH-carbonate system,  as discussed  in Chapter 4.

     Nitrogen  is important in water quality modeling for reasons other than
its role as a nutrient.   For example,  the oxidation of ammonia to  nitrate
during  the nitrification  process  consumes  oxygen and may represent a
significant portion  of  the  total BOD.  Also,  high  concentrations  of
unionized ammonia can be  toxic to  fish and other aquatic organisms.

                                   244

-------
5.2  NUTRIENT CYCLES

     Nutrients are present  in several  different forms in aquatic systems:
     •    dissolved inorganic nutrients
     •    dissolved organic nutrients
     •    particulate organic (detrital)  nutrients
     •    sediment nutrients
     •    biotic  nutrients (algae,  aquatic  plants, zooplankton, fish,
         benthic organisms)

Only the  dissolved inorganic forms are available  for algal growth.  These
include dissolved C0?,  ammonia, nitrite, and  nitrate  nitrogen,
orthophosphate, and dissolved silica.

     Each nutrient  undergoes  continuous  recycling between the major forms
listed  above.  For example, dissolved  inorganic nutrients are removed  from
the water  column by algae and aquatic plants during photosynthesis.  These
nutrients are distributed to the other aquatic organisms through the  food
web.   Dissolved  inorganic nutrients are  returned to the water through the
soluble excretions of all organisms, the decomposition of organic detritus
and  sediments,  and the hydrolysis  of  dissolved organic nutrients.   In
addition,  dissolved CCL and N2 gases exchange with  the atmosphere.
Suspended  particulate  nutrients  are generated through the particulate
excretions  of aquatic animals and  the death of planktonic organisms.
Organic  detritus and phytoplankton which settle to the bottom contribute to
the sediment nutrients.  Decomposition of  suspended organic detritus  and
organic  sediment releases both dissolved organic and dissolved inorganic
nutrients to the water.

     Many of the above  interactions are  shown  in  Figure 5-1 for carbon,
nitrogen, and phosphorus  and in Figure 5-2  for silicon.  Figures 5-3 and 5-4
present more detailed descriptions of  the nitrogen and phosphorus cycles.

     In. addition to  the internal recycling  of nutrients within the
waterbody,  nutrients are also introduced through wasteloads  (both point and
nonpoint  sources),  river or tributary  inflows, runoff, and atmospheric
precipitation.
                                  i-T1 D

-------
                                 TOTAL
                                INORGANIC
                                 CARBON
Figure 5-1.   Nutrient interactions for carbon, nitrogen, and phosphorus
             (from Tetra Tech, 1979).
                                  246

-------
5.3  GENERAL MODELING APPROACH FOR ALL NUTRIENTS

     Nutrient dynamics are governed by the following processes;

     •    dissolved  inorganic  nutrients
          -  photosynthetic uptake
          -  excretion
          -  chemical transformations  (e.g.,  oxidation  of NH.J
          -  hydrolysis of dissolved organic  nutrients
          -  detritus decomposition
          -  sediment decomposition and release
          -  external  loading
                                       SETTLING   SETTLING
                                          IN        OUT
              ^RESPIRATION,
  Figure 5-2.   Nutrient interactions for silica (from Tetra Tech, 1979).

                                      247

-------
co
                                                                                VaATIZATION
                                                                                   OFNHj
                     ATMOSPHERIC
                       EXCHANGE
                          I
                     LIVING PARTICULAR N
                                                                                                                 I
FIXATION
                      DISSOLUTION
   f
UPTAKE j
    RELEASE
      1
                           MOLECULAR
                          NITROGEN (N?)
                                                          RESPI
                                     AMMONIFICATION
                                        DENITRIFICATION
                                                           NITRIFICATION
                 DENITRIFICATION
                            LJL
                                                                      RELEASE
N03-N
NITRIFICATION
DENITRIFICATION

N02-N
                                            UPTAKE
                                           FIXATION
NATION
     RESPIRATION
                                  SOLUBLE
                                  ORGANIC N
                                                                                     SORPTION
                                     DESORPTION
                                         I
                                                                                           NON-LIVING
                                                                                          PARTICULATE N
                                                              T
                                                                                I
                                   |              SETTLING                        I
                                      ~
                                                       SEDIMENT PROCESSES

                                                    ASSIMILATION
                                                    FIXATION
                                                    NITRIFICATION
                                                    DENITRIFICATION
                                                    DECOMPOSITION
                                                    AMMONIFICATION
                                                    LOSS (SEDIMENT TRAPPING)
                                 Figure  5-3.   Nitrogen  cycle  (from Baca and  Arnett,  1976).

-------
                  UPTAKE
1X1
-pi
1
1


1
EASE |
.IVING PARTICULATE P UPTAKE
i |
1
1
RELE
i
ASE UP
t
At
n I /
/

RELEASE ^
(E SOLUBLE COMPLEX P
                     SOLUBLE
                     ORGANIC P
        HYDROLYSISi

               \J
                                                                             J
                  r
DISSOLVED REACTIVE
PHOSPHORUS (P0
-------
     •    dissolved  organic nutrients
          - excretion
          - hydrolysis
          - detritus decomposition
          - sediment decomposition and release
          - external loading

     •    particulate organic nutrients
          - particulate excretions
          - plankton mortality
          - decomposition
          - settling
          - zooplankton grazing
          - external loading

     •    sediment nutrients
          - detritus settling
          - algal settling
          - sediment decomposition and release

Only processes  affecting  the  abiotic forms of nutrients are discussed in
this chapter  since the biotic components  of water quality models  are
discussed in Chapters 6 (Algae)  and 7 (Zooplankton).

     Nutrients are  modeled by using a system of  coupled  mass  balance
equations  describing each  nutrient compartment  and each  process listed
above,  plus the transport processes of advection and dispersion discussed in
Chapter  2.  The general equations for each nutrient, omitting the transport
and external loading terms, can  be expressed  as  follows:

     dissolved inorganic nutrients:

       at = - Vs * fl es * Kl S'  - K2 S * Korg  Sorg * f2 Kdet Sdet
              f3 Ksed Ssed
                                    250

-------
     dissolved organic nutrients:

            dS
                             es - Korg Sorg + ^  '  V  Kdet Sdet
                         ~ f3> Ksed Ssed
     particulate organic nutrients:

                   dS
                         - ep * MP - Kdet Sdet -  Ks  Sdet ' Gz
     sediment  nutrients:
                              ' Ks Sde«t * \ - Ksed  Ssed
where S    = dissolved inorganic nutrient concentration, mass/volume
      S1    = another  inorganic form of the nutrient  which decays to the
            form S  (e.g., NH,   NO,) , mass/ volume
      S    = dissolved organic nutrient concentration, mass/volume
      Sdet  = susPendecl particulate organic  nutrient concentration,
            mass/ volume
      S  .  = organic  sediment nutrient concentration, mass/volume
      K,    = transformation rate of S1 into S,  I/time
      K~    = transformation rate  of  S  into  some other dissolved
            inorganic form of the nutrient,  I/time
      K    = hydrolysis rate of dissolved organic nutrient, I/time
      Kdet  = decomP°s"itlon rate °f particulate  organic nutrient, I/time
      K  ,  = decomposition rate of organic  sediment  nutrient, I/time
      K    = settling rate for particulate  organic nutrient, I/time
      V    = photosynthetic  uptake  rate  for  nutrient S, mass/volume-
            time
      e    = soluble  excretion  rate of nutrient  by  all  organisms,
            mass/ volume-time
      f,    = fraction of soluble excretions which are inorganic
                                    251

-------
      f    = fraction  of detritus decomposition products which are
            immediately available for algal uptake
      f,    = fraction  of sediment decomposition products which are
            immediately available for algal uptake
      e    = particulate excretion rate  of nutrient by all  animals,
            mass/volume-time
      M    = total rate of plankton mortality, mass/volume-time
      G    = detritus grazing rate by zooplankton, mass/volume-time
      A    = algal settling rate  to sediment, mass/volume-time

     Note  that all of  the  transformations between  the  various abiotic
nutrient  compartments are described by first-order kinetics.  This approach
is  used  in almost  all water  quality models.  Nutrient models differ
primarily in the specific nutrients simulated (i.e.,  C, N, P, and Si)  and in
the number of  compartments  used to  describe each nutrient cycle  (i.e.,
dissolved inorganic forms  such  as  NH,, NCL, and NO.,;  dissolved organic
components; particulate organic components; sediments;  and biotic components
such as algae and zooplankton).

     For  example, many  models  omit carbon  since it  does not limit algal
growth in most  situations.  Silicon is generally  modeled  only when diatoms
are simulated as a separate phytoplankton group.

     The  nutrient cycles are often simplified by  combining or omitting  some
of the forms described above.  For  example, many models do not simulate
sediment nutrients  explictly  with  a  mass balance  equation  such  as
Equation (5-4).   Instead,  user-specified sediment  fluxes are specified in
Equations (5-1) and (5-2).  Dissolved organic nutrients are also left  out of
most models.  In these cases, the decomposition products  of the detritus and
sediments as well  as  all  soluble  excretions go directly to the dissolved
inorganic  nutrient  compartments.  This in effect combines the suspended
particulate and dissolved organic compartments into a- single "unavailable"
nutrient  compartment which decays to produce available  inorganic forms.
                                    252

-------
     Nitrogen models also differ  in the forms of inorganic  nitrogen which
are included,  as  well as in some of the processes modeled.   For example,
some models include only ammonia  and nitrate, rather than the full  oxidation
sequence of ammonia to nitrite to nitrate.  While most models include the
nitrification reactions, only  a few include denitrification.   Also, only a
few models  include nitrogen-fixation by blue-green  algae.

     Sediments and particulate organic detritus are often modeled as single
compartments,  rather than having a separate compartment for each  nutrient.
In  this case,  the corresponding  compartments  for each  nutrient  are
determined  from  the  product  of the  total  sediment  and  detritus
concentrations  and the stoichiometric  ratios for  each nutrient.   The
stoichiometric  ratios are generally the same as  those used for algae (see
Section 6.3 of  Chapter 6) so that  mass is conserved during  nutrient
recycling.

     Table  5-1 presents a comparison of the various nutrient forms  included
in  several models.   Transformation  processes and  the corresponding rate
coefficients for each specific nutrient  are discussed below, along with
model formulations for nutrient uptake,  excretion, and sediment release.
Formulations for plankton mortality and zooplankton grazing are discussed  in
Chapters 6 and  7.  Settling formulations for particulate organic detritus
are essentially the same as the simplest formulations  used for phytoplankton
settling described in Chapter  6 (i.e.,  the settling rate equals  the user-
specified settling velocity divided by the depth of the model segment).

5.4  TEMPERATURE EFFECTS

     Temperature influences the rates of all of the nutrient transformation
processes  discussed above.  All of  the first-order rate coefficients  in
Equations (5-1) through (5-4)  are therefore temperature dependent.  Almost
all models use  the exponential Arrhenius or van't Hoff  relationship  to
describe these effects.  A reference temperature of 20°C is usually assumed
when specifying each rate coefficient, resulting in the following equation:
                                    253

-------
                                        TABLE  5-1.   COMPARISON OF NUTRIENT  MODELS
Model
(Author)
AqUA-IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
DEM
DOSAG3
EAM
ESTECO
EXPLORE-1
HSPF
LAKECO
MIT Network
QUAL-I1
RECEIV-II
SSAM IV
WASP
WQRRS
Bierman
Canale
Jorgensen
Lehman
Nyholm
Scavia
Nutrients
C N
X
X X
X X
X X
X X
X
X
X X
X X
X X
X X
X X
X
X
X
X
X X
X X
X
X
X
X X
X
X X
Modeled
F Si
X
X
X
X
X X
X
X
X X
X
X
X
X

X
X
X
X X
X
X X
X X
X
X
X
X

Dislvd.
Inorg.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

Dislvd.
Organic
N

X
X
X







N



X

1
X



N

Partic.
Organic
X
X
X
X
X


X
X
X
X
X
X



X-
X
X
X
X

X
X
Nutrient
Sedi-
ments
X
X
X
X
X
X*
*
X
X
X
p
it
X
X

*
X


X
X


X

X
X
Forms
Algae
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

Zoo- Other
plankton Organisms
X
X X
X X
X X
X X


X X
X X
X
X
X X
X



X
X X
X
X
X X


X
Inorganic
NH3 N02
X X
X X



X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X
X
X X

X



X
Nitrogen Forms
Total
N03 Avail
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
References
Baca i Arnett (1976)
WES (EWqOS) (1982)
Bloomfield et aT_. (1973)
Scavia & Park (1976)
Park et al.. (1980)
Feigner & Harris (1970)
Duke & Masch (1973)
Tetra Tech (1979, 1980)
Brandes & Masch (1977)
Baca et al_. (1973)
Johanson et jil_. (1980)
Chen & Orlob (1975)
Harleraan et al_. (1977)
Roesner et a±. (1981)
Raytheon (1974)
Grenney & Kraszewski (1981)
Di Toro et al_. (1981)
Smith (1978)
Bierman et al.. (1980)
Canale et al.. (1975, 1976)
Jorgensen (1976)
Lehman et aj.. (1975)
Nyholm (1978)
Scavia et al_. (1976)
ro
01
    Specify flux.

-------
                             K  - K      -                           5 R)
                             KT - K2Q                                b-b)

where KT  =  rate coefficient at temperature T,  I/time
      T   =  temperature,  C
      K2Q  =  rate coefficient at 20°C, I/time
      6   =  temperature adjustment coefficient

This relationship  is derived in Section 3.3 of  Chapter 3.

     A few models  use different temperature adjustment  formulations.   For
example, Canale  (1976) uses a linear relationship  and Grenney and Kraszweski
(1981) use a logistic equation as a temperature adjustment function.

5.5  CARBON  TRANSFORMATIONS

     Table 5-2 presents rate coefficients for carbon decay  processes  along
with  the  corresponding  temperature  adjustment  factors.  As shown in the
table, these coefficients have a broad range, indicating a lack of detailed
process characterization.   Process characterization has been neglected in
carbon models since the relationship  of  carbon dynamics  to water quality
modeling  has not been considered essential.  In fact, most water quality
models do  not include carbon since it is  not usually a  limiting nutrient.
In  the  Lake Erie version of WASP (Di Toro and Connolly, 1980), the rate of
decay of particulate organic carbon to C02 has  been further reduced by using
a saturation relationship (Di Toro and Connolly,  1980).  However, the decay
rates in all other models are computed according to the first-order kinetics
discussed  above.

     Most  of the temperature adjustment factors  in Table 5-2 range from 1.02
to  1.047, corresponding to  Q,Q values  ranging  between 1.2 and 1.6.  The
exception  is the Lake Erie WASP model  (Di Toro  and Connolly,  1980),  which
uses  a  temperature correction  factor  of  1.08 (Q,n = 2.16)  for decay of
settled algae and  sediment organic matter.  Also,  the decay  rate constants
for these  compartments are generally higher than those used  in other models.
                                    255

-------
                                  TABLE  5-2.   RATE COEFFICIENTS  FOR  CARBON TRANSFORMATIONS
POC -
K
0.1**
0.05
0.001
0.003
0.02
0.1
0.005-0.05***
0.001-0.02***
- co2
e
1.04
1.045
1.02
1.020
1.020
1.047
1.02-1.04***
1 .040***
SOC *
K
0.00025

0.001
0.0015
0.001
0..0015
0.001-0.01***
0.001-0.02***
C02 SA -•• SOC
Ff If f\
"* \J
1.08 0.02 1.08

1.02
1.047
1.020
1.047
1.02-1.04***
1.040***
SA •* C02 References
K e
0.02 1.08 Di Toro & Connolly (1980)
O'Connor et. aK (1981)
Chen & Orlob (1972, 1975)
Tetra Tech (1980)
Bowie et a]_. (1980)
Porcella et aK (1983)
Smith (1978)
Brandes (1976)

  *Abbreviations are defined as follows:

      POC - Participate  Organic Carbon
      C02 - Carbon Dioxide

      SOC - Sediment Organic Carbon

      SA  - Settled Algae                                  n
                                                         U2
 **This rate is multiplied by an oxygen limitation factor, 'RT+OT, where K,  is a half-saturation constant for oxygen.

***Model documentation values.

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5.6  NITROGEN TRANSFORMATIONS

     Nitrogen dynamics are modeled in a considerably more complex manner
than carbon because of their substantial  biogeochemical  role,  important
oxidation-reduction  reactions, and because other important water quality
variables such as oxygen  are affected by nitrogen.  The processes  that are
simulated in water quality models include:

     •   Ammonification  - release of ammonia due  to  decay processes
         (deamination,  hydrolysis).

     •   Nitrification - oxidation  of ammonia to  nitrate  (NOZ)
         directly (one-stage process)  or  to nitrite (NOl)  and then to
         nitrate (two-stage process).   Nitrification  is  discussed in
         detail  in  Section  3.4  of Chapter 3  in reference to its
         ^effects on dissolved oxygen.

     •   Denitrification - reduction of nitrate to N~ under anaerobic
         conditions.  This process  also produces  N?0  (  10  percent of
         total  reduced), but since N?0 has not been  shown to have an
         appreciable effect on water quality, N^O  production has not
         been modeled.

     •   Uptake - accumulation of inorganic nitrogen by plants during
         photosynthetic growth.   Both ammonia and  nitrate are
         accumulated, with preference for  ammonia over oxidized forms,
         although not all models include this preference.

     •   Nitrogen fixation - reduction of N2 to ammoniated compounds.
         Nitrogen fixation by blue-green algae is  an  important
         external  input of nitrogen accumulation in  waterbodies that
         materially  affects  nitrogen dynamics.   However,  uptake  of
         inorganic ions takes precedence over nitrogen fixation.
                                   257

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In addition to the above processes, unionized  ammonia can play a  significant
role  as a toxicant  depending  on the ammonia concentration,  pH, and
temperature.

     Table 5-3 presents  rate coefficients for the major nitrogen decay and
abiotic  transformation processes along with the corresponding  temperature
ajdustment factors.   The decay processes shown include breakdown of complex
organic  compounds (particulate organic nitrogen,  PON) to simpler  organics
(dissolved organic  nitrogen, DON) or to ammonia, the breakdown  of sediment
nitrogen to ammonia, and the oxidation  of  ammonia  to nitrate.   Rate
constants for ammonia decay to nitrite and then to nitrate  or  from ammonia
to nitrate directly are approximately  commensurate as an overall  rate
process.  The rate  coefficients for  some of the  decay processes in some
versions of WASP are  further reduced  by saturation  kinetics  (Di Toro and
Connolly, 1980;  Di  Toro and Matystik,  1980;  Thomann and Fitzpatrick,  1982;
O'Connor et al. ,  1981).  For example,  the decay of particulate  organic
nitrogen to  ammonia  is reduced  as  chlorophyll a decreases,  and the
nitrification rate is reduced as dissolved oxygen decreases, according to
saturation kinetics.

     The temperature  adjustment  factors have a wide  range  of  values,
indicating some  uncertainty in this coefficient.  The Q.Q values generally
range from 1.2 to 2.4, but with one value as high as  3.7.

5.6.1 Denitrification and Nitrogen Fixation

     Both of these processes affect the mass  balance of nitrogen  because
nitrogen is transported to (denitrification) or from (nitrogen fixation) the
atmosphere rather than recycling within  the water.  Although  both processes
have  been shown to  be important in  certain aquatic  environments,
denitrification is not commonly included in models.  HSPF (Johanson  ert  al.,
1980),  CE-QUAL-R1 (WES,  1982), Jorgensen (1976), AQUA-IV (Baca  and Arnett,
1976), and some versions  of WASP (Di  Toro and  Connolly, 1980; Thomann and
Fitzpatrick, 1982; O'Connor et a/L, 1981)  include denitrification.
                                   258

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TABLE 5-3.   RATE COEFFICIENTS  FOR  NITROGEN TRANSFORMATIONS
PON 'DON DON - NH3 PON -
K 6 K 6 K

0.035
0.03**
0.03***
0.03***
0.075

0.14
0.001
0.020 (linear) 0.020 (linear)
0.020 (linear) 0.020 (linear)
0.02 1.020 0.02 1.020
0.02 (linear) 0.024 (linear)
0.003
0.1
0.01**
0.005**
0.1**
0.2**
>NH NH *
6 K

(linear)
i.o'a
1.08
1.08
1.08

(linear)
1.02 0.003-0.03




1.020 0.02
1.047 0.02
NI
1.08
1.02
1.072
N02 NH3 -- N03 N02 - N03 SEDN •*• NHj References
6 K 6 K 6 K 8
Calibration Values
0.04 (linear) Thonann et ah (1975)
Thomann et ah (1979)
0.12*** 1.08 0.0025 1.08 Di Toro & Connolly (1980)
0.20 1.06 Di Toro & Hatystik (1980)
0.09-0.13*** 1.08 0.0004 1.08 Thomann & Fitzpatrick (1982)
0.025*** 1.08 O'Connor et al_. (1981)
Salas & Thoraann (1978)
1.02 0.09 1.02 0.001 1.02 Chen & Orlob (1972, 1975)
0.060 (linear) Scavia j^t aK (1976)
0.1 (linear) Scavia (1980)
0.1 1.020 Bowie et ah (1980)
0.16 (linear) Canale et^ al_. (1976)
1.047 0.25 1.047 0.0015 1.047 Tetra Tech (1980)
1.047 0.25 1.047 0.0015 1.047 Porcella et al_. (1983)
0.95-1.8*** 1.14 Nyholm (1978)
Bierman et al_. (1980)
Jorgensen -(1976)
Jorgensen et aj_. (1978)
                               (continued)

-------
                                                                             TABLE  5-3.    (continued)
ro
CT>
o

PON » DON DON -» NH3 PON - NH3 NH3 * NI
K 6 K 6 K 6 K

0.1-0.4 NI 0.1-0.5
0.02-0.04 1.02-1.09 0.1-0.5
0.1-0.5
0.1-0.5
0.005-0.05 1.02-1.04 0.05-0.2
0.001-0.02 1.040 0.05-0.2


D2 NH3 -> N03
8KB
Model Documentation Values
NI
1.02-1.09
1.047
1.047
1.02-1.03
1.02
0.04-3.0 (logistic)
0.001-1.3**** NI
N02 + NOj SEDN •* NH
KB K

5. -10. NI
3. -10. 1.02-1.09 0.01-0.1
0.5-2.0 1.047
0.5-20 1.047
0.2-0.5 1.02-1.03 0.001-0.01
0.2-0.5 1.02 0.001-0.02


,, References
6

Baca et a]_. (1973)
1.02-1.09 Baca 4 Arnett (1976)
Duke & Hasch (1973)
Roesner e_t aK (1978)
1.02-1.04 Smith (1978)
1.040 Brandes (1976)
Grenney 4 Kraszewski (1981)
Collins 1 Wlosinski (1983)

         *Abbreviations are defined as follows:

               NI   -  No Information
               PON  -  Particulate Organic Nitrogen
               DON  -  Dissolved Organic Nitrogen
              SEDN  -  Sediment Organic Nitrogen
        "Unavailable nitrogen decaying to algal-available  nitrogen.
                                                                                                                              Chi a
                                                                                                                              i~n I  a
       *"Di  Toro  &  Connolly (1980) and Di Toro & Matystik  (1980) multiply the PON NhL rate by a  chlorophyll limitation factor,  "K.+CH1 a^,
          where  K. is  half-saturation constant = 5.0 »ig CHa a/1.                                                                '
                                                                                                                              2
          Di  Toro  &  Connolly (1980) and Thomann & Fitzpatrick  (1982) multiply the NH, NO, rate by an  oxygen limitation factor, K_+0?)  where
          K2  is  a  half-saturation constant - 2.0 mg02/l.                                    0
          O'Connor et  al.  (1981) multiply the NH, NO, rate  by  an oxygen  limitation factor, K,-KL, where  K,  is a half-saturation constant
          = 0.5  mg02/l.                         J   J                                      J   i         J
          Nyholm (1978)  uses a sediment release constant which is multiplied by the total sedimentation  rate of algae and detritus.

      ""Literature value.

-------
     Denitrification rates  and  the corresponding temperature  adjustment
coefficients are listed in  Table 5-4.  The decay rates for the WASP model
are further modified according to  a saturation  type relationship based on
the dissolved  oxygen concentration.  The  rate decreases  rapidly as 0^
increases above 0.01 mg/1.  This rate would  be equivalent  to that of
Jorgensen (1976) when 0?  =  5  mg/1.  This  indicates disagreement in
conceptualization of the process or in  its quantitative response  between the
two models.  Sediment nitrate denitrification helps decrease  the  gradient of
the sediment oxygen demand (SOD) and may  lead to a reduced requirement for
SOD (see Chapter  3.5; also,  Di Toro, 1984).

     Nitrogen  fixation  by  blue-green algae  is modeled by  assuming that
growth  is not  limited  by  nitrogen and that nitrogen fixation makes up for
all nitrogen requirements which  cannot  be satisfied by ammonia and nitrate.
Some type of saturation relationship is typically used  to partition the
nitrogen requirements between nitrogen  fixation  and uptake  of ammonia and
nitrate.  The  major features of  these relationships are as  follows:  1) no
fixation occurs  when ammonia plus  nitrate are above some critical  threshold
concentration;  2) for concentrations  below the threshold, nitrogen fixation
increases as ammonia and nitrate decrease; and 3) when ammonia and  nitrate
become  very low, all of the nitrogen  requirements are supplied by fixation.
Nitrogen fixation is included in the EAM  (Tetra Tech, 1979),  Scavia  e_t al.
(1976),  Canale et_ a]_. (1976), and  Bierman e_t al_._ (1980) models.

5.6.2  Unionized  Ammonia

     Although nitrogen  is an important nutrient required by  microorganisms,
plants,  and animals, certain forms such as unionized ammonia  (NFL)  can be
toxic.   Unionized ammonia  is  toxic  to fish at fairly low  concentrations.
For example, water quality criteria ranging from 0.0015 to 0.12  mg  N/l  for
the 30-day average concentration have  been suggested (USEPA,  1984).  This
range exists because the biological response varies at different  temperature
and pH  values.

     Both analytical measurement techniques and most model formulations for
ammonia  are based on total ammonia:
                                    261

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              TABLE 5-4.  RATE COEFFICIENTS FOR DENITRIFICATION

Nitrate
K
0.1*
0.1**
0.09*
0.1*
0.002
0.02-0.03
o.-r.o***
-* Nitroaen Gas
0
1.045
1.045
1.045
1.045
No Information
No Information
1.02-1.09***
References

Di Toro & Connolly (1980)
Di Toro & Connolly (1980)
Thomann & Fitzpatrick (1982)
O'Connor et al_. (1981)
Jorgensen (1976)
Jorgensen et al. (1978)
Baca & Arnett (1976)

  *This rate  is multiplied by an oxygen limitation factor, K,+0^,
   is a half-saturation constant = 0.1mgO?/l.
 **The same  rate  applies to sediment NO, dentrification.
***Model  documentation values.
                           where K
                                  1
                       X = total  ammonia = NH-, + NH.
                                 (5-6)
The concentrations of NH3  and  NH*  vary considerably over the range of pH and
temperature found in  natural  waters, but  each  can be readily calculated
assuming  that  equilibrium  conditions exist  (Stumm and  Morgan,  1981).
Unionized ammonia exists in  equilibrium with ammonia ion and hydroxide  ion
(Emerson, et aj_., 1975):
NH(g)
= NH
                                             OH
(5-7)
The reaction  occurs  rapidly and is controlled largely by pH and temperature.
Thus, unionized  ammonia  is calculated from the equilibrium expression:
                                    262

-------
                             (NH*)(OH")    (NH*)Kw
                        Ki  =  (NH3)(H20) = --—
Rearranging and taking  the negative logarithm:

                            (NH!)
                        log Tfjyj-y = pKw - pK.j  -  pH                     (5-9)

The quantity pKh is  called the hydrolysis constant.  Substituting and taking
the inverse logarithms,

                          'X - NH,\      (pKh-pH)
                                    = 10   n     = R                 (5-10)
and solving for  NH.,.
                                 3   1  +  R
                                                                    (5-11)
Thurston  ei^ a! . , (1974)  determined the  temperature correction  for the
hydrolysis constant as follows:

                       pKh = 0.09018  +  2729. 92/T                    (5-12)

where T =  absolute temperature,   K

Substituting  this relationship into Equation  5-7,  unionized  ammonia in
moles/liter becomes a function of measured  ammonia, temperature,  and pH.
Most water quality models predict the concentration of measured ammonia (X)
in units of weight/volume  as  a  resultant  of  processes of nitrification,
ammoni f ication, respiration, and  assimilation.  For NH^-N,  there are
14,000  mg/mole  and
                         NH -H. mg/1  .                               (5-13)
                                    263

-------
Although  more cumbersome,  a table of  equilibrium  values for unionized
ammonia can  be used  in a model (e.g.,  USEPA,  1984).   Figure  5-5 illustrates
the relationship  between pH, water temperature,  and  unionized ammonia.
       Q
       LU
       N

       O
       I
       111
       O
       DC
       ai
       Q.
         0.01
              0
      Figure 5-5.
             TEMPERATURE (°C)


Effect of pH  and  temperature on unionized ammonia
(from Willingham,  1976).
                                  264

-------
5.7  PHOSPHORUS TRANSFORMATIONS

     Table  5-5 presents rate coefficients and temperature  correction factors
for  the  various  phosphorus  transformation processes  included  in water
quality  models.   The transformations  include the decay  of particulate
organic  phosphorus (POP), sediment phosphorus (SEDP), and  settled algae  (SA)
directly  to PO.-P or into intermediate forms (dissolved organic phosphorus,
OOP)  before  decaying  to  PO.-P.   The decay rates  have  a broad range,
indicating  some uncertainty  in  quantifying these processes.  Similarly,
there is a broad  range in temperature coefficients, with a Q,0 range  from
1.2 to 2.4, except for a  QIQ value  of 3.7 for Nyholm  (1978).  Several of
the  WASP  models  adjust the phosphorus decay rates using a saturation
equation  based on algal biomass  (Di  Toro and Connolly,  1980; Di Toro and
Matystik,  1980; Salisbury £t  a/L_, 1983; Thomann and Fitzpatrick, 1982).  In
the case  where chlorophyll a is  used to estimate algal biomass, the half-
saturation  constant is 5.0  g/1, and where carbon is used to estimate algal
biomass,  the value is 1.0 mgC/1.

5.8  SILICON TRANSFORMATIONS

     Silicon can be limiting only for diatoms,  so its biogeochemical cycle
is simulated  only when diatoms are modeled as a separate algal group.
Diatoms  are important because  of their role in phytoplankton succession,
their role  in aquatic food chains,  and  their potential effects  on water
treatment plants.   Table  5-6 presents decay rates and temperature adjustment
coefficients  for  silicon.   In  contrast to the  other nutrients, particulate
and sediment silicon decay directly to dissolved inorganic  silicon rather
than passing  through a  dissolved  organic phase.  The range of the first-
order decay rates  for particulate silica decay is 0.003-0.1  (I/day).  The
temperature adjustment factor  varies between 1.02 and 1.08, corresponding to
a Q1Q range of 1.2 to 2.2.
                                   265

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                                          TABLE  5-5.    RATE  COEFFICIENTS  FOR  PHOSPHORUS  TRANSFORMATIONS
r-o
CTi
CTv
POP -OOP POP -
K () K
0.14
0.03
0.03"
0.22" 1.08
0.14
0.001
0.02
0.2 (linear)
0.003
0.02
0.1
0.1
0.005
0.1
0.5-0.8
0.1-0.7***
0.1-0.7***
0.005-0.05***
0.001-0.02***
Sediment Sediment Sedirent
• P04 OOP - P04 StOP - OOP SEOP ., po OOP - P04 SA - OOP SA - PO
fl K0K0 K 9 K 0 f. A K «
(linear)
l.OB
l.OB
0.22" 1.08 0.0004 1.08 0.0004 1.08 0.0004 1.08 0.02 1.08 0.02 1.08
(linear)
1.02 0.001 1.02
(linear)
0.2 (linear)
1.020 0.0015 1.047
1.020 0.001 1.020
1.047 0.0015 1.047
1.14 1.0-1.7 1.14**
1.08
1.02 0.0018 1.02
1.072
1.02-1.09*** 0.1-0.7*" 1.02-1.09*"
1.02-1.09*"
1.02-1.04*** 0.001-0.01*" 1.02-1.04*"
1 .040"*
References

Thomann et aj.. (1975)
Thomann et •]_. (1979)
01 Toro I Connolly (1980)
01 Toro 4 Matyslik (1980)
Salisbury et a_L (1983)
Thomann I Fltzpatrlck (1982)
Salas 1 Thomann (1978)
Chen » Or lob (1972. 1975)
Scavia et al. (1976)
Scavla 11980)
Canale el aK (1976)
Tetra Tech (1980)
Bowie et t\_. (1980)
Porcella et, a_K (1983)
Nyholm (1978)
Blernan et i\_. (1980)
Joroensen (1976)
Jorgensen ejt a_[. (1978)
Baca et aj. (1973)
Baca I Arnett (1976)
Smith (1978)
Brandes (1976)

Abbreviations are defined as
fol lows:

POP - Participate Organic Phosphorus SEOP - Sediment Organic Phosphorus
OOP - Dissolved Organic Phosphorus SA - Settled Algae
P04 - Phosphate Chl a
          •*Di Toro t Connolly (1980), Ot  Toro i Matystlk  (1980) and Salisbury  et a^.  (1983) multiply this rate by a chlorophyll  limitation factor, C.»CH1 a^,
            •here Kj Is a half-saturation  constant - 5.0 fig Chl a/1.                           Al al  C

            ThoMnn S Fitzpatrlck (1982) •ultlply this  rate by an algal carbon  limitation factor, ic^TAlgal^, where 1^ is a half-saturation constant - l.(tagC/l.

            Nyhola (1978) utilizes a sediment release constant which is multiplied by  total sedimentation  of algae and detritus.

         •••Model documentation values.

-------
                            TABLE 5-6.   RATE COEFFICIENTS FOR SILICA TRANSFORMATIONS
ro
en

Particulate _
Silica
K
0.0175
0.1
0.04
0.03
0.003
0.01
0.04
0.005
^ Dissolved
Silica
8
1.08
1.08
(linear)
(linear)
1.020
1.020
1.047
1.08
Sediment + Dissolved
Silica Silica References
K 8
Thomann et^ al_. (1979)
Di Toro & Connolly (1980)
Scavia (1980)
Canale ert aj_. (1976)
0.005 1.047 Tetra Tech (1980)
0.001 1.020 Bowie et al_. (1980)
0.0015 1.047 Porcella et. al. (1983)
Bierman et al_. (1980)

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5.9  ALGAL UPTAKE

     Two major approaches are used  to simulate nutrient uptake by  algae in
water  quality  models.  The most  common method is  the  fixed stoichiometry
approach in which the nutrient  composition of the algae is assumed to remain
constant.  Under this assumption, the nutrient uptake rates are equal to the
algal gross growth rate times the corresponding  nutrient fractions  of  the
algal cells:

                         Vs =  «s M A                                (5-14)

where  V  = uptake rate for nutrient S, mass/volume-time
       a  = nutrient fraction of algal cells, mass nutrient/mass algae
       fji  = gross growth rate of algae, I/time
       A  = algal concentration, mass/volume

This formulation is used in all fixed stoichiometry  models.  Typical values
of the nutrient compositions of algae  are given  in  Tables  6-2 to  6-4 of
Chapter 6.  Algal  growth formulations  and the  corresponding model
coefficients  are discussed  in Section 6.4 of Chapter  6.

       The second approach  to modeling nutrient uptake is the  variable
stoichiometry approach.  In this method, the internal  nutrient composition
of the  algal cells  varies with time  depending on  the  external  nutrient
concentrations in the water column  and the relative rates of nutrient uptake
and algal  growth.   The uptake rate depends on the  difference between  the
internal  nutrient  concentration  in the algal  cells and  the external
concentration in the water.  The internal concentration of each nutrient is
assumed to  range between a  minimum  stoichiometric requirement (called  the
minimum cell  quota  or subsistence  quota)  and  some  maximum  internal
concentration.  In general, the uptake rate increases  both as the  external
nutrient  concentration increases and as the internal  nutrient concentration
decreases toward the minimum cell quota.  However, the uptake rate decreases
as the internal  concentration approaches the maximum internal  level,
regardless  of the external  concentration in the water.

                                   268

-------
       In  contrast to fixed  stoichiometry models, the uptake formulations
used in variable stoichiometry models vary from model to model.  Some models
even  use different  formulations  for different nutrients.   Variable
stoichiometry  formulations  for nutrient  uptake  are discussed  in
Section 6.4.4.3  of Chapter 6,  since nutrient uptake is an integral part of
the algal  growth formulations  in variable stoichiometry  models.   The  major
formulations are given in Equations  (6-63) to (6-67).

5.9.1  Ammonia Preference Factors

       Since algae use  two forms of nitrogen, ammonia and nitrate, during
uptake and growth, many models use ammonia preference factors in  the uptake
formulations  to  account for the fact  that algae tend  to  preferentially
uptake ammonia over nitrate.   Ammonia preference factors are generally used
in  fixed  stoichiometry models  when both ammonia and nitrate are simulated.
In this case, the 'uptake equations for ammonia and nitrate become:
and
where  VMM   =  ammonia uptake rates mass/volume-time
        NH3
       VMH   =  n"itrate uptake rate, mass/volume-time
         M3
      /3N,,   =  ammonia preference  factor
         O
      a..   =  nitrogen fraction of algal cells

Ammonia preference  factors  are  generally  not needed  in  variable
stoichiometry  models since separate formulations  with different coefficients
can be used  to distinguish between ammonia and nitrate uptake rates.

       The  ammonia preference  factor  .,„   partitions the nitrogen uptake
                                                                    w
required for a given amount of algal  growth  between ammonia and nitrate.
The preference  factor can range from 0 to 1,  with 1 corresponding  to  a

                                    269

-------
situation  in  which all the nitrogen requirements are obtained from ammonia
uptake, and  0 corresponding  to a situation  in  which all the nitrogen  is
obtained from nitrate.  The value of the preference factor is generally  a
function of the ammonia and nitrate concentrations  in the water.

       The simplest form of the ammonia  preference  factor  assumes there  is
no  preference for  either  form of nitrogen and partitions the uptake
according  to  the relative proportions  of ammonia and nitrate in the water:

                                   NH3
                              =                                     (5-17)
where NH.-,  =  ammonia concentration,  mass/ volume
      NO.,  =  nitrate concentration,  mass/volume

This approach  is used in EXPLORE-1  (Baca et  al. ,  1973), LAKECO  (Chen and
Orlob, 1975), WQRRS (Smith, 1978), CE-QUAL-R1 (WES, 1982),  EAM (Tetra  Tech,
1979), ESTECO  (Brandes, 1976),  and  earlier versions of WASP  (Thomann  et a!.,
1975).
     Other models which assume  there  is a preference for ammonia uptake have
used the  following formulations for the preference factor:

                                  yi NH3
                                                                    (5-18)
                                     3  +  N03
                                  NH.,
                                    3                                (5-19)
                                     NH3
                                                                    (5-20)
                                VNfl+M- V  I NO
                                /•) Mil .3  T  (i   I •)] MU-j
                                 o   o         o    o

                                                                    (5-21)


where y,, y2,  y3,  y. = coefficients  in ammonia preference factor
                      formulations

                                    270

-------
Equation (5-18)  is  used  in SSAM IV (Grenney and  Kraszewski, 1981) and Scavia
e_t al.  (1976),  Equation  (5-19) in an early Lake  Erie WASP model by Di Toro
et al. (1975), Equation  (5-20) in AQUA-IV (Baca  and Arnett, 1976) and Canale
e;t al.  (1976), and  Equation (5-21)  in more recent versions of WASP  by
Thomann and Fitzpatrick  (1982) and O'Connor et al.  (1981).

5.10 EXCRETION

       Nutrient excretion by algae  and zooplankton is  one of the  major
components of  nutrient  recycling.  In almost all  models, nutrient excretion
is modeled as the  product of the respiration mass flux  and the nutrient
stoichiometry  of  the organisms.  The  equations for algal  excretion and
zooplankton excretion are:
and
                            esa ' "sa ra
                            esz - asz rz Z                          (5-23)
where  e   = algal  excretion rate of nutrient S, mass/volume-time
        sa
       e   = zooplankton excretion rate of nutrient S9 mass/volume-time
       a   = nutrient  fraction of algal cells,  mass nutrient/mass algae
        sa
       a   = nutrient fraction  of zooplankton,  mass  nutrient/mass
             zooplankton
       r   = algal  respiration rate, I/time
        a
       r   = zooplankton respiration rate, I/time
       A   = algal  concentration, mass/volume
       Z   = zooplankton concentration, mass/volume

The excretion formulations  for other organisms such as fish or benthic
animals is the same as for zooplankton.  Respiration rate  formulations for
algae  and zooplankton are  discussed  in  Section 6.5  (Chapter 6) and 7.4
(Chapter 7), respectively. The nutrient compositions of algae are presented
in Tables 6-2 to  6-4 of Chapter 6.  The nutrient compositions of zooplankton
are typically assumed  to be the same as  for algae in fixed  stoichiometry
models so that nutrient mass is conserved  as biomass cycles through the food
web.

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5.11  SEDIMENT RELEASE

     Three  major approaches have been  used  to simulate nutrient release from
the sediments in water quality models.   The simplest approach is to specify
an areal  flux from the bottom in the mass balance equations  for dissolved
nutrients.   This  technique  is commonly used  in river models and in models
which do  not dynamically simulate sediments as  a separate constituent (e.g.,
QUAL-II  (Roesner  et al.,  1981),  DOSAG3  (Duke  and Masch, 1973),  and HSPF
(Johanson et, aj_._, 1980)).   Sediment release rates are highly site-specific,
and are determined largely by model calibration of the dissolved nutrients.

     The  second approach is to model sediment  nutrients as a  dynamic pool
using  a  mass  balance equation such  as Equation  (5-4).  In  this method,
nutrients are released according to a  first-order decay rate:

                       Sed                                          (5-24)

where R    = sediment release rate  of  nutrient S, mass/volume-time
      a    = stoichiometric ratio of nutrient per mass organic sediment
      K  .  = organic sediment decay rate, I/time
      Sed  = concentration of organic  sediment, mass/volume

The organic sediment pool increases as algae and suspended organic detritus
settle to  the bottom, and decreases as  the  sediment decomposes.  This
approach  is used in LAKECO  (Chen and Orlob, 1975), Chen et al.  (1975),  WQRRS
(Smith,  1978),  CE-QUAL-R1 (WES,  1982), EAM (Tetra Tech, 1979), and ESTECO
(Brandes, 1976).  In some models, a fraction of the settled particulates  is
assumed to  be refractory and unavailable  for mineralization.

     The  third approach to modeling sediment  release uses a  more complex
mechanistic approach in which:  1) organic sediments undergo  the same decay
sequences as particulate organics  in  the water column but with the  decay
products going  to the interstitial  water rather than the overlying water,
and 2) the  nutrients in the interstitial waters diffuse  to  the overlying
water at  a  rate depending on  the concentration gradient between the

                                   272

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interstitial  water and  overlying water.  This  approach is  used  in some
versions  of WASP  (e.g., Di Toro and  Connolly, 1980; Thomann and Fitzpatrick,
1982).  A few models also  include denitrification in the transformation
reactions.

     Nyholm  (1978) simulates sediment  release dynamically without  actually
modeling sediments by assuming  the release  rates  equal the product of a
temperature dependent coefficient  times  the sedimentation rates of algal and
detrital  nutrients to the bottom.

5.12  SUMMARY

     Carbon,  nitrogen, phosphorus, and silicon are the major growth  limiting
nutrients included in water qua'lity models.   Nitrogen is also  important
because  of  the effects of nitrification on dissolved oxygen dynamics and
because of ammonia toxicity.   All nutrients recycle continuously in the
water  column  between particulate and sediment  forms, dissolved organic
forms,  dissolved  inorganic forms,  and  biotic forms.  The important processes
are decomposition of organic particulates and sediments, decay of dissolved
organic to inorganic forms, chemical  transformations such as nitrification,
photosynthetic uptake of  dissolved inorganic forms, and  soluble and
particulate excretion by aquatic organisms.  Denitrif ication  and  nitrogen
fixation  are also important in some  situations.

     First-order  kinetics  are used in  almost  all models to  describe the
various  decay  processes and transformations.   The exponential  Arrhenius or
van't  Hoff  relationship  is  used to adjust the  rate  coefficients  for
temperature effects.  Some of the  processes are modified by Michaelis-Menten
type saturation kinetics in a few  models.  Uptake and excretion are  based on
algal  growth rates and algal and zooplankton respiration rates  combined with
the nutrient stoichiometries of the  organisms.  More complex  formulations
are used for  nutrient uptake  in variable stoichiometry  models.   Sediment
release rates are usually modeled  either by specifying a nutrient  flux or
modeling sediments  as a nutrient pool  subject to first-order  decay.  A few
models  use more complex formulations which include decay reactions in the

                                   273

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Interstitial  waters and diffusion  between the interstitial waters in the

sediment and the overlying water  column.

5.13  REFERENCES

Baca, R.G., W.W. Waddel, C.R.  Cole,  A. Brandstetter,  and D.B.  Clearlock.
1973.   EXPLORE-I: A  River  Basin Water Quality  Model.  Battelle,  Inc.,
Pacific Northwest  Laboratories, Richland, Washington.

Baca, R.G.  and  R.C. Arnett.   1976.  A  Limnological  Model  for  Eutrophic Lakes
and Impoundments.  Battelle,  Inc., Pacific Northwest Laboratories, Richland,
Washington.

Bierman, V.J.,  Jr.  1976.  Mathematical Model of the Selective  Enhancement
of  Blue-Green  Algae by Nutrient  Enrichment.  In:   Modeling  Biochemical
Processes in Aquatic Ecosystems.   R.P. Canale  (¥3.),  Ann Arbor  Science
Publishers, Ann Arbor, Michigan,   pp.  1-31.

Bierman, V.J.,  Jr., D.M. Dolan, E.F. Stoermer, J.E. Gannon, and  V.E.  Smith.
1980.   The Development and Calibration of a Multi-Class  Phytoplankton Model
for Saginaw Bay, Lake  Huron.   Great  Lakes  Environmental Planning  Study.
Contribution No. 33.  Great Lakes  Basin Commission, Ann Arbor, Michigan.

Bloomfield, J.A.,  R. A. Park,  D.  Scavia, and C.S. Zahorcak,   1973.   Aquatic
Modeling in  the Eastern  Deciduous Forest Biome.   U.S.  International
Biological Program.  ln_:  Modeling the Eut^rophi  cation Process.
E.J. Middlebrook, D.H. Talkenborg,  and  I.E.  Maloney,  (eds.).  Utah State
University, Logan, Utah.  pp.  139-158.

Bowie,  G.L.,  C.W. Chen, and D.H. Dykstra.  1980.  Lake Ontario Ecological
Modeling, Phase III, Tetra Tech,  Inc., Lafayette, California.  For National
Oceanic  and Atmospheric Administration, Great Lakes Environmental Research
Laboratory, Ann Arbor, Michigan.

Brandes, R.J.   1976.   An  Aquatic Ecologic Model for Texas Bays  and
Estuaries.  Water  Resources  Engineers, Inc., Austin, Texas.  For the Texas
Water Development  Board, Austin, Texas.
                                                           "%
Brandes, R.J. and  F.D. Masch.   1977.   ESTECO--Estuarine Aquatic Ecologic
Model:   Program Documentation  and  User's Manual.   Water Resources Engineers,
Inc., Austin, Texas.  For the  Texas Water Development Board,  Austin, Texas.

Canale,  R.P.,  L.M.  Depalma, and A.H.  Vogel.   1975.  A Food Web Model for
Lake Michigan.  Part 2 - Model  Formulation  and  Preliminary Verification.
Tech. Report 43, Michigan Sea  Grant Program, MICHU-SG-75-201.

Canale,  R.P., L.M. Depalma,  and A.H. Vogel.   1976.   A  Plankton-Based  Food
Web Model for Lake Michigan.   In:  Modeling  Biochemical Processes in Aquatic
Ecosystems.  R.P.  Canale (ed.).  Ann Arbor Science Publishers,  Ann  Arbor,
Michigan, pp.  33-74.
                                   274

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Chen, C.W.  and  G.T.  Orlob.  1972.   Ecologic Simulations  of Aquatic
Environments.   Water Resources Engineers,  Inc., Walnut Creek, California.
For the  Office of Water Resources Research.

Chen,  C.W.  and C.T. Orlob.   1975.   Ecological  Simulation  for  Aquatic
Environments.  In:  Systems Analysis  and  Simulation in Ecology,  Vol.  3.
B.C. Patten  (ed.).  Academic Press, Inc.,  New York, New York.  pp. 476-588.

Chen, C.W.,  M. Lorenzen, and D.J. Smith.   1975.   A Comprehensive Water
Quality-Ecological Model  for Lake Ontario.  Tetra Tech,  Inc., Lafayette,
California.  For  National Oceanic and  Atmospheric  Administration, Great
Lakes Environmental  Research Laboratory, Ann  Arbor,  Michigan.

Collins,  C.D. and J.H.  Wlosinski.  1983. Coefficients for Use  in the U.S.
Army Corps  of Engineers Reservoir Model,  CE-QUAL-R1.   U.S. Army Corps  of
Engineers, Waterways Experiment Station, Vicksburg,  Mississippi.

Di  Toro, D.M.,  D.J.  O'Connor, R.V.  Thomann,  and J.L. Mancini.  1975.
Phytoplankton-Zooplankton Nutrient Interaction Model  for  Western Lake Erie.
In:  Systems Analysis and Simulation in Ecology,  Vol. III.  B.C. Patton
(ed.).   Academic  Press, Inc., New York,  New York.  423 pp.

Di> Toro,  D.M. and  J.P. Connolly.  1980.   Mathematical Models of Water
Quality  in Large  Lakes.  Part II:  Lake  Erie.  U.S.  Environmental Protection
Agency,  Ecological Research Series.   EPA-600/3-3-80-065.

Di Toro,  D.M. and W.F.  Matystik, Jr.   1980.   Mathematical Models of Water
Quality  in Large  Lakes.    Part  I:   Lake  Huron  and Saginaw Bay.
U.S. Environmental Protection Agency,   Ecological  Research Series.  EPA-
600/ 3-80-056.

Duke, J.H.,  Jr.  and  F.D.  Masch.  1973.   Computer Program Documentation for
the Stream  Quality Model  DOSAG3, Vol.  I.  Water Resources  Engineers, Inc.,
Austin, Texas.   For  U.S.  Environmental  Protection  Agency,  Systems
Development  Branch,  Washington, D.C.

Emerson,  K.,  R.C.  Russo, R.E. Lund, and  R.V.  Thurston.  1975.  Aqueous
Ammonia Equilibrium  Calculations:   Effect of pH and Temperature.  J. Fish.
Res. Board Can.,  32(12):2379-2383.

Feigner, K.D.  and H.  Harris.   1970.   FWQA Dynamic  Estuary  Model,
Documentation Report.   U.S.D.I., F.W.Q.A., Washington, D.C.

Grenney, W.J. and  A.K.  Kraszewski.   1981.  Description and Application  of
the Stream  Simulation and Assessment Model:   Version  IV  (SSAM IV).
Instream Flow Information Paper.   U.S. Fish  and  Wildlife Service,  Fort
Collins,  Colorado, Cooperative Instream  Flow  Service Group.

Harleman, D.R.F.,  J.E.  Dailey, M.L. Thatcher, T.O.  Najarian, D.N. Brocard,
and R.A.  Ferrara.   1977.  User's Manual  for  the  M.I.T. Transient Water
Quality Network  Model — Including Nitrogen-Cycle  Dynamics for Rivers and
Estuaries.   R.M.  Parsons  Laboratory  for  Water Resources and Hydrodynamics,

                                   275

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Massachusetts Institute of Technology,  Cambridge, Massachusetts.   For  U.S.
Environmental  Protection Agency, Corvallis,  Oregon.  EPA-600/3-77-010.

Johanson,  R.C.,  J.C.  Imhoff,  and H.H. Davis.   1980.  User's Manual  for
Hydrological  Simulation Program - Fortran (HSPF).  Hydrocomp,  Inc.,  Mountain
View,  California.   For  U.S.  Environmental  Protection  Agency,  Athens.
Georgia.   EPA-600/9-80-015.

Jorgensen,  S.E.  1976.  A Eutrophication Model for a Lake.   Ecol. Modeling,
2:147-165.

Jorgensen,  S.E.,  H.  Mejer, and  M.  Friis.  1978.   Examination of a Lake
Model.   Ecol.  Modeling, 4:253-278.

Lehman, J.T., D.B.  Botkin, and  G.E.  Likens.  1975.   The Assumptions and
Rationales  of a  Computer Model  of  Phytoplankton  Population  Dynamics.
Limnol.  and  Oceanogr., 20(3):343-364.

Nyholm,  N.   1978.  A Simulation  Model for Phytoplankton  Growth  and Nutrient
Cycling  in  Eutrophic, Shallow Lc :s.  Ecol. Modeling, 4:279-310.

O'Connor,  D.J., J.L. Mancini,  and J.R.  Guerriero.   1981.   Evaluation of
Factors  Influencing  the Temporal Variation  of  Dissolved Oxygen in  the
New York  Bight, Phase II.   Manhattan College, Bronx,  New York.

Park, R.A.,  C.D.  Collins,  C.I.  Connolly, J.R. Albanese, and  B.B.  MacLeod.
1980.   Documentation of the Aquatic Ecosystem Model MS.CLEANER.  Rensselaer
Polytechnic  Institute, Center  for  Ecological Modeling,  Troy, New York.  For
U.S. Environmental Protection Agency,  Environmental  Research Laboratory,
Office  of  Research and Development, Athens, Georgia.

Porcella,  D.B., T.M. Grieb,  G.L. Bowie, T.C..Ginn,  and M.W.  Lorenzen.  1983.
Assessment  Methodology for New  Cooling  Lakes, Vol.  1: Methodology to Assess
Multiple Uses for  New Cooling Lakes.   Tetra Tech,  Inc., Lafayette,
California.   For Electric  Power  Research  Institute.  Report  EPRI EA-2059.

Raytheon  Company, Oceanographic  &  Environmental Services.  1974. New England
River Basins  Modeling Project,  Vol.  Ill - Documentation  Report,  Part 1 -
RECEIV-II Water Quantity and Quality Model.  For Office  of Water Programs,
U.S. Environmental Protection Agency, Washington, D.C.

Roesner,  L.A., P.R.  Giguere,  and  D.E.  Evenson.   1981.  Computer  Program
Documentation for  the Stream  Quality Model  QUAL-II.  U.S.  Environmental
Protection  Agency, Athens, Georgia.  EPA  600/9-81-014.

Salas, H.J.  and R.V. Thomann.   1978.   A  Steady-State Phytoplankton  Model of
Chesapeake  Bay.  Journal WPCF,  50(12):2752-2770.

Salisbury,  D.K.,  J.V. DePinto,  and  T.C. Young.   1983.   Impact of Algal-
Available Phosphorus on Lake Erie  Water  Quality:   Mathematical Modeling.
For U.S.  Environmental Protection  Agency, Environmental  Research Laboratory,
Duluth, Minnesota.


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Scavia,  D.,  B.J.  Eadie, and  A.  Robertson.  1976.   An Ecological Model for
Lake Ontario  -  Model Formulation,  Calibration, and Preliminary Evaluation.
Natl. Ocean,  and  Atmos. Admin.,  Boulder, Colorado.   NOAA  Tech. Rept. ERL
371-GLERL 12.

Scavia,  D.  and R.A. Park.   1976.   Documentation of Selected Constructs and
Parameter Values in the Aquatic Model  CLEANER.  Ecol.  Modeling, 2:33-58.

Scavia,  D.   1980.  An Ecological  Model of Lake Ontario.   Ecol. Modeling,
8:49-78.

Smith, D.I.   1978.   Water Quality for River-Reservoir  Systems.  Resource
Management Associates, Inc., Lafayette,  California.   For U.S.  Army Corps  of
Engineers, Hydrologic Engineering  Center  (HEC), Davis,  California,  pp 210.
Stumm, W.  and J.J. Morgan.  1970  (First Edition).
Wiley-Interscience.  New York,  New  York.  583 pp.,
      1981 (Second Edition).
     780  pp.
Tetra Tech,  Inc.  1979.  Methodology for Evaluation of Multiple Power  Plant
Cooling  System Effects,  Volume  II.   Technical  Basis  for Computations.
Tetra Tech,  Inc.,  Lafayette,  California.  For  Electric Power Research
Institute.   Report EPRI EA-1111.

Tetra Tech,  Inc.  1980.  Methodology for Evaluation of Multiple Power  Plant
Cooling  System Effects, Volume V.  Methodology Application to Prototype -
Cayuga Lake.  Tetra Tech, Inc.,  Lafayette, California.   For Electric  Power
Research  Institute.  Report EPRI EA-1111.

Thomann, R.V., D.M.  Di Toro,  R.P.  Winfield, and  D.J.  O'Connor.   1975.
Mathematical Modeling of  Phytoplankton in Lake  Ontario,  Part 1.  Model
Development  and Verification.  Manhattan College,  Bronx, New York.  For U.S.
Environmental Protection Agency, Corvallis, Oregon.  EPA-600/3-75-005.

Thomann,  R.V.,  J. Segna, and R.  Winfield.  1979.  Verification Analysis  of
Lake  Ontario and Rochester  Embayment Three-Dimensional Eutrophication
Models.  Manhattan College, Bronx,  New York.   For  U.S. Environmental
Protection Agency, Office of Research and Development.

Thomann,  R.V. and J.J. Fitzpatrick.  1982.  Calibration and Verification  of
a Mathematical  Model of the Eutrophication  of the  Potomac Estuary.
Government of the District of  Columbia, Washington, D.C.

Thurston,  R.V., R.C. Russo, and  K. Emerson.   1974.   Aqueous  Ammonia
Equilibrium  Calculations.   Fisheries  Bioassay Laboratory, Montana  State
Univ., Boseman, Montana.  Technical Report No. 74-1.
U.S.  Environmental Protection  Agency.  1984.
Protection  of  Aquatic Life  and  Its  Uses -
Standards.   Washington, D.C.
Water Quality Criteria for the
Ammonia.   USEPA, Criteria and
WES (Waterways  Experiment Station).  1982.  CE-QUAL-R1:  A Numerical  One-
Dimensional Model of Reservoir Water Quality, Users Manual.   Environmental
                                    277

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and Water Quality Operational  Studies (EWQOS), U.S.  Army Corps of Engineers,
Waterways Experiment Station,  Vicksburg, Mississippi.

Willingham, W.T.   1976.   Ammonia Toxicity.   EPA 908/3-76-001.
                                      278

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                               Chapter 6
                                ALGAE

6.1   INTRODUCTION

     Algae  are important components of water quality  models for several
reasons.  For example:

     •    Algal  dynamics and nutrient dynamics  are  closely  linked
         together since nutrient uptake during algal growth  is  the
         main  process which removes dissolved  nutrients  from  the
         water,  and  algal respiration and decay are major  components
         of nutrient recycling.

     •    Algal  processes can cause diurnal variations  in  dissolved
         oxygen  due to  photosynthetic  oxygen  production  during the
         daylight combined  with  oxygen consumption due  to algal
         respiration  during the night.   Seasonal  oxygen dynamics may
         also be closely  tied  to  algal  dynamics,  particularly  in
         highly  productive  stratified systems, since the  respiration
         and decomposition of algae which settles below  the  photic
         zone is often a major source of oxygen depletion.

     •    Algae  can  affect  pH through  the uptake of dissolved  CO,,
         during photosynthesis  and  the recycling of  C0_  during
         respiration.

     •    Algae  are  the dominant component  of  the  primary producers in
         many systems, particularly in lakes and estuaries.   Since
                                  279

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          they form the base of the food chain, they play a major  role
          in the dynamics of all successive  trophic levels.

     •    Suspended algae are often a major  component of turbidity.

     •    Algal  blooms can restrict  recreational uses of  water,
          sometimes resulting in fish kills  under severe conditions.

     •    Algae can cause  taste and odor problems in water supplies,
          and filter clogging problems  at water treatment facilities.

     Two general approaches have been used to simulate algae in water
quality models:  1)  aggregating all algae  into  a  single constituent (for
example, total algae or chlorophyll _a),  or 2) aggregating  the algae  into  a
few  dominant  functional  groups  (for  example, green algae,  diatoms, blue-
greens,  dinoflagellates, etc.).

     The first approach  is commonly  used  in river models since the major
focus is  on short  term simulations (days  to  weeks)  where the  primary
interest is the effects of algae on general water quality parameters such as
dissolved oxygen,  nutrients,  and turbidity.  Typical examples  include
QUAL-II (Roesner  et .aJL, 1981; NCASI,  1982, 1983), DOSAG3 (Duke and Masch,
1973), and RECEIV-II (Raytheon, 1974).   In  contrast,   lake  and reservior
models tend to  use the second approach since the focus is on long term
simulations (months to years)  of  eutrophication  problems where  seasonal
variations in  different types of algae  are important (Bierman, 1976; Bierman
£t aj_.,  1973,  1980; Canal e et aj_. ,  1975, 1976; Chen et  al_. ,  1975;  Tetra
Tech, 1979, 1980; Park et aK, 1974, 1975,  1979, 1980;  Scavia et al_., 1976;
Scavia, 1980;  Lehman ^t a]_., 1975).   Species-specific  differences  in
nutrient  requirements, nutrient uptake rates,  growth rates, and  temperature
preference ranges result in a"seasonal  succession of dominance by different
phytopl ankton  groups.  It  is  often important to distinguish these
differences  in order to  realistically model  both nutrient dynamics  and
phytopl ankton dynamics, and to predict the  occurrence  of specific  problems
such as  blue-green algal blooms.   Multi-group models typically use  the same

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general  model formulations  for  all groups, but provide different coefficient
values  to  characterize the  differences between groups.

6.2  MODELING APPROACHES

     Phytoplankton dynamics  are governed  by  the following processes:
growth, respiration  and excretion,  settling, grazing  losses, and
nonpredatory mortality (or decomposition).  A  general  equation  which
includes all  of these processes  and forms the basis for almost all
phytoplankton models can be expressed  as:

                       $ = (/i-  r -  ex - s - m) A - G                (6-1)

where A  = phytopl ankton biomass  or concentration  (dry weight biomass,
          chlorophyll _a, or equivalent mass of carbon, nitrogen,  or
          phosphorus), mass or mass/volume
      ^  = gross growth rate,  I/time
      r  = respiration rate, I/time
      e  = excretion rate,  I/time
       A
      s  = "sett!ing rate, I/time
      m  =, nonpredatory mortality  (or  decomposition)  rate,  I/time
      G  = loss rate due to grazing, mass/time or mass/volume-time

     This equation is appropriate  when phytopl ankton  are modeled in terms  of
either  biomass  or nutrient equivalents (carbon, nitrogen, phosphorous,
etc.).  However, if phytoplankton  are  expressed in terms  of cell numbers,
the growth rate is replaced with the cell division  rate, and the respiration
and excretion terms are omitted since  they  pertain  to  changes in biomass
rather than  cell numbers.  The  resulting equation  is:

                           dA
                           dT '  for,  - S - m) An  - Gn                 ^

where A  = phytoplankton cell  numbers, numbers or  numbers/volume
      fi  = cell division rate,  I/time
                                   281

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      G  =  1 o s s rate  due  to   grazing,   numbers/time   or
           numbers/volume-time

The cell  division rate  in  Equation .(6-2)  is assumed  to  be a continuous
process although in  reality cell  division is  a discrete  event which is often
expressed in  terms of the number of divisions per day, n..   The continuous
division rate u.   is  related to the discrete  rate  n ,  by u  = n . In2.
              r n                                a      n    Q

     Most models express phytoplankton  in terms of biomass  (or nutrient  or
chlorophyll  a  equivalents) rather than cell  numbers.   This facilitates the
modeling of both nutrient cycles and food web dynamics since it allows  a
more direct linkage  between the phytoplankton equations  and the mass balance
equations for both nutrients and higher trophic levels such as zooplankton
and  fish.   Phytoplankton cell numbers are  used  in  a few models whose focus
is restricted to phytoplankton dynamics (e.g., Lehman et aJL, 1975;  Cloern,
1978).

     The major  differences  between different  phytoplankton models  are:
1) the number of phytoplankton groups  modeled, 2) the specific formulations
used for each process, and 3) the manner in which the various processes  and
corresponding terms in Equations (6-1) or  (6-2) are combined.  Some of the
basic features of different phytoplankton models  are compared in Table  6-1.
The specific  process formulations are discussed in later sections.

     Many models combine several of the processes in Equation (6-1)  into  a
single term,  thereby simplifying the equation.  For  example, respiration and
excretion are usually combined into a single  respiration term.   Respiration
is often combined with growth so that the  growth rate  n represents the net
growth rate,  rather  than the gross growth rate as in Equation (6-1).   This
is consistent with net growth  rates  typically reported  in the literature
from laboratory  cultures.  Some models  combine respiration with the other
loss terms  to give a net loss rate which includes respiration and mortality.
Other  models combine grazing and nonpredatory mortality  into a single
mortality term,  particularly when algal grazers are  not  modeled explicitly.
                                    282

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                                TABLE 6-1.  GENERAL COMPARISON  OF ALGAL MODELS
Model
(Author)
AQUA- IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
DEM
OOSAG3
EAM
ESTECO
EXPLORE-1
HSPF
LAKECO
MIT Network
QUAL-II
RECEIV-II
SSAM IV
WASP
WQRRS
Bierman
Canal e
Jorgensen
Lehman
Nyholm
Scavia
Number of Groups
Phyto-
ilankton
1
2
2
3
4
1
1
4
2
1
1
2
1
1
1
1
2
2
5
4
1
5
1
5
Attached Zoo-
Algae plankton
1
1
1 3
1 3
1 5


1 3
1
1
1 1
1
1


1
2
2 1
2
9
1


6

Growth
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
"recesses
Respir-
ation
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X

X
Computed
Settling
X
X
X
X
X
X
X
X
X

X
X

X


X
X
X
X
X
X
X
X
Separately in
Nonpredator^
Mortality
X

X
X
X





X

X

X
X
X

X

X
X
X
X
Model
Predatory
Mortality
X
X
X
X
X


X
X
X
X
X
X



X
X
X
X
X


X
Algal Units
Dry Wt. Other Cell
Biomass Chi a Carbon Nutrient Numbers
X
X
X
X
X
X
X
X
X
X
X
X
N
X
X
X
X X
X
X
X
X
X
X
X
Reference
Baca & Arnett (1976)
WES (EWQOS) (1982)
Bloomfield et al_. (1973)
Scavia & Park (1976)
Park et al_. (1980)
Feigner & Harris (1970)
Duke & Masch (1973)
Tetra Tech (1979, 1980)
Brandes & Masch (1977)
Baca et al_. (1973)
Johanson et al . (1980)
Chen & Orlob (1975)
Harlerean et ah (1977)
Roesner et ah (1981)
Raytheon (1974)
Grenney & Kraszewski (1981
Di Toro et aK (1981)
Smith (1978)
Bierman et a]_. (1980)
Canale et al.. (1975. 1976)
Jorgensen (1976)
Lehman et^ ah (1975)
Nyholm (1978)
Scavia et a]_. (1976)
ro
co
CO

-------
     Because of these  variations, it is very  important to understand  the
assumptions of a particular model when  selecting coefficients.  Care must be
taken both when extracting  values from one model  and applying them  to
another, or when using experimental  measurements reported in the literature.
For the  latter case, the experimental conditions should be checked to make
sure they are consistent  with the assumptions of the model.  If they are
different, the appropriate adjustments  should be made.

     Attached algae  (periphyton)  and aquatic macrophytes  have  the  same
growth requirements as phytoplankton (light and nutrients) and are subject
to  the  same  basic  processes  of growth,  respiration and excretion,
grazing,and nonpredatory mortal ity.  Therefore,  they are usually modeled
using the same  general approach and process formulations as  phytoplankton,
although the specific  values of the model coefficients will vary.  The major
differences are:  1}  periphyton and macrophytes  are associated with  the
bottom substrate and are expressed in terms of area! densities rather than
volumetric densities or concentrations;  2) periphyton and macrophytes  do  not
have settling losses, but  instead they have additional  losses  due  to
sloughing or  scouring  from  the bottom substrate; 3) periphyton  and
macrophytes are not subject to hydrodynamic transport; and 4) macrophytes
use nutrients from the  sediments  and interstitial  waters  rather  than
nutrients  in the water column.  The general  model equation for attached
algae and macrophytes  can be expressed  as:

                     dA
                     ^- (,-r-ex-Sl -m)Ab-Gb             (6-3)

where Ab = periphyton or  macrophyte biomass (dry weight  biomass,
          chlorophyll a, or equivalent mass  of carbon,  nitrogen,  or
          phosphorus), mass or mass/area
     S.j = sloughing or scouring rate,  I/time
     Gb = loss rate due to grazing, mass/time or mass/area-time

Benthic  algae or macrophytes are included in only a few models such as CLEAN
(Park  £_t  aU,  1974),  CLEANER (Park  et  aH.. ,  1975), MS.CLEANER
                                   284

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(Park et a]..,  1980), EAM (Tetra Tech,  1979, 1980), WQRRS  (Smith, 1978), HSPF
(Johanson ^t  aj_. ,  1980), SSAM IV  (Grenney and  Kraszewski, 1981), and in
Canale and Auer  (1982) and Scavia et aj_.  (1975).

6.3  CELL COMPOSITION

     The majority of models express algae and other biological constituents
as either dry weight biomass (Chen and Orlob, 1972; Chen _et .al_., 1975; Park
et a_L, 1974,  1975, 1979, 1980; Tetra  Tech, 1979, 1980;  Brandes and Masch,
1977;  Smith,  1978; Johanson  et _al_., 1980; Grenney and  Kraszewski,  1981;
Bierman jst _al_.,  1973, 1980; Jorgensen, 1976; Jorgensen et aj_., 1978; Nyholm,
1977,  1978) or  carbon  (Baca  and Arnett, 1976;  Baca _et  a]_. , 1973,  1974;
Canale jrt aj_., 1975, 1976; Scavia _et _al_., 1976;  Scavia,  1980).  Nitrogen  or
phosphorus  have also been  used in  a few models, which  focus on a single
nutrient cycle and assume that particular  nutrient  always limits  algal
growth (Najarian  and Harleman, 1975; Harleman et_ £]_.,  1977).  Some models
express phytoplankton as chlorophyll   a since both field measurements and
water quality standards are often' reported in  these units (Roesner et al.,
1981; Duke  and Masch, 1973;  Raytheon, 1974; Di  Toro  et al_., 1971,  1977;
Di Toro and Matystik,  1980;  Di Toro and Connolly, 1980; O'Connor et al_.,
1975; Thomann  et al_., 1975., 1979).

      Dry weight  biomass  is related to  the major nutrients  (carbon, nitrogen,
and phosphorus)  and chlorophyll d. through stoichiometric ratios which give
the  ratios  of each nutrient  to the  total biomass. Typical algal nutrient
compositions  are summarized  in Tables  6-2 to  6-4.   Algae expressed  as
carbon, nitrogen,  phosphorus, or chlorophyll  a can  be  converted to dry
weight biomass or any of the other units  by using the stoichiometric ratios
presented in the tables.

      Most conventional water quality models assume the  nutrient compositions
of the cells  and the resulting stoichiometric  ratios are constant.  In
reality, cell  stoichiometry varies with species,  cell  size,  physiological
condition,  and recent  environmental  conditions  (external  nutrient
concentrations, light, and  temperature), although it is often assumed

                                   285

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Diatoms
Green Algae
                       TABLE  6-2.   NUTRIENT  COMPOSITION  OF  ALGAL CELLS
                                      -  PERCENT OF  DRY  WEIGHT  BIOMASS
Percent of Dry Weight Biomass
Algal Type
Total
Phytoplankton
C
40. -50.
N P
8. -9. 1.5
Si Chi a_ References
Tetra Tech (1976)
                     40.
                     60.
                   40.-50.*
             7.2
             1.0
             6.1
            7.-9.*
            8.-9.*
             0.88
           1.-1.2*
           1.2-1.5*
                     50.*         9.*          1.2*
                 42.9-70.2**   0.6-16.**   0.16-5.**
                               1.5-9.3**   0.08-1.17**
40.
40.
7.2
7.2
1.0
                  19.-50.**    2.7-5.9**    0.4--2.0**
                  20.-53**
1.0
                  35.-48.**    6.6-9.1**   2.4-3.3**
                  15.-74.**
20. -24.
                                                           50.
              Chen  &  Wells  (1975, 1976)
              Tetra Tech  (1980)
              Bowie et  al.  (1980)
              PorcelTa  et al_.  (1983)
    2.        Bierman (1976)
              Nyholm  (1978)
              Jorgensen (1976)
              Smith (1978)
5. -10.*       Roesner et al .  (1980)
              Duke  &  MascTT(1973)
              Brandes (1976)
              Baca  &  Arnett (1976)
              Jorgensen (1979)
              Tetra Tech (1980)
              Bowie et al.  (1980)
              PorcelTa ef al.  (1983)
              Bierman e_t *\_.  ("1976)
              Di Toro et al.  (1971)
              Bierman et al_.  (1980)

              Tetra Tech (1980)
              Bowie et al.  (1980)
              Porcella et al_.  (1983)
              Di Toro et ah  (1971)
              Bierman et al .  (1980)
Blue-green
Algae
40.
7.2
1.0
                  28.-45.**    4.5-5.8**    0.8-1.4**
                  38.-39.**
                                                                    1.-3.**
                                                                     0.25**
              Tetra Tech (1980)
              Bowie et al. (1980)
              PorcelTa et. al. (1983)
              Di  Toro et al_. (1971)
              Bierman e_t a]_. (1980)
              Baca & Arnett  (1976)
              Jorgensen (1979)
                                                 236

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                               TABLE 6-2.  (continued)
                             Percent of Dry Weight Biomass
Algal Type
            N
                      Si
                                          Chl-a
    References
Dinoflagel lates
Flagellates
Benthlc Algae
               37.-47**    3.3-5.0**    0.6-1.1**
               10.-43.**
          7.2
40.
7.2
          1.0
40.
               29.-67.**
Chrysophytes      35.-45.**   7.8-9.0**   1.2-3.0
                     1.0
                40.-50.*     7.-9.*     1.-1.2*
                                         275.      O'Connor et a]_. (1981}
                                                  Di Toro et al.  (1971)
                                                  Bierman et al.  (1980)
Tetra Tech (1980)
Bowie et al.  (1980)
Porcella et ah (1983)
Bierman et al. (1980)
                                                 Jorgensen  (1979)
Tetra Tech (1980)
Bowie et al.  (1980)
PorcelTa e_t al- (1983)
Smith (1978)
 *Hode1 documentation values.
**Literature values.
  constant for  modeling purposes.   Several  of the more recent  algal models,
  however,  have  included variable cell  stoichiometry in their  formulations to
  simulate processes  such as luxury  uptake and storage of  nutrients (Bierman
  et_al_., 1973,  1980; .Bierman, 1976;  Lehman et _aj_.,  1975;  Jorgensen,  1976;
  Jorgensen et  al_.,  1978;  Nyholm, 1977,  1978;  Park et _§_]_.,  1979,  1980;  Canale
  and Auer, 1982).  These models are discussed  later with reference  to
  phytoplankton  growth  and  nutrient uptake  formulations.

  6.4  GROWTH

       Algal  growth  is  a  function of  temperature, light, and  nutrients.  The
  major growth limiting nutrients are  assumed  to be phosphorus, nitrogen,  and
  carbon,  with  the  addition  of  silicon  for  diatoms.   Other essential
  micronutrients such  as  iron, manganese,  sulfur,  zinc,  copper, cobalt,
                                         287

-------
molybdenum, and  vitamin B,2  may also  limit growth under  conditions of
restricted availability (particularly in  oligotrophic systems).  However,
these  effects are  generally  not included in models since micronutrients
are usually not  simulated.   The algal  growth rate formulations used in
almost all models can be expressed in general functional  form as:
       =/zmax(T
                               ref
                                  )  f(T)
where
          ^ ref'
      f(T)
      T
      f(L,P,N,C,Si)
      L
      P
      algal growth rate, I/time
      maximum growth rate  at  a particular reference
      temperature Tref under optimal  conditions of
      saturated light intensity and excess nutrients,
      I/time
      temperature function for growth
      temperature,  C
      growth limiting function for light and nutrients
      light intensity
      available  inorganic  phosphorus  concentration,
      mass/volume
                TABLE  6-3.   NUTRIENT COMPOSITION  OF  ALGAL  CELLS
                               -  RATIO  TO  CARBON
Algal Type
Total
Phytoplankton
N
C
0.17 - 0.25
0.18
P
C
0.025
0.024
Si
C References
Thomann & Fitzpatrick (1982)
Di Toro et al_. (1971)
Scavia et al . (1976)
   Diatoms
    0.2
0.05 - 0.17**  0.024 - 0.24**
0.05 - 0.43**  0.025 - 0.05**

    0.18        0.024        0.6
0.067 - 0.21** 0.003 - 0.14** 0.06-0.77**
Scavia (1980)
Canale et a]_. (1976)
Baca & Arnett (1976)
Jorgensen (1979)

Scavia (1980)
Jorgensen (1979)
  **Literature Values.
                                    280

-------
                   TABLE  6-4.   NUTRIENT COMPOSITION OF  ALGAL CELLS
                                -  RATIO TO  CHLOROPHYLL  a
Algal Type
             	N
             CFTa
          	P
          ChTa
  Si
WTa
References
Total
Phytoplankton
Diatoms
Green Algae
Blue-green
Algae
Dinoflagellates
 50.-100.      7.-15.      0.5-1.0
                              7.2

                25.-112.**   7.-29.**

                10.-100.**  2.7-9.1**
                        0.5

                        0.63

                        1.0**
   100.       10.-15.      0.5-1.0     40.-50.



                         0.5

50.-200.*

18.-500**  2.2-74.6**  0.27-19.2**   2.4-50.7**


25.-100.*



 14.-67.*
   275.
19.3
             Thomann et al.  (1975, 1979)
             O'Connor et al.  (1981)
             Di Toro & Matystik (1980)
             Di Toro & Connolly (1980)
             Salas & Thomann  (1978)

             Salisbury et al_. (1983)

             Larsen et aj_.  (1973)

             Jorgensen (1979)

             O'Connor ejt al_.  (1981)


             Di Toro & Connolly (1980)
             Di Toro & Matystik (1980)
             Thomann e^ al.  (1979)

             Salisbury e^ al_. (1983)

             Baca & Arnett  (1976)

             Di Toro et al-  (1971)


             Baca & Arnett  (1976)



             Baca & Arnett  (1976)


             O'Connor et al.  (1981)
 *Model documentation values.
**Literature values.
       N


       C


       Si
      =  available  inorganic  nitrogen concentration,
         mass/volume
      =  available  inorganic  carbon concentration,
         mass/volume
      =  available  inorganic  silicon concentration,
         mass/volume
       Note  that the  growth limiting function f(L,P,N,C,Si)  is simplified  in
many models  by  excluding  some  of  the  nutrients.   For  example,  silicon  is

                                         289

-------
included  only in models  which simulate  diatoms as a separate  algal  group
(Bierman _et _§]_.,  1973, 1980;  Bierman,  1976;  Canale e_t a]_.,  1975, 1976;
Scavia £t  al_., 1976;  Scavia, 1980;  Chen  et_ _al_.,  1975; Tetra  Tech,  1979,
1980; Lehman _et _a]_,  1975; Park et _aj.,  1979, 1980; Di Toro and  Connolly,
1980).  Carbon is frequently omitted since it  is often available in excess
relative  to phosphorus and nitrogen (Bierman  e_t jj_., 1980;  Scavia et al.,
1976; Nyholm,  1978;  Canale* et aj_., 1975,  1976;  Baca and Arnett,  1976;
Di Toro  and Matystik, 1980).  Some  models include only  one nutrient,
phosphorus or nitrogen,  and assume that  nutrient,is  limiting at all  times
for the  particular system  under consideration (Najarian and  Harleman, 1975;
Canale and Auer, 1982).

     It  should  also  be  noted that the nutrient  concentrations in the growth
limiting function f(L,P,N,C,Si) correspond to  the "external"  nutrient
concentrations  in the water for some models,  and to the "internal"  nutrient
concentrations in the algal cells for other models.  These distinctions will
be discussed in  more  detail below.

6.4.1 Temperature Effects  On Maximum Growth Rates

     The  quantity f*  ^(T^ J f(T)  in Equation  (6-4) represents  the effects
                   fflaX  i  GT
of temperature variations on maximum algal growth rates under  conditions  of
optimum  light and nutrients.  The maximum  growth rate u_av must  be  specified
                                                    tHaX
at a reference temperature  T  - which  is consistent with the  particular
temperature function f(T)  used in the model.  The reference  temperature may
correspond  to  20°C,  optimum  temperature  conditions, or  some other
temperature, depending  on  the form of the temperature function.  Therefore,
maximum growth rate coefficients obtained from one model may  have  to  be
adjusted before using  the coefficients in another model  which  has  a
different  temperature adjustment function.  Maximum growth rates for  algae
are  tabulated  in Table  6-5,  along with  the  corresponding reference
temperatures.

     Although numerous temperature adjustment functions have  been used to
model a.lgae, most of them  fall  into one  of three  major  categories

                                   290

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                       TABLE  6-5.   ALGAL MAXIMUM  GROWTH  RATES
Algal Type
                     Maximum Growth
                     Reference,
Rate (I/day)     Temperature (  C)
                           References
Total
Phytoplankton
  1.3   2.5
                        1.   2.5




                         1.   2.

                           1.5

                        1. - 2.7


                           1.5

                       1.8   2.53


                           2.4

                        0.2   8.*

                        1.   3.*

                        1.   3.*


                        0.2   8.*

                        1.5   2.*

                       0.58   3.**
20°C
                       20°C
                       20°C

                       20°C
                       'opt
                       20°C
                        opt
                       'opt
                       20°C
                       'opt
                       20°C
                       20°C

                       20°C

                       20°C
O'Connor et al_. (1975, 1981)
Thomann et al_.  (1974, 1975,  1979)
Thomann & Fitzpatrick (1982)
Di Toro & Connolly (1980)
Di Toro & Matystik (1980)
Di Toro et al_.  (1971, 1977)
Salas & Thomann (1978)
Salisbury et al_.  (1983)

Chen (1970)
Chen & Orlob (1975)
Chen & Wells (1975, 1976)
Tetra Tech (1976)

Battelle (1974)

Grenney & Kraszewski  (1981)

Scavia & Park (1976)
Younjgberg (1977)

Nyholm (1978)

Jorgensen (1976)
Jorgensen ejt al_.  (1978)

Larsen et al_. (1973)

Baca & Arnett (1976)

Smith (1978)

Roesner et. al_.  (1980)
Duke & Masch (1973)

Grenney & Kraszewski  (1981)

Brandes (1976)

Jorgensen (1979)
 Diatoms
     2.1



   2.0   2.5



  2.0 - 2.1

     2.1

     1.6

  1.8 - 2.5


     3.0
                                             20°C
                                              'opt
                                             20°C

                                             25°C

                                         10° - 14°C
                                              'opt


                                              Topt


                                            29.1
                Di Toro & Connolly (1980)
                Thomann et al_. (1979)
                Salisbury et aJL.  (1983)

                Tetra Tech (1980)
                Bowie et al_.  (1980)
                PorcelTa et a]_. (1983)

                Canale et al_.  (1976)

                Bierman (1976)

                Bierman et^ al_. (1980)

                Scavia et al_.  (1976)
                Scavia TT980)

                Lehman et al.  (1975)

-------
TABLE 6-5.  (continued)
Maximum Growth Reference
Algal Type Rate (I/day) Temperature ( C)
1.75**
0.55 3.4**
1.1 5.0**
Green Algae 1.9
1.4
2.0 - 2.5
1.9
1.8 - 2.5
1.6
3.0
1.5 3.9**
0.7 - 2.1**
0.9 4.1**
9.0 9.2**
1.4 2.4**
1.5 3.9**
1.3 4.3**
5.65**
Blue-green Algae 0.8
0.7 - 1.0
1.6
1.4 - 1.9
1.1 - 2.0
1.1
2.5
1.6 2.5
0.41 - 0.86**
0.2 4.9**
2.0 3.9**
0.5 11.**
27°C**
20°C**
20°C**
25°C
20°C
Topt
20°C
Topt
25°C
Topt
25°C**
20° C
25°C**
39°C**
20°C**
25°C**
35°C**
40°C**
25°C
20° - 25°C
20°C
Topt
Topt
25°C
Topt
Topt
20°C**
25°C**
35°C**
40°C**
References
Di Toro et al. (1971)
Collins & Wlosinski (1983)
Jorgensen (1979)
Bierman (1976)
Bierman_£t al. (1980)
Tetra Tech (1980)
Bowie et al. (1980)
PorcelTa et al_. (1983)
Canale et a]_. (1976)
Scavia et al. (1976)
Scavia "(T980)
DePinto ejt al_. (1976)
Lehman et al_. (1975)
Di Toro et al. (1971)
Collins & Wlosinski (1983)

Jorgensen (1979)


Bierman (1976)
Bierman ejt &\_. (1980)
Canale et al. (1976)
Youngberg (1977)
Scavia & Park (1976)
Scavia (1980)
DePinto et al- (1976)
Lehman et a^ (1975)
Tetra Tech (1980)
Bowie et al. (1980)
PorcelTa et ah (1983)
Jorgensen (1979)
Collins & Wlosinski (1983)

        292

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                           TABLE 6-5.   (continued)

Algal Type
Dinoflagellates


Flagellates


Chrysophytes

Maximum Growth Reference
Rate (I/day) Temperature ( C)
0.2 - 0.28
2.16**
0.2 2.1**
1.6
1.2
1.5
1.5
0.4 2.9**
20°C
20°C
20°C
Topt
20°C
Topt
Topt
25°C**
References
O'Connor e_t aj_. (1981)
Di Toro et af[. (1971)
Collins & Wlosinski (1983)
Tetra Tech (1980)
Porcella et_ aj_. (1983)
Bierman et aj_. (1980)
Lehman et aj_. (1975)
Lehman et_ al. (1975)
Collins & Wlosinski (1983)
Coccolithophores

Benthic Algae
                      1.75   2.16"
                        0.5   1.5
25°C**
                                         opt
Jorgensen (1979)
             Tetra Tech (1980)
             Porcella et al.  (1983)
1
1
0.2
0.5
.08
.5
0.8*
1.5*
Topt
20°C
20°C
Topt
Auer and Canale (1982)
Grenney & Kraszewski (1981)
Grenney & Kraszewski (1981)
Smith (1978)
     *Model  documentation values.
    **Literature values.

(Figure 6-1):   1)  linear increases in growth rate  with-temperature, 2)
exponential increases in growth rate  with temperature, and 3)  temperature
optimum curves in which the growth  rate  increases  with  temperature up to the
optimum temperature and then decreases with  higher temperatures.

     The simplest  type of temperature  adjustment function assumes a linear
temperature  response  curve  above some minimum  temperature  T^.   This
relationship can be expressed in  general form as:
                                      293

-------
                         f(T) =
 T - Tmin

ref ~  min
(6-5)
                                      1.
                                'Tref " Tmin
                                             T -
                      min
                   ref    min
                                   T + j8
where T .   = lower temperature  limit at which the growth rate is zero,

                 °C
                                                    Exponential  /
                                                    Curve       .'
                                                      Temperature
                                                      Optimum
                                                       Curve
                                   TEMPERATURE,°C
         Figure 6-1.   Major types  of  temperature  response curves for
                      algal growth.
                                    294

-------
      T   - = reference  temperature corresponding to the value  of the
            maximum growth  rate u   (T  f),  C
                                ITlaX  i cl

      y   =  TJ	j-^	r  = slope of growth vs. temperature curve
               ref   min

       j3  =  T	Y	 = y-intercept of growth vs. temperature
              ref "  min   curve
This equation  is  typically used in  simplified form by choosing a lower
temperature limit Tmi. equal to zero so that Equation (6-5)  becomes:


                              f(T) =  J—                          (6-6)
                                      ref

Reference temperatures of either 20°C or 1°C  are usually used which  results
in:
                               f(T) =  o                           (6"7)

or                             f(T) = T                            (6-8)

This approach  is  used in EXPLORE-I  (Baca _et  a]_.,  1973) and  RECEIV-II
(Raytheon,  1974) and by Di Toro _et al. (1971)  in an early version of WASP.

     Some models use  piecewise  linear functions for  algal  growth with
different  slopes  over- different temperature ranges (Bierman _et  TQ                                     (6-9b)

                                   295

-------
with                     u    (T   _) = n   (T  J                     (6-9c)
                         ^     ref    ^maxv opt'                     v
where T    = optimum temperature at which the growth rate is maximum,
       °P    °c

This  assumes growth  increases  linearly with temperature until the maximum
growth rate is attained,  and then remains at the maximum rate as temperature
increases further.
     The most commonly used exponential temperature adjustment functions are
based on the Arrhenius or van t Hoff equation:

                                        10
where K,   = reaction  rate at temperature T,
      K~   = reaction  rate at temperature T,,
      Q1Q = ratio  of  reaction rates at 10°C temperature increments

This equation can  be  rearranged into a more useful form as:
                            K2 = Kj Q10\~TO~7                       (6-11)

                                            f'M
°r                        K(T) = K(Tref) Q10\  10  /                 (6-12)
                               = K(Tref) f(T)

where f(T)  is  the  temperature adjustment function:
                             f(T) = Q10V^^~/                      (6-13)

The temperature adjustment function (Equation (6-13)) is generally expressed
in a more simplified  form as:

                                    296

-------
                         f(T) - Q-ref                     (6-14)
                              - fl
where 0 =  Q-,^      ' = temperature adjustment  coefficient

The  temperature  adjustment coefficient 8 typically has a value between  1.01
and 1.2, with  a value of 1.072 corresponding to a doubling  of the growth
rate  for  every 10°C increase  in temperature.  Eppley (1972) found that 6
equals  1.066  for an exponential envelope  curve  of growth  rate  versus
temperature data compiled  from a large number of studies involving  many
different  species  (Figure 6-2).

     Most  models which  use exponential temperature functions assume a
reference  temperature of 20°C which gives the familiar equation (Chen  and
Orlob, 1975; Baca  and Arnett, 1976; Roesner et_ _a]_. , 1981; Brandes and Masch,
1977; Duke and Masch, 1973; Thomann et _al_. , 1979; Thomann  and  Fitzpatrick,
1982;  Di  Toro and Matystik,  1980; Di  Toro and Connolly, 1980;  O'Connor
et_al., 1981):

                             f(T) = 0 (T'20  C)                      (6-15a)

with                    Mmax(Tref) = /VX(20°C)                     (6-15b)

However, Thomann _et jil_. (1975) and Eppley (1972)  use a reference temperature
of 0°C which results in:

                                f (T)  = #T                          (6-16a)

With                     "max^ref > * "C>                     (6-16b)
     The above  equations assume that the  temperature adjustment coefficient
8 has the same value regardless of the reference temperature.   However,  a
few models  have applied Equation (6-14)  in  a piecewise manner assuming  that
the value of 0 varies over different temperature intervals.
                                   297

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     Many formulations have been used to generate temperature  optimum  curves
for algal growth.   The reference temperature is generally set  at  the optimum
temperature for maximum growth, and the temperature adjustment  function  is
normalized so it  has  a maximum value of 1.0 at the optimum temperature and
smaller  values elsewhere.  Most curves begin with a zero value at  the  lower
temperature tolerance  limit, increase to a maximum value  of  1.0  at the
optimum  temperature, and then decrease back to a value  of zero at  the  upper
temperature tolerance limit.  These types of curves are  typically  based on
growth vs.  temperature data for a single species.  These data  generally show
no growth at very low temperatures followed by an  exponential increase in
                       10
                                  20          30
                                 TEMPERATURE °C
    Figure 6-2.
Envelope curve  of  algal growth rate versus temperature
for data compiled  from many studies involving many
different species  (adapted from Eppley, 1972; Goldman,
1981).
                  298

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growth with  temperature  over a large  part of the  temperature range.
However,  the growth rate eventually levels  off  to  some maximum value at  the
optimum  temperature, and  then begins  to  decline at very high temperatures
until growth finally ceases at some upper temperature limit.

     Lehman et_ _al_. (1975) use a skewed  normal  distribution as a temperature
optimum curve  for  phytoplankton growth.   The equation is:
with
                      f(T) = exp
                   M   (T  *
                   ^maxv ref
[ 2 3 ( T ' Ml
[ • (\ - v' J
,) = a (T . )
f ^max opt'
(6-17a)
(6-17b)
where T    = optimum temperature at which the  growth rate is maximum,
       °P    °c
Tx   = Tmin
                     T <-
           = Tmax  for  T > Topt
      Ti  = lower temperature limit at which the  growth rate is zero,
      T    = upper temperature tolerance limit at  which growth ceases,
       Ilia A
Jorgensen (1976)  and Jorgensen _et al_. (1978) use a  modified form of Equation
(6-17a) which is  expressed as:
                         f(T) = exp (-2.3
                                             T  - T
                                           opt
                                            opt  ~  min
                                                              (6-18)
    Several  models including  CLEAN (Bloomfleld  et _al., 1973),  CLEANER
(Scavia  and Park, 1976),  MS.CLEANER  (Park  et ^1,  1979, 1980), and Scavia
^t _al_. (1976) use  a temperature optimum function originally developed  by
Shugart e_t jTL  (1974).  This formulation can be expressed as:
                            f(T) = Vx ex(1'V)
                                                             (6-19a)
                                    299

-------
                                V =   ma* "	                       (6-19b)
                                     max"  opt
                                x =
(6_19c)
                                W ' 
-------
where K  = a scaling  constant used in the original  equation  from which
           Equation  (6-21a) was derived,
                        df(T]
                         dt
            =  K
/  Tmax  -  T   \
\  max  ~  opt/
                                                (6-21c)
These equations  result  in a temperature optimum curve  which  is  always skewed
to the right.

     Thornton  and Lessem (1978)  developed  a temperature  optimum curve by
combining two  logistic  equations, one describing  the rising  limb  of the
curve  below the optimum temperature and one describing  the falling  limb of
the curve above  the optimum temperature.  The second curve  is rotated about
the y-axis  and shifted to the right along the x-axis until  the  approximate
peaks of both  curves  coincide.  The left side  of the  temperature  curve is
expressed as:
VT>	Vy.(T-T_.
        1  +  1<
                                                                   (6-22a)
1
1 (Topt(l)
., 1n
- T '. ) '"
min'
~K2 (1 - Kj)"
Kj (1 -
K2)
                                                                   (6-22b)
and the right  side  is expressed as:
                                           max
                                              -T)
                                                '
                                              •T)-  l]
                                                                   (6-23a)
                                                                   (6-23b)
                                    301

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where T   tm=  lower limit of optimum  temperature range,  C
      opt { i j
      T   t(p\=  upper limit of optimum  temperature range,  C
      y,     =  rate coefficient for left  side of curve
      y~     =  rate coefficient for right  side of curve
      K,     =  rate multiplier near the lower temperature limit
      K.     =  rate multiplier near the upper temperature limit
      K2     =  0.98
      K3     =  0.98

The  temperature curve  is  defined as  the  product of Equations (6-22a)
and (6-23a):

                            f(T)  = KA(T)  Kgd)                      (6-24a)

with
By using different values of the logistic  equation parameters for each  side,
an assymmetric  growth curve can be generated.  The values of K»  and K, are
set equal  to 0.98 rather than 1.0 so  that the peak of the combined  logistic
equation is close to 1.0 (since the logistic equation would  otherwise only
approach  1.0  assymptoti cal ly) .   Two values of the optimum temperature,
^oot(l)  anc' ^oDt(2)' are usec^ to a^ow an  opt"1'"111111 temperature range, rather
than a  single  optimum temperature value.  This formulation is  used in CE-
QUAL-R1  (WES, 1982), WQRRS  (Smith, 1978), and EAM (Tetra Tech, 1979, 1980).
The left  side  of the curve (the  basic logistic equation, Equation  (6-22a))
is also  used as a temperature adjustment curve in SSAM IV  (Grenney and
Kraszewski, 1981).

     The MIT one-dimensional network model (Najarian and Harleman,  1975;
Harleman ^t aj_. , 1977) uses a temperature  optimum curve which is  defined as:
                                                    forT<  V
                                   302

-------
                           rT - T
                         T    _ °pt  1              for T > T
                          max    opt '
with                       maxref    maxopt                  (6-25c)
The values of the exponents n and m are  2.5 and 2.0,  respectively (Najarian
and Harleman, 1975) .

     Some type of temperature  optimum  curve is generally more appropriate
than a linear or exponential formulation when  considering a single algal
species  or functional  group, since growth usually slows  down and eventually
ceases above  some upper temperature  limit for any  given species.  This
approach  is  used in  most models which simulate several  algal groups (e.g.s
Chen^t aj_.,  1975; Tetra Tech, 1979, 1980; Park et a]_. ,  1979, 1980; Canal e
_et aj_.,  1975,  1976;  Scavia _et aj_. , 1976; Lehman et ^K ,  1975; Smith, 1978;
WES, 1982), since seasonal  variation  in temperature is one of the major
factors  causing  seasonal  succession in the dominance  of different groups
(diatoms, greens, blue-greens, etc.).  However,  since many species are
lumped  into  a  few functional  groups, the temperature optimum curves and
maximum  growth  rates should  be defined  so  that  they  encompass  the
temperature-growth  curves  of all dominant species  in  the defined groups.
Canale and Vogel  (1974) developed  a set of temperature-growth curves for
diatoms, green  algae, blue-green algae,  and  flagellates based on a
literature review of growth data for many species (Figure 6-3).

     Since the temperature function includes both the effects of increasing
temperature on the growth rates of many individual species as well as shifts
in the  species  composition  toward dominance by warmer  water species,  some
modelers  have  preferred to  use exponential  or linear  formulations
over  the whole  temperature range, particularly when  only one or two groups
are simulated (Chen and Orlob, 1975; Thomann  _et  al . ,  1979; Di Toro and
Matystik, 1980;  Di  Toro and Connolly, 1980; Nyholm,  1978).  This assumes
that as temperature increases, the  species  composition changes  so that
species  with  optimum temperatures near the ambient temperature (and  with

                                    303

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                                Mixed Population  .
                              TEMPERATURE,°C
       Figure 6-3.  Temperature-growth curves  for  major algal groups
                   (from Canale and Vogel, 1974).
higher maximum growth rates)  tend to dominate the phytoplankton assemblage.
Eppley (1972) showed that an  exponential relationship describes the envelope
curve of growth rate versus temperature data from a large  number of  studies
with  many  different species  (Figure 6-2).  However, this approach may
overestimate the net growth of  the assemblage if the growth  rates  are  based
on the  maximum  growth rate of the  species assumed to  be dominant at any
given  instant,  since much of the  biomass will  include  species which
predominated earlier under  different temperature conditions  (Swartzman and
Bentley, 1979).  Exponential  or linear functions which increase indefinitely
with  temperature can also be  justified in situations where the maximum water
temperatures  are always  below the  optimum temperatures  for the  species
present. For example, Canale and Vogel (1974)  assumed a linear relationship
below the temperature optimum for each algal group in Figure 6-3.
     The temperature  formulations  used in different models  are compared in
Table 6-6.

                                   304

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TABLE 6-6.  COMPARISON OF TEMPERATURE ADJUSTMENT FUNCTIONS FOR ALGAL GROWTH

Temperature Formulation (Equation No.)
Model Optimum Other
(Author) Linear Exponential Curve Curve
AQUA-IV 6-14
CE-QUAL-R1 6-24
CLEAN 6-19
CLEANER 6-19
MS. CLEANER 6-19
DEM 6-14
DOSAG3 6-14
EAM 6-24
ESTECO 6-14
EXPLORE-1 6-6
HSPF piecewise
linear
saturation
LAKECO 6-14
MIT Network 6-25
QUAL-II 6-14
RECEIV-II 6-6
SSAM IV logistic
equation
WASP 6-14
WQRRS 6-24
Bierman piecewise piecewise
linear linear
saturation
Canal e piecewise
1 inear
Jorgensen 6-18
Lehman 6-17

Nyholm 6-14
Scavia 6-19
Reference
Temperature
20°C
Topt
Topt
Topt
Topt
20°C
20°C
Topt
20°C
1°C



20°C
Topt
20°C
1°C
20°C

20°C
Topt



1°C

Topt
rtn-f
opt
20°C
Topt
Reference
Baca & Arnett (1976)
WES (EWQOS) (1982)
Bloomfield et al. (1973)
Scavia & Park (1976)
Park et a]_. (1980)
Feigner & Harris (1970)
Duke & Masch (1973)
Tetra Tech (1979, 1980)
Brandes & Masch (1977)
Baca et al. (1973)
Johanson et aK (1980)


Chen & Orlob (1975)
Harleman et al. (1977)
Roesner et a]_. (1981)
Raytheon (1974)
Grenney & Kraszewski (1981)

Di Toro et al. (1981)
Smith (1978)
Bierman e_t al. (1980)


Canale et al- (1975, 1976)

Jorgensen (1976)
Lehman et a^ (1975)

Nyholm (1978)
Scavia et al. (1976)
                                    305

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6.4.2   Algal Growth Limitation

     In addition to temperature  effects, algal growth rates are  limited by
both  light and  nutrient availability.   As  mentioned above, only
macronutrients (phosphorous, nitrogen, carbon, and  silicon) are  generally
included  in models.   Growth limitation was expressed previously as the
factor f(L,P,N,C,Si) in the algal  growth equation:

                     H =  n   (T   ,) f(T) f(L,P,N,C,Si)               (6-4)
                     r    pmax  ref  v '  v  '  '  '  '  '                   '

Separate  growth  limiting factors are typically computed for light and each
potentially limiting nutrient.   The number of nutrients considered will vary
between models depending on the  particular system under consideration.  Each
growth limitation factor can range from a value of 0 to 1.  A  value of 1
means  the  factor does not limit  growth (i.e., light  is at optimum  intensity,
nutrients  are available in excess, etc.) and a value of 0 means  the  factor
is so  severely limiting that growth is stopped entirely.

     Four  major approaches have  been  used to  combine the limiting  factors
for light  and each limiting nutrient:

     1)  a multiplicative formulation in which all  factors are multiplied
         together:

                     f(L,P,N,C,Si)  = f(L) f(P)  f(N) f(C) f(S1)        (6-26)

        where f(L)  = light limitation factor
              f(P)  - nutrient  limitation factor for phosphorous
              f(N)  = nutrient  limitation factor for nitrogen
              f(C)  = nutrient  limitation factor for carbon
              f(Si) = nutrient  limitation  factor  for silicon (for
                      diatoms)

     2)  a minimum formulation  in  which the most severely limiting  factor
         alone is assumed to limit growth:
                                   306

-------
      f(L,P,N,C,Si) = min [f (L) ,f (P) ,f (N) ,f (C) ,f (Si )]        (6-27)

where min l~x, jX^.x^ , .. .1 = minimum of each  factor  x.
                                                          .
     3)   a  harmonic mean formulation  which combines the reciprocal  of each
         limiting factor in the following manner:
             f(L,P,N,C,Si) =  1 - - - - —     (6-28)
                            1TL7 +
        where n = number of limiting  factors  (5 in this case)

     4)  an arithmetic  mean formulation  which uses the average of each
        1 i mi ting factor:
             f(L,P,N,C,Si) = f(L) * f(P)  *  f(N) * f(C) * f(S1)         (6_2g)

     The multiplicative formulation  has been used in many models  (Chen and
Orlob,  1972,  1975; Di Toro et al_. , 1971,  1977; Di Toro and Matystik,  1980;
Di Toro  and  Connolly,  1980;  Thomann et  a_K , 1975, 1979; O'Connor et _al_. ,
1975; Jorgensen, 1976; Jorgensen et al_. ,  1978;  Canale el ll- ,  1975,  1976;
Lehman _et  ci]_. ,  1975; Roesner e_t aj_., 1981; Baca et aj_. , 1973; Duke and
Masch,  1973;  Brandes and Masch, 1977).  This  approach assumes  that several
nutrients  in short supply  will more severely  limit growth  than a  single
nutrient in short supply.  The major criticism of this approach is  that the
computed growth rates  may  be excessively  low  when several  nutrients are
limiting.  Also, the severity of the reduction increases with the  number of
limiting nutrients considered in the model, making comparison between  models
difficult.  Many models assume that light limitation is multiplicative, but
use  one  of the  other approaches for nutrient  limitation (e.g., Bierman
et jj]_., 1980; Bierman, 1976; Baca and  Arnett,  1976; Nyholm, 1978;  Raytheon,
1974).

     The minimum formulation is based  on  "Liebig's law of the minimum" which
states  that  the factor  in shortest supply  will control the growth  of  algae.

                                  307

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This approach  has been popular in  many recent algal  models  (Bierman et a!. ,
1980; Park  et aj[. , 1979, 1980; Scavia, 1980; Smith 1978;  Tetra Tech, 1979,
1980; WES,  1982; Johanson et a\_.,  1980; Grenney and Kraszewski ,  1981; Chen
j?t _al_.,  1975;  Baca and Arnett, 1976).  The minimum formulation  is  often used
only for nutrient limitation, with a multiplicative formulation for the
light limitation factor.

     The harmonic mean  formulation is based on  an electronic  analogy of
several  resistors in series.  The rationale for this formulation  is that it
includes some  interaction between  multiple limiting nutrients,  but it  is not
as  severely limiting as the multiplicative formulation.   This approach has
been used in only a  few models, for example, the original  CLEAN (Bloomfield
et  a_K, 1973) and CLEANER (Scavia and Park, 1976) models  and Nyholm  (1978).
The current version  of MS.CLEANER   (Park _et ^1_. ,  1980) has  abandoned this
formulation in favor of the minimum formulation.  In fact,  the  harmonic mean
formulation and minimum formulation produce similar growth  response curves
under a wide range of conditions (Swartzman and Bentley, 1979).

     The rationale for the arithmetic mean formulation is  the same as for
the  harmonic mean  formulation (i.e., it considers the effects  of multiple
nutrient limitation, but  is not as severely limiting as the  multiplicative
formulation).   However, this  formulation  (e.g., Patten, 1975; Patten et aj_.,
1975) is rarely used since it does not restrict growth enough.  For example,
the  arithmetic mean formulation allows growth even if a  critical  nutrient
such  as phosphorus is totally absent,  as long  as  other  nutrients  are
available.

     These  and other formulations  for combining multiple growth  limitation
factors are reviewed in De Groot (1983),

6.4.3  Light Limitation

     Light  limitation  formulations consist  of two  components: 1)  a
relationship describing the attenuation of light with depth  and  the effect
                                   308

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of  algae on light attenuation, and  2) a relationship  defining the effect  of
the resulting light levels on algal  growth and photosynthesis.

     The attenuation of light with depth  is  defined in essentially all
models by the Beer-Lambert law:

                              I(z)  = IQ e'yz                        (6-30)

where I(z)  = light intensity at depth z below the surface
      z    = depth, length
      I    = light intensity at the  surface
      y    = light extinction coefficient, I/length

The light intensity at the surface I  is  a  function of location,  time of
year, time  of  day, meterological  conditions, and shading from topographic
features  or  riparian vegetation.  The surface light  intensity used  in the
algal growth  formulations  corresponds  only to the visible range, which  is
typically about 50 percent of  the total  surface solar radiation used  in the
heat budget  computations.  Almost all radiation outside of  the visible range
is absorbed  within the first meter  below  the surface (Orlob, 1977).  In
addition, some models (for  example,  MS.  CLEANER) assume that only a portion
of the visible  radiation  (about 50%)  is  available for photosynthesis  (Park
tst a].., 1980; Strickland, 1958).

     Light attenuation in models differs  primarily in the way  the  light
extinction  coefficient X is formulated.  The simplest approach is to assume
a constant  value  of   y.   This approach  is reasonable  for short term
simulations  or over  periods when turbidity does not change  significantly.
However,  in  long term simulations,  y should be computed dynamically to
account  for  seasonal variations  in turbidity due to  algal shading or
variations in suspended solids  loads.

     The  light  extinction coefficient is  most commonly defined as  the linear
sum of several  extinction coefficients representing each component of light
absorption.   The  components include  all  suspended particulates
                                   309

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(phytoplankton, zooplankton, organic and  inorganic particulates) as well  as
dissolved organic matter.  The general  equation is:


                           y = y  + i>,                          (6~31)
                                0   1=1  1

                             = y  + Eajci                        (6~32)
                                    i=l

where y  = base  light  extinction coefficient  for water without
          particulates or dissolved organic matter,  I/length
      y. = light extinction coefficient corresponding to  each component
          of light absorption i, I/length
      n  = total number of absorption  components considered  in  the
          formulation
      C. = concentration of absorption component i, mass/volume
      a. = coefficient  for  absorption component i  relating  the
          concentration C. to the light  extinction coefficient  y^

     Many models include the effects of  all components except phytoplankton
in the base  extinction  coefficient  y   (by assigning a higher  value),  and
then compute  the temporal variations  in  y as  a  function of the  algal
densities  only.  This assumes phytoplankton  blooms are the major  cause  of
turbidity  changes.  Equation  (6-32) then  becomes:

                             y = yQ +  aj_ A                        (6-33)

where y  = light extinction coefficient for  all absorption  components
          but phytoplankton, I/length
      a, = coefficient relating the phytoplankton concentration A to
          the corresponding  light extinction  coefficient  for
          phytoplankton  (also called the self-shading factor),
          I/(length-mass/volume)
      A  = phytoplankton concentration,  mass/volume
                                  310

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This provides a way of incorporating self-shading  effects in the light
limitation  portion of the algal growth formulation.  Some models which  use
this approach use a nonlinear  formulation to describe  the relationship
between the phytop 1 ankton  concentration  and the  light  extinction
coefficient.  The general  expression is:

                                             b?
                          Y =  yQ + a1 A + a2 A *                     (6-34)

where apa^  = coefficients of the equation relating phytop 1 ankton
             concentrations to  the light extinction coefficient
      ^2    ~ exponent  of the  equation  relating  phytop 1 ankt on
             concentrations to  the light extinction coefficient

     The second component of the  light limitation  formulation represents  the
light  limitation factor f(L)  in Equations (6-26) through  (6-29).  f(L)
defines the  relationship between  ambient light levels  and algal  growth rates
or rates of photosynthesis.   Essentially all formulations fall  into one of
two major categories (Figure 6-4):   1)  saturation type  relationships  in
which  the growth rate increases linearly with light at low intensities, but
gradually levels off at high intensities to reach a maximum  value at the
optimum (or  saturating) light  intensity, or 2) photoinhibition relationships
which are similar to the above  curves below the optimum light intensity, but
which  predict  decreases  in growth rates above the optimum intensity due to
photoinhibition effects.

     Saturation type  responses are  typically described  by either a
Michael is-Menten (1913) type relationship (Chen and Orlob, 1975; Jorgensen,
1976; Duke and Masch, 1973;  Tetra Tech, 1979; Roesner et al_. , 1981;  Johanson
et_a]_., 1980; Smith, 1978;  WES,  1982):
where f(L)  =  light limitation  function for algal  growth
      I     =  light intensity
                                  311

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           =  half-saturation constant defining the light  level  at  which
             growth  is one-half the maximum rate
or a Smith  (1936) formulation (Park et _a_L,  1980):
                           f(L) =
                                                                   (6-36)
where a.  =  constant in the Smith formulation (1/a^ is the  slope  of  the
           linear portion  of the photosynthesis  vs.  light curve),
           I/light
LU

CC
X
  o
  oc
                                             Photoinhibition
                                             Curve
                              LIGHT  INTENSITY

      Figure 6-4.   Comparison of light response curves for algal  growth.

                                   312

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     Vollenweider  (1965)  modified the  Smith formulation  to  give a more
general relationship  of  which the Smith  equation is a special  case.  The
Vollenweider form includes photoinhibition effects, and is expressed  as:
                   f(L) = /	^=W .	L=\           (6-37)
where a^  =  photoinhibition factor,  I/light
      n   =  exponent

Baca and  Arnett  (1976) use this  formulation in AQUA-IV  with the exponent  n
equal to  1.

     The  most commonly used  photoinhibition relationship is the Steele
(1965) formulation:
                                                                   (6-38)
where I   =  optimum (saturating)  light intensity

This  formulation is used  in many models including  Di Toro et aj_. (1971,
1977), Di Toro and Matystik (1980), Di  Toro and  Connolly (1980), Thomann
et £]_. (1975, 1979), Thomann and Fitzpatrick (1982), O'Connor et a].. (1981),
Bloomfield  _et al.. (1973),  Park jet aj_. (1974, 1975,  1979, 1980), Scavia
jet aj_.  (1976),  Najarian and Harleman  (1975), Bierman  eit ail_. (1980), Canale
et il. (1975, 1976), Lehman et a\_.  (1975), and Baca et  al.  (1973).

     Park et _aj_.  (1980)  use the Steele  formulation above the saturating
light intensity  I  and the Smith formulation below I    They feel  that  the
Steele  formulation is not accurate  below the inhibition threshold since the
predicted photosynthesis response is partially dependent on the  response
above the  threshold  (Park  jet jiT_. , 1979).  Under non-inhibiting  light
                                   313

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conditions, this may result in a light  limitation  factor which is too low
(Groden,  1977).

     Walker (1975) found that the Steele formulation  underpredi cts
photosynthesis  rates  at high light intensities (above  saturation) for some
algae, so he modified it by adding an additional parameter n:
                                                                  (6-39)
where n  =  parameter for modified Steele formulation

This parameter adjusts the rate of decline of the photosynthesis vs. light
curve for  light  intensities  above and  below the optimum.   The original
Steele formulation assumes n=l, while Walker used n values  of 0.67, 0.80,
and 1.0  for three different algal groups.

     A few models include light  adaptation  algorithms  in  their  light
limitation formulations  to  account for the fact that algae adapted  to low
Vight levels have  a more rapid response to changing  light conditions
(steeper slope of photosynthesis vs.  light curve)  than algae adapted to high
light levels.  Algae  adapt  to changing light conditions  by varying the
chlorophyll  content  of  their cells,  with algae adapted  to lower light
intensities having more chlorophyll.

     Nyho.lm  (1978) simulates this effect by varying the  value of the
saturating light intensity at different times of the year to shift the peak
of the  light limitation  function f(L).  The I  values are maximum  during
summer  and minimum during  winter.   This shifts the slope  of the light
response  curve  so  it is  steepest during the winter when the algae are
adapted  to low light levels.

     Groden  (1977) developed  a  more complicated formulation for the
MS.CLEANER model  which dynamically computes the slope of the photosynthesis

                                  314

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vs.  light  curve as a function of light  intensity, and then  uses this
information  to  compute the saturating  light  intensity as a function  of both
light and temperature.  The equation for the slope of the photosynthesis vs.
light curve  in  the light inhibited range is:

                             a = Kj_ ln(I) - K2                       (6-40)

where a     = slope of photosynthesis  vs.  light curve
      K«,K?  = constants

This is based on  the  assumptions that  1) the slope a is a linear  function of
the  chlorophyll content  of the cells  and 2)  chlorophyll  decreases
exponentially  with  light  intensity until it  reaches some minimum value
(Groden,  1977).   The  values of ^ and  K2 used in MS.CLEANER are 0.1088  and
0.0704,  respectively  (Groden, 1977;  Park  et a]_., 1980).  The  equation for
the saturating  light  intensity is:
    Smith  (1980)  developed a formulation  for computing the saturating light
intensity as a function of the maximum photosynthetic quantum  yield, maximum
growth rate, temperature, light extinction coefficient per unit  chlorophyll,
and the carbon to  chlorophyll ratio of the algae.  The equation  is:

                               Mmax(Tr ef) f(T) C  e
                          I  =  max  reT - H—                (6-42)
                           s              ac
where C    =  carbon to chlorophyll  ratio
      ^mT.v,  =  maximum  photosynthetic quantum yield,  moles carbon
       max
             fixed/mole photons absorbed
                                   315

-------
      a    = coefficient for light extintion per unit  chlorophyll,
            1/Oength-mass chlorophyll/volume)

The effects of  light adaptation are included in the  carbon to chlorophyll
ratio  C  .  This ratio typically ranges from 20 to 100,  with  20 corresponding
to low-light, high-temperature conditions, and 100 corresponding to high-
light,  low-temperature conditions  (Smith, 1980;  Eppley,  1972).  Based on
observations  that  the maximum photosynthesis rate typically occurs at the
depth  where the light intensity is about 30 percent of  the surface value (I
=0.3 I ), Smith (1980)  suggested the following relationship for estimating
C  as  a  function of the ambient light levels:

                               °-3Ta                      ,6
                                                                  (6~
where I  = daily average light intensity at the surface

These formulations are used by Thomann  and Fitzpatrick (1982)  in  the Potomac
Estuary  version of WASP.   One advantage of this approach  is  that  I  and C
are  defined  in terms of  parameters  which are  well  documented in  the
literature (


-------
    Since light  also varies continuously with  time,  most models  integrate
the  light  limitation function  f(L) over 24  hours to get a daily  average
value for a given time of the year and set of  meteorological  conditions.
This  is  generally approximated by multiplying the light limitation function
by the photoperiod (expressed as  the  fraction of the day in  which  the sun is
out)  and  by using the average light intensity during the daylight hours as
I  in the formulation.  This approach is  used  in  steady-state models and
dynamic  models  which use  daily time steps.  The alternative approach when
short  time steps (minutes to hours) are used  is  to compute  the  light
limitation and  algal growth  formulations dynamically throughout the day
using instantaneous values of IQ.  The latter method simulates the  diurnal
variations  in  algal photosynthesis.

    The depth  and time integrated Michael is-Menten  formulation  for light
limitation (Equation (6-35)) is expressed  as:
                                                                   (6'44)
where f  = photoperiod (expressed as  a fraction of the day)
      d  = water  depth,  length
      I  = average light  intensity  at the  surface during the daylight
           hours

when averaged over  the whole water depth or  as:
                    f(L) =  y (z  P2 i  In  -^	^H           (6-45>
where z, = depth  at  top of layer, length
      z2 = depth  at  bottom of layer, length

when  averaged over a  single layer (for example, in a vertically segmented
lake model).

                                   317

-------
     The analogous expressions  for  the Smith formulation (Equation  (6-36))
are:
f(L)  =/n
and
f(L)  =
                                                                   (6-46)
              In
                                        (6-47)
      For  the Steele formulation  (Equation (6-38)),  the depth and  time
integrated expressions are:
                                                     '
                    f(L) =
2.718 f
   y d
                                                    (6-48)
and
 f(L)  =
              2.718 f
              (Z9 - zi)
                                        (6-49)
     Light limitation factors  are compared for several  models in Table  6-7.
Saturating  light intensities  and half-saturation  constants for  light
limitation are presented in Tables 6-8 and 6-9.

6.4.4 Nutrient Limitation

     Two major approaches have been used  to  compute nutrient limitation
factors  in  algal models.  The  first  approach is based on  Monod (1949)  or
Michaelis-Menten  (1913)  kinetics  and  assumes that  the  growth rates are
determined  by the external  concentrations of available  nutrients.  External
here refers to the nutrient concentrations in the water column as opposed to
the internal concentrations in the algal  cells.   This approach assumes  the
nutrient composition of the  algal  cells remains constant, and is generally
referred to as fixed stoichiometry models.
                                   313

-------
          TABLE 6-7.   COMPARISON  OF LIGHT LIMITATION  FORMULATIONS
Model
(Author)
AQUA- IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
DEM
DOSAG3
EAM
ESTECO
EXPLORE-1
HSPF
LAKECO
MIT Network
QUAL-II
RECEIV-II
SSAM IV
WASP
WQRRS
Bierman
Canale
Jorgensen
Lehman
Nyholm
Scavia
Light Limitation Formulation
Michael is-
Steele Smith Menten Vollenweider Other Reference
X Baca & Arnett (1976)
X WES (EWQOS) (1982)
X Bloomfield ejt a]_. (1973)
X Scavia & Park (1976)
X* X* Park et a]_. (1980)
X Feigner & Harris (1970)
X Duke & Masch (1973)
X Tetra Tech (1979, 1980)
X Brandes & Masch (1977)
X Baca et a]_. (1973)
X Johanson et al_. (1980)
X Chen & Orlob (1975)
X Harleman et a_l_. (1977)
X Roesner et al_. (1981)
X Raytheon (1974)
none Grenney & Kraszewski (1981)
X Di Toro et al_. (1981)
X Smith (1978)
X Bierman e_t a]_. (1980)
X Canale et a\_. (1975, 1976)
X Jorgensen (1976)
X Lehman et al_. (1975)
piecewise Nyholm (1978)
linear
saturation
X Scavia et aK (1976)
*Smith formulation  used below light  saturation, Steele formulation used above light saturation.
                                        319

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            TABLE 6-8.   ALGAL  SATURATING  LIGHT  INTENSITIES
Algal Type
Saturating Light Intensity
      (1 angleys/day)
        References
Total
Phytoplankton
       300   350
                            250   350



                            200   300

                              216

                              288
Thomann et a]_. (1975, 1979)
Salas & Thomann (1978)
Di Toro et al_. (1971)
Di Toro & Connolly (1980)
Di Toro & Matystik (1980)
O'Connor et al. (1975)

Scavia et al_. (1976)
Scavia & Park (1976)
Scavia (1980)

Youngberg (1977)

Desormeau (1978)

Larsen et al. (1973)
Diatoms
          225


          300


         8 - 100


          225

          144
Thomann et al_. (1979)
Di Toro & Connolly (1980)

Scavia et jj]_.  (1976)
Scavia TJ980)

Bierman (1976)
Bierman e_t jj]_. (1980)

Canale et .a_l_.  (1976)

Lehman et al_.  (1975)
Green Algae
        88    100


         160

          65
Bierman (1976)
Bierman et al_. (1980)

Canale et al_.  (1976)

Lehman et al.  (1975)
Blue-green Algae
        44    50


           43

         600

       300    350

         250
Bierman (1976)
Bierman et a]_. (1980)

Lehman et al_. (1975)

Canale et a\_. (1976)

Youngberg (1977)

Scavia (1980)
Flagellates
Chrysophytes
          288

          100


           86
Lehman et al_. (1975)

Bierman et ^1_. (1980)


Lehman et al. (1975)
                                      320

-------
       TABLE  6-9.    HALF-SATURATION  CONSTANTS  FOR LIGHT  LIMITATION
                 Half-Saturation  Constant
Algal Type            (Kcal/m2/sec)
                                             References
Total
Phytoplankton
  0.002 -  0.006
                           0.0046


                       0.002  -  0.006*

                           0.005*


                       0.003    0.005*

                       0.004    0.006**

                          0.0044**
Chen (1970)
Chen & Orlob (1975)
Chen & Wells (1975,  1976)
U.S. Army Corps of Engineers  (1974)
Tetra Tech (1976)

Jorgensen (1976)
Jorgensen ejt aj_.  (1978)

Smith (1978)

Roesner et al_.  (1980)
Duke & Masch (1973)

Brandes (1976)

Jorgensen (1979)

Collins & Wlosinski  (1983)
Diatoms
Green Algae
      0.003



      0.002*

0.00005   0.0012**

0.00005   0.0026**


  0.002 -  0.004



      0.002*

0.0003   0.0011**

0.0003 - 0.0106**
Tetra Tech (1980)
Bowie et al.  (1980)
PorcelTa et  aj_.  (1983)

Tetra Tech (1979)

Jorgensen (1979)

Collins & Wlosinski  (1983)


Tetra Tech (1980)
Bowie et aj_.  (1980)
Porcella et  aj_.  (1983)

Tetra Tech (1979)

Jorgensen (1979)

Collins & Wlosinski  (1983)
Blue-green Algae
   0.002 - 0.004
                           0.002*
Tetra Tech (1980)
Bowie et al_. (1930)
PorcelTa et al.  (1983)

Tetra Tech (1979)
Dinoflagellates
      0.002*

0.0043 - 0.0053**
Tetra Tech (1979)

Collins & Wlosinski  (1983)
                                    (continued)
                                         321

-------
                           TABLE 6-9.  (continued)
     Algal Type
Half-Saturation Constant
    (Kcal/m2/sec)
                                                      References
     Flagellates
     Chrysophytes
     Benthic Algae
   0.002  0.004

     0.0044**

      0.002*
 0.0014  0.0017**
     Coccolithophores    0.0003  0.0016**
    0.01  0.005
                       0.002  0.006*
Tetra Tech (1980)
Porcella et_ al_.  (1983)
Collins & Wlosinski (1983)
Tetra Tech (1979)
Collins & Wlosinski (1983)

Collins & Wlosinski (1983)
Tetra Tech (1980)
Bowie et aj_. (1980)
Porcella et al_ (1983)
Smith (1978)
      *Model documentation values.
     **Literature values.
     The  second  approach  assumes  that algal growth is a two-step  process,
the first step being  nutrient  uptake and the second step  being  cell growth
or  division.   Cell growth  depends  on the  internal  concentrations  of
nutrients within the  cells,  rather than external  concentrations in the
water.   The  uptake  rates are  dependent on both the external  and  internal
concentrations.   Since  uptake and growth are  modeled  separately,  the
nutrient composition  of the  cell  may change with time, resulting in  variable
stoichiometry or  internal  pool  models.   These  models  simulate  processes
such  as  luxury  uptake of nutrients which allows growth even when  external
nutrients are depleted.

6.4.4.1  Nutrient Limitation in  Fixed Stoichiometry Models

     The majority  of water quality models  are of the fixed stoichiometry
type.   These models are generally based  on conventional Monod or Michael is-
Menten  kinetics.  The algal  growth equation for a single limiting  nutrient
under conditions  of optimum  temperature  and light can be expressed as:
                                     322

-------
                                                                  <6-50>
where  s  = concentration  of  the  limiting  nutrient  in  the
           water,  mass/volume
       KS = half-saturation constant for  the limiting nutrient,
           mass/volume

The  quantity  f(s)  = (v s,   )  is the growth  limitation  factor for the
                       Ks + s
nutrient s.  The half-saturation  constant refers to the concentration of the
nutrient at which the  growth rate is one half of its maximum value.  The
above equation results in  a hyperbolic  growth  curve  (Figure 6-5)  in  which
growth increases approximately linearly with nutrients at very low nutrient
concentrations, but gradually levels off to a  maximum growth  rate at  high
nutrient levels  (growth  saturation).  At this  point, the nutrient is no
longer limiting, so further increases  in the external nutrient supply do not
affect growth.

       Fixed  stoichiometry models typically compute  a separate growth
limitation factor f(s)  for each nutrient modeled, and then combine the
factors using  any  one of the four methods discussed  above  in Equations
(6-26) to (6-29)  (i.e.,  multiplicative formulation, minimum formulation,
harmonic mean formulation, or arithmetic mean  formulation).  The specific
nutrient limitation factors are:

                                     PO
                                     (NH. + NO,)
                                     + (NH3 * N03)                 <6

                                     C0y
                                                                  (6-53)
                                  323

-------
                                                                  (6-54)
where PO,
      (NH3+N03)
      CO,
      Si
      KSi
available dissolved  inorganic  phosphorus
concentration (orthophosphate), mass/volume
available  dissolved inorganic nitrogen concentration
(ammonia plus nitrate),  mass/volume
available  dissolved inorganic carbon  concentration
(carbon dioxide), mass/volume
available dissolved silicon  concentration,
mass/volume
half-saturation constant for phosphorus,  mass/volume
half-saturation constant for nitrogen,  mass/volume
half-saturation constant for carbon, mass/volume
half-saturation constant for silicon, mass/volume
 LU
 h-
 cr
 i
 o
 cr
 O

       Figure 6-5.
          NUTRIENT CONCENTRATION

  Michaelis-Menten saturation  kinetics for algal
  growth limitation by a single nutrient.
                                 324

-------
     The  number of growth limiting factors included in a given model depends
on both the  particular algal  species present and  the chemistry of  the  water
body  under  consideration.   For example, silicon limitation  is only
appropriate  for diatoms.   Nitrogen limitation can  generally  be  omitted for
nitrogen-fixing blue-green algae  (although nitrogen kinetics  for blue-greens
must still be included to correctly describe the nitrogen cycle).   Carbon
limitation  is  frequently excluded from algal models since  carbon  is often
assumed to be available in excess and is therefore not modeled as  a  state
variable.   Lake models often assume phosphorus is the  only limiting
nutrient, while estuary models  often  assume nitrogen is limiting at all
times.

     The  way  in which nitrogen  limitation is computed also  varies  from model
to model. For example, some  models simulate available nitrogen  as a single
constituent  (Bierman ej^ aj_., 1980; Jorgensen et^ _§_]_.,  1978; Nyholm, 1978;
Thomann _et _al_., 1979), while  other models simulate ammonia, nitrite,  and
nitrate  separately  and assume both ammonia and nitrate  are available for
algal growth  (Chen and Orlob,  1975; Baca and Arnett,  1976; Baca  et al.,
1973; Smith,  1978;  Najarian and Harleman,  1975;  Duke and Masch, 1973).
QUAL-II simulates the various forms of nitrogen, but assumes  algal growth is
only limited  by nitrate (Roesner  et_ aj_., 1981).   Some models  include factors
to  account  for ammonia preference by algae in their nutrient uptake
formulations  (Scavia _e_t  al., 1976; Canale e_t al., 1976;  Grenney and
Kraszewski,  1981; Thomann and Fitzpatrick, 1982;  O'Connor et  al_.,  1981; JRB,
1983). Ammonia preference factors are discussed  in Chapter 5.

     Values  of  the Michaelis-Menten  half-saturation constants for each
limiting nutrient are available from many sources, including both the
modeling  literature and the experimental literature.  However, care  must be
taken when  using this information since the values reported will depend on
the particular model  formulations used for the modeling literature, and on
the  experimental conditions  for the scientific literature.  For example, if
a multiplicative formulation  is  used to  compute  algal  growth
(Equation(6-26) ), the half-saturation constants  should be smaller  than the
corresponding  constants where a minimum formulation is  used  (Equation

                                  325

-------
(6-27)).   In general,  the  more limiting nutrients that are considered with a
multiplicative formulation, the smaller the  value of each  half-saturation
constant.  This  is  necessary in order to get  the same growth response with
both formulations when more than one nutrient is limiting  simultaneously.
This  is true  of both  the modeling  literature and  the experimental
literature.  When the harmonic mean formulation is used  (Equation (6-28)),
the half-saturation constants should  generally be somewhere  between the
values of  the minimum and multiplicative formulations.   Half-saturation
constants  for each limiting nutrient are tabulated in Table 6-10.

     Table 6-11 compares the algal  growth formulations  used  in several
models, including  the  growth  limiting factors used,  the  specific
formulations for nutrient  limitation, and the methods for combining multiple
limiting factors.

6.4.4.2 Nutrient Limitation  In Variable Stoichiometry Models

     Variable Stoichiometry models assume that the growth limiting factor
for nutrients, f(P,N,C,Si) in Equation (6-4), is  a function of the internal
levels of the nutrients  in the  algal cells rather than the external
concentrations in the water  column.   The  internal  concentrations are
generally  defined as:

                    _ internal mass of nutrient in  cells             /fi cc\
                  H      dry weight biomass of cellsID-OD;

where q =  internal nutrient concentration, mass nutrient/biomass algae

Internal  nutrient levels depend on the  relative magnitudes of the nutrient
uptake rates and the algal growth rates.  The uptake rates are functions of
both  the  internal  and external nutrient  concentrations, while the growth
rates depend primarily on the internal concentrations.

     Variable  Stoichiometry models differ in 1) the  specific process
formulations used to simulate uptake and  growth, 2)  the number of nutrients
considered, and 3) the ways  in which multiple limiting factors are combined.
                                   326

-------
  TABLE  6-10.   HALF-SATURATION  CONSTANTS FOR MICHAELIS-MENTEN  GROWTH FORMULATIONS
                                          Half-Saturation Constant
Algal  Type
Nitrogen
 (mg/1 )
Phosphorus
  (mg/1 )
Carbon
(mg/1 )
Silicon
 (mg/1)
References
Total  Phytoplankton
  Diatoms
                             0.025
                                         0.0005   0.03
                          0.01    0.4
                              0.2


                             0.025

                          0.06  0.08

                             0.015

                             0.014

                         0.025  0.3*

                         0.04   0.10*

                          0.2   0.4*
                                         0.004   0.08
              0.02   0.03


             0.006   0.025

                 0.02

                0.0025

                 0.001

             0.006   0.03*

             0.02   0.05*

             0.03   0.05*
                         0.015   0.3*   0.0025   0.08*

                          0.10   0.4*    0.03   0.05*

                       0.0014   0.018       0.006**

                         0.025   0.2**   0.002   0.08**

                        0.0015   0.15**

                                        0.02   0.075**
                      0.015   0.03
                          0.025
                                             0.002
                                         0.001    0.002
                                                          0.03   0.8
                                                             0.5
              0.02   0.04*
                                 0.15*
                                                            0.03
                      0.025   0.030      0.004   0.009


                          0.015             0.0025



                         0.015*              0.03*           0.03*

                     0.0063   0.12**    0.01    0.025**

                                            0.025**

                     0.003   0.923**    0.001   0.163**
                                             0.08



                                           0.030   0.1



                                             0.03


                                             0.03

                                              0.1

                                             0.08*
                             O'Connor et al.  (1975,  1985)
                             Thomann et aTT (1974,  1975, 1979)
                             Thomann & Fltzpatrick  (1982)
                             Di  Toro & Hatystik (1980)
                             Di  Toro & Connolly (1980)
                             Di  Toro et al_. (1971,  1977)
                             Sal as & Thomann  (1978)
                             Salisbury et al_.  (1983)

                             Chen (1970)
                             Chen & Orlob (1975)
                             Chen & Wells (1975,  1976)
                             U.S. Army Corps  of Engineers  (1974)
                             Tetra Tech (1976)

                             Jorgensen (1976)
                             Jorgensen et al_.  (1978)

                             Battelle (1974)

                             Grenney 8 Kraszewski  (1981)

                             Canale et al_.  (1976)

                             Larsen et §1-  (1973)

                             Baca & Arnett (1976)

                             Smith (1978)

                             Roesner e_t al_. (1980)
                             Duke & Masch  (1973)

                             Grenney & Kraszewski  (1981)

                             Brandes (1976)

                             Di  Toro et aj_. (1971)

                             Jorgensen (1979)

                             O'Connor et al_.  (1981)

                             Collins & Wlosinski  (1983)


                             Tetra  Tech  (1980)
                             Bowie  et aj_.  (1980)
                             Porcella et. al_.  (1983)

                             Thomann et  al_. (1979)
                             Di  Toro &  Connolly (1980)
                             Salisbury  et  al_.  (1983)

                             Scavia et  al_. (1976)
                             Scavia  (T980)

                             Canale et  aj_. (1976)

                             Bierman  (1976)

                             Tetra  Tech  (1979)

                             Di  Toro  et al_.  (1971)

                             Jorgensen  (1979)

                             Collins  &  Wlosinski (1983)
                                                          327

-------
                                          TABLE  6-10.    (continued)
                                            Half-Saturation  Constant
Algal  Type
   Nitrogen
    (mg/1)
  Phosphorus         Carbon
    (mg/1)           (mg/1)
Silicon
 (mg/1)
                                                                                                       References
 Green Algae
 Blue-green Algae
 Dinoflagellates
 Flagellates
 Chrysophytes


 Coccolithophores

 Benthic Algae
                          0.03   0.035
                                                0.004
                                                                0.03
                              0.15               0.01
                          0.001   0.035      0.005   0.024
     0.15
     0.03*
0.005   0.15**
0.006   1.236**
      0.

     0.001


     0.015
      0.*
0.062   4.34**

     0.005
     0.08*
0.007   0.13**
0.019   0.589**

     0.08

0.0084   0.13**
0.001   0.052**

    0.015
   0.006**
    0.0025
     0.03*           0.03*
    0.01**
0.002   0.475**  0.068 -  1.5**
 0.010.- 0.02        0.03

 0.01   0.015

     0.01
    0.0025
     0.06*           0.03*
    0.006**     0.031   0.088**
                                                0.06*
                                                 0.012
                                                                0.03*
                                                                0.03
     0.02*
0.047   0.076**
                                                                0.03*
0.006   0.019**

  0.05   0.1        0.004   0.008    0.03    0.1

 0.06   0.08            0.02
 0.04   0.10*       0.02   0.05*    0.02   0.04*
 0.015   0.3*      0.0025   0.08*
  *Model documentation values.
 "Literature values.
                  Tetra Tech (1980)
                  Bowie et al.  (1980)
                  PorcelTa el al.  (1983)
                  Di Toro et al. (1971)
                  Scavia ejt al_.  (1976)
                  Scavia & Park  (1976)
                  Scavia (1980)
                  Canale et al_.  <1976)
                  Tetra Tech (1979)
                  Jorgensen (1979)
                  Collins & Wlosinski (1983)
                  Tetra Tech (1980)
                  Bowie et al_.  (1980)
                  Porcella et al_.  (1983)
                  Scavia & Park  (1976)
                  Scavia (1980)
                  Di Toro et aj_. (1971)
                  Canale et al..  (1976)
                  Tetra Tech (1979)
                  Collins & Wlosinski (1983)

                  O'Connor ei_ al_.  (1981)
                  Tetra Tech (1979)
                  Di Toro et al. (1971)
                  Collins & Wlosinski (1983)

                  Tetra Tech (1980)
                  Porcella et al_.  (1983)
                  Jorgensen (1979)
                  Collins & Wlosinski (1983)

                  Tetra Tech (1979)
                  Collins & Wlosinski (1983)

                  Collins & Wlosinski (1983)

                  Tetra Tech (1980)
                  Bowie et al. (1980)
                  Porcella et al..  (1983)
                  Grenney & Kraszewski  (1981)
                  Smith (1978)
                  Grenney & Kraszewski  (1981)
                                                         328

-------
                                           TABLE  6-11.    COMPARISON  OF  ALGAL GROWTH FORMULATIONS
Model
(Author)
AQUA- IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
DEM
DOSAG3
EAM
ESTECO
EXPLORE-1
HSPF
LAKECO
MIT Network
QUAL-II
RECEIV-II
SSAM IV
WASP
WQRRS
Bierman
Canale
Jorgensen
Lehman
Nyholm
Scavia
Growth Limiting Factors
Light P04 N03 NH3 C02 Si
X X X X
X X X X X
X X X X X
X X X X X
X X X X X X
XXX
XXX
X X X X X X
X X X X X
X X X X
X X X X X
X X X X X
X XX
XXX
X XXX
XXX
X X X X X
X X X X X
X X X X X
X X X X X
X X X X X
X X X X X X
X X X X
X X X X X
Stoichiometry
Fixed Variable
X
X
X
X
C & Si N & f
X
X
X
X
X
X
X
X
X
X
X
X
X
Si N & F
X
X
X
X
X
Nutrient Limitation
Formulation
Michaelis-
Menten Other
X
X
X
X
X* 6-51*
X
X
X
X
X
X
X
X
X
X
X
X
X
X** 6-52**
X
6-53
6-53
6-54, 55
X
Method for Combining Factors
Multipl- Harmonic
icative Minimum Mean
light nutrients
X
X
X
X
X
X
X
X
X
X
X
light
X
light nutrients
X
X
X
light nutrients
X
X
X
light nutrients
X
Reference
Baca & Arnett (1976)
WES (EWQOS) (1982)
Bloomfield et_ aT_. (1973)
Scavia & Park (1976)
Park et a]_. (1980)
Feigner & Harris (1970)
Duke & Masch (1973)
Tetra Tech (1979, 1980)
Brandes & Masch (1977)
Baca et al_. (1973)
Johanson et al . (1980)
Chen & Orlob (1975)
Harleman et al . (1977)
Roesner et al. (1981)
Raytheon (1974)
Grenney & Kraszewski (1981)
Di Toro et a_K (1981)
Smith (1978)
Bierman et al . (1980)
Canale et. aj_. (1975, 1976)
Jorgensen (1976)
Lehman et. al_. (1975)
Nyholm (1978)
Scavia et al. (1976)
oo
ro
              *Fixed Stoichiometry Michaelis-Menten formulation used for carbon and silicon, with variable Stoichiometry formulations for nitrogen and phosphorus.
             **Fixed Stoichiometry Michaelis-Menten formulation used for silicon,  with variable Stoichiometry formulations for  nitrogen and phosphorus.

-------
     Several  different formulations have  been  used to compute  nutrient
limitation  factors  in  variable stoichiometry models.  As with  fixed
stoichiometry models,  the  limitation factors  may  range from 0 to  1.   Most
models assume  a minimum  internal stoichiometric  nutrient requirement at
which growth  is zero.   This minimum level  is  often called the minimum  cell
quota or subsistence quota.   Algal  growth (and the nutrient limitation
factors) are  assumed to increase with  increasing  internal nutrient  levels
above the minimum  cell  quota until  the maximum growth rate is attained.
Some type of hyperbolic  function is  typica-lly used  to express  this
saturation type relationship.

     The following expressions have been  used to determine growth limitation
factors  in variable stoichiometry models:
               f(q) =
                                                                  (6-56)
where f(q)
      q

      q  .

      q
f(q)

f(q)

f(q)


f(q) H
                        1 -
                           "•mm
                        q - q
                            'mm
                       iax
                      K, + (q - q .  )
                          VM   Hmin;
                                       q - q
                                         + (
                                           ^
                                                 -  q  •  )
                                                   H'
(6-57)


(6-58)

(6-59)


(6-60)
                nutrient limitation  factor
                internal nutrient concentration, mass  nutrient/biomass
                al gae
                minimum internal stoichiometric requirement  (cell
                quota), mass nutrient/biomass algae
                maximum  internal  nutrient concentration,  mass
                nutrient/biomass algae
                   ^'Saturation constants for growth limitation
                                  330

-------
Equation  (6-56)  is  equivalent in form to the Michaelis-Menten  relationship
except that the internal  rather than the external nutrient concentration is
the independent  variable.  This equation  is  used in MS.CLEANER for both
nitrogen  and phosphorus limitation  (Park e_t  al., 1980).  Equation  (6-57)
also  has the  same form as the Michaelis-Menten relationship,  but the
independent variable is the  internal nutrient concentration in excess of the
minimum cell  quota.   This  equation  is  used  by Bierman   (1976)  and
Bierman et al_. (1973, 1980)  for nitrogen and  phosphorus.  Equation  (6-58)
was originally developed  by Droop (1968), and  it is used in  several models
including Lehman et aj_. (1975), Jorgensen (1976), Jorgensen e_t  al.  (1978,
1981), and Canale and Auer (1982)  for  all nutrients simulated in these
models.  Equation  (6-58)  can be derived from  Equation (6-57) by  assuming K~
= q .  , as was demonstrated  by  Rhee (1973, 1978) for phosphorus  and nitrogen
(Bierman, 1981).   Equations  (6-59) and (6-60) are used by Nyholm (1978)  for
nitrogen and  phosphorus,   respectively. Note that Equation  (6-59) is a
linear rather  than hyperbolic relationship.   Also,  Equation  (6-60)  is
similar  to Equation  (6-57) since the second factor in  Equation  (6-60) is a
constant  once qm.  , qm_, and K., are defined.
              m I n   max       j

      Since  variable  stoic hiometry formulations have not been  widely used,
data for  the model parameters are limited.  Values for the various  half-
saturation constants are   presented  in  Table  6-12.  Note that the half-
saturation constants (K..,K2, and K.)  have different values  since  the
corresponding  equations are different. Minimum cell quotas  and maximum
internal  nutrient  concentrations are tabulated in Tables 6-13 and 6-14.

    The  ways in  which  variable stoichiometry  formulations are  used varies
between  different models.  Some models  use variable stoichiometry
formulations  only  for phosphorus and nitrogen, combining  them with
conventional Michael is-Menten kinetics for carbon and silica (Park  et a*1 . ,
1980;  Bierman ^t  jaj., 1980). while other models use variable stoichiometry
formulations for all  nutrients modeled  (Lehman j^t a_[.,  1975;  Jorgensen,
1976).   In a few  cases, different internal nutrient formulations are used
for different nutrients in the same model  (Nyholm, 1978).  In some models.
                                  331

-------
TABLE  6-12.   HALF-SATURATION CONSTANTS FOR  VARIABLE  STOICHIOMETRY FORMULATIONS
Half-Saturation Constant
Nutrient Type Value
Phosphorus Kj 0.005 g/m
K, 0.724xlO"7 /imole/cell
0.0005 mg/mg (D.W.)
0.312xlO"8 ^mole/cell
0.0005 mg/mg (D.W.)
0.148xlO"7 (/mole/cell
0.0005 mg/mg (D.W.)
0.488xlO"8 /^mole/cell
0.0007 mg/mg (D.W.)
0.566xlO~8 /^mole/cell
Algal Type
Total Phytoplankton
Diatoms
Green Algae
Flagellates
Blue-greens (N-fixing)
Blue-greens (non N-fixing)
Reference
Desormeau (1978)
Bierman et aj_. (1980)




   Nitrogen
                           0.0007 mg/mg (D.W.)
                           0.003 mg/mg (D.W.)
0.05 g/m
                           O.SOlxlO'5 ^mole/cell
                           0.025 mg/mg (D.W.)

                           0.345xlO"6 (/mole/cell
                           0.025 mg/mg (D.W.)

                           0.163xlO"5 ^mole/cell
                           0.025 mg/mg (D.W.)

                           0.377xlO"6 ^mole/cell
                           0.025 mg/mg (D.W.)

                           0.438xlO"6 /^mole/cell
                           0.025 mg/mg (D.W.)

                           O.HxlO"7 ^mole/cell

                           0.14x10
                           0. 23x10" 7 //mole/cell

                           0.14x10" jimole/cell
   Total Phytoplankton



   Total Phytoplankton


       Diatoms


      Green Algae


      Flagellates


  Blue-greens (N-fixing)


 Blue-greens (non N-fixing)


       Diatoms

      Green Algae

  Blue-greens (N-fixing)

Blue-greens  (non N-fixing)
Nyholm (1978)



Desormeau (1978)


Bierman et al_. (1980)
                                    Bierman (1976)
carbon and  silica are  not  included  as potentially  limiting  nutrients
(Nyholm, 1978).


      The  combined  effects  of multiple limiting nutrients in  variable
stoichiometry models are dealt with in  the  same  basic ways as  in  fixed

stoichiometry models  (i.e.,  multiplicative  formulation (Equation  (6-26)),
minimum  formulation (Equation (6-27)), or  harmonic  mean  formulation

(Equation (6-28)).   However,  when  a minimum  (or threshold)  formulation is
used,  the limiting nutrient  is often  determined by  comparing  the  internal
                                         332

-------
                                       TABLE 6-13.   MINIMUM  CELL QUOTAS

Algal -Type
Total
Phytoplankton



Diatoms



co Green Algae
CO
CO


Blue-green Algae



Dinoflagellates
Flagel lates
Chrysophytes
Benthic Algae

Nitrogen
0.015-0.02
0.015
0.04

0.520xlO"7
O.SOlxlO"5
0.025
-7**
6-xlO '

0.520xlO"7
0.345xlO"6
0.025


0. 520-0. 853xlO"7
0. 377-0. 438xlO"6
0.025
-7**
1.1x10 '

_7**
3.9x10
0.163xlO"5
0.025
0.18-0.3xlO"7**

Minimum Cell Concentration
Phosphorus Carbon Silicon
0.001-0.003 0.15-0.18
0.001 0.15-0.4
0.00146
0.3-0.7**
0.20xlO"8
0.724xlO"7
0.0005
0.9-30.X10"9** 0.2-40.X10"7**
0.45-0.6**
0.20xlO~8
0.312xlO"8
0.0005
1.7-4.5xlO~9**
>0.5**
0. 583-1. 34xlO~9
0. 488-0. 566xlO"8
0.0007
_Q**
2.5x10
>0.5**
-Q**
ll.xlO
0.148xlO"7
0.0005
0**
0.5x10
0.0005
Units
mg/mg (D.W.)
mg/mg (D.W.)
mg/mg (D.W.)
mg/mg (D.W.)
jimoles/cell
^moles/eel 1
mg/mg (D.W.)
^moles/eel 1
(ig/mm cell
volume
^moles/cell
fjmoles/cel 1
mg/mg (D.W.)
jjmoles/cell
//g/mm cell
volume
/^moles/cell
^moles/cell
mg/mg (D.W.)
//moles/cell
fig/mm cell
volume
^moles/cell
/imoles/cell
mg/mg (D.W.)
^moles/cell
mg/mg (D.W.)
References
Jorgensen (1976, 1983)
Jorgensen et aj_. (1978, 1981)
Nyholm (1978)
Jorgensen (1981)
Bierman (1976)
Bierman et al . (1980)
Lehman et al . (1975)
Jorgensen (1979)
Bierman (1976)
Bierman et al . (1980)
Lehman et al_. (1975)
Jorgensen (1979)
Bierman (1976)
Bierman et al . ( 1980)
Lehman et al_. (1975)
Jorgensen (1979)
Lehman et !]_. (1975)
Bierman et al . (1980)
Lehman et al_. (1975)
Auer and Canale (1982)
"Literature values.

-------
                         TABLE  6-14.   MAXIMUM INTERNAL NUTRIENT  CONCENTRATIONS
CO
-F*
                              Maximum  Cell Concentration
 Algal  Type
                                Nitrogen
Phosphorus
Carbon     Silicon
Units
References
 Total
 Phytoplankton     0.08-0.12
                                               0.013-0.03
                  0.6
                     0.1            0.02

                 0.08-0.12**     0.013-0.035**
                     mg/mg  (D.W.)    Jorgensen  (1976, 1983)
                                    Jorgensen  et al_. (1978, 1981)

                     mg/mg  (D.W.)    Nyholm (1978)

                     mg/mg  (D.W.)    Jorgensen  et al_. (1981)
**Literature values.

-------
phosphorus to  internal  nitrogen ratio  with a threshold  ratio, rather than
computing  the  growth limitation factor  for  each nutrient and using  the
smallest value.

     Table 6-11 compares  the growth formulations  used in  several variable
stoichiometry  and  fixed stoichiometry  models.  The comparisons show which
limiting  factors  are included, which  formulations are used to compute
nutrient limitation, and  how multiple limiting factors are combined.

6.4.4.3 Nutrient Uptake  In Variable Stoichiometry Models

     In fixed  stoichiometry  models, the nutrient composition of the algal
cells is assumed to remain  constant, so nutrient uptake is directly related
to the algal  growth rate by the  stoichiometric ratio of nutrient mass to
cell  biomass.   The nutrient uptake rate can then be expressed as:

                                v = fz q                           (6-61)
                                       Vrf

where  v   = nutrient uptake rate, mass nutrient/mass algae-time
       f*  = algal growth  rate, I/time
       q   = constant internal  nutrient  concentration,  mass
           nutrient/biomass algae

The  growth rates  are assumed to  be  functions  of the external nutrient
supplies  (plus temperature and light) as computed by Michaelis-Menten type
relationships (Equation (6-50)).

     In contrast, nutrient  uptake rates in variable stoichiometry models are
functions of  both  internal  nutrient levels  in  the cells and  external
nutrient concentrations in  the water.  The general relationship is typically
of the form:

                    v =  vmax(Tref} f(T)  f(q»s) f(L)                 (6

where vm   (T   .) = maximum  nutrient  uptake rate  at reference
       max  rer
                                   335

-------
                  temperature T   ,, mass nutrient/mass algae-time
      f(T)       = temperature function  for uptake
      f(q,s)     = nutrient uptake  limitation function
      q          = internal nutrient concentration, nutrient mass/cell
                  biomass
      s          = external nutrient concentration, mass/water volume
      f(L)       = light limitation function for uptake

The temperature and light functions for  uptake are essentially the same as
those used  for algal growth.

      Variable  stoichiometry models  are distinguished primarily by the
specific formulations used for the  uptake limitation function f(q,s).  These
functions  define the feedback  between uptake  rates and  both internal
and  external nutrient levels. Some formulations attempt a  more mechanistic
approach, while others tend to be empirically based.  In general, the  uptake
rates increase  with the  external nutrient supplies but  at the  same time
decrease as the internal nutrient levels approach their saturation values.
Uptake  rates  approach zero  when  either external nutrients are depleted or
when internal nutrients reach their  maximum saturated levels.  However,
neither  of these conditions  can  persist since  nutrients are continually
recycled and since phytoplankton  growth  increases the algal  biomass  relative
to the  internal nutrient mass which in  effect reduces the internal  nutrient
concentrations under conditions of  restricted uptake.

      The following  formulations have  been  used to  express internal and
external  nutrient effects on uptake rates in variable stoichiometry models:
                                                                    (6-64)
                                   336

-------
                  f(q»s) =
                                                                  (6-65)
with                      q  = q.  e\min    /                    (6-67b)
where qm=         = maximum  internal  nutrient concentration,  mass
       fflaX
                   nutrient/biomass algae
      q •         = minimum internal stoichiometric  requirement (cell
                   quota), mass nutrient/biomass  algae
      q,         = internal  available nutrient  concentration, mass
                   nutrient/ volume
      q . .       = minimum internal available nutrient concentration,
                   mass nutrient/volume
      C.         = internal  concentration of  uptake inhibitor, mass
                   nutrient/biomass algae
      f .         = fraction  of total internal  nutrient concentration
                   which acts as an inhibitor to  nutrient uptake  (this
                   corresponds to  the acid-soluble  polyphosphate
                   fraction of  total  internal  phosphorus, or the
                   cellular  free amino acid  fraction of total internal
                   nitrogen)
      Kul'Ku2'Ku3 = nalf~saturation  constants for  nutrient uptake,
                   mass nutrient/volume water
                                   337

-------
      K.          = half-saturation constant for inhibition of nutrient
                   uptake,  mass  nutrient/biomass algae
      K          = affinity coefficient, volume/mass  nutrient
       cl

Equation  (6-63)  is used by Koonce  and Hasler  (1972), Equation (6-64)  by
Lehman et  al_.  (1975) and Jorgensen  (1976), Equation  (6-65)  by Rhee  (1973)
and Park  e_t  a]_.  (1980), Equation  (6-66) by Di Toro  (1980), Auer and Canale
(1982), and Canale and Auer  (1982),  and Equations (6-67a)  and (6-67b)  by
Bierman et al_.  (1973, 1980).

      Maximum  nutrient uptake rates and half-saturation constants for uptake
are presented in  Tables 6-15 and 6-16.   Minimum cell quotas and  maximum
internal nutrient concentrations were presented  previously  in Tables 6-13
and 6-14.  Some  of the more model  specific parameters are presented  in
Table  6-17.

      Although  variable stoichiometry models more realistically represent
nutrient  uptake and cell growth  than fixed stoichiometry models, they do  it
at the expense of additional model  complexity  and  computational   costs.
Algal  growth  computations  in variable stoichiometry  models require  shorter
time steps since the time scale for nutrient uptake is on the order of hours
while  the time scale for  algal  growth is on  the order  of days.   Also,
spatial variability in external  and  internal  nutrient concentrations
complicates  transport since algae with different internal  stoichiometries
will be transported into the same  model segment, requiring some type  of
averaging  procedure at each  time  step.

      Another  criticism of variable stoichiometry models is that more model
coefficients  are  required  than  in  fixed stoichiometry models.  Several
coefficients  are  required  for both  the uptake  and  growth  formulations.
Since  these  coefficients must describe the response  of species assemblages
rather than the single species evaluated in laboratory  experiments, they
must be determined largely by model calibration.  This introduces additional
uncertainty  in the model   results.   Also, the  data base  for  variable
stoichiometry  coefficients  is much smaller than for conventional Michaelis-
Menten parameters.
                                  338

-------
                                       TABLE  6-15.  MAXIMUM NUTRIENT UPTAKE RATES
GO
OJ
UD
Maximum Uptake Rate
Algal Type
Total
Phytoplankton





Diatoms




Green Algae



Blue-green Algae


Flagellates
Chrysophytes

Coccolithophores
Benthic Algae
Nitrogen
0.15
0.012-0.03
0.14
0.01-0.035**
0.01-0.035**
0.0024**
0.015
0.125
0.72-4.32**
_n**
0. 3-120. xlO
1.52-8.33xlO~6**
0.060
0.125
-ft**
2.2-10.6x10 H
2.14-5.56xlO"6**
0.040
0.125
0.042xlO"6**
0.125
ft**
1.4-3.8x10 B

-i n**
4.-9.X10

Phosphorus
0.0014
0.0014-0.008
0.1
0.003-0.01**
0.003-0.01**
0.02-2.95**
0.024
0.500

q**
0.7-8. xlO y

0.133
0.500
ft**
1.2-4. xlO B

0.042-0.059
0.500

0.500
_7**
2.4x10 '
2.01-13.9xlO~9**

0.045
Carbon Silicon Units
0.55 I/day
0.40-1.21 I/day
I/day
0.2-0.7** I/day
0.2-1.4** I/day
pmoles/hr
I/ day
I/ day
I/day
2.6-950.X10"9** pmoles/cell-hr
0. 073-26. 6xlO"6** ymoles/cel 1-hr
I/day
I/ day
umoles/cell-hr
ymoles/cell-hr
I/day
I/day
u moles/eel 1-hr
I/day
pmoles/cell-hr
pmoles/cell-hr
pmoles/cell-hr
I/day
References
Jorgensen (1983)
Jorgensen et aj_. (1978, 1981)
Desorraeau (1978)
Jorgensen e^ aj_. (1978)
Jorgensen (1981)
Jorgensen (1979)
Bier-man (1976)
Bierman et aj_. (1980)
Jorgensen (1979)
Lehman et al. (1975)
Jorgensen (1979)
Bierman (1976)
Bierman et aj_. (1980)
Lehman e;t aj_. (1975)
Jorgensen (1979)
Bierman (1976)
Bierman et al . (1980)
Jorgensen (1979)
Bierman et al_. (1980)
Lehman e_t aj_. (1975)
Jorgensen (1979)
Lehman et_ a]_. (1975)
Auer and Canale (1982)
            "Literature values.

-------
               TABLE 6-16.   HALF-SATURATION  CONSTANTS  FOR  NUTRIENT  UPTAKE
Phytoplankton
Group
Total Phytoplankton



Diatoms



Green Algae



Blue-green Algae


Dinoflagellates


Flagel lates

Chrysophytes


Coccol ithophores


Bacillariophyceae
Benthic Algae

Nitrogen
(mg/1)
0.2
0.2
0.05
0.0014-0.007**
0.030*
0.0028-0.105**
0.0014-0.130**
0.0042-0.105**
0.030*
0.0024-0.02**
0.0014-0.02**
0.0024-0.02**
0.030*
0.980**
0.0067-0.980**
0.0015-0.133**
0.0015-0.144**
0.0014-0.133*
0.030*
0.007-0.077**
0.0014-0.0084**
0.0014-0.0084**
0.0014-0.0084**
0.0014**
0.0014-0.0028**
0.0014-0.0043**
0.0063-0.120**

Half-Saturation Constant
Phosphorus Carbon Silicon
(mg/1) (mg/1) (mg/1)
0.02-0.03 0.5
0.02 0.5-0.6
0.07
0.0028-0.053**
0.060*
0.18-0.053 0.022-0.098**

0.0002-0.053** 0.0053-0.098**
0.020*
0.019-0.155**

0.0009-1.500**
0.015-0.060*





0.060*

0.016-0.496**

0.009-0.496**




0.125
References
Jorgensen (1976, 1983)
Jorgensen et_ al_. (1978)
Desormeau (1978)
Jorgensen (1979)
Bierman e_t al_. (1980)
Lehman et al_. (1975)
Eppley et al_. (1969)
Jorgensen (1979)
Bierman et al_. (1980)
Lehman et a]_. (1975)
Eppley et al_. (1969)
Jorgensen (1979)
Bierman et. al_. (1980)
Lehman et al_. (1975)
Jorgensen (1979)
Lehman et al_. (1975)
Eppley et al_. (1969)
Jorgensen (1979)
Bierman et, aj_. (1980)
Jorgensen (1979)
Lehman et al_. (1975)
Eppley e_t al_. (1969)
Jorgensen (1979)
Lehman et. aj_. (1975)
Eppley et aj_. (1969)
Jorgensen (1979)
Jorgensen (1979)
Auer and Canale (1982)
 *Apparent half-saturation values under nutrient-starved conditions.
**Literature values.
                                               340

-------
         TABLE 6-17.  MODEL-SPECIFIC NUTRIENT UPTAKE PARAMETERS

Model Parameter
Nutrient Type Value
Phosphorus K. 0.0001 g/m3
Ki 0.0007 mg/mg (D.W.)
fi 0.01%
K O.SlSxlO^l/mol
0.167xlO/l/mol
0. 518-2. OxlOn/mol
0.518 x 10°l/inol
K O.SOxlO^l/mol
a 0.50xlO°l/mol
0.90-1.0x10 1/mol
tt S/'i
0.5 yg/1
0.5 yg/1
qdmin 0.215xlO~ynol/l cell vol.
0.215x10 "imol/l cell vol.
0.107xlO"/mol/l cell vol.
Nitrogen KI- 0.0005 g/m3
f. 0.05%
K O.lOOxlO^l/mol
a O.lOOxlo'l/mol
O.lOOxlo'l/mol
0.100x10 1/mol
K O.lOxlO^l/mol
a O.lOxlo'l/mol
0.10x10 1/mol
I Is/'!
3. yg/1
3. yg/1
^Hm-in 0.267xlO"^mol/l cell vol.
0.267xlO~V>l/l cell vol.
0.267xlO~V>l/l cell vol.
Algal Type
Total Phytoplankton
Benthic Algae
Total Phytoplankton
Diatoms
Green Algae
Blue-green Algae
Flagellates
Di atoms
Green Algae
Blue-green Algae
Diatoms
Green Algae
Blue-green Algae
Flagellates
Diatoms
Green Algae
Blue-green Algae
Total Phytoplankton
Total Phytoplankton
Diatoms
Green Algae
Blue-green Algae
Flagellates
Diatoms
Green Algae
Blue-green Algae
Diatoms
Green Algae
Blue-green Algae
Flagellates
Diatoms
Green Algal
Blue-green Algae
Reference
Desormeau (1978)
Auer and Canale (1982)
Desormeau (1978)
Bierman et_ al_. (1980)
Bierman (1976)
Bierman et aj_. (1980)
Bierman (1976)
Desormeau (1978)
Desormeau (1978)
Bierman e;t aj_. (1980)
Bierman (1976)
Bierman et al_. (1980)
Bierman (1976)
1
      Di  Toro (1980) and  Di Toro and Connolly (1980) have shown that  since
the time  scale for nutrient uptake is a fraction  of the time scale for  algal
growth and  is  usually much smaller than the time  scale  for changes  in
external  nutrient concentrations,  many of the complexities  of variable
stoichiometry models can be avoided by assuming cellular equilibrium with

                                   341

-------
external  nutrient concentrations  at each time  step.   This allows  algal
growth to  be  computed using  conventional Michaelis-Menten  kinetics, but at
the same  time  allows the internal stoichiometry of the  algae  to vary.  Since
the cells  are assumed to equilibrate immediately with  the external nutrient
concentrations  during transport,  both the computational  difficulties
associated with the rapid uptake  dynamics and  the  problem of algae with
different internal stoichiometries  being transported  into  the same  model
segment  are  eliminated.  Variable stoichiometry  formulations are  more
important to accurately simulating  nutrient re-cycling than to computing
algal growth,  so this scheme may  be  a reasonable compromise between the
variable  stoichiometry formulations  discussed above and  conventional  fixed
stoichiometry  formulations.

6.5  RESPIRATION AND EXCRETION

      Respiration and excretion  are generally combined and modeled  as  a
single term which includes all metabolic losses and  excretory processes.
These losses represent the difference between gross growth  and net growth.
Since net  growth (rather than  gross  growth)  is typically  reported in the
literature, some models lump respiration, excretion,  and gross growth into  a
single net growth term, rather than  simulating each process separately.
However,  it is generally more  appropriate to compute  growth and respiration
separately since growth rates  are sensitive to nutrient supplies while
respiration rates depend primarily on temperature.   Also,  respiration  and
excretion are  important components of nutrient recycling, so  these processes
are usually computed separately for  use in the nutrient  dynamic equations.

      Most models express respiration (plus excretion)  as either a constant
loss term or as a function of  temperature.  The general  expression is:

                           r =  r(Tref} VT)                       (6'68)

where r        =  rate of respiration  plus excretion, I/time
      i"(T  *)  =  respiration rate at a particular reference  temperature
              Tref, I/time
      f  (T)    =  temperature function for respiration
                                   342

-------
     The  temperature functions  for respiration  use  the same formulations
discussed  above for growth (Equations (6-5)" through (6-25)).  Most models
use the same  temperature function  and coefficients for both processes.  The
major approaches are 1) linear  increases in respiration  with temperature,  2)
exponential  increases in respiration with temperature,  and 3) temperature
optimum  curves  in which respiration  increases with temperature up to the
optimum temperature and then decreases with higher temperatures.  The  most
commonly used-exponential  formulation  is the Arrhenius relationship with a
reference temperature of 20°C (Equation  (6-15a)).  Some models, for  example
CE-QUAL-R1 (WES, 1982), use  the left hand side of a temperature optimum
curve  or a logistic equation  (Equation (6-22a))  to define temperature
effects  on  respiration.   This approach assumes  respiration increases
exponentially at low temperatures, but eventually levels off to some maximum
value at  higher  temperatures.

     A few models  use formulations which relate the respiration rate to the
physiological condition of the algal  cells.   For example, Scavia (1980)
represents respiration as the sum of two components, 1) a low maintenance
rate representing  periods of minimal growth, and 2)  a rate which is directly
proportional  to  the  photosynthesis rate  (as defined by the growth limitation
factor):

                                                ?,K,C,Si}           (6-69)

where r  . (T  .)  = base  respiration rate under conditions of minimal
       minv ref
                  growth (poor physiological  condition)  at  reference
                  temperature  T  ,., I/time
      K  (T  f)   = maximum incremental  increase in  respiration  under
                  conditions  of maximum growth (optimum physiological
                  condition) at reference temperature T  -, I/time

Both rates are multiplied by a  temperature adjustment function.

     The MS.CLEANER  model  uses  a similar  formulation which  expresses
respiration as the sum  of endogenous respiration and photorespiration

                                  343

-------
(Groden,  1977; Park et _al_. ,  1980).  The endogenous  respiration  is  defined
as:

                            re  =  .0175 e'069T                        (6-70)

where r  =  endogenous respiration  rate, I/time
      T  =  temperature,  C
Photorespiration is defined as  a  constant  fraction of the temperature
adjusted maximum photosynthesis rate  in early versions of MS. CLEANER
(Groden,  1977):

                        rP  =  Kpl 

where r  =  photorespiration rate, I/time
      K , =  fraction of maximum  photosynthesis rate which  is  oxidized
            by photorespiration  (typically 5 to 15%)

and as a  fraction of the actual  photosynthesis rate  (including temperature,
light, and  nutrient limitati'on  effects) in later  versions (Park et a! . ,
1980):

                   rp - Kp2 M                                       (6-72)
where K « =  fraction of actual  photosynthesis rate which is  oxidized by
            photorespiration

    MS. CLEANER also considers  excretion as a separate loss term,  in contrast
to most  models which lump respiration and excretion together.   Excretion is
formulated  similar to photorespiration.  However, since  the excretion of
photosynthate and photorespiratory  compounds relative to carbon assimilation
(photosynthesis)  is highest  at  both  low light levels and inhibitory high
light levels, the excretion rate  is expressed as (Desormeau, 1978;  Collins,
1980):
                                   344

-------
                           e  = K   1 - f(L)   11                     (6-73)
                            x    e \       /
where e    = excretion  rate, I/time
       X
      Kg   = fraction of  photosynthesis excreted
      f(L) = light limitation factor
      fj.    = growth (photosynthesis)  rate,  including effects  of
             temperature,   light, and nutrient  limitation, I/time
    Lehman et _al_.  (1975), Jorgensen (1976), and  Jorgensen^taj_.  (1978,
1981) use variable stoichiometry  formulations which relate  the  respiration
rate to  the  internal carbon  levels  of  the cells.  The ratio of the  internal
carbon level  to the maximum internal  carbon  level  is  used to define the
physiological  state of the cells.   The respiration rate increases  with the
internal  carbon  level according  to  the equation:
                            -  WTref> li^l                    (6-74>

where r   (T  f) = maximum  respiration rate  at  reference temperature
       max  ret
                  Tref, I/time
      C.         = internal  carbon  level, mass carbon/biomass algae
      C         = maximum internal  carbon level, mass carbon/biomass
       max
                  al gae

     Algal  respiration rates are tabulated in Table 6-18.

6.6  SETTLING

     Phytoplankton settling rates depend on the  density, size,  shape,  and
physiological state of the phytoplankton cells, the viscosity and density of
the water, and the turbulence and velocities  of  the  flow  field.   The
settling  velocities for spherical  particles in still  water can  be computed
from S.toke's law.  Stoke1 s law can  be modified to account for non-spherical
phytoplankton  cells by using an  "equivalent radius"  and "shape factor" in
the formulation  (Scavia, 1980):

                                   345

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                        TABLE  6-18.   ALGAL  RESPIRATION RATES
Algal Type
Respiration
Rate (I/day)
   •Reference
Temperature (  C)
          References
Total
Phytoplankton
 0.05    0.15
    20°C
                       0.05  -  0.10



                          0.08

                          0.10

                       0.088  0.6


                          0.051

                          0.05

                      0.005    0.12*

                       0.05    0.2*

                       0.05  -.0.5*


                       0.02    0.8*

                      0.05   0.10**

                      0.05 - 0.20**
                       20°C
                       20°C

                       20°C
                        'opt
                       20°C

                       20°C

                       20°C

                       20°C

                       20°C
                       20°C

                       20°C

                       20°C
 Di Toro et al. (1971, 1977)
 O'Connor etai. (1975, 1981)
 Thomann etal. (1974, 1975, 1979)
 Di Toro & Matystik (1980)
 Di Toro & Connolly (1980)
 Thomann & Fitzpatrick (1982)
 Salisbury et al_. (1983)

 Chen & Orlob (1975)
 Chen & Wells (1975, 1976)
 Tetra Tech (1976)

 Canale et al_. (1976)

 Lombardo (1972)

 Jorgensen (1976)
 Jorgensen et^ a\_.  (1978)

 Brandes (1976)

Grenney & Kraszewski  (1981)

 Baca & Arnett (1976)

 Smith (1978)

 Roesner et jH_.  (1980)
 Duke & Masch (1973)

Grenney & Kraszewski  (1981)

Collins & Wlosinski (1983)

Jorgensen (1979)
Diatoms
                      0.04   0.08




                      0.07   0.08


                      0.03   0.05


                      0.05   0.25



                     0.05 - 0.59**
                       20°C
                       20°C
                       20°C
                        opt
                       20°C
                 Thomann et^ al. (1979)
                 Di Toro & Connolly (1980)
                 Salisbury et al_. (1983)
                 Di Toro et al. (1971)

                 Porcella et_ al_. (1983)
                 Tetra Tech (1980)

                 Bierman (1976)
                 Bierman ejt al_. (1980)

                 Scavia et a]..  (1976)
                 Scavia TJ980)
                 Bowie et al.  (1980)

                 Collins & Wlosinski (1983)
                                   (continued)
                                          346

-------
                             TABLE  6-18.   (continued)

Algal Type
Green Algae

Respiration
Rate (I/day)
0.05 0.07
0.05 0.25
Reference
Temperature ( C)
20°C

References
Tetra Tech (1980)
Porcella e_t al_. (1983)
Scavia et al . (1976)
                        0.03    0.05


                       0.01    0.46**


 Blue-green  Algae       0.05    0.065


                        0.05    0.25



                        0.03    0.05


                       0.10    0.92**


 Dinoflagellates          0.047
                                                opt
20°C
20°C
20°C
 opt
20°C
20°C
20°C
Scavia TT980)
Bowie et al_.  (1980)

Bierman (1976)
Bierman e_t al_.  (1980)

Collins & Wlosinski  (1983)
Tetra Tech (1980)
Porcella et al_.  (1983)

Scavia et aj_.  (1976)
Scavia T1980)
Bowie et_ al.  (1980)

Bierman (1976)
Bierman et^ al_.  (1980)

Collins & Wlosinski  (1983)
O'Connor et al.  (1981]
Flagellates 0.05
0.05 - 0.06
Chrysophytes 0.15 0.32**
Benthic Algae 0.02 0.1
0.44
0.1
0.02 0.8*
0.05 - 0.2*
20UC
20°C
20°C
20°C
Topt
20°C
20°C
20°C
Bierman et_ aj_. (1980)
Tetra Tech (1980)
Porcella et al. (1983)
Collins & Wlosinski (1983)
Tetra Tech (1980)
Bowie et al . (1980)
Porcella e_t al- (1983)
Auer and Canale (1982)
Grenney & Kraszewski (1981)
Grenney & Kraszewski (1981)
Smith (1978)
 *Model  documentation  values.
**Literature values.
                                          347

-------
                                       (P  - P )
where V   =  settling velocity,  length/time
       s                                      2
      g   =  acceleration of gravity, length/time
      R   =  equivalent radius  (based on a sphere of equivalent  volume),
           length
                                         3
      p  =  density of the cell, mass/length
      P   =  water density, mass/length
      v  =  kinematic viscosity
      F   =  shape factor

     The  shape factor has a value  >1.0 and accounts  for  all  factors  which
reduce the  settling velocities  below that of  an  equivalent spherical
particle,  for  example increased  drag  due to diatom spicules,  flat  or
elongated  cells,  clusters or colonies  of cells, etc.  In a model of Lake
Ontario,  Scavia (1980)  used  a shape  correction  factor of 1.3 for  small
diatoms,  2.0  for large diatoms, and 1.0 for all other  algal groups.

     In  practice, very few model s  use  Stoke's law as a  model formulation
(Scavia  _et £]_.,  1976; Scavia, 1980; Park et a]_. , 1980) .  Most model s lump
many species  into a few algal  groups, so representative values of  the cell
radius,  shape factor, and cell density are difficult  to  define, making this
level of  detail unnecessary.   Since the shape factor  is really a calibration
parameter, it  is more  direct to  simply use the settling velocity as a
calibration parameter.  Also,  Stoke's law does not account for turbulence
and  flow velocities which tend  to  keep algae in suspension or  resuspend
settled algae.  Additional factors which further complicate settling include
the production of gas vacuoles or  gelatinous sheaths  which make some species
buoyant,  and  the fact that settling velocities may vary with the nutritional
state or  physiological condition of the cells.

     Settling rates are also partly dependent on the  structure of the model.
For  example, one-dimensional layered  lake models  typically use settling
velocities  which are an order  of magnitude  lower  than measured values or

                                  348

-------
values used  in  two-or  three-dimensional models which  simulate hydrodynamic
processes (Scavia  and  Bennett, 1980).  This  is  probably  because  one-
dimensional  models  do  not adequately  represent vertical transport process
such as  upwelling  or  entrainment of phytoplankton  in large-scale
circulations which  effectively reduce the net settling rates (Scavia  and
Bennett,  1980).

     Because  of the above factors, most models  specify  phytoplankton
settling  velocities  directly as model  coefficients.  The settling rate in
Equations  (6-1) or (6-2) is generally  expressed as:

                                    V.
                                 s = -r-                          (6-76)
                                     d
      V   = settling velocity, length/time
where  s  = settling rate, I/time
      V  = settling velocity,
      d  = water depth,  length
      In  layered models,  algae settling  in from the above layer, as well  as
algae settling out of the layer, must be included in  the formulation.  This
also requires consideration of the bottom topography,  since  a  fraction  of
the algae will settle onto the bottom area associated  with each  layer.

      Equation (6-76) is  refined in some models by including  a  temperature
function which accounts  for  changes in  settling  velocities due  to
temperature effects on the density and  viscosity of  water.  The settling
rate is  then expressed as:

                               V(T   )
                           s =          fs(T)                      (6-77)

where V  (T   ,) = settling velocity  at  reference temperature T   -,
                length/time
      .f  (T)    = temperature adjustment  function for the  settling
                velocity
                                  349

-------
Typical examples of temperature adjustment  functions include  (Tetra Tech,
1980):
                      f,(T) =
where T = temperature  in  C.
or  (Scavia and Park,  1976):
                                       157.5
                               0.069T -  5.3T + 177.6
                                                     (6-78)
                              fs(T)  =  1 +  as T
                                                     (6-79)
where a  = slope  of  settling velocity vs.  temperature curve
    Scavia _et al_.  (1976) have also expanded the settling rate formulation to
account for variations  in  settling velocities  due to the  physiological
condition of the  phytopl ankton cells.  The  basic assumption is  that the
cells  are healthiest and the settling  rates  smallest when neither  light nor
nutrients are limiting growth.  The settling  rates are therefore  expressed
as  a  function of the growth limitation factor  f (L,P,N,C,Si ) .   Potential
formulations include (Scavia et al_. ,  1976; Scavia, 1980):
                               .                    _
                                   ' \f(L,P,N,C,STT+ K
                                                      set.
                                                     (6-80)
or
    V     (T   }
  ,   smaxv ref; f /-,-%
5        H      T<-V' 1
f(L,P,N,C,Si)
(6-81)
where vsmax(Tref) = maximum  settling velocity at reference  temperature
                   Tref  under  P°°i" physiological  condition,
                   length/time
      Kset  'Kset  = constants of  tne settling formulations

     A few models  require specification of the settling rate  s rather than
the settling velocity Vg as a model calibration coefficient.   When  used in

                                   350

-------
this way,  the  settling rate may  take  on a wide range of values since  it
depends as  much on the water depth  as the settling  velocities of the algae.

     Phytoplankton  settling  velocities are presented  in Table 6-19.
Additional  data are available in a  review by Smayda  (1970).

6.7  NONPREDATORY MORTALITY

     Nonpredatory mortal ity  accounts  for all algal  losses  which are not
explicitly accounted for by the grazing term or  other loss processes  in the
model  (for example,  settling and respiration  if they are  not  computed
explicitly).  Nonpredatory mortality includes processes such as senescence,
bacterial decomposition of cells (parasitism), and  stress-induced mortality
due to  severe  nutrient deficiencies, extreme environmental  conditions, or
toxic substances.  The nonpredatory  mortality rate in Equations (6-1),
(6-2),  or  (6-3)  is generally specified as a constant model coefficient.
This is in  contrast to the  predatory  mortality or grazing  rate  which is
computed dynamically to reflect changes in the predator densities.

     In some models,  a  temperature adjustment  function  is used  with
nonpredatory mortality which results in:

                            m = m(Tref)  fm(T)                       (6-82)

where m      = nonpredatory mortality rate, I/time
      m(T  -) = nonpredatory mortal ity rate  at reference temperatur*e
               Tref» I/time
      fm(T)  = temperature function for mortality

The temperature functions for mortality generally  use the same formulations
used for growth and respiration (Equations (6-5)  through (6-25)).  However,
if a temperature optimum curve is  used for growth, the temperature function
for mortality will often use only  the left hand  portion of the curve to
produce  a  temperature response curve  in which mortality  increases with
temperature until some maximum mortality rate is  reached.

                                   351

-------
              TABLE  6-19.    PHYTOPLANKTON  SETTLING VELOCITIES
Algal Type
Settling Velocity  (m/day)
         References
Total
Phytoplankton
Diatoms
       0.05    0.5
                        0.05   0.2
       0.02    0.05

          0.4

       0.03    0.05

          0.05

       0.2   0.25

       0.04    0.6


       0.01  -  4.0*

        0.    2.0*


       0.15    2.0*


        0. -  0.2*

       0.  -  30.**


       0.05  -  0.4


        0.1  -  0.2


       0.1 -  0.25


       0.03  -  0.05

        0.3  -  0.5

          2.5

      0.02    14.7**

      0.08 -  17.1**
Chen & Orlob (1975)
Tetra Tech (1976)
Chen (1970)
Chen & Wells (1975, 1976)

O'Connor etjj]_. (1975, 1981)
Thomann etal_.  (1974, 1975,  1979)
Di Toro & Matystik (1980)
Di Toro & Connolly (1980)
Thomann & Fitzpatrick (1982)

Canale et aj_.  (1976)

Lombardo (1972)

Scavia (1980)

Bierman et^ al.  (1980)

Youngberg (1977)

Jorgensen (1976)
Jorgensen j^t a^.  (1978,  1981)

Baca & Arnett (1976)

Chen & Orlob (1975)
Smith (1978)

Duke & Masch (1973)
Roesner et^ al_.  (1977)

Brandes (1976)

Jorgensen (1979)


Bierman (1976)
Bierman et^ a\_.  (1980)

Thomann et a]_.  (1979)
Di Toro & Connolly (1980)

Tetra Tech (1980)
Porcella et al_. (1983)

Canale £t al_.  (1976)

Smayda & Boleyn (1965)

Lehman et al_.  (1975)

Collins & Wlosinski (1983)

Jorgensen (1979)
                                      (continued)
                                         352

-------
                       TABLE  6-19.   (continued)
 Algal  Type
Settling Velocity (m/day)
          References
 Green Algae
 Blue-green Algae
 Flagellates
 Dinoflagellates
 Chrysophytes
       0.05 - 0.19

       0.05   0.4


          0.02

           0.8

       0.1   0.25


           0.3

      0.08   0.18**

      0.27 - 0.89**


       0.05   0.15


           0.

          0.2

          0.1

       0.08   0.2


      0.10   0.11**


          0.5

          0.05

       0.09 - 0.2


      0.07   0.39**


          8.0

       2.8   6.0**


          0.5
 Coccolithophores        0.25   13.6

                          0.3   1.5**
Jorgensen ejt aj_. (1978)

Bierman (1976)
Bierman et_ al. (1980)

Canale et a]_. (1976)

Lehman et_ al_. (1975)

Tetra Tech (1980)
Porcella et. ah  (1983)

DePinto e_t al. (1976)

Collins & Wlosinski (1983)

Jorgensen (1979)


Bierman (1976)
Bierman e_t al. (1980)

Canale et. al. (1976)

Lehman et al- (1975)

DePinto e_t al. (1976)

Tetra Tech (1980)
Porcella et ah  (1983)

Collins & Wlosinski (1983)


Lehman et al. (1975)

Bierman ejt al. (1980)

Tetra Tech (1980)
Porcella et ah  (1983)

Collins & Wlosinski (1983)


O'Connor et al.  (1981)

Collins & Wlosinski (1983)


Lehman e_t al. (1975)


Collins & Wlosinski (1983)

Jorgensen (1979)
 *Model  documentation values.
**Literature values.
                                    353

-------
     A few models  use more sophisticated  formulations for nonpredatory
mortality which  try  to relate the mortality  rate to the physiological
condition of  the algal  cells or to the  size  of the decomposer population
(De Pinto, 1979).  For example, Scavia _et _aj_.  (1976) use the  value  of the
growth limitation  factor f (L ,P ,N ,C ,Si )  as  a  measure of cell health and
express the mortality  rate as:
where m   (T   ,.) = maximum nonpredatory  mortal i ty under  poor
       max ref                K         J            J
                  physiological  conditions at reference  temperature
                  Tref,  I/time
This  assumes  minimal  mortality and  algal  decomposition when  growth
conditions are optimal, and maximum mortality when conditions are  severely
limiting.

    Lehman ^t al . (1975)  use  a similar approach, but  also  include the
duration  of growth limiting conditions  in the formulation.  They define the
mortal ity  rate as:
                 m - WTref>

where T   = number of days of suboptimal  conditions (defined  as  ..
      50                                                        ma X
           .05) , time
      KSQ = coefficient  defined as In2  divided by the number  of days at
           suboptimal conditions until  m increases to % m
     MS. CLEANER expresses  nonpredatory mortality as a function of  both  the
internal  nutrient  concentrations and temperature such that the mortality
rate increases exponentially under conditions of either nutrient  starvation
or critical ly  high temperatures.  The equation is (Desormeau, 1978; Park
et al., 1980):

                       Kn(Ncrit-f(P'N'C'S1))  
-------
where  K          = nonpredatory mortality rate coefficient, I/time
       K          = exponent for nutrient starvation
       f(P,N,C,Si) = variable stoichiometry nutrient limitation  factor
                    for algal  growth
       N  ..       = critical  value of f(P,N,C,Si) for  starvation
        O I I L
                    mortality
       T  ..       = critical temperature for nonpredatory  mortality
        C i I L
This  assumes that  when  the internal nutrient levels drop below  the
subsistence quota,  increased senescence,  bacterial  colonization, and cell
lysis occur.
     Bierman _e_t jaj_.  (1980) use a nonpredatory  mortality function which
indirectly includes the  size of the  decomposer bacteria  population in  the
formulation.   Although the  bacteria are  not  modeled explicitly, they  are
assumed  to increase  in proportion to the total algal concentration (the  sum
of all algal  groups in the model).  Therefore,  increases in the bacteria
associated with  the bloom of one algal  group will  result  in higher mortality
rates  for all other groups  since a  higher decomposer population  is
established.   The  equation is:
where K (T  f)  =  nonpredatory mortality rate coefficient  at reference
                 temperature T  f,  1/time-algae
      A.       =  concentration of algal  group i, mass/volume
      n        =  total number of algal  groups

     Nyholm  (1978)  uses a Michael is-Menten type saturation function of the
algal concentrations  in his formulation  for algal mortality:
                                   355

-------
where m   (T  r) = maximum nonpredatory mortality rate  at  reference
       max  ref
                  temperature T  f> I/time
      A         = algal concentration,  mass/volume
      K ,        = half-saturation constant for algal  nonpredatory
       ml
                  mortality, mass/volume
At high  algal concentrations, this is  equivalent  to  the basic first  order
formulation  (Equation (6-82)), while at  very low algal  levels, the mortality
rate is essentially a  second  order relationship  analogous to Equation
(6-86).  However,  even though the mortality rate  is second order at low
algal  densities,  the Michaelis-Menten term  reduces  the net rate at  low
densities below the maximum first-order  rate at high  algal  densities.

    The Michaelis-Menten formulation  is also used by Di Toro and Matystik
(1980), Di Toro  and Connolly (1980), and Thomann and  Fitzpatrick (1982)  in
their formulation  for  the  decomposition of organic  matter (dead algal
cells), although a basic  first-order formulation is used for  algal
nonpredatory mortality.  These models  use the Michaelis-Menten formulation
to account for the  effects  of the bacterial population on decomposition
rates, assuming that decomposers (and the resulting  decomposition rates)
increase in proportion to  the algal densities  at  low concentrations,  but
that other factors  limit  decomposition rates  at  high algal   densities
(Di Toro and Matystik,  1980; Di Toro  and Connolly, 1980).  These mechanisms
could  also be assumed for nonpredatory mortality.

    Rodgers  and Salisbury  (1981) use  a  modified Michaelis-Menten
formulation for nonpredatory mortality which includes  the effects of  both
bacterial  activity  and the  physiological condition  of the  algal  cells on
algal  decomposition:

         "  ' Vx

where M   = algal  growth rate, I/time
         =  half-saturation  constant for  algal nonpredatory mortality,
           mass-time/volume
                                  356

-------
The  mortality rate is directly  proportional to  the  algal  biomass  (an
indicator  of  bacterial activity)  and  inversely proportional  to the algal
growth rate (an indicator of the  physiological  condition of the cells),  both
through a  saturation type relationship which limits the maximum rate.

     Some models  include  formulations to account  for  stress-induced
mortality  due to factors such as  extreme temperatures  or  toxic  substances.
Stress  related mortality is typically modeled by  expanding the nonpredatory
mortality  term to include additional terms for these  effects, for example:
              m
= m(Tref)  fm(T) + mT(Tref}  fT(T) + mx fx(X)          (6'89)
where mj(T e^)  =  thermal  mortality rate  at  reference temperature
                 Tpef, I/time
      fy(T)    =  thermal mortality response curve
      m        =  toxic mortality rate, I/time
       A
      f (X)    =  dose-response curve for toxic mortality
       A
      X        =  concentration of toxicant, mass/volume

Toxic  effects  can also be  included in  the  growth and  respiration
formulations.
      Algal  nonpredatory mortality  rates are presented in Table 6-20.

6.8  GRAZING

      Algal  grazing losses can be modeled in several ways,  depending on 1)
whether  predator populations  are simulated in the model, and 2)  whether
alternate food  items are available  for the predators.

      When  predators  are not explicitly modeled,  predator-prey dynamics
cannot be simulated, so grazing effects are typically  handled by either
assuming  a  constant grazing loss  which is specified by the user as  a model
input parameter:
                                   357

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               TABLE  6-20.  ALGAL  NONPREDATORY  MORTALITY RATES
                      Nonpredatory Mortality
       Algal Type           Rate  (I/day)
                                          References
       Total
       Phytoplankton
       Diatoms
       Benthic Algae
              0.02

          0.003   0.17

              0.03

          0.005   0.10

           0.01   0.1



              0.03


             0.- 0.8
Thomann & Fitzpatrick (1982)

Baca & Arnett (1976)

Scavia et al_. (1976)

Salas & Thomann (1978)

Jorgensen (1976)
Jorgensen et al_. (1978)


Scavia et al. (1976)
Tetra Tech (1980)
Bowie et a]_.  (1980)
Porcella et al. (1983)
                                  G =  constant
                                                           (6-90)
where  G =  loss rate  due  to grazing, mass algae/time


or  by  assuming  a loss  rate  which  is  directly proportional  to  the algal
densities  (e.g., RECEIV-II (Raytheon,  1974)):
                                  G = e   A
or
              G =
                         (6-91)


                         (6-92)
where  e
         (T  .)
         v  ref;
       VT)
= grazing  rate coefficient, I/time

= algal  biomass or  density, mass  or mass/volume

  grazing rate  coefficient  at  reference temperature

  Tref,  I/time

  temperature function for grazing
                                       358

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The second formulation is equivalent  to that  often  used for non-predatory
mortality (Equation (6-82)),  so both nonpredatory mortality and grazing
losses  are typically combined into a single  total  mortality term  when
predator populations are not directly simulated:
                    mtot
where m.  .       = total mortality rate, I/time
      mtot^ref^ ~ total mortality rate at reference temperature T  ,,
                  I/time
      fm(T)      = temperature function for mortality

The  temperature functions used for  grazing are the same  as those discussed
previously for  algal growth, respiration, and mortality (Equations  (6-5)  to
(6-25)).

      Many general water quality models include a single zooplankton  group
to provide  a more realistic  grazing formulation  for algae (Baca et al . ,
1973; Johanson _et ^]_. , 1980; Najarian and Harleman,  1975).  The zooplankton
are  often  added only to obtain better simulations of algal dynamics, rather
than to evaluate the zooplankton dynamics of the system.   The coupled  algae
and  zooplankton equations provide the major  features  of predator-prey
interactions  since the algal grazing  rate is defined as a function of  the
zooplankton  density which in  turn  varies dynamically with the food supply
(algal  concentration).  The algal  grazing rate in these models is typically
expressed either in terms of a zooplankton filtration rate:

                                G =  Cf A Z                          (6-94)

or                         G = Cf(Tref) fg(T) A Z                     (6-95)

where Cf       = zooplankton  filtration rate, water  volume/mass
                   zooplankton-time

                                    359

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     Z        =  zooplankton biomass or concentration, mass  or
                mass/ volume
     Cf(T  f)  =  filtration  rate at  reference  temperature T  ,.,
                water volume/mass zooplankton-time

or in terms of  a  zooplankton ingestion rate:

                               G = C  Z                          (6-96)

or                         G =  Cg(Tref) fg(T) Z                    (6-97)

where C        =  zooplankton ingestion  rate,  mass  algae/mass
                zooplankton-time
     C  (T  ,.)  =  ingestion  rate at  reference  temperature T   f)
      gv ref      s                                           ref
                mass algae/mass  zooplankton-time

     Ingestion rates are often back-calculated from computed  zooplankton
growth rates based on the equation (Chen and Orlob, 1975;  Smith, 1978;  Tetra
Tech, 1979; WES,  1982):
                                Cg =                             (6-98)

where g  = zooplankton growth rate, I/time
      E  = zooplankton assimilation efficiency

In this  approach,  zooplankton growth rates are first computed as  a  function
of food supply and temperature, and  then the  amount of algae  which would
have  to  be consumed  to produce the growth is computed from Equation  (6-98).
The  alternative  approach  is to  specify or compute the  ingestion  rates
directly, and  then  calculate the  zooplankton growth rates  based on  the
amount  of food  consumed  and the  assimilation efficiencies.   Specific
formulations for  zooplankton filtration rates, ingestion rates, growth
rates, and assimilation efficiencies are discussed in detail  in Chapter 7.
                                  360

-------
      Models which simulate  only a single algal and zooplankton  group tend
to oversimplify predator-prey dynamics since  a  single constituent  represents
all primary producers and another  single  constituent represents  all
consumers.  This ignores  the complexities of the food web,  as  well  as
differences in foraging strategies,  grazing rates, and food preferences
between different types  of predator  organisms.  This approach may be
adequate in short term simulations where  one  group of  phytopl ankton  and
zooplankton are dominant.   However, in long  term simulations, more  than one
group of algae  and zooplankton should  be  used  to adequately simulate
predator-prey interactions  and population dynamics.

      Algal grazing rates  in multi-group models are functions of  alternative
food  sources  and food preferences,  as well  as  predator densities, algal
densities, and temperature.  The basic grazing  formulations are essentially
the same as those mentioned above  for  a  single zooplankton group, except
that 1)  grazing losses must  be considered for each potential  predator  which
grazes the algae, and 2)  total grazing rates  calculated for a given  predator
must be  partitioned among  the various food  items  which it consumes.   Some
models  also  consider  differences  in  the ingest ion or assimilation
efficiencies between different food items (Scavia _et aTL ,  1976; Park et al . ,
1980),  and differences  in the feeding  behavior of different  zooplankton
groups (e.g., non-selective filterers,  selective filterers, carnivorous
raptors, omnivores, etc.)  ( Canal e _et aj_. , 1975, 1976; Park _et aj_. , 1980).

      Grazing losses for  non-selective feeders  can be partitioned  between
different algal  groups  by distributing  them in proportion to the algal
concentrations:
                                                                  (6-99)
                                   361

-------
where G..  =  loss rate of algal  group i due  to  grazing by zooplankton
            group j, mass algae/time
      C.   =  total ingestion rate of zooplankton group j on  all  food
       J
            items, mass food/mass zooplankton-time
      A.   =  biomass or concentration of  algal  group i,  mass  or
            mass/volume
      F,   =  biomass or concentration of potential  food  item k  consumed
            by zooplankton group j, mass or mass/volume
      n   =  number of potential food items
      Z.   =  biomass or concentration of  zooplankton  group j, mass or
       J
            mass/volume

When grazing is expressed in  terms of a filtration rate this partitioning  is
done  automatically since  the grazing  losses  are simply the algal
concentrations times the volumetric filtration  rates.

      The  above expression can  be modified to account for selective  feeding
behavior  by using  food preference  factors.   These  are weighting factors
which reflect the probability that a given food will be consumed relative  to
the  others  when all  foods  are  present in equal concentrations.  The
preference factors account for  feeding differences due  to factors like food
particle  size  and  shape, desirability and quality of  food,  and zooplankton
feeding behavior.   The grazing losses  for each algal group subject  to
selective  feeding can be expressed as:

                                    P. . A.
                          G..= C. —U—1— Z.                    (6-100)
                            ij    J  n         j                    v
                                   k=l kj' k

where P..  =  preference  factor  for zooplankton  j  grazing on algal group
              i
      P..  =  preference factor for zooplankton j grazing on food item k

The total  ingestion rates  C.  for each  predator are the  same  as discussed
                          J
above for  a  single zooplankton  group (Equations (6-94)  through (6-98)).

                                   362

-------
      When  several predators are modeled, the total  grazing loss for a given
algal  group is the sum of the grazing losses from each  predator:
                                6. =  £G...                        (6-101)

where G.  =  loss rate for algal  group i due to grazing  by  all predators,
           mass algae/time
      n  =  total number of predators grazing on algal  group i

Any of the  previous formulations can be used  to  define the incremental
grazing rates  G. . associated with each predator.

      Zooplankton grazing rates are tabulated in Chapter  7, along with more
detailed  descriptions of  the grazing  formulations for zooplankton.

6.9  SUMMARY

      Phytopl ankton  and attached algae are generally modeled as a biomass
pool using  the same mass  balance approach used  for nutrients and other
constituents. The simpler models lump all algae into a  single group, while
more complex  models distinguish between different functional groups such as
green algae, diatoms,  and  blue-green algae.   Single-group models are
commonly used in rivers, while multi-group models are  more common in lakes
where long-term simulations of the seasonal succession of different types of
phytoplankton are important.

      Algal  dynamics  depend on  growth,  respiration, excretion, settling,
nonpredatory  mortality, and predation.  Although some  of  these processes  can
be  measured  in the field  or  laboratory, most of the coefficients defining
the process rates are  usually determined by  model  calibration.  This is
necessary  since  the  rates will vary with environmental  conditions such as
temperature,  light, nutrient concentrations, and predator densities as well
as  with the species composition  of the  algae, all of which change
continually with time.  Literature values from laboratory experiments  are
useful  for establishing  reasonable  ranges for the coefficients.  However,
                                  363

-------
specific experimental  results are difficult  to apply directly  since
experiments  typically  use  a  single  species rather than  the species
assemblages represented  in models, and  since  experimental conditions may not
represent conditions in the field.  Model  constructs must be relied upon to
describe  the effects of  changing environmental and ecological conditions on
the process rates.

      Most  processes in algal models are  assumed  to be  temperature
dependent.  Three major  approaches have been  used to describe these effects:
linear temperature response curves, exponential curves, and  temperature
optimum  curves.   The exponential Arrhenius relationship is  commonly used
when only one algal group is simulated, while temperature optimum  curves are
more common in multi-group models.

      The most important and complex formulations in algal  models are the
growth formulations.  Growth is a function  of temperature,  light, and
nutrients.  Light limitation is typically  defined by either  a  saturation
type  relationship  or a  photoinhibition  relationship in  which  growth
decreases at  light intensities  above the  optimum.   Most  models  use
Michaelis-Menten kinetics to describe nutrient limitation effects  and  assume
the nutrient  composition  of the algal cells  rema.ins constant.   More
sophisticated models allow the internal  stoichiometry of the  algae to vary
with changes in the external nutrient concentrations.  These  models simulate
nutrient uptake and algal growth  as two separate steps.  Nutrient uptake is
first computed as a function of both the  internal  nutrient levels  in the
cells and the external concentrations in the water.  Algal growth is then
computed based  on the  internal   nutrient concentrations  in  the cells.
Various  formulations have been used to describe uptake and  growth kinetics
in variable stoichiometry models.  These formulations are more  complex and
involve more model coefficients than fixed  stoichiometry models.

      Most models use simple temperature-dependent first-order relationships
to describe respiration, settling, and  nonpredatory mortality.   A few  models
include the effects of the physiological  condition of  the  algae on  these
processes by  making them  a function  of the growth rate, growth limitation
factor, or internal nutrient level (in  variable stoichiometry models).  Some
                                  364

-------
models  also  include the effects  of the decomposer bacteria population on
nonpredatory  mortality.  These' latter effects  are  modeled indirectly by

assuming  the decomposers  increase  in proportion to  the  algal densities and

using algal concentrations  as  an indicator of  the  bacterial  population,
rather  than  by simulating  the  decomposers directly.   Both  second-order
mortality  formulations and  Michaelis-Menten type  saturation relationships

have been  used  to describe  these  effects.


      Algal  grazing is  usually modeled  as  a  first-order  loss when
zooplankton  are not simulated.  When  zooplankton are modeled, algal  grazing

is  a  function  of the algal densities, zooplankton  densities,  and  the
zooplankton  filtration rates or consumption rates.  In multi-group models

which  include  several  algal  and  zooplankton  groups,  selective feeding
behavior  can be simulated  by including food  preference factors  in  the

grazing formulations.


 6.10   REFERENCES

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 Battelle, Inc.  1973.  EXPLORE-I: A River  Basin  Water Quality  Model.
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                                   365

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Grenney, W.J.  and A.K. Kraszewski.  1981.  Description and Application of
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                                  369

-------
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                                  374

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                               Chapter 7
                               ZOOPLANKTON
7.1  INTRODUCTION
     Zooplankton  are  included  in water quality models primarily because of
their  effects on algae and nutrients.   Algal dynamics and  zooplankton
dynamics  are closely tied through  predator-prey interactions.   Nutrient
dynamics are  also  influenced by  zooplankton since zooplankton  excretion is
an  important component of nutrient recycling, and because of the effects
zooplankton  have on algal dynamics.   These  interrelationships  are
particularly important for long-term simulations in lakes  and  estuaries
since both zooplankton and algal  densities may change by orders of  magnitude
over periods  of several months.

     As with  phytoplankton,  zooplankton have been modeled both  as  a single
constituent representing total zooplankton and as several functional  groups.
The  functional  groups may represent different  feeding types  (e.g.,
herbivores,  carnivores, omnivores,  non-selective filter feeders,  selective
filter feeders, etc.) or different taxonomic groups  (cladocerans,  copepods,
rotifers,  etc.).   While many models  use only one group, multiple-group
models more realistically represent trophic interactions since,  for example,
herbivorous  zooplankton can be distinguished from carnivorous species.
However, multi-group models  require more coefficients and model  parameters,
as well as more detailed information  for model calibration.

     Zooplankton dynamics are governed by the  same general  processes as
.phytoplankton:  growth, respiration  and  excretion,  predation,  and
nonpredatory  mortality.   The major difference is that zooplankton are not
subject to settling losses since they are motile and migrate  vertically in
the water  column, typically  in a  diurnal pattern. As a result,  zooplankton
                                  375

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are usually simulated using the same types of  equations and formulations  as
used for  phytoplankton.   The general zooplankton equation  which forms the
basis of  almost all models  is:

                      § • 
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                               TABLE  7-1.   GENERAL  COMPARISON  OF  ZOOPLANKTON  MODELS
Model
(Author)
AQUA- IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
EAM
ESTECO
EXPLORE-1
HSPF
LAKECO
MIT Network
WASP
WQRRS
Blerman
Canale
Jorgensen
Scavia
Number of Groups
Zoo-
lankton
1
1
3
3
5
3
1
1
1
1
1
2
1
2
9
1
6
Phyto-
plankton Fish
1
2 3
2 3
3 3
4 8
4 20
2 3
1
1
2 3
1
2
2 3
5
4
1 I
5
Zooplankton
Growth
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Processes
Respiration
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Computed Separately In Model
Nonpredatory
Mortality
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Predatory
Mortality

X
X
X
X
X
X


X

X
X

X
X
X
Zooplankton Units
Dry Wt. Other
Blomass Carbon Nutrient
X
X
X
X
X
X
X
X
X
X
N
X
X
X
X
X
X
Reference
Baca & Arnett (1976)
WES (EWQOS) (1982)
Bloomfleld e_t al_. (1973)
Scavia 4 Park (1976)
Park e_t al_. (1980)
Tetra Tech (1979, 1980)
Brandes 8, Masch (1977)
Baca e_t al_. (1973)
Johanson et al . (1980)
Chen & Orlob (1975)
Harleman et al_. (1977)
D1 Toro e_t al_. (1981)
Smith (1978)
Bierman £t aj_. (1980)
Canale e_t al_. (1975, 1976)
Jorgensen (1976)
Scavia et^ aj[. (1976)
CO

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nonpredatory mortality are generally direct functions of temperature, and
predation  is indirectly related through temperature effects on  the
consumption rates of zooplankton predators. In most models,  the  temperature
response formulations used for zooplankton  are identical to  those  used for
phytoplankton,  and  the same temperature function is generally used for all
processes  affecting a given  zooplankton group.  The major differences in the
response functions  between  different organisms  are  the  particular
coefficient values used to  define the  shapes  and slopes of the  response
curves, the optimum temperatures, and the  upper-and lower lethal limits.  A
few models  use different formulations for each  process.   For example, CE-
QUAL-R1 (WES,  1982) uses an optimum curve for growth, a logistic equation
for respiration, and a reverse logistic equation for nonpredatory mortality.

      The various formulations used  to  define  temperature effects are
described in  detail  in  the  algal  growth  section  of  the  report
(Section  6.3.1),  and they will not  be repeated here.  In general,  all
formulations can be classified as either linear response curves,  exponential
response curves, or temperature optimum curves which exhibit  maximum process
rates at the optimum temperature and  decreasing  rates  as the temperature
moves away from the optimum.

7.3  GROWTH

      Zooplankton growth formulations represent increases  in the biomass of
the population due to both reproduction and the growth of individuals.   The
growth rate depends on the amount of  food which is ingested and assimilated,
and  is therefore  a  function of food  densities, ingestion rates,  and
assimilation  efficiencies.   Part  of  the  assimilated  food goes  into
individual growth and metabolic losses,  and part goes into  reproduction.

      Both ingestion rates and assimilation efficiencies  vary according to
many factors, including (Leidy and Ploskey, 1980):

     •  Zooplankton factors such as species, age, size, feeding type,
        sex, reproductive  state, and physiological  or  nutritional
        state
                                  378

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    •   Food related  factors such  as  food  concentration,  type,
        particle  size, quality, and desirability  of the food

    •   Temperature

Ingestion  rates  also vary  on a  diurnal basis, with maximum feeding rates
typically occurring at night.  Peak nighttime grazing rates  have  been shown
to range from 2 to 27 times the minimum  daytime  rates (Leidy and  Ploskey,
1980).

     Almost all zooplankton growth formulations are based on  the  following
fundamental relationship:

                             9Z = Cg E                               (7-2)

where g  =  zooplankton growth rate, I/time
      C  =  ingestion or grazing rate, mass food/mass zooplankton-time
      E  =  assimilation efficiency, fraction

Since most  zooplankton  are  filter  feeders,  the ingestion  rate  is often
expressed  in  terms of  a  volumetric filtration rate multiplied  times the
total  available  food concentration.  In this  case, the above  equation
becomes:

                            gz =  Cf FT  E                             (7-3)

where Cf =  zooplankton filtration rate, water volume/mass zooplankton-
           time
      FT =  total  available food concentration, mass/volume

For raptorial feeders, the previous equation  (Equation (7-2)) is  generally
used.

      The simplest growth formulations assume constant filtration  rates and
assimilation efficiencies (Figure 7-1).  For  this situation, the  growth  rate
                                  379

-------
LU
fe
CC
                        FOOD CONCENTRATION, FT
     Figure 7-1.  Growth  rate and grazing rate as  a function of food supply
                 for zooplankton with constant filtration rates and
                 assimilation efficiencies (adapted from Leidy and
                 Ploskey,  1980).

  is  directly proportional  to the food supply.   More sophisticated models
  include  more complex  formulations for the ingestion (or filtration)  rates
  and the assimilation efficiencies to account for  variability due to factors
  like  food densities, food types, different  feeding methods, and temperature
  effects on feeding  and  growth (Canale  eit  al., 1975, 1976;  Scavia et  al.,
  1976;  Scavia, 1980; Scavia and Park,  1976; Park et al., 1975, 1979,  1980).
  The effects of food density and temperature  on zooplankton growth rates  can
  be  expressed in general functional form as:
  or
                            Emax(Tref) f(T)
WTref>
                                              (7-4)
                     ff(FpF2,...Fn)
(7-5)
  where  C    (T  ,.)
        gmaxv ref
maximum ingestion rate at reference temperature
Tref  under  conditions of  saturated feeding
                                     380

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                      (excess food  supply),  mass  food/mass
                      zooplankton-time
                    = maximum filtration rate  at  reference
                      temperature  T   f,  water  volume/mass
                      zooplankton-time
     E   (T  .p)      = maximum  assimilation efficiency  at reference
                      temperature  T  f, fraction
     f(T)           = temperature  function  for ingest ion or
                      filtration and assimilation
     f (FpF2,...Fn) = growth  limitation factor for ingestion
      j
                      formulation (Equation  (7-2)) accounting for
                      food  density effects on  ingestion  rates and/or
                      assimilation rates (where [ri»F2''"|rn  are the
                      concentrations of the potential food items)
     ff(F,,Fp,...F ) = growth  limitation  factor for  filtration
                      formulation (Equation  (7-3)) accounting for
                      food density effects on filtration  rates and/or
                      assimilation rates

     In  some models,  the maximum  ingestion  rate  and the  maximum
assimilation efficiency are combined into a single parameter representing
the maximum growth (or assimilation) rate (Chen and Orlob,  1972, 1975; Chen
et^jfL,  1975; Jorgensen,  1976; Jorgensen et aU, 1978, 1981, 1983; Najarian
and Harleman, 1975; Smith, 1978; WES,  1982; Tetra Tech,  1979).   In this
case, Equation (7-4) becomes:

                  9z ' 3max  f fg              (?-6)

where ci   (T  f)  = maximum  zooplankton  growth  rate at reference
     ~rnax  rer
                  temperature T f, I/time

    Maximum  consumption rates, filtration rates,  and  growth rates are
presented in Tables 7-2,  7-3, and 7-4, respectively.
                                 331

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       TABLE  7-2.   ZOOPLANKTON MAXIMUM CONSUMPTION RATES
Zooplankton Maximum
Group Consumption Rate (I/day)
Total
Zooplankton 0.8
0.35 - 0.50
0.24 1.2**
Omnivores 1.4
0.43
Carnivores 1.6
0.7
Fast Ingesters 0.7
Slow Ingesters 0.1
Cladocerans 1.6 1.9
0.045 13.8**
0.045 2.3**
References
Scavia & Park (1976)
Bierman (1976)
Collins & Wlosinski (1983)
Scavia (1980)
Bowie et al. (1980)
Canale et al_. (1976)
Scavia et al_. (1976)
Canale et al_. (1976)
Bierman ejt al_. (1980)
Bierman ejt al_. (1980)
Scavia et al. (1976)
Scavia TJ980)
Bowie et al. (1980)
Leidy & Ploskey (1980)
Collins & Wlosinski (1983)
Copeods
Rotifers
Mysids
  1.7    1.8



0.10   0.47**


  1.8    2.2



   3.44**

   3.44**


  1.0  - 1.2
Scavia  et al_. (1976)
Scavia  TT980)
Bowie et al- (1980)

Collins & Wlosinski (1983)
Scavia  et al. (1976)
Scavia  TJ980)
Bowie ejt al. (1980)

Leidy & Ploskey (1980)

Collins & Wlosinski (1983)
Scavia  et al- (1976)
Scavia  TT.980)
Bowie et a]_.  (1980)
**Literature values.
                                  382

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             TABLE  7-3.  ZOOPLANKTON  MAXIMUM  FILTRATION RATES
Zooplankton Group
Total Zooplankton


Herbivores
Carnivores
Cladocerans






Copepods






Rotifers


Maximum
Filtration Rate
0.13
0.05
0.8
0.7
1.0
3.5
0.2
0.192
0.2
0.009
0.18
0.18
1.0
0.05
0.161
0.05
0.02
0.02
0.006
0.6
0.6
0.007
1.2
- 0.2*
1.10**
- 1.4
3.9
4.0
1.6**
0.682**
1.6**
177**
9.4**
9.4**
6.5
- 2.2**
2.21**
2.2**
- 4.1**
- 5.28**
35.**
1.5**
- 1.5**
0.576**
Units
1/mgC-day
1 /mg C- day
l/mg(D.W.)-day
1/mgC-day
1/mgC-day
l/mg(D.W.)-day
l/mg(D.W.)-day
l/mg(D.W.)-day
l/mg(D.W.)-day
ml/animal-day
ml/animal-day
ml/animal-day
l/mg(D.W.)-day
l/mg(D.W.)-day
l/mg(D.W.)-day
l/mg(D.W.)-day
ml/animal-day
ml/animal-day
ml/animal-day
l/mg(D.LJ.)-day
ml/animal-day
ml/animal-day
References
Di Toro et al . (1971)
O'Connor et al_. (1975, 1981)
Baca & Arnett (1976)
Di Toro et al_. (1971)
Thomann et al . (1975, 1979)
Di Toro & Connolly (1980)
Di Toro & Matystik (i960)
Salisbury et a]_. (1983)
Thomann et al . (1975, 1979)
Di Toro & Connolly (1980)
Di Toro & Matystik (1980)
Salisbury et jH_. (1983)
Canale et_ al_. (1976)
Di Toro et al. (1971)
Lombardo (1972)
•Jorgensen (1979)
Leidy & Ploskey (1980)
Wetzel (1975)
Jorgensen (1979)
Canale et al_. (1976)
Di Toro et al_. (1971)
Lombardo (1972)
Jorgensen (1979)
Wetzel (1975)
Jorgensen (1979)
Leidy & Ploskey (1980)
Di Toro £t al_. (1971)
Jorgensen (1979)
Leidy & Ploskey (1980)
 *Model documentation values.
**Literature values.
                                     383

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     The temperature function f(T)  in  the above  equations  uses  the same
types of formulations  discussed  previously  for  phytoplankton.   Experimental
results  suggest optimum type  response curves for  short term  changes in
temperature,  but more  of  a  linear  response  curve when  acclimation has time
to  occur  (Leidy  and Ploskey,  1980).  Work  by Geller (1975)  indicates
acclimation times may  range  from 4 to 6 weeks, which is short  enough  for
zooplankton  to acclimate to the typical seasonal variations  in temperature,
but not to  rapid changes  (for example, thermal plume effects).   However,
since feeding  is expected  to slow down or cease as the temperature
approaches the upper  lethal  limit,  an optimum  type  response  curve  is
appropriate if it is skewed  so that the optimum occurs near the upper  lethal
limit.   Table 7-5 presents a  comparison of  the  temperature' adjustment
functions used in several zooplankton models.

                TABLE  7-4.   ZOOPLANKTON MAXIMUM GROWTH RATES
     Zooplankton Group
     Maximum
Growth Rate (I/day)
       References
     Total Zooplankton
   0.15  0.25


   0.175  0.2

    0.1  0.3*
Chen (1970)
Chen & Orlob (1975)
Chen & Wells (1975, 1976)
Jorgensen (1976)
Jorgensen et jil_. (1978)
U.S. Army Corps of Engineers (1974)
Brandes (1976)
Smith (1978)

Cladocerans

Copepods
Rotifers

Mysids
0.15 0.30** Jorgensen (1979)
0.35 0.5 Tetra Tech (1980)
Porcella et a]_. (1983)
0.27 0.74** Jorgensen (1979)
0.5 Tetra Tech (1980)
0.44 0.45 Porcella et al_. (1983)
0.24 - 0.76** Jorgensen (1979)
0.14 Tetra Tech (1980)
     *Model documentation values.
    **Literature values.
                                    384

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             TABLE 7-5.   COMPARISON OF TEMPERATURE  ADJUSTMENT
             FUNCTIONS FOR  ZOOPLANKTON GROWTH AND CONSUMPTION
Temperature Formulation
Model
(Author) Linear Exponential
AQUA- IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
EAM
ESTECO 6-14
EXPLORE-1 X
HSPF 6-14
LAKECO 6-14
MIT Network
WASP X
WQRRS
Bierman X
Canale piecewise
linear
Jorgensen
Scavia
(Equation No. )
Optimum Other
Curve Curve
none
6-24
6-19
6-19
6-19
6-24



6-25

6-24

6-18
6-19
Reference
Temperature

Topt
Topt
Topt
Topt
Topt
20°C
1°C
20°C
20°C
Topt
1°C
Topt
20°C
1°C
Topt
Topt
Reference
Baca & Arnett (1976)
WES (EWQOS) (1982)
Bloomfield e_t al_. (1973)
Scavia & Park (1976)
Park et aj_. (1983)
Tetra Tech (1979, 1980)
Brandes & Masch (1977)
Baca et. al. (1973)
Johanson jrt al_. (1980)
Chen & Orlob (1975)
Harleman et aJL (1977)
Di Toro et al. (1981)
Smith (1978)
Bierman et. aj_. (1980)
Canale et. aj_. (1975, 1976)
Jorgensen (1976)
Scavia e_t al. (1976)
7.3.1  Growth Limitation


     The growth  limitation  functions  used in  the above equations,
f (FpF2,...F ) and ff (FpF2,.. .Fn), are somewhat different since the latter
function is multiplied times  the total available food concentration FT to
give the  net grazing rate.   Therefore:
                   fg(F1,F2,...Fn)^ff(F1,F2,...Fn)
(7-7)
                                   385

-------
Both functions  typically represent  some type of saturation response  to
feeding, assimilation,  and growth.  Experimental observations show that  at
low food  concentrations,  zooplankton ingestion  rates increase with increases
in the food  supply.   For filter feeders  which are filtering water at a
constant rate,  the  grazing rate is directly proportional  to th'e food
concentration  (Figure 7-1).   Grazing  rates for predatory zooplankton also
increase  with the food supply at low food concentrations  since less energy
and time are required to find and capture prey items as the prey density
increases.   However,  as food becomes  more  abundant, the grazing rates
eventually become saturated and level off at some maximum value after which
the grazing rate becomes  independent of  the  food  supply.  Filter feeders can
regulate their ingestion rates  at high  food levels  by  reducing  their
filtering rates  as the food concentration increases.  At low concentrations,
the feeding  rate  is limited by the ability  of the zooplankton to filter
water,  while  at  high concentrations, it  is limited by the ability to ingest
and digest the food (Leidy and Ploskey,  1980).  Similarly, the feeding rates
for carnivorous  zooplankton are limited  at low  prey densities by the ability
of  the zooplankton to find and capture prey items, while  at high prey
densities, they  are limited by the ability to  process, ingest, and digest
the prey.  Also,  at very high ingestion  rates, zooplankton growth may  be
limited  by assimilation rates since  ingested  food remains  in the gut for
less time, resulting in only partial  digestion and reduced assimilation
efficiencies.

     While  the  saturation type  feeding response has been demonstrated  in
numerous studies,  work  by  Mayzaud  and Poulet (1978) indicates  that
zooplankton may be  able to acclimate  to  changing food concentrations  by
adjusting their  digestive enzyme levels,  allowing them to filter at maximum
rates over a much  wider range than suggested  by the saturation  response
curves of short term experiments (Leidy  and  Ploskey, 1980).  This results  in
a linear response  curve with ingestion rates directly proportional to the
food supply.  However,  some upper limit  on  feeding and growth must exist
based on theoretical  arguments, so a saturation response curve is  probably
appropriate, even though  the saturating  food levels may be much higher than
                                  386

-------
typically  experienced in the  field except perhaps  during phytoplankton
blooms.

     Two major  approaches are used  to  simulate saturation  responses in
zooplankton models, the Michaelis-Menten  (1913)  formulation and the  Ivlev
(1966)  formulation.  The Michaelis-Menten formulation is a hyperbolic
function analagous to that used  in  phytoplankton growth calculations, and is
probably  the most common approach  used in water quality models (Chen and
Orlob, 1972,  1975; Di Toro and Connolly,  1980; Di Toro  and Matystik,  1980;
Bloomfield  et af[., 1973; Park et _al_.,  1974, 1975, 1979,  1980; Scavia et a]_.,
1976; Scavia, 1980; Canale  jjt jfL,  1975,  1976; Bierman,  1976;  Bierman
et _al_.,  1980; Baca et _§]_., 1973, 1974; Baca and Arnett,  1976; Najarian  and
Harleman,  1975).  The basic equation  is:
where F  = total  available food supply, mass/volume
           half-saturation  c<
           growth, mass/volume
K  = half-saturation  constant for  zooplankton feeding  and
The Ivlev formulation is an exponential function which  is more popular  in
biologically oriented models (Kremer  and Nixon,  1978).  The general  equation
is:

                                             -K F
                       VFl'F2""Fn) = * - e                        (7~9)

where K = proportionality constant for Ivlev formulation

     Figure 7-2 shows a  comparison of the Michaelis-Menten and Ivlev
functions where both functions  have the same half-saturation value (i.e.,
K = -ln(%)/K ).   Both response  functions range from minimum values of  0  at
very low food concentrations to  maximum values of 1  at  food saturation.
However,  for food  concentrations below the half-saturation constant  (K  ),
the Ivlev function is slightly  lower  than the Michaelis-Menten function.

                                   387

-------
   For food  concentrations above K    the Ivlev function is higher and
   approaches saturation  sooner than the Michaelis-Menten  function.   Note that
   both functions are used with the total ingestion  form of the growth equation
   (Equation (7-4))  rather  than with the  filtration form  (Equation  (7-5)),
   since  the growth  limitation function in the  filtration form must always be
   multiplied times  the total  food supply to get  the net response.

       Both the Michael is-Menten  and Ivlev formulations can be modified to
   allow for threshold food concentrations  below  which zooplankton do not feed.
   This  provides a  refuge for prey organisms when they are present in very low
   concentrations.  The resulting equations are:
LU
*
DC
o
z
N
<
DC
O
DC
O
LU
!Sc
DC
O
DC
O
LLJ
LU
DC
                                        MICHAELIS-MENTEN
                                                 F
  Figure 7-2.
                 Kz                    2K;
               FOOD CONCENTRATION, FT
Comparison  of  the Ivlev and Michael is-Menten functions with the
same half-saturation value (i.e.,  K =  -ln(%)/Kz) (adapted from
Swartzman and  Bentley, 1977, and Leidy and Ploskey, 1980).
                                      383

-------

and                  VFl'F2"--Fn)  =  1  - e    T  °                 (7'12)

where F   =  threshold food  concentration below which feeding does  not
           occur, mass/volume

     Zooplankton half-saturation constants and threshold feeding levels  are
presented in Tables 7-6 and 7-7.

     A few models,  for example  CLEAN, CLEANER, and MS.CLEANER (Bloomfield
et_al_.,  1973; Park et _§]_., 1974,  1975, 1979, 1980; Scavia and  Park, 1976),
use  a modified Michael is-Menten formulation in which the half-saturation
constant  varies as a function  of zooplankton  densities to  account  for
competition and  feeding interference effects.  The equation  is:

                             Kz  = Kzl + Kz2 Z                        (7-13)

where K  ,  = feeding area coefficient,  mass/volume
      K  2 = competition or interference  coefficient

      Other saturation response functions besides the Michaelis-Menten  and
Ivlev formulations have been used in some  models.  For example,  rectilinear
saturation curves have  been constructed by assuming feeding increases
linearly with food concentration  until a critical food density  is reached,
and  then  levels off at  a  maximum rate  for  all  concentrations above  the
critical  density.  This is expressed as:

                 _*• /1-  r-     i- \ _   i
                                           for FT > Fsat
                                   389

-------
TABLE  7-6.   MICHAELIS-MENTEN HALF-SATURATION CONSTANTS  FOR  ZOOPLANKTON
                              CONSUMPTION  AND GROWTH

Zooplankton
Group
Total
Zooplankton

Half- Saturation
Constant*** Units
0.010 0.060 mg(Chl a_)/l
0.5 (growth) mg/1
References
Di Toro et al . (1971)
O'Connor et al_. (1975,
Chen (1970)

1981)

                     0.5  - 2.0
mg/1
                        1.0                mg/1

                0.2   0.6*   (growth)       mg/1
                    0.06   0.6*
mg/1
Chen & Orlob  (1975)
Chen & Wells  (1975, 1976)

Jorgensen  (1976)
Jorgensen  et  aj_.  (1978)

Bierman et^ jil_.  (1980)

U.S.  Army  Corps of Engineers (1974)
Brandes (1976)
Smith (1978)

Baca  & Arnett  (1976)
 Herbivores         0.010   0.015       mg(Chl a_)/l      Thomann et  al_.  (1975,1979)
                                                      Di Toro & Connolly (1980)
                                                      Di Toro & Matystik (1980)
                                                      Salisbury et  al.  (1983)
 Carnivores
 Omnivores
 Cladocerans
 Copepods
0.010
0.02
0.2
0.2
0.15
0.375
0.16 0.2
0.5
0.8 (growth)
1.8 (growth)
0.16 0.4
1.0
1.2 (growth)
mg(Chl aj/l
mgC/1
mgC/1
mgC/1
mgC/1
mg/1
mgC/1
mg/1
mg/1
mg/1
mgC/1
mg/1
mg/1
             Thomann  et^ al. (1975)

             Scavia et  al_. (1976)

             Canale et  al_ (1976)


             Canale et^  al. (1976)

             Scavia (1980)

             Bowie et_ al.  (1980)


             Scavia e_t  al. (1976)
             Scavia "(1980)

             Bowie et_ al-  (1980)

             Tetra Tech (1980)

             Porcella et  al.  (1983)


              Scavia  et a]_. (1976)
              Scavia  "(1980)

              Bowie et_  al. (1980)

              Tetra Tech  (1980)
 Rotifers
                     0.2   0.6
mgC/1         Scavia et al. (1976)
              Scavia TJ980)
                                        390

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                         TABLE 7-6.  (continued)

ZoopTankton
Group


Mysids


Half-Saturation
Constant***
0.5
2.0 (growth)
0.10 0.20
0.5
2.0 (growth)
Units
mg/1
mg/1
mgC/1
mg/1
mg/1
References
Bowie et_ al_. (1980)
Porcella et al_. (1983)
Scavia et al. (1976)
Scavia TT980)
Bowie et aj_. (1980)
Tetra Tech (1980)

        *Model documentation values.
       ***Half-saturation constants are for consumption unless specified for growth.
where F  .  = food  concentration when  feeding saturation occurs,
             mass/volume
              VFl'F2"--Fn' '
                                              for FT > Fsat
when a threshold feeding  concentration F  is used.

     The growth limitation  functions used with  the filtration  form of the
growth  equation (Equation  (7-5)) are different than the saturation  response
functions discussed  above since  they must be multiplied by  the  available
food  concentration  to get the  total response.  In contrast to  the  previous
functions,  these functions  generally decrease  with increases  in the food
supply  to  account for factors  like reduced filtering rates,  adjustments  in
particle size selectivity,  and reduced assimilation efficiencies which  occur
at  high food concentrations.  These types of  functions generally have
maximum values  of 1  at  low food densities and  decrease  assymptotical ly
toward some minimum  value as the food density increases.

                                    391

-------
     Di  Toro and Matystik  (1980)  and  Di Toro  and Connolly (1980)  use  a
reverse Michaelis-Menten formulation to simulate reductions in  filtration

rates  as food concentration increases:
ff(FlfF2,...Fn) =
                                                                            (7-16)
where Kf  =  food  concentration at  which  the  filtration  rate is  1/2  of
            its maximum  value, mass/volume

           TABLE  7-7.   THRESHOLD  FEEDING'LEVELS FOR ZOOPLANKTON
Zooplankton Group
Total Zooplankton


Carnivores
Omnivores

Threshold Feeding Level
0.028 mg/1
0.01 mg/1
0.20 mg/1
0.01 mgC/1
0.001 mgC/1
0.025 mg/1
References
Scavia & Park (1976)
Youngberg (1977)
Bierman et al_. (1980)
Scavia et aj_. (1976)
Scavia (1980)
Bowie et al_. (1980)
       Cladocerans
       Copepods
       Rotifers
       Mysids
       0.02   0.05 mgC/1


          0.05 mg/1


       0.02   0.05 mgC/1


          0.05 mg/1


       0.02 - 0.05 mgC/1


          0.05 mg/1


       0.02   0.05 mgC/1


          0.05 mg/1
Scavia et a]_.  (1976)
Scavia TJ980)

Bowie et_ al_. (1980)
Scavia et aj_.  (1976)
Scavia TT980)

Bowie et al. (1980)
Scavia et al_.  (1976)
Scavia TT980)

Bowie et al. (1980)
Scavia et al_.  (1976)
Scavia TT980)

Bowie et al. (1980)
                                     392

-------
This function  approaches 0 assymptotically at high food densities, resulting
in a saturation response for total  consumption (Figure 7-3a).

     Canale  et _al_. (1975,  1976)  use a slightly  different formulation to
account for reductions in filtering rates and  changes  in particle size
selectivity  at high food levels:

                                        K1 FT + K2
                      ff =   FT I K,                   <7-17)

where K, = multiplier for minimum filtering rate (minimum value of f-r)
      Kp = food  concentration  at  which the filtering rate is half way
          between its minimum and  maximum value,
          ff = 1/2 (K1 + 1),  mass/volume

This function  approaches K, assymptotically at high food levels rather  than
0.   As a result, the  total  consumption rate  continues to increase in
proportion  to  the food supply at high food  concentrations  since  the
volumetric  filtration rate remains  at  a  constant minimum level
(Figure 7-3b).  However,  a saturation type  response can  be generated by
setting the  minimum multiplier K, equal to 0, in which case this formulation
is identical to Equation (7-16).

     A reverse Michael is-Menten formulation has  also been used to simulate
reductions  in the  assimilation efficiencies of filter  feeders at high  food
concentrations  (Di  Toro et a^., 1971, 1977; Di Toro  and Matystik, 1980; Di
Toro and Connolly, 1980; Thomann et _al_. , 1975,  1979;  Canale  et _al_. , 1975,
1976). The  equation is:
where K  =  food concentration  at which the assimilation  efficiency is
       a
           1/2  of its maximum value, mass/volume
                                   393

-------
LJJ
tc
QC
                      Consumption Rate
                     FOOD CONCENTRATION, FT
                                 (a)
LU

fe
QC
Consumption  Rate
                      FOOD CONCENTRATION, FT
                                  (b)
 Figure 7-3.  Comparison of reverse Michaelis-Menten formulation  (a) and
            Canale et. aj_. 's (1975,  1976) formulation (b)  for  filtration
            rate as a function of food concentration.
                               394

-------
If a constant volumetric  filtration  rate is used (Di Toro et aj_.,  1971,
1977;  Canals _§t _§_]_.,  1975, 1976),  this results in a Michael is-Menten  type
relationship for total  consumption in which the maximum assimilation rate
(growth  rate) equals  the product of the constant filtration rate,  maximum
assimilation efficiency,  and  the food  concentration at half-maximum
assimilation efficiency K  (ignoring temperature  effects):
                      9z    fmax  max  T
However, Di Toro and Matystik (1980) and Di  Toro and Connolly (1980) also
use this formulation with  a reverse  Michael is-Menten  formulation for the
filtration rate, which results  in  a more complicated expression for total
consumption involving the product of a Michael is-Menten term and a reverse
Michaelis-Menten term:
                 9z-cf..xE»axl(8lr4T-ilT-T-r)            (7-?°>

     Zooplankton growth and consumption formulations are compared  for
several models in Table 7-8.
7.3.2   Food Supply

    The  total  available food concentration FT used in  all of the  above
growth  formulations  can be defined in several ways.  The simplest approach
is to  assume all  potential food items can be consumed with  equal  efficiency
and define FT as the sum of the available food concentrations:

                             FT -     FK                         (7-21)
                                  395

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                                     TABLE  7-8.   COMPARISON OF  ZOOPLANKTON GROWTH  FORMULATIONS
Model
(Author)
AQUA- IV
CE-QUAL-R1
CLEAN
CLEANER
MS. CLEANER
EAH
ESTECO
EXPLORE-1
HSPF
LAKECO

Phyto-
plankton
1
2
2
3
4
4
2
1
1
2
Food Sources
Preference
Zoo- FKtors
Detritus plankton Used

1 X
1 3 X
1 3 X
2 5 X
1 3 X
1 X


1 X
MIT Network 1
HASP
HQRRS
merman
Canals
Jorgensen
Scavlt
2
2
5
4
1
5
1
1 X
X
9 X

1 6 X
Basic Approach
Growth Total Filtration
Computed Ingestlon Rate
Directly Computed Computed
X
X
X
X
raptorial filter
feeders feeders

X
X
X

X
X
X
X
carnivores filter
feeders
X
X
Growth Limitation Formulation
Variable Variable Threshold
M1chael1s- Assimilation Filtration Feeding
Menten Ivlev Efficiency Rate Included
X
X
X X
X X
raptors » X* X
saturation
fllterers
X
X
X
X
X
X
X X
X
X X
carnivores nonselecttve selective
fllterers fllterers
X X
X X
Assimilation Efficiency
Varies Varies
with with
Constant Food Type Food Cone.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
carnivores S selec- nonselectlve
tlve fllterers fllterers
X
X
GO
         *Hax1muB assimilation rate used for constant rate filters, with excess consumption egested as pseudofeces.

-------
where F,  = concentration of  potential food item  k, mass/vol ume
      n   = total number of potential food items

     A more realistic  approach  recognizes that food  items vary in  the
efficiency and frequency at which they are utilized by zooplankton, even if
all food items  are present in equal concentrations.  This is due  to  factors
such  as  food particle size  and shape, desirability and quality of different
types of food,  ease of  capture,  and zooplankton feeding  behavior.   For
example, many  filter feeders are  able to selectively filter different food
items with different efficiencies, varying their selectivity according to
the  abundance  and desirability of  the  various  food items present.  Food
particle shape  and size are  important distinguishing features  since,  for
example, filamentous algae are often  actively  rejected  or avoided while
individual cells of the same species in suspension may be consumed (Leidy
and  Ploskey, 1980).   However, the quality and  desirability of the food are
also important, since senescent cells are less  likely to be  consumed  than
healthy cells of the same species.  For raptorial feeders, particle size and
shape are not quite as critical since they are able to tear  large prey items
into smaller pieces  before consuming them.  Prey desirabil ity  and ease of
capture then become more important.

     The above  factors  are  accounted for in models by assigning  feeding
preference factors to each  potential  food item.  Preference  factors  can have
values ranging  from 1 to 0,  with  1  corresponding to a food  item which is
desirable  and  easily captured  and  consumed  (or  filtered), and 0
corresponding  to a food item which is never consumed.   Food  preference
factors have  been called  selectivity coefficients, electivities, ingestion
efficiencies, and  several other  names in different models,  but  they all
basically  represent the same thing--weighting  factors which  reflect the
probability that a given food  item will be consumed relative  to  the others
when all foods are present in  equal concentrations.  They account for the
fact that  some food items may  be  less  available for consumption  than
indicated  by their concentrations alone.  When food preference  factors are
specified, the  total available food concentration  FT is defined as:
                                  397

-------
                             FT=  E Pk F                         (7-22)
                              I    k=1  K  k

where P.  =  food preference factor  for  food item k
       K
      F,  =  concentration of food item  K, mass/volume
       K
      n  =  total number of potential food items

Vanderploeg and Scavia (1979)  show how preference factors  can  be  derived
from  the different forms  of data reported in zooplankton  feeding
experiments.  Infield situations,  preference'factors may change as the
composition of the food supply changes.  However,  this level  of
sophistication is generally not  included in current  ecological  models.

7.3.3  Assimilation  Efficiencies

     In addition to differences  in food  preferences or  ingest ion
efficiencies for different food  types, food items  may also differ  in their
assimilation efficiency by zooplankton.  The assimilation  efficiencies for
different  food types varies with  the energy content, digestibility, and
quality  of  the food  (Leidy  and  Ploskey,  1980).   For  example,  the
assimilation efficiencies for  algae  are typically  higher than for  detritus
and bacteria, although the assimilation efficiencies for  blue-green algae
are also generally  low.  Algae  with gelatinous sheaths or resistant cell
walls and masses of  colonial  cells may  pass through  a zooplankton gut intact
and in viable  condition  (Wetzel ,  1975), indicating minimal assimilation
efficiencies for these food items.  The animal foods of  raptorial  feeders
are assimilated more efficiently than plant foods.  Also, since the energy
content and digestibility of algae and  detritus vary much  more widely than
animal  foods,  the  assimilation  efficiencies  for  herbivores  and
detritivores typically cover  a  much wider range than  for  carniv.orous
zooplankton (Leidy and Ploskey,  1980).

    Variations  in the assimilation efficiencies  of different food items can
be modeled in  several ways.  One approach is  to incorporate these effects in
the food preference factors, for example,  by assigning a  low  value to  the
preference factor for blue-green algae relative to the other  algal  groups.
                                 398

-------
This in  effect  lowers the amount  of blue-green  algae  available  for
zooplankton  assimilation and  growth.   Another approach  is  to  define
different maximum assimilation  efficiencies for different  food  items, to
compute  net assimilation separately for each food  item, and then  to sum the
individual  assimilation terms  to  get the total  zooplankton  growth rate
(Scavia  _et  al . ,  1976; Scavia, 1980).  This can be expressed  for the total
consumption  formulation (Equation  (7-4)) as (ignoring temperature  effects):
                 Com,v Z-,  Em=,v  ^r, (FijF,,...!
                        gmax (<1maxk  gkl'2
                                             n'
                                                                   (7-23)
where C               = maximum  total consumption rate, mass food/mass
                        zoopl ankton-time
      E               = maximum  assimilation efficiency for food item
       III QAi
                        k
      f  (F,,F9, ...F ) = growth limitation factor  for food item k
       gk  i  ^     n
      n               = total  number of potential  food items

and for the filtration formulation (Equation (7-5)) as:


                                          raLE-k P* F>]         (7-24)

where C,,             = maximum   volumetric  filtration,  volume/mass
                       zoopl ankton-time
      ff (F, ,F?,.. .F ) = gr owth 1 i mi tat i on f uncti on for f il trati on
                       formul ation
                       food prefere
      F.              = concentration of food item  k, mass/vol une
P.              = food preference factor for food item k
Note that  growth limitation factors  must be  computed separately for each
food item in  the  total consumption formulation since the  quantities which
are summed must reflect both the assimilation  efficiencies and the  amounts
of food consumed  for each different food item.
                                   399

-------
      For the Michael is-Menten formulation, the individual growth limitation
factor may be defined as:
f  I?   F     F)=
    :  2"""
                                         PI  F,
                                          ^ -               (7-25)
                                           k=l
This is  equivalent to the total  Michael is-Menten factor when summed over all
food items:
                                                   n
          n                    n     P.  F.         APiA
          •^ ,•  / r-  r-     r \ _ V"1      K   K 	'  _   K~i  K  K
                                                rTTn(7-26)
Analogous  expressions for the Ivlev formulation are more difficult to
formulate,  since the individual terms are  not  consistent with the  total
growth  limitation  function,  even under conditions  of  equal assimilation
efficiencies.

     As discussed  previously,  assimilation efficiencies  may decrease with
increases in ingestion rate at high food  concentrations since the retention
time in the gut  decreases  resulting in incomplete  digestion and reduced
assimilation.  Model formulations to describe these effects have  already
been discussed in the growth limitation section (Equation  (7-18)).

     Zooplankton average assimilation  efficiencies  are presented  in
Table 7-9.  Figures  7-4 and 7-5 present frequency histograms of assimilation
efficiency  data compiled by Leidy and  Plosky (1980).

7.4  RESPIRATION AND MORTALITY

     Zooplankton respiration  and  mortality are modeled using  the same
general formulations as phytopl ankton.   Almost all  models represent both
respiration and nonpredatory mortal ity rates as either  constant coefficients
or simple functions  of temperature. The  basic equations are:
                                  400

-------
            TABLE 7-9.   ZOOPLANKTON  ASSIMILATION EFFICIENCIES
Zooplankton
   Group
     Assimilation Efficiency
                                                                  References
Total
Zooplankton
Herbivores
           0.60 - 0.75


              0.63


               0.7


               0.6

           0.5   0.8*


           0.5   0.7*


           0.6 (max.)
Carnivores                   0.6  (max.)




                                 0.5

                          0.4 (Cladocerans)

Omnivores                        0.5
                 (0.2 for detritus, blue-green algae)

                                 0.4
Cladocerans
                                 0.5
Copepods
                 (0.2 for detritus,  blue-green algae)
                                 0.5
                             0.8 (max/
                0.5
(0.2 for detritus, blue-green algae)
                                 0.7
Di Toro et al_.  (1971)
O'Connor etal_.  (1975,  1981)

Jorgensen (1976)
Jorgensen et_ a]_.  (1978)

Tetra Tech (1976)
Chen & Wells (1975,  1976)

Bierman e_t aj_.  (1980)

Brandes (1976)
Smith (1978)

Baca & Arnett (1976)
Thomann et al_.  (1975,  1979)
Di Toro F~Connolly (1980)
Di Toro & Matystik (1980)
Salisbury et ^1_.  (1983)
                                        Thomann et al_.  (1975,  1979)
                                        Di Toro S~~Connolly (1980)
                                        Di Toro & Matystik (1980)
                                        Salisbury et al_.  (1983)

                                        Scavia et al_.  (1976)

                                        Canale et_ al_.  (1976)

                                        Scavia (1980)
                                        Bowie et_ al_.  (1980)

                                        Canale et al.  (1976)
                                        Scavia et al.  (1976)
                                        Scavia TTgM)
                                        Bowie et al.  (1980)

                                        Tetra Tech (1980)
                                        Porcella et al.  (1983)

                                        Canale et al.  (1976)
Scavia et al- (1976)
Scavia TT980)
Bowie et al.  (1980)

Canale et al. (1976)
                                       401

-------
                              TABLE 7-9.   (continued)
        Zooplankton
           Group
        Assimilation Efficiency
    References
        Rotifers
        Mysids
                0.5
   (0.2 for detritus, blue-green algae)
                                  0.5
                0.5
   (0.2 for detritus, blue-green algae)
                                  0.5
Scavia et a]_. (1976)
Scavia TT980)
Bowie et al_. (1980)

Tetra Tech (1980)
Porcella et al.  (1983)
Scavia et al_. (1976)
Scavia TT980)
Bowie et a]_. (1980)

Tetra Tech (1980)
        *Model documentation values.
and
where r

      r!(T.
      fr(T)

      m
      f (T)
       nr  '
                            r  =  r  (T  f)  f  (T)
                             z    zv  ref   rv  '
           m  = m  (T  f) f  (T)
            z    zv ref  nr  '
                                                      (7-27)
                   (7-28)
          ref)
zooplankton respiration rate,  I/time
respiration rate at reference  temperature T   f,  I/time

temperature function for respiration
zooplankton nonpredatory mortal ity rate,  I/time

nonpredatory mortal ity  at reference  temperature
Tref,  I/time

temperature function for nonpredatory mortality
Since  the respiration  and nonpredatory mortal ity rate equations have the
same basic form and typically use the same temperature functions,  many
models combine  both processes into  a single  loss  term:
                                                                       (7-29)
where dz(Trgf) = total  loss  rate  due  to  both  respiration  and

                 nonpredatory mortality  at  reference  temperature T   f>
                 1/time
                                    402

-------
16 -
12 •
4 •
n •










—
—

—

TOTAL
ZOOPLANKTON






•"^

	
                    .20
                              .40        .60        .80
                           ASSIMILATION EFFICIENCY
.1.0
                                                                            16
                                                                            12

                                                                           e  •'•
                                                                           i 8-.
                                                                             4- •
                                                                                                            CLADOCERANS
                                                                                       .20
                                      M         .60
                                  ASSIMILATION EFFICIENCY
                                                         .80
                                                                    1.0
O
GO
          6 •
                                         ROTIFERS
                                              nn
                              AO        .60
                            ASSIMILATION EFFICIENCY
                                                            uo
                                                                             8-
                                                                             6-
                                                                             2-
                                                 COPEPODS
                                                                                       .20
                                     M         £0
                                     ASSIMILATION  EFFICIENCY
UO
     Figure  7-4.    Frequency  histograms for zooplankton  assimilation  efficiencies  (from Leidy  and  Ploskey,  1980)

-------
     In a few  models, the  respiration rate is  partitioned into two
components,  1)  the standard  respiration  rate  representing  the  combined basal
metabolism and  digestion  energetics  and  2) the  active  respiration rate which
represents  the additional  respiration  associated with zooplankton activity.
These two components  can  be  distinguished  by using different  temperature
response functions for each  component.   For example, standard  respiration  is
FREQOEHCY
*••
> «• 00 M
(
3REEN ALGAE AS FOOD

















                       .20        ,40       ,CO        ,80
                              ASSIMILATION EFFICIENCY
1.0
            12-
             8.
             4- •
                                          BUTE-GREEN ALGAE AND/OR
                                          DETRITUS AS FOOD
                      .20        >0        ,60        .80
                             ASSIMILATION EFFICIENCY
1.0
   Figure 7-5.  Frequency histograms showing variations in zooplankton
               assimilation efficiencies with different food types
               (from Leidy and Ploskey, 1980)
                                    404

-------
typically associated with an  exponential  temperature curve which  increases
until the  upper  lethal  limit is approached, while the active respiration
rate may be  associated with a temperature optimum curve:

                                                 fa(T)            (7-30)

where rstcj(Tref) = standard respiration rate  at reference  temperature
                  Tref,  I/day
      fs(T)      = temperature function for standard respiration
      ract(Tref) = active respiration rate  at  reference temperature
                  Tref,  I/day
      fa(T)      = temperature function for active respiration

     Another  approach is to assume that the  activity level (and  active
respiration)  is  proportional  to the feeding level  by using a Michaelis-
Menten or  Ivlev function:

                                                f (F1'F2' • • -Fn)      ^7

where f (F,, F?,.. .F ) = growth limitation factor as  a function of  food
                      supply

This  approach  is  used by Scavia et_ _a_K (1976) and Scavia  (1980)  where the
first term  represents the minimum endogenous respiration rate under
starvation  conditions and the second  term represents the  increase  in
respiration  associated with feeding.

     A similar  formulation is used in CLEANER (Scavia and Park,  1976)  and
MS.CLEANER  (Park et _al_., 1979, 1980) where the active respiration  rate is
expressed as  a  fraction of the total consumption rate:

                      r =\r  . (T  f) + K C  1 f(T)                  (7-32)
                         |_rmir ref    r  gj v '                  v    '

where r  .  (T  ^)  = minimum endogenous respiration under starvation
      m i n  r et'
                  conditions at reference temperature T  .,  1/tii

                                  405
i me

-------
      K         = fraction  of  ingested food which  is respired
      C         = ingestion rate, I/time

     The CLEANER and MS. CLEANER models also include additional  factors  to
account  for  crowding effects and population age  effects on both respiration
and nonpredatory mortal ity rates.  The crowding factor is expressed as:
                                                                   (7-33)
where f  , = crowding factor
       crd          3
      K   = crowding coefficient
      Z   = zooplankton carrying capacity, mass or mass/volume
       C dp

This factor increases  the respiration  and mortal ity rates as  zooplankton
density increases.   The age factor  accounts  for  the effects  of  the
population  age  structure on the net  respiration and mortal ity  rates since
these rates  generally vary with age.   The  basic assumption is that the
population  consists  primarily of immature individuals at  low  zooplankton
densities  and  of adults at high population  densities  (Scavia and Park,
1976).  The age factor  represents the difference  between adult and juvenile
rates.   The  age factor for respiration is expressed as:
                        W • 1 + Kl -^ - 1                   '7-34>

where f aae = age factor for respiration
      Krx   = fractional  increase in respiration  rate between young
             zooplankton and adults

and the age factor for mortality is expressed as:
where fmage = age factor  for nonpredatory mortality

                                  406

-------
      K     =  fractional  decrease in mortality rate between  young
       III X
              zooplankton and  adults

Both the  crowding and age structure factors are  multiplied with  the
respiration and no npredatory mortal ity rates  defined  in Equations  (7-32) and
(7-28)  to incorporate these effects into the  rates.

     Some versions  of  CLEANER (Youngberg, 1977)  also include an oxygen
reduction factor in the respiration equation to account for  decreases in
respiration at low dissolved oxygen levels.   The  equation is:

                                  00 - 0 .
                           _      2    mm                          -
                              ox     2    mi n

where f    =  oxygen reduction  factor
       \J A
      Op   =  ambient oxygen  concentration, mg/1
      0 .  =  minimum oxygen  requirement, mg/1
      K    =  half-saturation constant for  oxygen  limitation (set at
             0.9 mg/1)

     Bierman  et _al_. (1980) use a second order  formulation for zooplankton
mortality  when  the zooplankton density exceeds  a critical level.  This
accounts for density dependent effects  on  both  natural mortality  and
predatory  mortality (which  is not directly simulated in this  model) at high
densities.  The equation is:

                    m= [-"l+Km Z]  f               f7'37'

where m, (T  J = mortality  rate below the critical  zooplankton density
                at reference  temperature T -, I/time
      K (T  f) = density dependent mortality coefficient for  increased
                mortality above the critical  zooplankton density at
                reference temperature Tref, I/mass zooplankton-time
                                  407

-------
     The nonpredatory mortal ity rate can also be partitioned into several
components  which account for  specific types  of  mortality such as natural
senescence,  thermal ly- induced mortal ity, toxic mortal ity, and stress-induced
mortality due to low dissolved oxygen, pH extremes, starvation, etc.   The
general  equation  is:
                                                     fl

                       f2(T) f(02,PH,...) + mf(Tref) f3(T) + ff(Fy)   (7-38)

where m (T  f)    = mortality rate due to  senescence at reference
                   temperature Trgf , I/time
      f (T)       = temperature function for senescent mortality
      mT(T  f)    = thermal  mortality rate  at  reference temperature
                   Tref,  I/time
      fy(T)       = thermal  mortality response curve
      m (T  f)    = toxic  mortality rate  at  reference temperature
                   Tpef,  I/time
      f-i(T)       = temperature function for toxic mortality
      f (X)       = dose-response curve for toxic mortality
       A
      X          = concentration of toxicant, mass/ volume
      m (T  _)    = stress- induced  mortality rate for  low dissolved
                   oxygen,  pH extranes,  etc., at reference temperature
                   Tref  1/time
      f2(T)       = temperature function  for stress-induced mortality
      f(0,>,pH...) = stress- induced mortal ity function for low dissolved
                   oxygen,  pH extremes,  etc.
      mf(Tref)    = starvation-induced  mortality rate  at  reference
                   temperature Tr f, I/time
      f^CO       = temperature function  for starvation mortality
      f-f(Fy)      = starvation mortality  function

Various  formulations could  be used to define these effects, although most
current models  deal  only with natural  mortality and  sometimes thermal
effects.

                                  408

-------
     Zooplankton respiration  rates  and mortality rates are presented  in
Tables  7-10 and 7-11.   Figures 7-6 and 7-7 present frequency histograms  of
respiration  rates  and nonpredatory mortality rates  from data compiled  by
Leidy and  Ploskey (1980).

7.5  PREDATORY MORTALITY

     Zooplankton predatory mortality is modeled using the same formulations
described previously for  phytopl ankton.  However,  since Zooplankton are
often the  highest trophic level included  in water qual ity model s,  predator-
prey dynamics  between Zooplankton and higher trophic  levels cannot  usually
be simulated.  Therefore, predation by fish and carnivorous  Zooplankton  is
modeled by either assuming a constant  predation loss which is specified as a
model input parameter:

                             GZ = constant                         (7-39)

where G = total  predatory mortality  rate by  all zoopl ankton
          consuners,  mass zoopl ankton/time
or by assuming a loss  rate which is directly proportional to the zoopl ankton
densities:
                               Gz =  ez Z                           (7-40)

or                       G, = e,(T^rf) fg(T) Z                     (7-41)
where e       = predatory mortality rate coefficient,  I/time
      Z       = zooplankton  biomass  or  concentration,  mass or
                mass/volume
      e (T  ,,) = predatory mortality rate  coefficient at reference
                temperature T  f,  I/time
      f (T)    = temperature function for predatory mortality

Since  these formulations  are  essentially the  same as  those  used  for
nonpredatory mortality, nonpredatory mortality  and predation losses  are
                                   409

-------
TABLE 7-10.   ZOOPLANKTON RESPIRATION  RATES

Zooplankton
Group
Total
Zooplankton







Herbivores
Carnivores


Omnivores

Cladocerans






Respiration Rate
0.01

0.02 - 0.035
0.36
0.02 0.16
0.005 0.02
0.001 - 0.11*
0.005 0.3*
0.02 - 0.03
0.007 - 0.02
0.30
0.04 - 0.06
0.08 0.33
0.04 - 0.06
0.1 0.36

0.017 - 0.10
0.04 - 0.06
0.157 - 0.413**
0.090 0.216**
0.006 0.772**
8.5 - 14.2**
Units
I/day

I/day
I/day
I/day
I/day
I/ day
I/day
I/day
I/day
I/ day
I/day
I/day
I/day
I/day

I/day
I/day
I/day
I/day
I/day
ml 02
Temperature
20°C

20°C
20°C
20°C
20°C
20°C
20°C
20°C
20°C
Topt
20°C
Topt
20°C
Topt

20°C
20°C
20°C
20°C
Topt
18°C
References
Chen (1970)
Chen & Orlob (1975)
Chen & Wells (1975, 1976)
Jorgensen (1976)
Jorgensen et al . (1978)
Lombardo (1972)
O'Connor et ah (1975)
Tetra Tech (1976)
U.S. Army Corps of Engineers (1974)
Brandes (1976)
Smith (1978)
Baca & Arnett (1976)
Thomann et al. (1975, 1979)
Di Toro & Connolly (1980)
Di Toro & Matystik (1980)
Salisbury .et al. (1983)
Thomann et al . (1975, 1979)
Di Toro 3TConnolly (1980)
Di Toro & Matystik (1980)
Salisbury et al- (1983)
Scavia e_t al. (1976)
Canale et al. (1976)
Scavia (1980)
Bowie et. al. (1980)
Canale et. 3K (1976)'
Scavia et al. (1976)
Scavia TT9f50~)
Bowie e_t aj_. (1980)
Tetra Tech (1980)
Porcella et. al- (1983)
Canale et al- (1976)
Lombardo (1972)
Leidy & Ploskey (1980)
Collins & Wlosinski (1983)
Di Toro et al . (1971)
         mg(D.W.)-day
                    410

-------
                            TABLE 7-10.  (continued)

Zooplankton
Group


Copepods







Rotifers


Mysids

Respiration Rate Units
5.4 14.2** ml °2
mg(D.W.)-day
14.2** ml °2
mg(D.W.)-day
0.1 0.35 I/day
0.04 0.06 I/day
0.017 I/day
0.085 - 0.550** I/day
0.064 - 0.738** I/day
0.043 - 0.695** I/day
3.0 12.2** ml °2
mg(D.W.)-day
2.93 - 18.9** m1 °2
mg(D.W.)-day
3.0 - 13.5** ml °2
mg(D.W.)-day
0.12 0.40 I/day
0.15 I/day
0.163 0.677** I/day
0.05 0.28 I/day
0.022 I/day
Temperature
20°C
20°C
Topt
20°C
20°C
20°C
20°C
Topt
20°C
20°C
20°C
Topt
20°C
20°C
Topt
20°C
References
Lombardo (1972)
Jorgensen (1979)
Scavia et al. (1976)
Scavia TT980)
Bowie et al.. (1980)
Canale et a]_. (1976)
Tetra Tech (1980)
Lombardo (1972)
Leidy & Ploskey (1980)
Collins & Wlosinski (1983)
Di Toro et al . (1971)

Lombardo (1972)
Jorgensen (1979)
Scavia et al. (1976)
Scavia TT980)
Bowie et al- (1980)
Porcella et ah (1983)
Leidy & Ploskey (1980)
Scavia et al. (1976)
Scavia TT980)
Bowie et al. (1980)
Tetra Tech (1980)
  *Model documentation values.
  **Literature values.
often combined  into a single total mortality term when higher trophic  levels

are not directly simulated:
"tot
                           =  m,(T rf) +  e  (T
'zv'ref
zvref
         UT)
                                          (7-42)
                                      411

-------
where m,         = total  mortality rate, I/time
      m
         t(T  f) = total mortality rate at  reference temperature
                  Tref,  I/time

     In ecologically oriented model s  where  long term  seasonal  changes in
population  dynamics  are important, zooplankton are often separated into
several functional groups  based on general  feeding types  (filter feeders,
carnivorous  raptors,  omnivores, etc.)  or on major  taxonomic groups
(cl adocerans, copepods, rotifers)  (Canal e  et_ al_., 1975,  1976;  Scavi a et
aj_.,  1976; Scavia,  1980; Parkejt^l_.,  1974,  1975, 1979, 1980; Chen  et _§]_.,
1975; Tetra Tech, 1979).   Although several  species must be lumped  into each
functional group, this approach recognizes  the  importance of complexities in
the  food web,  different  foraging strategies,  and predator population
dynamics  in evaluating both zooplankton  and phytoplankton dynamics.  Several
planktivorous fish groups are also sometimes provided for the same reasons.
(Chen et  a].., 1975;  Tetra Tech, 1979;  Park et aj_., 1979, 1980).

     In these situations, zooplankton  predation rates are computed  as the
sum  of the consumption  rates  by all potential  predators,  including
carnivorous or omnivorous zooplankton  and planktivorous fish.  The  general
relationship for predatory mortality can be expressed as:
                            n
                      G
                        Z .    f-4
                         1   J = -
  Cy
*  A •
                                             Fkj
                                                                  (7-43)
where G   = total  predatory mortality rate  for  zooplankton group  i,
           mass zooplankton/time
      n   = total number  of  zooplankton consumers
      C-  = total consumption rate by predator group j, I/time
      X.  = biomass or  concentration of predator  group j, mass  or
           mass/volume
      P.. = food preference factor for predator group j feeding  on
           zooplankton group i
                                   412

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TABLE 7-11.  ZOOPLANKTON MORTALITY RATES

Zooplankton
Group
Total
Zooplankton









Carnivores

Omnivores
Fast Ingesters
Slow Ingesters
Cladocerans






Copepods




Mortality Rate (I/day)
0.075
0.125
0.025 0.033
0.005
0.02
0.015
0.005*
0.001 - 0.005*
0.005 - 0.02*
0.003 - 0.075**
0.01
0.01
0.005
0.05
0.01
0.01
0.04 - 0.05
0.001 - 0.005
0.01
0.1
0.0007 - 0.027**
0.001 - 0.027**
0.01
0.05
0.002
0.003 - 0.005
0.01
Mortality Type
total
nonpredatory
nonpredatory
nonpredatory
nonpredatory
total
nonpredatory
nonpredatory
nonpredatory
total
nonpredatory
fish grazing
fish grazing
nonpredatory
nonpredatory
nonpredatory
fish grazing
fish grazing
nonpredatory
nonpredatory
nonpredatory
nonpredatory
nonpredatory
fish grazing
fish grazing
nonpredatory
nonpredatory
References
Di Toro et al_. (1971)
Jorgensen (1976)
Jorgensen et al_. (1978)
Chen and Wells (1975, 1976)
Tetra Tech (1980)
O'Connor e_t al_. (1981)
U.S. Army Corps of Engineers (1974)
Brandes (1976)
Smith (1978)
Jorgensen (1979)
Scavia et_ aK (1976)
Scavia et a]_. (1976)
Scavia (1980)
Bierman ejt al_. (1980)
Bierman et_ al_. (1980)
Scavia et a]_. (1976)
Scavia ejt a1_« (1976)
Scavia (1980)
Tetra Tech (1980)
Porcella e_t a]_. (1983)
Leidy & Ploskey (1980)
Collins & Wlosinski (1983)
Scavia ejt al_. (1976)
Scavia et al_. (1976)
Scavia (1980)
Canal e et aj_. (1976)
Tetra Tech (1980)
                  413

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                          TABLE 7-11.   (continued)
Zooplankton
Group


Rotifers

Mysids



Mortality Rate (I/day)
0.0005 0.153**
0.003 - 0.155**
0.01
0.12
0.01
0.1
0.08
0.01
Mortality Type
nonpredatory
nonpredatory
nonpredatory
nonpredatory
nonpredatory
fish grazing
fish grazing
nonpredatory
References
Leidy & Ploskey (1980)
Collins & Wlosinski (1983)
Scavia et al_. (1976)
Porcella et_ al_. (1983)
Scavia et al_. (1976)
Scavia et aj_. (1976)
Scavia (1980)
Tetra Tech (1980)
       *Model documentation values.
       **Literature values.
      Z.  = biomass or concentration of zooplankton group i, mass or
            mass/volume
      n.  = total  number of potential  food items for predator group j
       J
      P^ •  = food  preference factor for predator group j feeding on food
            item  k
      F..  = biomass or concentration of potential food item k consumed
            by predator group j, mass  or  mass/volume

                      A
The quantity (P... I./  £  P^. p  )   in Equation  (7-43)  represents the
fraction of the total food consumption by predator group j which is provided
by zooplankton group i.  The quantity  C.X. represents the total rate of food
                                      J  v
ingestion  by predator group j.   Ingestion rate formulations for carnivorous
zooplankton were  discussed in the previous section.  Consumption rates for
planktivorous fish are generally modeled in the same way.  As discussed  in
the algae  chapter, consumption rates  are sometimes back-calculated from
computed  growth rates and known  assimilation efficiencies using the
equation:
                                   414

-------
 12  --

 10  -•

 8  ..  r-

 6  ••

 4  • •

 2  ••
                                                  CLADOCERANS
                         n   n
                           rfl
m
                     .25      .50      .75       1.0
                            RESPIRATION RATE (I/day)
                                            1.25
                                                    1.50
          1?
 10 • •

  8 ••
'3
I 6
£
* 4

  7
                                                 COPEPODS
                                               n
                       .25         .50         .75
                             RESPIRATION RATE (I/day)
                                                         1.0
          12

          10
           4 ••
                                          ROTIFERS
                                                  m
                                                   r
                        .25         .50         .75
                             RESPIRATION RATE (I/day)
                                                          1.0
FIGURE 7-6.   Frequency histograms  of zooplankton  respiration
                rates (from  Leidy  and  Ploskey,  1980).
                                   415

-------
                                c  -
                                     EJ
                                                           (7-44)
where C.
       vJ
      EJ
total  consumption rate  for  predator  group j, I/time
growth rate for  predator  group j,  I/time
assimilation efficiency for  predator group j
When  different  assimilation efficiencies are used for different food items,
consumption rates  are  generally calcul ated directly for each  food item  and
combined  with the food specific assimilation efficiencies to determine net
growth (as discussed in Section 7.3.3).

7.6  SUMMARY

     Zooplankton are typically modeled as a biomass pool  using the same mass
balance  approach  used for  nutrients, phytoplankton, and other constituents.

24 -

20 -
16 -
5
z
o- 1? '
8 -
4 '















0




























TOTAL ZOOPLANKTON






	
1 1
11 III
.01 .02 .03 .04 o05
                     NONPREDATORY MORTALITY RATE (I/day)

     Figure 7-7-   Frequency  histogram of  nonpredatory mortality rates
                  for zooplankton  (from Leidy and Ploskey, 1980).

                                   416

-------
The simplest models lump all  zooplankton  into a single group, while  more
complex models  distinguish between different feeding types or different
taxonomic  groups.

     Zooplankton dynamics  depend  on growth, reproduction, respiration,
excretion, predation,  and nonpredatory mortal ity.  However, these processes
are not generally  measured in the field for  a specific model  application
since:  1) many of them  are  difficult or impossible to measure directly;  2)
the rates  depend on environmental conditions  (e.g., temperature), ecological
conditions  (e.g.,  food  supply and  predator  densities),  and the species
composition of  the zooplankton, all of which change continually with time;
                              «•
and 3)  the fluxes depend largely on  the zooplankton densities, which may
vary by orders of magnitude  over a seasonal cycle.

     As a  result, many of the model  coefficients must be  determined by model
calibration rather than by measurement.  Model constructs must be  relied
upon to describe  the effects of different  factors on these processes.
Literature  values  from 1 aboratory experiments  are useful for establishing
reasonable ranges of the process rates and coefficients.   However, specific
experimental  results are  difficult to  apply directly since  experiments
typically use a single species rather  than  the  species assemblages
represented  in  models, and since experimental  conditions may not represent
conditions in  the field.

     Most  models include formulations to describe the effects of temperature
on all  process rates.   Food  density effects  on growth and consumption  are
typically modeled using saturation kinetics  similar to those used for
phytoplankton.  Respiration  and mortal ity  rates  are most commonly modeled as
first-order losses, although a few models use more complicated formulations
which include  the effects of other factors, for  example, crowding effects.
Since  few models  include  higher trophic levels such  as  fish, predatory
mortality  is typically treated  in a simplistic manner.
                                  417

-------
7.7  REFERENCES

Baca, R.G.,  W.W.  Waddel , C.R. Cole,  A.  Brandstetter, and D.B. Clearlock.
1973.  EXPLORE-I:  A River Basin Water Quality Model.   Battelle, Inc.,
Pacific Northwest Laboratories, Richlahd, Washington.

Baca, R.G., M.W. Lorenzen,  R.D. Mudd, and L.V.  Kimmel.  1974.  A Generalized
Water Quality  Model  for Eutrophic Lakes and Reservoirs.  Battelle,  Inc.,
Pacific Northwest Laboratories, Richland, Washington.

Baca, R.G. and R.C. Arnett.  1976.  A Limnological Model for Eutrophic  Lakes
and Impoundments.  Battelle, Inc., Pacific Northwest  Laboratories, Richland,
Washington.

Bierman,  V.J., Jr.  1976.   Mathematical  Model  of the  Selective Enhancement
of Blue-Green  Algae by Nutrient Enrichment.  J_n:  Modeling Biochemical
Processes in  Aquatic Ecosystems.  R.P. Canale  (ed.).  Ann Arbor Science
Publishers, Ann Arbor, Michigan,  pp. 1-31.

Bierman,  V.J., Jr., D.M. Dolan, E.F. Stoermer,  J.E. Gannon, and V.E. Smith.
1980.  The Development and Calibration of a Multi-Class Phytoplankton  Model
for Saginaw Bay, Lake Huron.   Great  Lakes Environmental  Planning Study.
Contribution  No. 33.  Great Lakes Basin Commission, Ann Arbor, Michigan.

Bloomfield, J.A., R. A. Park,  D. Scavia, and C.S. Zahorcak.  1973.  Aquatic
Modeling in the Eastern Deciduous  Forest Biome.  U.S. International
Biological  Program.   I_n :  Modeling the  Eutrophication  Process.
E.J. Middlebrook,  D.H. Falkenborg, and I.E.  Maloney, (eds.).  Utah  State
University, Logan,  pp. 139-158

Bowie, G.L., C.W.  Chen, and D.H. Dykstra.  1980.   Lake Ontario Ecological
Modeling, Phase III.  Tetra Tech, Inc., Lafayette, California.  For National
Oceanic  and  Atmospheric  Administration, Great Lakes Environmental Research
Laboratory, Ann Arbor, Michigan.
              1976. An Aquatic Ecologic Model  for Texas Bays and Estuaries.
Water Resources  Engineers, Inc.,  Austin,  Texas.  For  the Texas  Water
              vrl  A11 c "f* n n  Tovac
Brandes,  R.J
Water Resoui -~^~,  ^.,,^,,,^.1., Jf *,,
Development Board, Austin, Texas
Brandes,  R.J. and F.D. Masch.   1977.   ESTECO--Estuarine  Aquatic Ecologic
Model:   Program Documentation  and User's Manual.   Water Resources Engineers,
Inc., Austin, Texas.  For the  Texas Water Development Board, Austin,  Texas.

Canale,  R.P.,  L.M. Depalma,  and A.H.  Vogel.   1975.  A  Food Web Model  for
Lake Michigan.  Part 2 - Model  Formulation and Preliminary Verification.
Tech. Report 43, Michigan Sea  Grant Program, MICHU-SG-75-201.

Canale, R.P., L.M. Depalma,  and A.H. Vogel.  1976.  A  Plankton-Based Food
Web  Model  for Lake Michigan.   In: Modeling Biochemical Processes in  Aquatic
Ecosystems.  R.P. Canale (ed.). Ann Arbor Science Publishers, Ann Arbor,
Michigan,  pp. 33-74.
                                   418

-------
Chen,  C.W.  1970. Concepts and Utilities of Ecological Model.  ASCE  Journal
of the Sanitary Engineering Division,  Vol. 96, No.  SA5.

Chen,  C.W. and G.T.  Orlob.   1972.  Ecologic Simulation for  Aquatic
Environments.  Water Resources Engineers, Inc., Walnut  Creek, California.
For the Office of Water Resources Research.

Chen,  C.W. and  G.T.  Orlob.   1975.   Ecologic Simulation  for Aquatic
Environments.   Systems Analysis and Simulation  in Ecology,  Vol.  3.  B.C.
Patten, (ed.).  Academic Press, New York, N.Y.  pp. 476-588.

Chen,  C.W., M.  Lorenzen,  and D.J. Smith.  1975.  A  Comprehensive Water
Quality-Ecological Model  for Lake Ontario.  Tetra Tech,  Inc.,  Lafayette,
California.   For National  Oceanic and Atmospheric Administration, Great
Lakes  Environmental Research Laboratory, Ann Arbor, Michigan.

Chen,  C.W.  and J.T. Wells, Jr..  1975.  Boise River Water Quality-Ecological
Model  for Urban Planning Study.  Tetra Tech, Inc.   For U.S. Army  Engineering
District,  Walla  Walla, Wash., Idaho  Water Resources Board, and  Idaho Dept.
of Environmental  and Community Services.

Chen,  C.W. and J.T.  Wells, Jr.   1976.   Boise River Model ing.   In:
Modeling Biochemical  Processes in Aquatic Ecosystems.   R.P. Canale (edTT.
Ann Arbor Science Publishers, Ann Arbor, Michigan,  pp. 171-204.

Collins, C.D. and J.H. Wlosinski.  1983. Coefficients for Use in the  U.S.
Army  Corps of Engineers Reservoir Model, CE-QUAL-R1.  U.S.  Army  Corps of
Engineers,  Waterways Experiment Station, Vicksburg, Mississippi.

Di Toro, D.M.,  D.J.  O'Connor, and R.V. Thomann.   1971.  A Dynamic Model of
the Phytoplankton Population  in the  Sacramento-San  Joaquin  Delta.
J_n:Nonequil ibrium Systems in Natural  Water Chemistry, Adv. Chem. Ser.  106.
American Chemical Society, Washington,  D.C.  pp.  131-180

Di Toro,   D.M., R.V. Thomann,  D.J.  O'Connor, and J.L.  Mancini.  1977.
Estuarine  Phytopl ankton Biomass Models  - Verification Analyses  and
Preliminary Applications.   J__n:  The Sea, Vol.  6,  Marine Modeling.
E.D.  Goldberg, I.N. McCave, J.J.  O'Brien, and J.H. Steele (eds.).   Wiley-
Interscience Publications, New York, N.Y.

Di Toro, D.M. and J.F. Connolly.  1980.  Mathematical  Models of Water
Quality in  Large Lakes.   Part II:  Lake Erie.  U.S. Environmental Protection
Agency, Ecological Research Series.  EPA-600/3-80-065.

Di Toro, D.M. and W.F. Matystik, Jr. 1980. Mathematical Models  of Water
Quality in Large Lakes.  Part  I:   Lake  Huron  and  Saginaw Bay Model
Development, Verification, and Simulations.  U.S. Environmental Protection
Agency, Ecological Research Series.  EPA-600/3-80-056.

Di Toro, D.M.,  J.J.  Fitzpatrick, and R.V. Thomann.  1981.  Water Quality
Analysis Simulation Program (WASP) and Model Verification Program  (MVP) -
Documentation.   Hydroscience, Inc., Westwood, New Jersey.  For  U.S.
Environmental Protection Agency,  Duluth, Minnesota.

                                  419

-------
Geller,  W.   1975.   Die Nahrungs  aufnahme von Daphnia pulex  in  Abhangigkeit
von der Futterhonzentration,  der Temperatur,  der Korpergroesse und dem
Hungerzustand der Tiere.  (The  food uptake of Daphnia pulex as  a function of
food concentration, temperature,  animals' body length, and  starvation).
Archivfuer  Hydrobiologie Supplementband.  48:47-107.  (Fisheries and Marine
Service of Canada Translation Series No. 4017, 1977, 96 pp.)

Harleman, D.R.F.,  J.E. Dailey, M.L. Thatcher, T.O. Najarian,  D.N.  Brocard,
and R.A. Ferrara.  1977.   User's Manual for the M.I.T. Transient Water
Quality Network Model — Including  Nitrogen-Cycle Dynamics for Rivers and
Estuaries.  R.M. Parsons Laboratory for Water Resources and Hydrodynamics,
Massachusetts  Institute of Technology, Cambridge, Massachusetts.   For U.S.
Environmental Protection Agency, Con/all is, Oregon.  EPA-600/3-77-010.

Ivlev,  V.S.   1966.  The Biological Productivity of Waters.   J.  Fish. Res.
Bd. Can., 23:1727-1759.

Johanson, R.C., J.C. Imhoff, and  H.H.  Davis.   1980.   User's  Manual for
Hydrological Simulation Program -  Fortran (HSPF).  Hydrocomp, Inc.,  Mountain
View,  California.  For U."S. Environmental Protection Agency,  Athens,
Georgia.  EPA-600/9-80-015.

Jorgensen,  S.E.  1976.  A  Eutrophication Model  for a Lake.  Ecol.  Modeling
2:147-165.

Jorgensen,  S.E. (ed.)  1979.  Handbook of Environmental  Data and Ecological
Parameters.  International Society for Ecological Modeling.

Jorgensen,  S.E.,  H.  Mejer, and  M.  Friis.   1978.   Examination  of a Lake
Model.   Ecol. Modeling, 4:253-278.

Jorgensen,  S.E.,  L.A. Jorgensen,  L.  Kamp-Nielsen, and H.F. Mejer.  1981.
Parameter Estimation  in Eutrophication  Modeling.   Ecol.  Modeling,
13:111-129.

Jorgensen, S.E.  1983.  Eutrophication Models of  Lakes.   Jji: Application of
Ecological  Modeling  in Environmental  Management, Part A.  S.E.  Jorgensen
(ed.).   Elsevier Scientific  Publishing Company.  Chapter 7.

Kremer,  J.N. and S.W. Nixon.   1978.  A Coastal Marine Ecosystem,  Simulation
and Analysis.  Springer-Verlag.  217 pp.

Leidy,  G.R. and G.R.  Ploskey,  1980.  Simulation  Modeling of Zooplankton and
Benthos in Reservoirs: Documentation and Development of Model  Constructs.
U.S. Fish and Wildlife Service, Fayetteville, Arkansas.   For U.S.  Army Corps
of Engineers, Waterways Experiment Station (WES), Vicksburg, Mississippi.

Lombardo, P.S.   1972.  Mathematical  Model of  Water Quality  in Rivers and
Impoundments.  Hydrocomp, Inc., Mountain View, California.
                                   420

-------
Mayzaud,  P.  and  S.A.  Poulet.  1978.   The  Importance of  the Time Factor in
the Response  of Zooplankton to Varying  Concentrations of Naturally Occurring
Particulate Matter.  Limnol and Oceanogr., 23:1144-1154.

Michael is, L. and M.L.  Menten.  1913.   Biochemische Zeitschrift., 49:333.

Naja*rian, T.O. and  D.R.F. Harleman.   1975.  A Nitrogen Cycle Water Quality
Model for Estuaries.   R.M.  Parsons Laboratory  for Water Resources and
Hydrodynamics,  Massachusetts  Institute of Technology,  Cambridge,
Massachusetts.  Tech. Report No. 204.

O'Connor,  D.J., D.M.  Di  Toro, and R.V.  Thomann.  1975. Phytoplankton Models
and  Eutrophi cati on  Problems.   In:  Ecological  Modeling in a Resource
Management Framework.   C.S.  Russell   (ed.).   Proceedings of Symposium
Sponsored  by  NOAA and Resources for the Future.

O'Connor,  D.J.,  J.L. Mancini, and J.R. Guerriero.  1981. Evaluation of
Factors Influencing the Temporal Variation of Dissolved Oxygen in the  New
York Bight, PHASE II.  Manhattan College, Bronx, New York.

Park, R.A.,  R.V.  O'Neill,  J.A. Bloomfield, H.H.  Shugart,  Jr., R.S. Booth,
R.A. Goldstein,  J.B. Mankin, J.F.  Koonce,  D. Scavia, M.S.  Adams,
L.S. Clesceri, E.M. Colon, E.H. Dettmann,  J.A. Hoopes, D.D. Huff,  S.  Katz,
J.F. Kitchell, R.C. Kohberger, E.J. LaRow,  D.C. McNaught,  J.L. Peterson,
J.E. Titus,  P.R. Weiler, J.W. Wilkinson, and C.S. Zahorcak.  1974.  A
Generalized Model  for Simulating Lake Ecosystems.  Simulation, 23(2):33-50.

Park, R.A., D. Scavia,  and N.L. Clesceri.  1975.  CLEANER, The Lake George
Model.  In:  Ecological Modeling in a Resource Management  Framework.  C.S.
Russell  (e"d.).  Resources  for  the Future, Inc., Washington,  D.C. pp.  49-82.

Park, R.A.,  C.D.  Collins,  D.K. Leung,  C.W.  Boylen,  J. Albanese,  P.
deCaprariis,  and  H.  Forstner.   1979.   The Aquatic Ecosystem Model
MS.CLEANER.   Proc. of First International Conf. on State of  the Art  of Ecol.
Modeling,  Denmark.

Park, R.A., C.D. Collins,  C.I. Connolly, J.R.  Albanese,  and B.B.  MacLeod.
1980.  Documentation  of the Aquatic Ecosystem Model MS.CLEANER. Rensselaer
Polytechnic Institute,  Center  for Ecological  Modeling, Troy, New York.   For
U.S. Environmental  Protection Agency, Environmental Research Laboratory,
Office of  Research and  Development, Athens,  Georgia.

Porcella,  D.B., T.M.  Grieb, G.L. Bowie, T.C.  Ginn,  and M.W.  Lorenzen.  1983.
Assessment Methodology for New Cooling  Lakes, Vol.  1: Methodology to Assess
Multiple Uses  for New Cooling Lakes.   Tetra Tech,  Inc., Lafayette,
California.   For Electric  Power Research Institute, Report EPRI EA-2059.

Salisbury, O.K.,  J.V.  DePinto, and T.C.  Young.   1983.   Impact of Algal-
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For U.S. Environmental  Protection Agency, Environmental Research Laboratory,
Duluth, Minnesota.
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Scavia,  D.   1980.  An Ecological  Model of Lake Ontario.   Ecol. Modeling,
8:49-78'.

Scavia,  D.,  B.J. Eadie, and  A.  Robertson.  1976.  An Ecological Model  for
Lake Ontario-Model Formulation, Calibration,  and Preliminary  Evaluation.
NOAA Tech.  Rept.  ERL 371-GLERL  12.  Nat!. Ocean, and Atmos.  Admin., Boulder,
Colorado.

Scavia,  D.  and R.A. Park.   1976.  Documentation of Selected Constructs  and
Parameter Values  in the Aquatic Model  CLEANER.  Ecol. Modeling,  2:33-58.

Smith,  D.J.   1978.   Water  Quality for River-Reservoir Systems.  Resource
Management Associates, Inc.,  Lafayette,  California.  For U.S. Army Corps of
Engineers,  Hydrologic Engineering  Center (HEC), Davis, California.

Swartzman,  6.L.  and R. Bentley.  1977.   A Comparison of Plankton Models with
Emphasis on  Application to Assessing  Non-Radiological Nuclear Plant  Impacts
on Plankton in  Natural Ecosystems.  Center for Quantitative  Science,  College
of Fisheries, University of Washington,  Seattle, Washington.

Tetra Tech,  Inc.   1979.  Methodology for Evaluation of Multiple  Power Plant
Cooling  System Effects, Volume  II.    Technical  Basis for  Computations.
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Tetra Tech,  Inc.  1980.   Methodology  for Evaluation of Multiple Power Plant
Cooling  System  Effects, Volume  V.   Methodology  Application  to Prototype-
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Thomann,  R.V., D.M. Di  Toro,  R.P. Winfield,  and  D.J. O'Connor.   1975.
Mathematical Modeling of Phytoplankton in Lake  Ontario,"Part 1.  Model
Development and Verification.   Manhattan College,  Bronx,   New York.   For
U.S. Environmental Protection Agency,  Corvallis, Oregon.   EPA-600/3-75-005.

Thomann,  R.V.,  J.  Segna,  and  R. Winfield.  1979.  Verification  Analysis of
Lake Ontario and Rochester Embayment Three-Dimensional   Eutrophication
Models.  Manhattan  College,  Bronx,  New York.   For U.S.   Environmental
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U.S. Army Corps of Engineers.   1974.   Water Quality for River-Reservoir
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Davis, California.

Vanderploeg, H.A. and D. Scavia.  1979.  Calculation and Use of Selectivity
Coefficients  of Feeding:   Zooplankton  Grazing.  Ecol. Modeling,  7:135-149.

WES (Waterways  Experiment Station).   1982.  CE-QUAL-R1:   A Numerical One-
Dimensional Model  of Reservoir  Water Quality, Users Manual.    Environmental
and Water Qualtiy  Operational Studies  (EWQOS), U.S. Army Corps of Engineers,
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Wetzel,  R.G.   1975.   Limnology.   W. B. Saunders Co., Philadelphia,
Pennsylvania.  743 pp.


                                   422

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Youngberg, B.A.   1977.   Application of the Aquatic Model  CLEANER  to
Stratified Reservoir  System.  Center for Ecological Modeling,  Report #1,
Rensselaer Polytechnic  Institute,  Troy, New York.
                                  423

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                               CHAPTER  8
                           COLIFORM BACTERIA

8.1  INTRODUCTION

     Coliform  concentrations  in natural  waters have been  used as an
indicator  of potential  pathogen contamination  since at  least  the 1890's
(Whipple, 1917).  Until  recently,  coliforms have been considered to be  less
sensitive  to environmental stresses than  enteric pathogens.   Accordingly,
coliforms were believed to be more persistent in natural waters and,
therefore, a "safe" or  conservative index of potential pathogen levels.

     However,  recent  evidence  about enteric  viruses,  opportunistic
pathogens, and pathogenic Escherichia coli  have  raised doubts that  coliforms
are the "ideal  indicator" (Sobsey and Olson,  1983).  First,  enteric viruses
appear to  generally have  both lower decay rates  than coliforms  and also a
lower  ID-50  (i.e.,  the  dose required  to  infect 50 percent of  the persons
exposed) than most bacterial enteric pathogens.  Second,  opportunistic
pathogens (e.g., Pseudomonas  aeruginosa,  Aeromonas hydrophila, and
Legionella pneumophila) often have major  non-fecal sources and are able to
grow  in natural waters.  These pathogens  generally have  a high ID-50,
threatening primarily immunologically compromised persons  such as  hospital
patients  who are  being  given immunological  suppressants.  Finally,  some
strains of _§_. coli produce an enteric toxin  that results in gastroenteritis.

      In the context of drinking water, Olivieri (1983) has recommended  that
different  indicators be used when different  aspects of pathogen behavior are
of  interest, e.g., indicator of  feces,  treatment efficiency,  or post-
treatment  contamination.   Chamber!in (1982)  has  compared coliform (combining
Total  Coliform,  Fecal Coliform, and £.  coli) decay rates with pathogen and

                                  424

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 virus decay rates measured  simultaneously and  has found that the respective
                                        2
 decay rates were  highly correlated  (r   = 0.73)  and that within-species

 variability was as great  as pathogen-to-coliform variation (see Figure 8-1).

 At low  decay  rates,  coliform decay rates  were approximately equal to

 pathogen decay rates while  at the highest decay rates, pathogen decay was
 slower.
        0.001
           0.001
                0.01
                              COLIFORM DECAY RATE (1/HR)
Figure 8-1.
Relationship  between pathogen or virus decay rates and  coliform
decay  rates  based on figure  presented by Chamber! in  (1982).
Decay rates were estimated  by Chamber!  in  based  on  data from
Baross et _al_.  (1975) (A),  Morita  (1980) (X), McFeters  et al .
(1974)  (T),  McCambridge and  McMeekin (1981)  (O),  LantrTp
(1983) (•),  and  Kapuscinski  and  Mitchell  (1981)  (D).  The
line shown represents coliform  decay rates equal  to pathogen
decay rates.
                                   425

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     In addition, epidemiological  studies have  revealed that enterococci
levels  are  more closely associated with enteric disease than are coliforms
(Cabelli et_  a_K  1982).  This work  has in part motivated  a proposed revision
of the  contact  recreation bacterial water quality criteria:  switching from
fecal  coliforms  to IE. coli and/or  enterococci (U.S.  Environmental Protection
Agency, 1984).

     Taken as a whole,  these issues may serve to motivate modelers  to
include  additional indicators as  state variables and  to use coliforms as jin
indicator rather than as the indicator.
8.2  COMPOSITION AND ASSAY

     The coliform group consists  of  both fecal and  non-fecal components.
The fecal  component includes mainly the Escherichia  and Klebsiella genera
while the  non-fecal component  includes  mainly  the Enterobacter  and
Citrobacter genera commonly associated with soils  and plants  (Dufour, 1977).

     Neither  the multiple tube  (MPN) nor the membrane filter  (MF) techniques
for Total  Coliforms (TC) effectively differentiates  between the fecal and
non-fecal components.  The Fecal  Coliform (FC) tests (either MPN or MF)
provide a  better  differentiation at the cost of  additional  labor and time
plus more  exacting  equipment requirements.  The  tests  require  either
supplemental  tests  run on TC  or  incubation at elevated temperatures within
precise  limits (i.e., 44.5°C ± 0.2°C).   These more stringent conditions
eliminate  most  of  the non-fecal  component while  still permitting the fecal
component  to survive.  FC represents  from 15 to  90 percent of the  TC,
depending  on sample source.   Unfortunately, there are  major non-fecal
sources  of  FC, most commonly of Klebsiella species  (Hendry et aj_. 1982).
Pulp mill  wastewater provides a frequent example.  Tests  for E_. col 1 are
even more specific to fecal sources, but again incur  further  costs for labor
and time.

     The non-fecal  components of the coliforms, especially the Enterobacter
and Citrobacter genera, are of  limited use in indicating fecal contamination
                                   426

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but do indicate prior contact with soil or plant  material.  In  addition,
these  genera are capable of  regrowth in nutrient-rich  natural waters or
where surfaces are available  for growth.

     Fecal streptococci  (FS) provide  another common indicator of fecal
contamination (Clausen et^ jil_.  1977).  Although all FS  belong to the  single
genus Streptococcus, there  are again fecal  and non-fecal components.
Enterococci and SL faecal is are more specific to fecal  sources than the non-
enterococcal streptococci.   FS  and particularly the  enterococci are often
considered to be  able to survive longer  in natural  waters than either  TC  or
FC.   Chamberlin  (1982) compared  FS (combining TC, FC,  and  E. coli results)
decay rates in cases where the rates were measured  in the  same experiments
                                 2
and  found a  high correlation (r  =  0.80) between the  logarithm of  the
respective rates.  In addition, the relationship between the logarithms  of
the  rates had   a slope  estimated  by linear regression that was  not
significantly different (p =  0.05)  from  1.0.  The intercept was marginally
distinguishable  from 0.0 at  p =  0.01 and was estimated  as  -0.31.   This
suggests that coliform decay rates  were  generally twice  as  large as FS decay
rates but that the rates  changed generally  by equal  amounts from  one
environment to another.  According  to Geldreich and Kenner  (1969), the FC/FS
ratio  is  useful  in discriminating between recent  human versus animal  fecal
contamination.  If the ratio exceeds approximately 1 (although 4 is  often
cited as  the cut-off value), the source is  presumptively human  fecal
material  while if the ratio  is less than 1, the  source  is assumed  to  be
animal  feces.   But as Dutka  and  Kwan (1980)  have observed, the ratio can
change dramatically once the  material enters natural waters.  They monitored
changes from an  initial ratio of  2.7 to a low of 0.07  and a high of 22.5 in
a single experimental run.

     Other proposed fecal indicators have been discussed by Olivieri  (1983)
and include Clostridium perfringens, yeasts, and  RNA coliphages.  None  of
these novel indicators has become  generally accepted.

     Beyond the selections of a particular indicator or set of indicators,
recent work  has shown the  importance of sublethal  stress or  injury of
influencing observed concentrations  in decay  studies  (Rose .ejt _al_.  1975;
                                  427

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Bissonette  et_ aj_. 1977).  Rhodes  and Kator  (1982)  and Kapuscinski  and
Mitchell  (1981) have, among others,  substantiated  these results and  have
suggested particular mechanisms of injury.   Consequently, the decision to
use or not  use  a resuscitation  step  (e.g., incubation at  35°C in  less
selective medium for two hours) can  have a major  impact on the observed
decay rates.

8.3  MODELING COLIFORMS

     Modeling of coliforms is  done for  one main reason—establ ishing  the
level of fecal  and/or soil pollution and potential pathogen contamination.
The usual  approach is simply to  simulate disappearance and' to estim-ate
coliform  levels as a function of initial loading and  the  disappearance  rate
which,  in turn, is a function  of time or distance of travel from the source
and of environmental conditions such as temperatures, salinity,  and  light
intensity.

8.3.1  Factors Affecting  Disappearance Rates

     Upon discharge to a water body,  environmental conditions determine  the
extent to which  coliform regrowth  and death occur.  Fecal  coliforms and
streptococci are occasionally  observed to increase in  numbers,  although  this
may be due  to disaggregation of clumps of organisms.  Non-fecal  organisms
may,  in fact, increase in numbers  in  natural  waters  where conditions  are
adequate  (Lombardo, 1972; Mitchell and Chamberlin, 1978).

     Factors can  be  conveniently  classified into three  categories:
physical, physicochemical, and biochemical-biological.   However,  note  that
synergisms (e.g., osmotic effects  and photo-oxidation)  and interferences
(e.g., sedimentation versus  photo-oxidation) may exist.  Kapuscinski and
Mitchell  (1980) and Bitton (1980) have reviewed factors  that  govern virus
inactivation  in  natural waters and present  essentially  a parallel  list to
the one given below.
                                   428

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     Physical  factors that  can  affect the  coliform population  in  natural
waters,  resulting  in  an  apparent  increase or decrease in the  coliform
disappearance rate  include:

     •    Photo-oxidation
     •    Adsorption
     •    Flocculation
     •    Coagulation
     •    Sedimentation
     •    Temperature

Physicochemical  factors  include

     •    Osmotic effects
     •    pH
     •    Chemical  toxicity
     •    Redox potential

Biochemical-biological  factors include:

     0    Nutrient  levels
     t    Presence  of  organic substances
     •    Predators
     •    Bacteriophages (viruses)
     t    Algae
     •    Presence  of  fecal matter

8.3.1.1   Physical  Factors

     Chamber!in and Mitchell  (1978) have noted that,  although many data have
been collected on coliform disappearance rates, mechanisms mediating the
rates have historically  been  poorly understood.   According  to Chamberlin and
Mitchell, however,  light is one of the most important factors.  They observe
that it is difficult to  show  statistically significant relationships between
coliform disappearance rates  and many factors usually hypothesized as

                                   429

-------
influencing  those rates.  In contrast,  significant relationships between
light  intensity and coliform disappearance rates can  be  demonstrated.
Chamberlin  and Mitchell (1978)  have  shown that field  data statistically
support the  photo-oxidation  model  (to be discussed),  and data presented  by
Wallis _e_t _al_.  (1977) also appear to implicate incident  light.  Subsequent
work by Sieracki  (1980),  Kapuscinski and Mitchell  (1983), Lantrip  (1983),
and others  has  demonstrated  that viruses and enteric  bacterial pathogens are
also sensitive  to  light but  that viruses are generally  less sensitive  than
coliforms.

     Chamberlin  and Mitchell  (1978) have elaborated upon possible mechanisms
by  which  light may increase coliform disappearance rates.  They point out
that  although  in many cases of  light  induced mortality,  one  or more
photosensitizing  substances  are involved,  visible  and near ultraviolet  (UV)
light  can  kill IE. col i  in the absence of exogenous  photosensi ti zers.
Grigsby and  Calkins (1980)  have confirmed the significance of the near UV.

     One  suggested mechanism  is that light  quanta drive  some exogenous  or
endogenous  chromophore to an  electronically excited state.  The chromophore,
in the process  of returning to the  ground state, transfers its absorbed
light  energy to another  substance to form  superoxides (Op), which,  in turn,
cause  damage to cellular components.    Alternatively, the activated
chromophore  may  cause  damage  directly,  without  the agency of  a
superoxygenated  intermediate.  Kapuscinski  and Mitchell  (1981) observed  that
injury to  the  catalase  system is the most likely  site of damage in £.  coli
and that  the damage can be repaired if the  coliforms  are  transferred to  an
appropriate recovery medium.  Krinsky (1977) has, on the other hand, argued
that the  "cause of death" may be division-inhibition,  mutation,  and/or
membrane  damage.

     Substances  within coliform and  other  bacterial cells are effective,
near-UV chromophores, including ubiquinones, porphyrins,  and tryptophan
(Krinsky  1977).  Exogenous  sources of photo-oxidants  include algal pigments,
lignins, and humic and fulvic acids.  More highly colored and turbid waters
have been shown to produce peroxides, singlet oxygen, and hydroxide radicals

                                   430

-------
at greater rates  than well waters (for example, Zepp ejt aj_.  1977;  Cooper and
Zika, 1983).

     Adsorption,  coagulation,  and flocculation may  affect coliform
disappearance rates, although  few  quantitative data are  available.
Adsorption refers to the  attachment of coliform organisms to  suspended
particles.   Coagulation refers to the  coalescence of bacteria  into clumps,
and  flocculation  refers  to  the  formation  of soft, loose  aggregates
incorporating  much water.

     According to  Mitchell and  Chamberlin (1978), early investigations by
several  workers have demonstrated that clays tend to adsorb conforms  more
than  do  silts or sands.  This is, of course, commonly the  case with sorbed
substances. As Mitchell and Chamberlin point out, the nature and  stability
of coliform aggregates incorporating other particulate matter depends to a
very large extent upon the physicochemical nature*of the particles.   Gannon
ejt al.  (1983) found that 90 to  96 percent of the coliforms entering a lake
from upland watersheds were associated with 0.45 to 5 fzm particles.

     Sedimentation  involves  the  settling out of bacterial particles  and
aggregates.   The rate of  disappearance may be  materially influenced by
aggregation and sedimentation,  but the magnitude and direction of the change
in rate  is not well understood.  The mechanism of apparent disappearance due
to sedimentation  is actually simple removal of cells from the water column--
that is,  transfer of matter from  one physical compartment (the water column)
to another (the benthos).  However simple, sedimentation may sometimes  be
the predominant mechanism of removal as Gannon ejt a]_. (1983) demonstrated in
a field  study of coliform  survival   in  a lake.   Accordingly,  modeling
coliform disappearance in  the  water column may  give misleading results,
particularly where shellfish are  harvested for human consumption.   Reduction
in coliform levels in the water  column may simply mean increased  numbers in
the benthos.

     Temperature  influences  most, if  not all,  of the the other  factors.
Bitton (1980) and Lantrip (1983) argue that temperature is the single most
important modifier of decay rates, especially in freshwater  and in  the dark.
                                   431

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8.3.1.2  Physicochemical Factors

     Mitchell  and Chamberlin (1978)  report  that  physicochemical factors  may
have significant effects on disappearance rates.  Survival rates of E_. coli,
for example,  are inversely proportional  to  salinity both in natural seawater
(due to  osmotic  and other  effects) and  in  artificial salt solutions.   In
addition, Sieracki  (1980) has observed a synergism with light effects.  Work
by Zaf iriou  and True (1979) suggest that nitrite photolysis in seawater may
be a partial  cause.  In general, E.  coli have  been found  to  survive  longer
in lower pH salt solutions (pH < 8)  than under alkaline conditions.

     Heavy metal toxicity toward microorganisms has been known  since  the
late nineteenth  century.   A  great number of studies have been done on  the
"oliogodynamic action" of silver and copper salts.   According to Mitchell
and  Chamberlin (1978),  heavy metals  have been implicated  as  important
mediators of  E,. coli disappearance rates, and  the heavy metal effects may be
reduced  by addition of  chelating agents.   Redox potential,  through  its
effect  on heavy metals solubilities, also affects disappearance rates.   In
addition to  this,  redox may  influence disappearance rates in other ways,
although data  on this are not extensive.

     Finally,  Kott  (1982) has presented  evidence that when coliforms undergo
the transition from the generally low oxygen environment  of sewage  to  the
higher  oxygen levels found  in seawater,  the  oxygen shock promotes rapid
decay.

8.3.1.3  Biochemical and Biological  Factors

     Nutrient  concentrations may be important  in determining disappearance
rates  under  some conditions.  In many nutrient  studies, the apparent impact
of nutrient addition to the coliform culture is  due to chelation of heavy
metal  ions (Mitchell and Chamberlin,^1978).   Thus, the apparent decrease in
disappearance  rate  in many cases may not be due  to the additional  nutrient,
but  instead  to reduce toxicity of  the culture medium.   Mitchell  and
Chamberlin (1978) cite the work of Jones (1964)  who found that E. coli would

                                   432

-------
not grow  at 37°C  in  either filter-sterilized natural  or  synthetic seawater
supplemented with  glucose, ammonium chloride,  and potassium phosphate.
Inhibition could  be  reversed by autoclaving,  by  addition of very small
amount  of  organic matter, or by addition of metal  chelating or complex ing
agents.   Jones  demonstrated  that two  levels of toxic metals would produce
the inhibitory  effect,  and  concluded that the  apparent influence on
disappearance rates  was  due  to naturally occurring  trace  heavy metals in
solution.  Furthermore,  as  Mitchell and Chamberlin (1978)  note, other
researchers have obtained experimental results implicating heavy metals, and
their chelation upon addition of nutrients,  in  apparent changes in
disappearance rates.

     In some situations,  it  appears  that nutrient levels influence
disappearance rates  in ways unrelated to toxic metals  availability.  Savage
and Hanes  (1971). and  Chamberlin (1977),  for example,  have  reported growth-
limiting  effects  of  available BOD or organic matter.  Recent work by Dutka
and Kwan  (1983) indicates that after-growth and  long-term  persistence is
particularly sensitive to nutrient levels.  Further,  it is possible that the
level  of  nutrients affects  coliform predators, thereby  influencing rates of
grazing on coliforms. Mitchell and Chamberlin (1978)  report that predators
in natural waters may be significant in  reducing coliform populations given
high predator levels.  They cite three groups of micro-organisms which may
be importantly in seawater.  These are cell wall-lytic  marine bacteria,
certain  marine amoebae, and  marine bacterial parasites similar to
Bdellovibrio  bacteriovorus.   Experiments performed by a number of
researchers have implicated predators in disappearance of coliforms in  both
fresh  and  seawater, although Lantrip (1983) did  not  observe a significant
predator  influence in chamber experiments using freshwater.   Bacteriophages,
on the other  hand,  are  apparently of minor importance,  despite their
demonstrated presence in sea water.  The relative insignificance of phages,
according to Mitchell  and Chamberlin (1978),  stems  from  their
ineffectiveness  in  killing    E. coli  where the bacterial cells are not
actively  growing and  multiplying,, and  the rapid inactivation of the  phages
by seawater.
                                  433

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     Some forms of  phytoplankton produce  antibacterial  agents which  are
excreted into the water  column.  These  substances are heat-liable macro-
molecules, and according to Mitchell and Chamberlin  (1978)  at least  one,  a
chlorophyllide,  is active only if the system is  illuminated.  The fact that
at  least one antibacterial agent is activated by  light  suggests that  algae
may play a mediating  role  in the effect  of light on disappearance rates.
Other mechanisms  of algal anti-coliform activity  have been suggested. One is
that  during algal blooms,  other organisms which prey on  both algae  and
coliforms may also  increase in numbers.

     Table  8-1  is  a summary  of  factors  influencing coliform disappearance
rates.

8.3.2  Modeling Formulations

     Traditionally,  coliform  modeling  has only  taken  into  account
disappearance, and a  simple  first-order  kinetics approach has been used
(Baca and Arnett, 1976;  Chen,  et_ _al_.,  1975; Chen ejt _al_.,  1976; U.S. Army
Corps  of Engineers,1974; Chen  and Orlob,  1975; Lombardo, 1973; Lombardo,
1972; Smith, 1978;  Anderson et aj_. 1976; Huber, et _al_.  1972;  Hydroscience,
1971; Chen and Wells, 1975; Tetra Tech, 1976b):

                                 dC _  ,c                             (8-1)
                                 dt    KU

or

                               Ct = CQe"kt                            (8-2)

where  C   =  coliform concentration,  MPN or count/100 ml
       CQ =  initial coliform  concentration,  MPN or count/100 ml
       C.  =  coliform concentration  at  time t, MPN or count/100 ml
                                           -1      -1
       k   =  disappearance rate  constant, day   or hr~
       t   =  exposure time,  days or  hours.
                                   434

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      A summarized  listing  of values for k  is  presented  in Table  8-2.   The

data summarize  30  studies  of rates measured in  situ.   Table  8-3  shows  values

for  k from a  number  of modeling  studies.   The  median  rate for  the jji  situ

studies  is  .04  hr" with 60  percent  of the values  less  than .05 hr"1  and  90
percent  less  than  .22 hr"1.


          TABLE 8-1.  FACTORS  AFFECTING  COLIFORM DISAPPEARANCE RATES
                 Factor
                                                               Effects
   Sedimentation
   Temperature


   Adsorption, Coagulation,  Flocculation

   Solar Radiation
   Nutrient Deficiencies



   Predation




   Bacteriophages

   Algae
   Bacterial Toxins
   Physiochemical Factors
Important  with regard to water column coliform
levels, particularly where untreated or  primary
sewage  effluent or stormwater is involved, and
under  low vertical mixing conditions.   May
adversely affect  shellfish beds  by  depositing
coliforms and fecal matter into benthos.

Probably the  most generally influential  factor
modifying all  other factors.

Inconclusive.

Important; high levels may cause more than  10-fold
increase in disappearance rate over corresponding
rate in  the dark  in seawater.  Rates  also
materially increased in freshwater.

Appear  to accelerate disappearance. Numerous
studies have indicated that  increasing nutrient
levels of seawater decrease disappearance rates.

Several species of organisms  (bacteria, amoebae)
have been shown  to attack  and destroy £.  coli.
Importance of predation depends strongly on the
concentration of predators.

Apparently not important.

Bactericidal  substances are known to be produced
by planktonic  algae.    Substances may  be
photoactivators, mediating the influence of  light
on coliform disappearance.  This might account for
variability  of  data in studies of light-induced
disappearance rates.  Another hypothesis is that
algal predators with blooms concomitant with  algal
blooms may produce substances toxic to £. col i  or
may prey upon them.

Antibiotic substances produced  by indigenous
bacteria are not  believed  important in coliform
disappearance.

Apparently,  pH, heavy metals content, and the
presence of organic chelating substances mediate
coliform disappearance rates.  Importance of  each,
however,  is poorly  understood at  present.
Salinity strongly enhances the effect of  solar
radiation.
                                           435

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      A number of  researchers have determined values for  the  half saturation
 constant (K  ) for  E.  coli  growth, using  the Monod expression:
b
TABLE 8-2. COLIFORM BACTERIA FRESHWATER DISAPPEARANCE RATES MEASURED
IN SITU (AFTER MITCHELL AND CHAMBERLIN, 1978)

System
Ohio River

Upper Illinois River



Lower Illinois River



"Shallow Turbulent Stream"
Missouri River
Tennessee River
(Knoxville)
Tennessee River
(Chattanooga)
Sacramento River
Cumberland River
Glatt River
Groundwater Stream
Leaf River
(Mississippi)
Wastewater Lagoon
Maturation Ponds

Oxidation Ponds

Lake Michigan
Ford Lake
(Ypsilanti, Michigan)
DeGray Reservoir
(Arkansas)


Temperature
Summer (20°C)
Winter (5°C
June-September
October and May
December-March
April and November
June-September
October and May
December-March
April and November

Winter
Summer

Summer

Summer
Summer

10°C


7.9-25.5°C

19°C
UTII

10-17°C
August
October 1976 (15°C)
March 1977 (10°C)
June 1977 (20°C)

k(l/hr)
0.049
0.045
0.085
0.105
0.024
0.043
0.085
0.037
0.026
0.029
0.63
0.020
0.043

0.005

0.072
0.23
1.1
0.021
0.017

0.00833-0.029
0.083
0.07
k = 0.108
•(1.19)T-20
0.36
0.4
0.052
0.109 and 0.016
0.138 and 0.114

Reference
Frost and Streeter (1924)

Hoskins et a].. (1927)



Hoskins et al_. (1927)



Kittrell and Kochtitzky (1947)
Kittrell and Furfari (1963)
Kittrell and Furfari (1963)

Kittrell and Furfari (1963)

Kittrell and Furfari (1963)
Kittrell and Furfari (1963)
Wasser et a].. (1934)
Wuhrmann (1972)
Mahloch (1974)

Klock (1971)
Marais (1974)

Marais (1974)

Zanoni et al_. (1978)
Gannon et &\_. (1983)
Thornton et al_. (1980)


Modified from Mitchell and Chamberlin (1978).
                                       436

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                                                                       (8-3)
  where   n  = growth rate at nutrient concentrations, day"1
         S   =
        PM ~
        K  =
concentration of growth  limiting nutrient, mg/1
maximum growth rate,  day"1

half-saturation constant producing the half-maximal  value
of ^, mg/1
  Table 8-4 shows some reported values  for  K  .


      However,  Gaudy et_  aj_.  (1971) have shown that the  Monod expression

  (Equation 8-3)  is not  adequate to describe transient  coliform growth
  behavior.  Accordingly, as suggested  by Mitchell and Chamberlin (1978), the
  utility of the  KS value  is  in evaluating  which nutrient  may be growth
  limiting rather than in estimating a  growth rate, ^.
      TABLE 8-3.   VALUES  FOR COLIFORM-SPECIFIC DISAPPEARANCE  RATES
                     USED IN SEVERAL MODELING STUDIES
         System
               k @20 C,
                 1/hr
North Fork Kings  River,          .042
  Cal i form'a

Various Streams               .0004-.146

Lake Ontario                   .02-.083

Lake Washington                  .02

Various Streams                .042-.125

Boise River, Idaho               .02

San Francisco  Bay Estuary        .02

Long Island  Estuaries,          .02-.333
  New York
Reference
                            Chen, et al_.  (1976)


                            Baca and Arnett (1976)

                            U.S. Army Corps of Engineers (1974)

                            Chen and Orlob (1975)

                            Hydroscience  (1971)

                            Chen and Wells (1975)

                            Chen (1970)

                            Tetra Tech  (1976)
                                    437

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         TABLE 8-4.  NUTRIENT K  VALUES FOR ESCHERICHIA COLI  (AFTER  MITCHELL  AND  CHAMBERLIN,  1978)

Nutrient Medium
Glucose minimal medium




seawater
OJ
co
Lactose seawater
minimal medium
Phosphate minimal medium
minimal medium
T
oc



30
30
20


20


30
Ks
Micromoles
22.
19.4
41.7
405.
550.
44.


50.
111.
0.7
17.35
Remarks Reference
Monod (1942)

Moser (1958)
Schultz and Lipe (1964)

Jannasch (1968)


Jannasch (1968)
Monod (1942)
uptake study Medveczky and Rosenberg (1970)
Shehata and Marr (1971)
Glucose
30
0.378
Shehata and Marr (1971)

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     Work  on coliforms  in  the Ohio River  by  Frost and Streeter  (1924)
revealed that the log decay rate for coliforms  is  nonlinear with  time.
Accordingly,  use of a simple decay expression such as Equation  (8-1) with a
single value of k is only  an approximation  to the  actual disappearance
process.   Such an approach must, to some extent as a function of time,
overestimate and/or underestimate dC/dt.   One  approach to solving  the
problem of a time-variable decay rate is to  decompose the death curve into
two components,  each having  its own decay rate (Velz,  1970).  This  approach
is predicated upon typical death rate curves such as those  shown  in Figure
8-2.   These curves have essentially two regions,  each with  its  own
characteristic slope, and the coliform concentration as a function of time
may be defined as:
                                  -let     '  L' t
                          Ct = Coe   + coe
where  C^     =  coliform concentration  at  time t, MPN or count/100 ml
       C ,C'   =  concentrations of each  of  the two hypothetical organism
                 types, MPN or count/100 ml
        k,k'   =  decay  rates for the two organism types, day

Table 8-5 shows  values for C , C'   k,  and k1 for  E_.  col i  as estimated  by
Phelps (1944).

     Lombardo  (1972),  in an effort to more meaningfully model coliforms, has
formulated  the  dynamics  of  the  coliform population plus  streptococci with
three separate first-order expressions:
                              CT  =  CT e'                            (8-5)
                               't     'o

                              CF  =  Cp e"kf*                         (8-6)
                               rt     ro

                              C.  =  C, e~kst                         (8-7)
                                   439

-------
   0.01
Figure 8-2.  Typical  mortality curves for coliforms as a function
             of time.  Curve A is for cool weather while curve B
             represents warm weather decay (redrawn from Velz, 1970).

-------
       TABLE 8-5.  VALUES OF  Co,  C1,  k, AND k1 FROM THE OHIO RIVER
                               PHELPS  (1944)

Parameter
C (percent)
k (I/day)
Half-life (day)
Cg (percent)
k1 (I/day)
Half- life (day)
Warm Weather
99.51
1.075
.64
.49
.1338
5.16
Cold Weather
97
1.165
.59
3.0
.0599
11.5

where  C,  =  organism  concentration at time t,  MPN  or  count/100 ml
       C  =  organism  concentration at time zero, MPN  or count/100 ml

Table  8-6 provides  data  for kj, k<-  and  kp  as summarized  from Lombardo
(1972).

     As discussed  earlier, recent studies have suggested that incident light
levels strongly affect  coliform  disappearance rates.   Chamberlin  and
Mitchell (1978)  have  defined a light  level-dependent  disappearance rate
coefficient  as

                              k'  = yoe'az                          (8-8)

where  k1  =  the  light dependent coliform disappearance rate, 1/hr.
                                                                2
       kn  =  proportionality constant for the specific organism, cm /cal
                                                      2
       ¥  =  incident  light energy at the surface,  cal/cm -hr
       a  =  light  attenuation coefficient per  unit depth
       z  =  depth  in  units consistent with a.
                                   441

-------
           TABLE  8-6.  SUMMARY OF  DECAY RATES OF TC,  FC, AND FS,
                       REPORTED BY  LOMBARDO (1972)

Indicator
TC
FC
FS
n
16
13
5
Median
k (1/hr)
0.038
0.048
0.007
Minimum
k (1/hr)
0.010
0.008
0.002
Maximum
k (1/hr)
0.105
0.130
0.063

Then, incorporating the vertical dispersion  of  bacterial cells,
                      -V7      -   - E7         - k'C(z.t)           (8-9)
                        7.   OL.       7-    O L.
                                                2
where  E  =  the vertical  dispersion coefficient, cm /hr
       V  =  the vertical  settling velocity,  cm/hr

An expression of this kind is useful  where the vertical distribution of
coliforms is nonuniform  over depth and where  disappearance is assumed to be
solely a function of light intensity.   Chamberlin (1977)  has  presented
solutions of Equation 8-2  for various ranges  of V , E ,  kn, a,  and H (depth
of water column) using dimensionless variables.

     According to  an  independent  development by Mancini  (1978)  and
Chamberlin  and Mitchell (1978), if  the bacterial  cells can be assumed
uniform  over depth  (i.e., the water column  is vertically mixed), then the
depth-averaged  light intensity and the depth-averaged  decay rate,
respectively, may be  computed:
and
                                  442

-------
                                 k = k                               (8-11)

where  f  = the depth-averaged  light intensity, cal/cm2/hr
       H  = the depth  of  the water column in units consistent with a
       k  = the depth-averaged  light-dependent disappearance rate, hr"

     The depth-averaged,  light-dependent, disappearance rate, k, may  be used
in  the first  order  disappearance  expression for a vertically mixed water
body so that:

                                 f =  -kC                           (8-12)

     It is clear that  the use of  such  a model  (Equation (8-12)) might  be
further refined by computing k  using a sinusoidal function to estimate light
levels and incorporating  the influence of such factors as latitude,  day  of
the  year,  time of day, and atmospheric conditions including cloud cover and
dust effects.  Table 8-7  presents some values for k«.

     Since coliforms and  other  indicators are  known to  decay  in  the dark,
Mancini (1978) and Lantrip (1983) have  developed decay rate  models combining
 light-dependent and light-independent  (i.e.,  dark) components.   The model
proposed by Mancini  expresses  k1  as a function of temperature,  percent
seawater, and  depth-averaged  light  intensity:

                 k. =  (0.8+0.006(%SH))1>07T-20 + ^                (8

where  T  = water temperature  in  C.L

The model coefficients were estimated  based  on  a combination  of
 laboratory, chamber, and field  studies.   Note  that k^ is not expressed
as  a function  of either salinity  or  temperature.
                                    443

-------
 TABLE  8-7.    COMPARISON  OF  k« ESTIMATES  BASED  ON  CHAMBERLIN   AND MITCHELL
                                (1978rWlTH  ADDITIONAL  VALUES
Organism
Conform Group











Study
14 field studies
Mean
5' percentlle
95 percentile
24 field studies
Mean
5 percentile
95 percentile
61 laboratory studies
Mean
5 percentlle
95 percentile
k£
(cm2/cal)

0.481
0.163
1.25

0.168
0.068
0.352

0.136
0.062
0.244
Data Source
Gameson and Gould (1975)



Foxworthy and Kneeling (1969)



Gameson and Gould (1975)



Fecal  Conform
Total  Conforms
Fecal  Conforms
Escherlchia coli
Seratla marcescens
Bacillus subtilis
  var. nlger

Fecal Streptococci
Estimated from diurnal
field  experiments  1n SW

Estimated from compilation of
field  and laboratory studies,
both SW and FW.

22 chamber studies  1n FW
Mean
Minimum
Maximum

22 chamber studies  1n FW
Mean
Minimum
Maximum

4 field studies
Mean
Minimum
Maximum

4 laboratory studies
Mean

4 field studies
Mean
Minimum
Maximum

1 laboratory study
3 laboratory studies
Minimum
Maximum

3 field  studies

1 field  study

12 field  studies,  Initial rates
Mean
Minimum
Maximum

23 chamber studies in FW
Mean
Minimum
Maximum
0.18 at  I = 1.0 cal/cm?hr   Bellalr et al. (1977)
0.07 at  I   0.1 cal/ci/hr

                          Manc1n1 (1978)
Salmonella typhimurlum    2 laboratory studies
                                                         0.042
                                                         0.004
                                                         0.000
                                                         0.013
                                                         0.005
                                                         0.000
                                                         0.011
                                                         0.362
                                                         0.321
                                                         0.385
                                                         0.354
0.192
0.093
0.360

0.002
                                                         0.048
                                                         0.123

                                                         0.000
                                                         0.007
                                                         0.091
                                                         0.004
                                                         0.184
0.008
0.001
0.028

1.48
6.40
Lantrlp (1982)




Lantrlp 91982)




Gameson and Gould (1975)




Gameson and Gould (1975)


Gameson and Gould (1975)




Gameson and Gould (1975)


Gameson and Gould (1975)



Gameson and Gould (1975)


Foxworthy  and Kneeling  (1969)




Lantrlp (1982)




Elsenstark (1970)
                                                    444

-------
     lantrip (1983)  developed a set of  temperature and  light-dependent
models based on a  series  of chamber studies conducted  in  freshwater.
Separate models were  determined for TC,  FC,  and FS.  He  used nonlinear
regression methods to determine the "best"  coefficient values  and  reported
both the "best"  estimates and associated  standard deviations.  • The three
models have the  same form:

                          k1 = kdj2(y-20 +  kf/                     (8-14)

where  kd 2Q = "dark"  decay rate at 20°C  (l/h\rl

     6 = temperature  correction term

The coefficients for  the  three models are summarized in Table 8-8. Note
that Lantrip also considers kf to be independent of temperature.

     Finally,  many investigators have noted an initially very low decay rate
in  laboratory and field studies.   For example, see Mitchell and Chamberlin
(1978), Mancini  (1978), and others.  Kapuscinski  and Mitchell  (1983)  and
Severin et _al_.  (1978)  have argued that this "shoulder" in  the decay  curve is
not the consequence of growth or particle  breakup but is instead  due to  the
nature of  the photo-oxidation  process.   Severin _e_t a±.  present  two
mechanistic models that would produce a "shoulder":

     •    Multi-target model  based on assumption that several  targets
          or sites in  the organism must be  hit before the  organism will
          be killed:
                        Ct-C0ll-|
-------
                         - c
                         "
where  n = event threshold for inactivation
(8-16)
Such models  are still novel  in  engineering applications and  have  not yet
been incorporated into water quality models.

 8.3.3  Methods of Measurement

     Estimates  of the coliform disappearance  rate, k, may be obtained in a
 number of ways in the laboratory chamber studies, or,  preferably, j_n  situ.
 For laboratory  estimates, samples of  effluent may be  taken along with
 samples of receiving water.  Then, under controlled  conditions of  light,
 temperature, and dilution, the time rate of  disappearance may be determined
 for  various combinations  of conditions.   Unfortunately  "bottle effects"
 often  distort laboratory  results as  shown  by Zanoni  and Fleissner (1982),
            TABLE 8-8.  PARAMETER ESTIMATES FOR  LANTRIP (1983)
                        MULTI-FACTOR DECAY MODELS

Indicator n
TC


FC


FS


Estimate 38
Standard
Error
Estimate 41
Standard
Error
Estimate 38
Standard
Error
Standard Error kd,20
Regression (1/hr)
0.0151 0
0

0.020 0
0

0.0183 0
0

.0301
.0044

.0305
.0057

.0294
.0050

1
0

1
0

1
0

6
.0893
.0208

.0978
.0280

.0859
.0234

(
0
0

0
0

0
0

z*
cm /cal )
.0022
.00065

.00377
.00081

.00502
.00076

                                   446

-------
since enteric bacterial growth  is promoted by availability of  surfaces for
attachment.

     In situ k values can be determined whether the flow  regime  is well
defined or not, although there are inherent errors involved  in each method.
Where there  are  no flow regime data,  or where flows are  of a  transient
nature, a commonly used method (e.g., Zanoni  et aj_. 1978 and  Gannon et aj_.
1983 provide recent examples)  is to  add a slug of a conservative  tracer
substance (a  dyes rare element, or  radioisotope) to the  steady-state
discharge.  Then the discharge  plume is sampled, dilution is  estimated from
concentrations of tracer,  and  the dilution corrected coliform  counts permit
k to be estimated.  It should be recognized that this technique may give
misleading results where the dilution of the tracer is due to mixing with
water heavily contaminated with the same discharge.  Since  the tracer had
been introduced as a slug,  there is no way to know how much of  the surviving
coliforms  originated in the tracer-dosed effluent and how  much  came from
pre-dosing or  post-dosing effluent.   However,  where the flow regime is
sufficiently  predictable and stable to  assure that  dilution  occurs
essentially with ambient water, and  where coliform levels in the ambient
water are  known, this should not be a problem.

     Another method,  which  is particularly useful where discharge is to a
channel,  is as follows.  First,  a base sampling site is established  below
the  discharge where the water  column is fully mixed normal to  the direction
of flow.   Then samples are taken at  the base site and at  several  points
downstream.   Based  upon known velocities and the change in coliform
concentration with distance (time), k  values may be estimated.  Clearly,
errors will be  introduced to the extent that there is incomplete lateral
mixing of  the  stream, nonuniform  longitudinal velocities laterally and
vertically across the channel, and  unknown inflows causing dilution or
introducing additional coliforms between sampling sites.

      Also,  sampling can be done so  that the same "parcel" or water is
sampled,  in case the discharge  is not at steady-state.  For example,  if the
first  sampling  site is one mile below the base site, and the channel flow

                                  447

-------
has a mean  velocity of 2 ft per second,  then the first sampling site should
be sampled:

                5280 ft v 1 second      1 hr     _  7, hr
                 mile   x   2 ft   x  3600 seconds   '/J nr

or 44 minutes  after sampling at the base site.  Clearly, however, this does
not  account  for dispersion,  and the 44 minutes  is  an average  figure
corresponding  to the peak  loading.   Where possible, dye studies or  other
techniques  should be used to characterize stream dispersion at the sampling
location.  Then,  by integrating under  the curve, total surviving coliforms
can be estimated.  If, on the other hand, discharge and  stream conditions
are clearly at  steady-state, sampling  times are of no consequence.

     Equation (8-17) may be used to estimate k where a slug  dose of tracer
has been introduced into the discharge (assuming first-order  decay):

                           k = -In (CtF0/FtC0)/t                     (8-17)

where  F = discharge concentration of tracer, mg/1
       Ft = observed concentration of  tracer, mg/1

If no tracer  is  used and conditions approximating plug flow exist, then:

                             k = -ln(Ct/C0)/t                        (8-18)

where  CQ = concentration of  coliforms at the base sampling site, MPN
           or  count/100 ml

     Regardless of  the technique used for estimating k, it is important to
concurrently quantify, to  the extent possible,  those variables which
influence  k.  For example,  light levels should be measured or at  least
estimated over  the period for which k  is estimated.  If  this is  not  done,
and if the  effects of the important parameters are not taken into account in
modeling coliforms, serious errors will  result.  Table 8-9 shows how serious
such  errors  can be.  The data show T-90 values for coliforms as a function
                                   448

-------
               TABLE 8-9.  EXPERIMENTAL HOURLY T-90 VALUES
                       (AFTER WALLIS, ET AL., 1977)
Time of Day
0100
0200
0300
0400
0500
0600
0700
0800
T-90
(hours)
40
40
40
40
40
19
8.0
4.6
Time of Day
0900
1000
1100
1200
1300
1400
1500
1600
T-90
(hours)
3.2
2.5
2.3
2.5
2.9
3.3
3.9
4.6
Time of Day
1700
1800
1900
2000
2100
2200
2300
2400
T-90
(hours)
5.3
6.7
8.5
11
14
20
27
34

of  incident light.  T-90  values are the times  required for 90 percent
mortality.   The  associated k values are  .058 hr~  in the dark  and  .1 hr~  at
midday.   It is clear that estimating a single value for a k could  result in
greater  than order-of-magnitude errors.

8.4  SUMMARY
     The coliform  group is of  interest  as an index of potential pathogen
contamination  in  surface  waters and has  become  one of the more  commonly
modeled  water quality parameters.   Modeling coliforms usually  involves the
use of a simple first-order decay expression  to  describe disappearance.
Since regrowth is generally neglected,  no  growth terms are normally included
in the model.

     The disappearance rate, k, is  a function of a number of variables, the
effects of  all of which are not well  understood.  It now appears  that  light
(in  the near-UV  and visible range)  is  important as are  a number of

                                    449

-------
physicochemical factors.   Rates of disappearance are  also sensitive to  the
salinity of  the water which  also  affects the  influence of light  on

disappearance rates.


8.5  REFERENCES

Anderson,  D.R.,  J.A. Dracup, T.J.  Fogarty, and R.  Willis, 1976.   Water
Quality Modeling of Deep Reservoirs, Journal Water Pollution Control
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Baca, R.G.  and R.C. Arnett,  1976.  A Limnological Model  for Eutrophic Lakes
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Baross,  J.A.,  F.J. Hanus, R.Y. Morita, 1975.  Survival  of Human Enteric  and
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Bel lair,  J.T., G.A. Parr-Smith,  I.G. Wallis, 1977.   Significance of Diurnal
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Bissonette,  G.K.,  J.J. Jezeski, G.A. McFeters,  D.G. Stuart, 1977. Evaluation
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Bitton,  G.,  1980.  Introduction to Environmental  Virology,  John Wiley & Sons,
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Chamberlin,  C.E.,  1977.   A Model  of Coliform Bacteria Survival in Seawater,
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Chamberlin, C.E., 1982.  Physical  Influences on  the  Survival of Enteric
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Chen, C.W.,  1970.  Concepts and Utilities of Ecological  Model, ASCE,  Journal
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Chen,  C.W. and  G.T.  Orlob,  1975.   Ecological  Simulation of Aquatic
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                                   450

-------
Chen,  C.W.  and  J. Wells, 1975.  Boise River Water Quality-Ecological  Model
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Chen,  C.  W., M.  Lorenzen, D. J. Smith,  1975.  A comprehensive Water  Quality
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Chen,  C.  W., D. J. Smith  and S.  S. Lee, 1976a.   Documentation of Water
Quality Models  for the  Helms Pumped Storage Project, Prepared for  Pacific
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Chojnowski, K.J., J.L.  Mancini, J.S. Jeris,  1979.   Influence of Light on
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2539.

Clausen,  E.M.,  B.L. Green, W. Litsky, 1977.   Fecal Streptococci:  Indicators
of Pollution, Bacterial Indicators/Health Hazards  Associated with  Water,
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Cooper,  W.J. and R.G. Zika,  1983.  Photochemical  Formation of Hydrogen
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Dufour,  A.P.,  1977.   Escherichia coli:  the Fecal  Coliform, Bacterial
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Evans, F.L., E.E. Goldreich, S.R.  Weibel, and G.G. Robeck,  1968.  Treatment
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Gameson,  A.L.H. and D.J.  Gould,  1975. In Proc. Int.  Symp. on Discharge of
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                                   451

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Gannon,  J.J.,  M.K.  Busse,  J.E. Schillinger, 1983.Fecal Coliform
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Geldreich,  E.E.  and B.A. Kenner,  1969.  Concepts  in Fecal Streptococci  in
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Kapuscinski,  R.B. and  R.  Mitchell, 1983.   Sunlight-Induced Mortality of
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