EPA-440/1-77-011
          A STUDY OF THE ENVIRONMENTAL BENEFITS OF
         PROPOSED BATEA AND NSPS EFFLUENT LIMITATIONS
         FOR THE OFFSHORE SEGMENT OF THE OIL AND GAS
              EXTRACTION POINT SOURCE CATEGORY
                          MAY 1977
              ENVIRONMENTAL PROTECTION AGENCY
           OFFICE OF WATER PLANNING AND STANDARDS
                    WASHINGTON, D.C.  20460

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EPA 44071-77-011
                   A STUDY OF THE ENVIRONMENTAL BENEFITS
               OF PROPOSED BATEA AND NSPS EFFLUENT LIMITATIONS
                 FOR THE OFFSHORE SEGMENT OF THE OIL AND GAS
                      EXTRACTION POINT SOURCE CATEGORY
                            CONTRACT NO. 68-01-4177
                     OFFICE OF WATER PLANNING AND STANDARDS
                      U.S. ENVIRONMENTAL PROTECTION AGENCY
                               WASHINGTON, D.C.
                         PROJECT OFFICER: A. MONTRONE
                                   May 1977

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This Page Intentionally Blank

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This report was prepared by Robert Shore,
Joseph Post, Myron Allen, Lisa Levin, and
William Taffel, Energy Resources Company Inc.,
Cambridge, Massachusetts, under contract
to the U.S. Environmental Protection Agency,
Anthony Montrone, Project Officer.  The
authors wish to express their appreciation to
Mr. Montrone for his helpful comments and
suggestions in the performance of this project.

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                      TABLE OF CONTENTS

                                                            Page
               LIST OF FIGURES                               v

               LIST OF TABLES                                ix

               PREFACE                                       xiii

               SUMMARY                                       xv

CHAPTER ONE    INTRODUCTION                                   1
  1.1  The Nature of the Problem:  Summary                    1
  1.2  Policy Background:  The Effluent Guidelines            2

CHAPTER TWO    PROJECT METHODOLOGY                            9
  2.1  General Outline                                        9
  2.2  Details of Project Methodology                        12
       2.2.1  Choice of Contaminants                         12
       2.2.2  Site Selection                                 12
       2.2.3  Characterization of Produced Water             13
       2.2.4  Fates of Contaminants in Discharged            16
              Produced Water
       2.2.5  Toxicology                                     18
       2.2.6  Ecological Characterization of Sites           18
       2.2.7  Impacts                                        19

CHAPTER THREE  COMPOSITION OF OILFIELD BRINES                21
  3.1  Major Cations and Anions:  Salinity                   22
  3.2  Trace Heavy Metals in Oilfield Brines                 22
       3.2.1  Heavy Metals and Other Constituents in         22
              Louisiana Produced Waters
       3.2.2  Heavy Metals and Other Constituents in         26
              Alaska Produced Waters
  3.3  Hydrocarbons in Oilfield Brines                       26
  3.4  Treatment Processes for Oilfield Brines               34


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                  TABLE OF CONTENTS  (CONT.)





                                                             Page





CHAPTER FOUR   DISPERSION MODELING                            39
4.1
4.2
4.3
4.4
Introduction
Simple Tidal Flushing Calculations for Shallow,
Enclosed Bays
Description of the Dispersion Model
Summary of Model Parameters
CHAPTER FIVE RESULTS OF CALCULATIONS WITH DISPERSION
5.1
5.2
5.3
5.4
5.5
5.6
MODEL
Introduction
Calculation Methodology
Hackberry Bay, Louisiana
Cook Inlet, Alaska
Near Offshore Gulf Waters
Far Offshore Gulf of Mexico Waters
CHAPTER SIX METHODOLOGY FOR IMPACT ASSESSMENT
6.1
6.2
6.3









6.4
Introduction
Methodology
Toxicity Data
6.3.1 Introduction
6.3.2 Sublethal Effects
6.3.3 Restrictions of the Data Base
6.3.4 Interpretation of Data
6.3.5 Adaptation Responses
6.3.6 Synergisms and Antagonisms
6.3.7 Interactions Between Metals and Other
Stressors
6.3.8 Note on Cyanide Toxicity
Effects of Salinity
39
39
44
52
55
55
55
65
68
71
77
109
109
109
114
114
145
147
152
162
162
168

168
169
                               -11-

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                  TABLE OF CONTENTS (CONT.)

                                                            Page

  6.5  Studies of Brine Toxicity and of the  Effects of      173
       Brine Discharges at Offshore Production Sites
  6.6  Human Health Risks Associated with Oilfield Brines   182
       6.6.1  Bioaccumulation of Trace Metals               183
       6.6.2  Hydrocarbon Bioaccumulation                   186
       6.6.3  Hazards of Methylmercury Contamination of     187
              Marine Organisms
       6.6.4  Human Health Impacts of Benz[a]pyrene         188

CHAPTER SEVEN  IMPACT ASSESSMENT                            191
  7.1  Introduction                                         191
  7.2  Results of the Hackberry Bay Assessment              195
       7.2.1  Area/Concentration Relationships              195
       7.2.2  Numerical Data Used in Impacts Analysis       198
       7.2.3  Difficulties Involved in Use of Application   203
              Factors
       7.2.4  Numerical Calculations for Hackberry Bay      204
       7.2.5  Ecological Considerations                     206
       7.2.6  Delineation of Alternative Impact Zones       207
  7.3  Analysis of Impacts at Other Sites:  General         207
       Comments
  7.4  Analysis of Impacts at Cook Inlet                    209
       7.4.1  Area/Concentration Relationships              209
       7.4.2  Ecological Considerations                     209
  7.5  Analysis of Impacts at Grand Isle                    212
       7.5.1  Area/Concentration Relationships              212
       7.5.2  Ecological Considerations                     214
  7.6  Analysis of Impacts at the Far Offshore Gulf of      214
       Mexico Site
       7.6.1  Area/Concentration Relationships              214
       7.6.2  Ecological Considerations                     214
                             -111-

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                  TABLE OF CONTENTS  (CONT.)
                                                             Page
  7.7  Summary of Impacts Analysis                           214
  7.8  Comments on Agreement of  Results  with Field Studies  214
CHAPTER EIGHT  CONCLUSIONS
                                              221
APPENDIX A

APPENDIX B

APPENDIX C


APPENDIX D

APPENDIX E


APPENDIX F
ECOLOGICAL CHARACTERIZATION OF  STUDY  SITES    227

DESCRIPTION OF DISPERSION MODELS              297

FATES OF HYDROCARBONS AND TRACE METALS        333
IN THE MARINE ENVIRONMENT

PRODUCTION PLATFORM AND DISCHARGE  DATA        353

CALCULATION OF DISPERSION MODEL INPUT        357
PARAMETER VALUES

HYDROCARBON BIOACCUMULATION                   369
                              -IV-

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                       LIST OF FIGURES
CHAPTER ONE

     1-1


     1-2
INTRODUCTION

The Baseline Dividing Onshore and Offshore
Regions of the Coastal Sea
Location of the Coastal Baseline in Cook
Inlet
 6

 7
CHAPTER TWO

     2-1



     2-2


     2-3

     2-4
PROJECT METHODOLOGY

Flowchart of Procedure for Assessing
Benefits of Proposed Offshore Oil and
Gas Effluent Regulations

Location of Gulf of Mexico Production
Sites
Location of Cook Inlet Production Sites
A Typical Set of Isodilution Contours
11
14


15
17
CHAPTER THREE  COMPOSITION OF OILFIELD BRINES
CHAPTER FOUR   DISPERSION MODELING
     4-1

     4-2

     4-3

     4-4

     4-5

     4-6
Tidal Flushing Calculation
Location of Hackberry Bay Study Area

Advection Due to Uniform, Steady Flow
Diffusion Due to Turbulent Flow
Dispersion of Brine Discharges
Forces Affecting Brine Dispersion
42

43

46
47

51

53
CHAPTER FIVE

     5-1

     5-2
RESULTS OF CALCULATIONS WITH DISPERSION MODEL

Isopleths for Near Offshore Site

Area/Concentration Curve for Same Site as
Used in Figure 5-1
58

59
                              -v-

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              LIST OF FIGURES (CONT.)
5-3       Plots of Area/Concentration Curves for         61
          for Sensitivity Analyses Performed for
          Hackberry Bay Site

5-4       Area/Concentration Curves for Cook Inlet       72

5-5       Area/Concentration Curve for Grand Isle        78
          Site in Near Offshore Gulf of Mexico

5-6       Area/Concentration Curve for Far Offshore      82
          Gulf of Mexico Site

5-7a      Percent Dilution Isopleths, Hackberry Bay,  La.  83
          HI:  Base Case

5-7b      Percent Dilution Isopleths, Hackberry Bay,  La.  84
          H2:  Diffusion Coefficient Sensitivity
5-7c      Percent Dilution Isopleths, Hackberry Bay,  La.  85
          H3:  Diffusion Coefficient Sensitivity

5-7d      Percent Dilution Isopleths, Hackberry Bay,  La.  86
          H4:  Initial Dilution Sensitivity

5-7e      Percent Dilution Isopleths, Hackberry Bay,  La.  87
          H5:  Initial Dilution Sensitivity

5-1f      Percent Dilution Isopleths, Hackberry Bay,  La.  88
          H6:  Tidal Velocity Sensitivity

5-7g      Percent Dilution Isopleths, Hackberry Bay,  La.  89
          H7:  Freshwater Current Velocity  Sensitivity

5-7h      Percent Dilution Isopleths, Hackberry Bay,  La.  go
          H8:  Freshwater Current Velocity  Sensitivity
5-7i      Percent Dilution Isopleths, Hackberry Bay,  La.  91
          H9:  Rotational Tidal Current Sensitivity

5-8a      Percent Dilution Isopleths, Trading Bay        92
          Facility, Cook Inlet, Alaska
          Cl:  Base Case

5-8b      Percent Dilution Isopleths, Trading Bay        93
          Facility, Cook Inlet, Alaska
          C2:  Diffusion Coefficient Sensitivity

5-8c      Percent Dilution Isopleths, Trading Bay        94
          Facility, Cook Inlet, Alaska
          C3:  Diffusion Coefficient Sensitivity

5-8d      Percent Dilution Isopleths, Granite Point      95
          Facility, Cook Inlet, Alaska
          C4:  Base Case
                        -vi-

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                   LIST OF FIGURES (CONT.)
     5-8e      Percent Dilution Isopleths, Granite Point      96
               Facility, Cook Inlet, Alaska
               C5:  Diffusion Coefficient Sensitivity

     5-9a      Near Offshore Dilution Percentage Isopleths    97
               N1A:  Base Case

     5-9b      Near Offshore Dilution Percentage Isopleths    98
               NIB:  Dilution Sensitivity

     5-9c      Near Offshore Dilution Percentage Isopleths    99
               NIC:  Current Velocity Sensitivity

     5-9d      Near Offshore Dilution Percentage Isopleths   100
               NlD:  Discharge Rate Sensitivity

     5-9e      Near Offshore Dilution Percentage Isopleths   101
               NlE:  Diffusion Coefficient Sensitivity

     5-9f      Near Offshore Dilution Percentage Isopleths   102
               N2A:  Base Case

     5-9g      Near Offshore Dilution Percentage Isopleths   103
               N2B:  Current Velocity Sensitivity

     5-9h      Near Offshore Dilution Percentage Isopleths   104
               N2C:  Diffusion Coefficient Sensitivity
     5-10a     Far Offshore Dilution Percentage Isopleths    105
               Fl:  Base Case
     5-10b     Far Offshore Dilution Percentage Isopleths    106
               F2:  Current Velocity Sensitivity

     5-10c     Far Offshore Dilution Percentage Isopleths    107
               F3 :  Diffusion Coefficient Sensitivity

     5-10d     Far Offshore Dilution Percentage Isopleths    108
               F4:  Initial Dilution Sensitivity
CHAPTER SIX    METHODOLOGY FOR IMPACT ASSESSMENT

     6-1       Outline of the Analysis                       110

     6-2       Explanation of Toxicity Tables                115
     6-3       Median Mortality-Times of Young Atlantic      159
               Salmon Exposed to Solutions of Copper and
               Zinc
     6-4       Comparison of  Median  Mortality-Times  of        164
               Young  Atlantic Salmon Exposed  to  Solutions
               Copper,  Zinc,  and Mixtures
                              -via. -

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                   LIST OF FIGURES (CONT.)
     6-5       Effects of Bipartite Mixtures of Equi-      166
               toxic Concentrations of Copper Sodium
               Citrate and Mercuric Chloride, Mercuric
               Iodide, and Ethylmercuric on the Survival
               of Artemia Larvae in Seawater

     6-6       Estimate of Percent Mortality of First      171
               Stage Zoeae of Sesarma cinerium

     6-7       Survival of Larval Tropical and Temperate   172
               Zone Fiddler Crabs Exposed to Different
               Salinities at 38° C

     6-8       Net Yield of Oysters at Various Distances   177
               from the Lake Barre Brine Discharge
     6-9       Trinity Field, Trinity Bay - Number of      179
               Species in Relation to the Brine Discharge
               at F, Platform Bottom Samples


CHAPTER SEVEN  IMPACT ASSESSMENT
     7-1       Outline of the Analysis                     192

     7-2       Typical Set of Isopleths for Hackberry      196
               Bay Site (Base Case)
     7-3       Plots of Area/Concentration Curves for      197
               Sensitivity Analyses Performed for Hack-
               berry Bay Site.
     7-4       Area/Concentration Curves for Cook Inlet    210
     7-5       Map of Cook Inlet                           211
                              -viii-

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                       LIST OF TABLES
CHAPTER ONE

     1-1.
     1-2


     1-3
INTRODUCTION

Contaminants Considered in the Study

Offshore Segment - Oil and Gas Extraction
Industry Effluent Limitations - BPCTCA

Offshore Segment - Oil and Gas Extraction
Industry Effluent Limitations - BATEA and
New Source
 1

 4
CHAPTER TWO

     2-1

     2-2
PROJECT METHODOLOGY
Contaminants Considered in the Study
Important Site Specific Features of the
Analysis
12
13
CHAPTER THREE  COMPOSITION OF OILFIELD BRINES
3-1
3-2
3-3
3-4
3-5
Major Cations and Anions in Oilfield Brines
Trace Heavy Metals in Oilfield Brines
Results of Analyses of Oilfield Brine
Discharged at Baytown, Texas
Produced Water Constituents
Hydrocarbon Concentrations of Crude Oil
23
24
25
27
30
     3-6
     3-7
     3-8
Water-Soluble Fractions

Aromatic and n-Paraffin Content of South
Louisiana and Kuwait Crude Oils and
their Water-Soluble Fractions  (WSF) and
Calculated Aromatic-Enrichment Factors
(AEF)

Hydrocarbon Composition of Aqueous Phase
of 1,000 ppm of Oil-in-Water Dispersions
(OWD) and Effects of 24-Hour Aeration

Performance of Treatment Systems
Louisiana Coastal
32
33
36
                               -ix-

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                   LIST OF TABLES (CONT.)
CHAPTER FOUR   DISPERSION MODELING
CHAPTER FIVE   RESULTS OF CALCULATIONS WITH DISPERSION MODEL
5-1
5-2
5-3
5-4
5-5
5-6
5-7
5-8
5-9
Qualitative Influence in Input Parameters
on Concentration Distribution
Listing of Computer Calculations Performed
for the Hackberry Bay Site
Parameter Values for Hackberry Bay
Calculations
Listing of Computer Calculations Performed
for Cook Inlet, Alaska
Parameter Values for Cook Inlet
Calculations
Listing of Computer Calculations Performed
for the Near Offshore Gulf of Mexico Site
Parameter Values for Near Offshore Gulf
of Mexico Calculations
Listing of Computer Calculations Performed
for the Far Offshore Gulf of Mexico Site
Parameter Values for Far Offshore Gulf
62
66
67
69
70
73
74
79
80
               of Mexico Calculations
CHAPTER SIX
     6-1

     6-2
     6-3
     6-4
     6-5
     6-6
     6-7
     6-8
     6-9
METHODOLOGY FOR IMPACT ASSESSMENT
EPA Water Quality Criteria for Brine
Constituents
Toxicity Table - Copper
Toxicity Table - Zinc
Toxicity Table - Chromium
Toxicity Table - Lead
Toxicity Table - Mercury
Toxicity Table - Silver
Toxicity Table - Cadmium
Toxicity Table - Crude Oils
112

116
118
119
120
121
122
123
126
                               -x-

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                   LIST OF TABLES (CONT.)
                                                            Paqe
     6-10
     6-11
     6-12
     6-13
     6-14

     6-15
     6-16

     6-17

     6-18
Toxicity Table - Nickel                      130
Toxicity Table - Phenol                      131
Toxicity Table - Arsenic                     132
Effects of Crude Oil Fractions               133
Factors Influencing the Toxicity of Heavy    153
Metals to Aquatic Organisms
Factors Affecting Petroleum Toxicity         156
Effect of Mercury and Copper on the Marine   165
Copepod Nitocra  (Percent Mortality)
Effects of Mercury, Lead and Zinc on the     167
Growth Rate of Cristigera
Bioassay Data on Oilfield Brines from        181
Chiltipin Creek Area (Texas)
CHAPTER SEVEN  IMPACT ASSESSMENT
     7-1
     7-2
     7-3

     7-4

     7-5
Values of Important Numerical Parameters     199
Calculations for Hackberry Bay               205
Types of Effects Reported in the Literature  208
for Silver at Various Ranges of Concen-
trations Found Inside the "Unsafe" Zone
Key Consumers - Near and Far Offshore Gulf   215
Waters
Summary of Impacts                           217
CHAPTER EIGHT  CONCLUSIONS
     8-1
Summary of Impacts
223
                             -xi-

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                           PREFACE
     The attached draft document is a contractor's study
prepared for the Office of Analysis and Evaluation of the
Environmental Protection Agency (EPA).   The purpose of the
study is to discuss the environmental benefits which could
result from the application of Best Available Technology
Economically Achievable (BATEA) effluent limitations and New
Source Performance Standards (NSPS) to be established under
sections 304 (b) and 306 of the Federal Water Pollution
Control Act, as amended for  the Offshore segment of the Oil
and Gas Extraction point source category.

     This study supplements the technical study (EPA Develop-
ment Document)  and economic study  (EPA Economic Impact
Analysis) supporting the issuance of proposed regulations
under sections 304(b)  and 306.   The Development Document
surveys existing and potential waste treatment control
methods and technology within particular industrial point
source categories and supports proposal of certain effluent
limitation guidelines and standards of performance based
upon an analysis of the feasibility of these guidelines and
standards in accordance with the requirements of sections
304(b) and 306 of the Act.  Presented in the Development
Document are the investment and operating costs associated
with the various alternative control and treatment technologies.
The Economic Impact Analysis provides further analysis by
estimating the broader economic effects which might result
from the required application of various control methods and
technologies.  The Economic Impact Analysis investigates the
effect of alternative approaches in terms of product price
increases, effects upon production and employment, the
continued viability of affected wells,  effects upon foreign
trade and other competitive effects.  The attached document
supplements this analysis by attempting to examine the
environmental benefits which would result from the implemen-
tation of the guidelines and standards.  This study investigates
the effects of produced water  (the brine produced in the
wells along with the oil and gas)  on marine and estuarine
biota, and on human beings.  This study does not purport to
be an analysis to balance the costs of implementing the
BATEA and NSPS regulations with the benefits of these regu-
lations nor does the study address any benefits other than
those direct environmental benefits mentioned above.

     This study has been prepared with the supervision and
review of the Office of Water Planning and Standards of the
EPA.  This report was submitted in partial fulfillment of
                            -xiii-

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Contract No. 68-01-4177 by Energy Resources Company Inc.
This report reflects work completed as of April 1977.  This
study was undertaken in a spirit of cooperation with concerned
parties whose position was that these limitations and standards
would do little to benefit the environment.  This report in
no way signals a departure from the Agency policy of developing
technology based standards nor does it in any way reflect a
change in the Agency determination that this type of study
is not required as part of its rulemaking procedure.

     This draft report is not an official EPA publication.
The study will be considered along with the information con-
tained in the Development Document and Economic Impact
Analysis and any comments received by EPA on these documents
before or during proposed rulemaking proceedings necessary
to establish final regulations.  Prior to final promulgation
of regulations, the accompanying study shall have standing
in any EPA proceeding or court proceeding only to the extent
that it represents the views of the contractor who studied
the subject industry.  It cannot be cited, referenced, or
represented in any respect in any such proceeding as a
statement of EPA's views regarding the subject industry.
                             -xxv-

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                           SUMMARY
     The purpose of this study is to attempt to examine the
environmental benefits which would result from the implemen-
tation of the Best Available Technology Economically Achiev-
able (BATEA) and New Source Effluent Limitations for the
offshore segment of the oil and gas extraction industry,
published by the Effluent Guidelines Division of the Office
of Water and Hazardous Materials, U.S. Environmental Protec-
tion Agency  (EPA).-'-  The major concern of these effluent
limitations is with the produced water (the brine produced
in the wells along with the oil or gas) that is discharged
into receiving waters after separation of oil or gas from
the brine has been effected by separation devices on the
production platforms.  Produced oilfield brines contain
substances, such as oil hydrocarbons and trace metals, with
toxic effects on marine and estuarine biota, and on human
beings.

     The BATEA and New Source regulations prohibit the
discharge of produced water into near offshore waters and
restrict the oil hydrocarbon content of produced water
discharged into far offshore waters.  Regulations similar to
the near offshore regulations are being considered for
onshore coastal waters (e.g., coastal bays and inlets).  The
BATEA regulations for near offshore waters have been the
subject of considerable criticism by the oil industry.  The
oil industry has claimed that the discharge of produced
water has only an insignificant impact on the coastal
environment, and hence, the considerable costs that would be
involved in implementing the no-discharge limitation are
unjustified in terms of the benefits that can be expected to
result.  In order to assess the merits of this claim, the
EPA has supported this study, whose objective is to attempt
to evaluate the benefits that may be expected to result from
implementation of the effluent regulations.

     The methodology adopted in this study was to assess
expected benefits of the effluent regulations at four
specific sites:  two in onshore coastal waters, and one each
in near and far offshore waters.  Benefits were measured in
terms of the reduced levels of brine-related impacts which
could be expected to result from the•BATEA regulations.
      U.S. Environmental Protection Agency, Development
Document for Interim Final Effluent Limitations Guidelines
and New Source Performance Standards for the Offshore
Segment of the Oil and Gas Extraction Point Source Category,
1975.

                            -xv-

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Impacts were evaluated in terms of (1) the area of an
"unsafe zone" surrounding the point of discharge (i.e., the
area that was predicted to be subjected to brine contami-
nants at concentration levels known to have toxic effects on
marine biota, or to present a potential human health threat
because of the bioaccumulation of contaminants in the
tissues of marine organisms used for food); (2) the relative
size of the unsafe zone compared to the size of the receiv-
ing waterbody; and (3) the biological productivity of the
impacted zone.  The major conclusions of this study follow.
•    Toxic Substances in Produced Water

     Produced brines contain a variety of substances known
to have lethal and sublethal toxic effects on marine and
estuarine organisms.  These toxic constituents include oil
hydrocarbons, trace metals  (including arsenic, cadmium,
chromium, copper, lead, mercury, nickel, silver, and zinc),
phenol, and cyanide.  Some of these toxicants have been
measured in produced waters at concentrations up to several
orders of magnitude higher than toxicologically safe levels.
In addition to their effect on marine organisms, some of the
brine components  (particularly mercury and the polynuclear
aromatic hydrocarbon benz[a]pyrene) are known to be bioaccu-
mulated in shellfish which may be used for human consump-
tion, and so present a potential human health threat.
*    Treatment Methods

     Current methods used for separating oil hydrocarbons
from produced water have little, if any, effect on levels of
dissolved contaminants.  These include the dissolved aro-
matic hydrocarbons which are among the most toxic hydro-
carbon components of brines, and the trace metals.
•    Benefits for Onshore Coastal Waters

     The benefits which would be achieved if the proposed
near offshore BATEA regulations are extended to apply to
discharges in onshore coastal waters are highly site spe-
cific.  Small, enclosed, shallow, and biologically produc-
tive bays with large brine discharges will probably stand to
benefit considerably.  The benefits to be achieved by
prohibiting  small discharges of produced water into larger
and deeper coastal embayments with adequate tidal and
freshwater mixing are likely to be correspondingly small.
                             -xvi-

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•    Near Offshore Benefits

     In near offshore Gulf of Mexico waters, the analysis
performed for a single site is insufficient to serve as a
complete basis for estimating regional impacts.  In order to
extrapolate from impact at a single platform to regional
impacts, data on platform locations and discharge rates
throughout the region are needed.  The benefits to be
achieved by prohibiting the discharge of produced waters
into near offshore waters will depend critically on the
density of production platforms and rates of discharge in a
particular region.  In areas where platforms are highly
concentrated, aggregate discharge levels are likely to be
large, and impact zones may overlap.  In such areas signi-
ficant benefits could probably be achieved.  In areas with
low platform densities and only small rates of brine dis-
charge the benefits are likely to be less pronounced.  The
analysis performed in this study should, therefore, be
supplemented by the assembly of a data base providing
information on the location and discharge rates of produc-
tion platforms in near offshore Gulf of Mexico waters.
•    Far Offshore Benefits

     In far offshore Gulf of Mexico waters, the major con-
clusion to be drawn from this study is that there would
probably be little reduction in impacts resulting from the
imposition of BATEA regulations over and above those already
achieved by the BPCTCA restrictions.  The more stringent
treatment requirements imposed on far offshore platforms by
the BATEA requirements will do little to remove the dis-
solved hydrocarbons and trace metals which are responsible
for much of the toxic impact of oilfield brines.

     These conclusions are documented and amplified in the
main body of this report.  The individual chapters of the
report are summarized in the remainder of this section.
•    Chapter One:  Introduction

     Oil extracted at offshore oil production platforms is
found to be mixed with a saline solution which, when sep-
arated from the oil, is known as produced water or oilfield
brine.  After separation from the oil, this brine is fre-
quently discharged into the estuary, bay, or open ocean in
which the platform is located.  Oilfield brines are gener-
ally highly saline — much more so than seawater — and
contain a variety of components known to be toxic to marine
                             -xvii-

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and coastal life, including oil hydrocarbons, phenols,
cyanide, arsenic, silver, nickel, chromium, copper, lead,
mercury, and cadmium.  Since brine constituents have a
demonstrated toxicity to marine life, and since they may be
bioaccumulated by marine organisms destined for human
consumption, their discharge into the ocean is a source of
concern for environmental policy makers.  In response to
this concern, the U.S. Environmental Protection Agency  (EPA)
has published a set of effluent limitations for the offshore
segment of the oil and gas extraction industry in order to
prevent any adverse effects which may be associated with
brine discharge.  These guidelines include Best Practicable
Control Technology Currently Available  (BPCTCA) regulations
which take effect in July 1977 and Best Available Technology
Economically Achievable  (BATEA) and New Source regulations
which take effect for existing sources in June 1983.  The
1983 regulations require zero produced water discharge  in
near offshore waters.  Similar regulations are being con-
sidered for oil production in onshore waters inside the
coastal baseline  (a legal demarcation line constructed  as a
"smoothed" version of the actual coast.  Inland bays such as
Barataria Bay, which contains significant oil production
activity, are inside this demarcation line).  Less stringent
BATEA requirements are imposed on far offshore oil platforms
(i.e., those lying outside of the 3-mile limit).  The far
offshore regulations require only reduced, rather than  zero,
oil discharge.  Since the expense of implementing the BATEA
regulations is expected to be great, it is important to
assess the level of benefits which could be achieved by
their implementation.  The analysis in this report is
addressed to that issue.
•    Chapter Two:  Project Methodology

     An approach was developed for analyzing the environ-
mental impacts of brine discharges in a site specific
fashion.  For each site a "zone of impact" is defined inside
of which particular levels of adverse effects can be ex-
pected to occur.  The site can then be characterized by the
area of the zone of impact, by the percent of the receiving
waterbody which it covers  (in the case of an enclosed
waterbody such as Hackberry Bay), and by the ecological
importance of the area being impacted.  Two classes of
adverse effects are considered:  toxic impacts on marine
communities  (fish, benthos, plankton), and potential toxic
impacts on humans as a result of the bioaccumulation of
brine constituents in food organisms.  Specific brine
components considered in the analysis are oil hydrocarbons,
cadmium, silver, copper, chromium, mercury, lead, nickel,
arsenic, zinc, cyanide, and phenol.
                            -xviii-

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     The analysis contains four principal steps:   (1) data
are collected on the concentrations of particular pollutants
in oilfield brines and of the volumes of brine discharged at
each site; (2) a computer dispersion model is used to
predict the quasi-steady state concentrations of each of
these constituents in the vicinity of the production plat-
form; (3) the nature and level of impacts associated with
various concentrations of each contaminants are determined,
and "safe" concentrations are estimated; and  (4) the areas
of impact zones are determined.

     The report focuses on four oil production sites:  two
onshore  (Hackberry Bay, Louisiana, and Cook Inlet, Alaska),
one near offshore (Grand Isle), and one far offshore (in the
Gulf of Mexico).
•    Chapter Three:  Composition of Oilfield Brines

     Oilfield brines contain trace metals, oil-derived
hydrocarbons, and a number of other toxicants including
ammonia and cyanide.  The brines are also highly saline.
Although some studies have been done on the trace metal
composition of oilfield brines, little is known about the
specific hydrocarbon components.  In general, these hydro-
carbons cannot be expected to occur in the same relative
concentrations at which they occur in crude oil, since the
more water-soluble components will be preferentially concen-
trated in the oilfield brines.  In particular, the brines
will be relatively enriched in aromatic hydrocarbons.  This
is significant since the aromatic components of crude oil
are those which create the most severe toxicity problems.
Some inference relating to the hydrocarbon composition of
oilfield brines can be made by analogy with data on the
composition of the so-called water-soluble fraction of crude
oil.

     Concentrations of trace metals in produced water vary
considerably from region to region and even from site to
site within the same region.  Some of the metals have been
measured at concentrations up to several orders of magnitude
higher than toxicologically safe levels.

     A number of treatment processes are available for
reducing the levels of oil contamination in produced waters,
but these generally only reduce the levels of suspended
contaminants in the brine.  As a result, they have little or
no effect on trace metal levels or on dissolved hydrocarbon
concentrations.  One treatment process, gas flotation, may
                           -xix-

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result in oxidation of some of the dissolved hydrocarbon
components, but it will be predominantly the non-aromatic
components which will be affected by this process.
•    Chapter Four:  Dispersion Modeling

     A plume of produced water discharged from an offshore
oil platform will disperse under the influence of three
principal forces:  advection (movement with the prevailing
current), diffusion ("spreading" of the plume due to spatial
inhomogeneities in the current field), and decay (loss of
brine constituents due to sedimentation, adsorption, or
biodegradation).   Advection will be influenced principally
by current velocity and direction; in general, there will be
two current components, a "steady" component  (due in an
estuary, for example, to the continuous influx of fresh-
water) and a periodically varying tidal component.  The
diffusion of a plume can be characterized by a set of three
diffusion coefficients  (one for each of three mutually
perpendicular directions) whose magnitude in general will
depend both on the scale  (size) of the pollutant plume and
on site specific dispersion characteristics.

     The dispersion of brine under the influence of these
three forces can be modelled by a set of differential
equations and associated boundary conditions as described in
detail in Appendix B.  These in turn can be solved numeri-
cally by a computer program which predicts quasi-steady
state concentration distributions through a tidal cycle.
Such a program was used in this project to predict tidally
averaged pollutant concentrations and to locate a series of
isopleths, or lines of equal predicted pollutant concentra-
tion.

     Isopleths were plotted for several concentrations at
each site, and the areas they enclosed were measured by
planimetry.  Area versus concentration curves  (showing the
total area at each site over which the pollutant concen-
tration is greater than or equal to a particular value) were
then drawn for each site.  Several model runs were made for
each site, using several sets of plausible values for input
parameters for which precise quantitative data were not
available  (the computer model requires a number of input
parameters, including volume of brine discharged, current
velocities and directions, magnitude of various diffusion
coefficients, and water depth at the discharge point).  For
each site best, worst,  and base case area versus concen-
tration curves were then defined.
                             -xx-

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•    Chapter Five:   Results of Calculations with Dispersion
     Model

     Each of the input parameters required by the model is
described in this chapter, and their qualitative effect on
final pollutant concentrations are discussed.  The deter-
mination of precise values for some of these parameters
would require extensive field studies at each site, so some
estimates were based on previous empirical and theoretical
work.  The rationale for the base values and ranges used for
the input parameters are discussed.

     In general, predicted brine concentrations showed a
high degree of site specific variability.
•    Chapter Six;  Methodology for Impact Assessment

     The toxicological data on the effects of oilfield brine
components were reviewed, and used to make estimates of
"safe" levels of brine constituents.  Safe levels were
defined which would prevent significant toxic impacts on
marine communities and prevent the bioaccumulation of brine
constituents to dangerous levels by human food organisms.  A
number of factors which may modify the toxicity of brine
components in the marine environment, including adsorption,
sedimentation, biodegradation, complexation, synergistic or
antagonistic interactions with other pollutants, and inter-
actions with the ef.fects of other environmental stresses,
are discussed.  Because of the lack of sufficient data,
these factors are not used in the quantitative analysis.
The chapter also discusses the available field data on
ecological impacts in areas surrounding offshore oil produc-
tion platforms.
•    Chapter Seven:  Impact Analysis

     Using data on safe levels in conjunction with data on
levels of each constituent in the discharged brine, a
Necessary Dilution Factor  (NDF) was calculated separately
for each constituent (this was the dilution necessary to
reduce the concentration of the constituent to its "safe"
level).  An analysis which assumed purely additive (i.e.,
neither synergistic nor antagonistic) interactions between
the toxic effects of different brine constituents was also
used to define an overall  safe level for brine itself, and
the necessary dilution factor implied by it.  Area versus
concentration curves for each site were then used to deter-
mine the area over which the actual brine dilution would be
                              -xxi-

-------
less than or equal to its NDF.  This was used as an estimate
of the impacted area for each site.  Qualitative ecological
desciptions of each site were also used in a discussion of
the relative ecological and economic importance of the areas
being impacted.

     The areas of the impact zones are highly site specific,
and depend to a significant extent on site specific dis-
persion patterns.  The severest impacts would probably be
felt in relatively small, enclosed, and highly fertile
regions such as Hackberry  Bay, and significant benefits
would probably result from the imposition of no-discharge
requirements in these areas.  Smaller benefits would prob-
ably result at sites such as mid Cook Inlet, where the
impacted area is relatively small, where there are no
significant fisheries or shellfish beds, and which is
relatively nonproductive due to high levels of tidal bottom
scouring and the extremely high turbidity naturally found in
that area  (these comments do not apply to other areas of
Cook Inlet, such as the highly fertile Lower Inlet).

     Some field studies have been conducted in the vicinity
of offshore oil production platforms.  With some exceptions,
the qualitative findings of these studies agree with the
predictions of our analysis, but the available quantitative
date is generally inadequate to accurately assess many
aspects of the model.  Particularly, field studies fre-
quently do not include the current and brine discharge
information which is necessary to meaningfully interpret
field impact data.  It is recommended that an extensive
program of field data collection be initiated in order to
provide further input data for this type of analysis and to
validate some of its conclusions.
•    Chapter Eight;  Conclusions

     In this chapter, the major conclusions of the report
are summarized.
                             -xxii-

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                         CHAPTER ONE
                         INTRODUCTION
1.1  The Nature of the Problem;  Summary

     Crude oil extracted from natural geological reservoirs
at offshore oil production platforms is generally found to
be mixed with a saline solution known as oilfield brine.
This brine is separated from the crude oil at the production
platform,, and the "produced water" thus formed is then
generally discharged into the estuary, bay, or open sea in
which the platform is located.  Oilfield brines are generally
highly saline — frequently much more so than seawater —
and contain a variety of components known to be toxic to
marine and estuarine life.  These components can be divided
into two broad classes:  trace heavy metals and oil-derived
hydrocarbons, although other types of contaminants, including
the cyanide ion, are also known to be present (Table 1-1).
                          TABLE 1-1

            CONTAMINANTS CONSIDERED IN THE STUDY
    ORGANICS              TRACE              OTHER
    ORGANlLfa              METALS           TOXICANTS
   Oil Hydrocarbons      Arsenic             Cyanide
   Phenol                Cadmium
                         Chromium
                         Copper
                         Lead
                         Mercury
                         Nickel
                         Silver
                         Zinc
                             -1-

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     Since brine components have a demonstrated toxicity to
marine and estuarine life, and since they may be bioaccumu-
lated by marine organisms destined for human consumption,
their discharge into the ocean is a source of concern for
environmental policy makers.

     In response to this concern, the U.S. Environmental
Protection Agency  (EPA) has published a set of effluent
limitations for the offshore oil extraction industry designed
to prevent adverse ecological impacts resulting from brine
discharges.  These guidelines include Best Practicable
Control Technology Currently Available (BPCTCA) regulations,
Best Available Technology Economically Achievable (BATEA)
regulations, and New Sources Performance Standards.   The
BPCTCA and BATEA regulations apply to existing sources and
take effect in July 1977 and July 1983 respectively.  The
proposed New Sources Performance Standards for the offshore
oil and gas extraction point source category are identical
with the BATEA regulations and are applicable to new sources,
construction of which is commenced after the promulgation of
the regulations for the offshore oil and gas extraction cate-
gory.  These effluent limitations are described in the
following section.

     Since the 1983 BATEA regulations for the offshore oil
and gas extraction point source category are considerably
more stringent than the BPCTCA regulations, it is important
to assess the level of potential ecological and health
benefits which could be achieved by their implementation.
The analysis described in this report is addressed to this
issue.  It attempts to estimate the ecological effects of
brine discharge from offshore and onshore oil production
platforms, and therefore the ecological benefits which would
result from reinjection of brines.
1.2  Policy Background:  The Effluent Regulations

     The Effluent Guidelines Division of the Office of Water
and Hazardous Materials of the U.S. Environmental Protection
Agency has published interim final effluent limitations and
proposed new sources performance standards for the offshore ,
segment of the oil and gas extraction point source category.
      U.S. Environmental Protection Agency, Effluent Guide-
lines Division, Office of Waste and Hazardous Materials,
Development Document for Interim Final Effluent Limitations
Guidelines and New Source Performance Standards for the
Offshore Segment of the Oil and Gas Extraction Point Source
Category, September 1975.
                             -2-

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These effluent limitations are given in Tables 1-2 and 1-3.
The limitations given in Table 1-2 are based on BPCTCA and
are to be met no later than July 1, 1977.  The more exacting
limitations given in Table 1-3 are based on BATEA and are to
be met no later than July 1, 1983.

     The major concern of the effluent limitations is with
the potential pollutants contained in the produced water
(the brine produced in the wells along with the oil and gas)
that is discharged after separation of oil or gas from the
water has been effected by the separators on the production
platforms.  These include oil hydrocarbons, phenols, heavy
metals, cyanide, chlorides, BOD, COD, and suspended solids.
Of these potential pollutants only oil is directly regulated
by the proposed effluent limitations.

     The BPCTCA limitations restrict the residual concentra-
tion of oil in produced water discharged into open waters to
be no greater than 72 mg/1 for any one day, and to be no
greater than an average of 48 mg/1 for any period of 30
consecutive days.  The BPCTCA limitations apply uniformly in
both near offshore (within the 3-mile limit) and far offshore
(outside the 3-mile limit) waters.  The BATEA limitations ~
distinguish between near offshore and far offshore waters.
     2
      The coastal waters of the United States are divided
into two separate regions, onshore and offshore, by a legal
demarcation line known as the coastal baseline.  This base-
line is used as a reference line for the calculation of the
3-mile line and other coastline-based demarcation lines, and
essentially represents a "smoothed" version of the U.S.
coastline.  Bays or inlets whose closure at the coast is
less than 24 miles are inside this reference line, which is
drawn across the mouth of such waterbodies.  All coastal
waters inside the line are known as onshore waters.  Included
in the onshore classification are areas such as Louisiana's
Barataria Bay region, and part of Alaska's Cook Inlet, both
of which contain significant oil production activities.  The
offshore production areas outside the baseline are further
subdivided into near offshore sites (inside the 3-mile
limit) and far offshore sites (outside the 3-mile limit).
Regulations similar to those which apply to brine discharges
from offshore platforms are being considered for onshore
platforms, so they too will be considered in this report.
Figure 1-1 shows the rationale for the construction of the
baseline.  Figure 1-2 shows the location of the baseline in
Cook Inlet.  The baseline in the Louisiana coast section of
the Gulf of Mexico lies along the string of barrier islands
separating open Gulf waters from enclosed coastal bays.

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                                      TABLE 1-2


                 OFFSHORE SEGMENT - OIL AND GAS EXTRACTION INDUSTRY
                            EFFLUENT LIMITATIONS - BPCTCA



SUBCATEGORY WATER SOURCE


Near Offshore produced water
deck drainage
drilling muds
drill cuttings
well treatment
sanitary M10C
M9IMC
domestic
produced sand
Far Offshore produced water
deck drainage
drilling muds
drill cuttings
well treatment
sanitary M10C
M9IMC
domestic
produced sand
POLLUTANT PARAMETER - EFFLUENT LIMITATIONS
OIL
MAXIMUM
ANY ONE


72
72
a
a
a
N/A
N/A
N/A
a
72
72
a
a
a
N/A
N/A
N/A
a
& GREASE - mg/1
FOR AVERAGE OF DAILY
DAY VALUES FOR 30
CONSECUTIVE DAYS
SHALL NOT EXCEED
48
48
a
a
a
N/A
N/A
N/A
a
48
48
a
a
a
N/A
N/A
N/A
a

RESIDUAL
CHLORINE
mg/1

N/A
N/A
N/A
N/A
N/A
greater than
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
greater than
N/A
N/A
N/A










lb








lb



      No discharge of free oil to the surface waters.

      There shall be no floating solids as a result of the discharge of these
materials.
     £»
      Minimum of 1 mg/1 and maintained as close to this concentration as possible.

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                                           TABLE  1-3
                      OFFSHORE SEGMENT -  OIL AND  GAS  EXTRACTION INDUSTRY
                          EFFLUENT LIMITATIONS  -  BATEA AND NEW SOURCE


SUBCATEGORY WATER SOURCE


Near Offshore produced water
deck drainage
drilling muds
drill cuttings
well treatment
sanitary M10
M9IMC
domestic0
produced sand
Far Offshore produced water
deck drainage
drilling muds
drill cuttings
well treatment
sanitary M10
M9IMC
produced sand
POLLUTANT
PARAMETER - EFFLUENT LIMITATIONS
OIL & GREASE - mg/1
MAXIMUM FOR
ANY ONE DAY


No
72
a
a
a
N/A
N/A
N/A
a
52
52
a
a
a
N/A
N/A
a
AVERAGE OF DAILY
VALUES FOR 30
CONSECUTIVE DAYS
SHALL NOT EXCEED
Discharge
48
a
a
a
N/A
N/A
N/A
a
30
30
a
a
a
N/A
N/A
a

RESIDUAL
CHLORINE
/ 1
mg/1

N/A
N/A
N/A
N/A
greater than 1"
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
greater than I*3
N/A
N/A
I
Ul
I
           No discharge of free oil to the surface waters.
           Minimum of 1 mg/1 and maintained as close to this concentration as possible.
          °There shall be no floating solids as a result of the discharge of these
     materials.

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                     Bfl$€Lin€
    FROfn  UUHICH TH6 T€RRITORiflL S€fl IS m€flSUR€D
                  Bay on uland coast


                      TERRITORIAL SEA
                     COURTESY U S. DEPARTMENT OF STATE
     Figure  1-1.  The baseline dividing
onshore and  offshore regions of the coastal
sea.   (J.  Leslie Goodier,  U.S. Federal and
Seacoast  State Offshore  Mining Laws  (Washington,
D.C.:  Nautilus Press, 1972).)
                     -6-

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ENLARGED AREA
     Figure 1-2.   Location of the coastal baseline in Cook Inlet

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For far offshore waters the BATEA limitations restrict the
residual concentration of oil in discharged produced water
to be no greater than 52 mg/1 for any one day, and to be no
greater than an average of 30 mg/1 for any period of 30
consecutive days.  For near offshore waters the BATEA limi-
tations prohibit the discharge of produced water.  This
generally means that produced water from near offshore
platforms must be reinjected.

     Although only oil, among the various above-mentioned
potential pollutants contained in the discharged produced
water  (see Table 1-1), is directly regulated by the proposed
effluent limitations, the other pollutants are indirectly
regulated.  If, under the BATEA limitations, produced water
in the near offshore is reinjected to meet the zero discharge
limitation on oil, then any and all contaminants that may be
present in the produced water are simultaneously disposed
of.

     The major purpose of the effluent limitations is, of
course, to protect the marine and coastal environment against
degradation resulting from the discharge of produced water
associated with routine offshore oil and gas production
operations.  As mandated by the law, the actual effluent
limitation levels, given in Tables 1-2 and 1-3, were based
primarily upon technological considerations and not on a
detailed knowledge of the environmental damage that might be
expected to result from the discharge of produced water
containing a specified concentration of oil and other pol-
lutants.

     The project described in this report deals with the
estimation of these impacts and benefits.  Since the BPCTCA
limitations are already widely in effect, the project focuses
on the impacts and benefits of BATEA limitations as compared
to the BPCTCA limitations.
                             -3-

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                         CHAPTER TWO
                     PROJECT METHODOLOGY
2.1  General Outline

     The starting point in developing a methodology for
assessing the benefits that may be expected to result from a
particular set of effluent limitations is the realization
that the benefits must be evaluated with reference to a
baseline.  The basic assumptions underlying the establish-
ment of a set of effluent limitations are (1) that a sub-
stance is being discharged, or will be discharged, into the
environment at a rate that results, or is likely to result,
in adverse effects on the environment; and  (2) that re-
stricting the discharge of the substance to the level speci-
fied by the effluent limitations is likely to result in a
significant reduction in the harmful effects, actual or
potential.  The benefits associated with a set of effluent
limitations are then the reduction in adverse effects brought
about, or expected to be brought about, by the effluent
limitations.  The assessment of the benefits expected to
result from a set of effluent limitations must accordingly
be based on a comparison; namely, a comparison of the state
of the environment if the effluent limitations under exami-
nation are not in effect (the baseline) with the state of
the environment if the effluent limitations are in effect.
In this study, since the objective is to assess the benefits
expected to ensue from the BATEA limitations over and above
those provided by the BPCTCA limitations, the baseline is
the state of the environment as impacted by the BPCTCA level
of discharge.  Therefore, the assessment of BATEA benefits
must be based on a procedure for evaluating the environmental
impacts of brine discharge under the BPCTCA regulations.

     The assessment of the environmental impact of oil and
other pollutants contained in produced water discharged at a
given site can be divided into five major components.  The
first component (termed Inputs)  is concerned with the charac-
terization of the produced water at the site, and the
concentrations of the pollutants contained in the produced
water.  The second component (Fates)  is concerned with what
happens to the oil and other contaminants once they are
discharged:  the physical and chemical processes (transport,
diffusion, sedimentation, etc.)  undergone, the extent to
which oil hydrocarbons are degraded by microorganisms, and
the resulting concentration distributions of the pollutants
                              — 9 —

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in the waters surrounding the discharge location.  The third
component (Toxicology)  is concerned with the toxic (lethal
and sublethal)  effects of the specified concentration levels
of the discharged contaminants, and with the bioaccumulation
of toxic brine constituents by organisms.  The fourth compo-
nent (Ecological Characterization)  is concerned with the
biota at the given discharge site:   the dominant species
present, their habitats and life cycles.  The fifth and last
component (Impacts)  is concerned with the impacts that the
discharged produced water can be expected to have on the
biota characterized in the Ecological Characterization,
taking into account the contaminant concentration distri-
butions determined in the Fates component, and the knowledge
of toxic effects and bioaccumulation developed in the
Toxicology component of the procedure.

     Given this five-component scheme for assessing the
impact of the discharge of produced water, the methodology
for assessing the benefits that may be expected to result
from a particular set of effluent limitations is basically
as follows (see Figure 2-1):

     STEP 1:  Choose site for impact assessment.

     STEP 2:  Estimate baseline (BPCTCA) level of discharge
     of oil and other contaminants utilizing information
     regarding production at the site under consideration
     provided in the Inputs component.

     STEP 3:  Estimate expected impacts due to baseline dis-
     charge level.  (This is done by proceeding through the
     Fates, Toxicology, Ecological Characterization, and
     Impacts components of the procedure for assessing
     impacts outlined above.)

     STEP 4:  Paralleling Step 2, estimate the level of dis-
     charge of contaminants given the set of effluent
     regulations  (BATEA) under examination, again in con-
     junction with the characterization of production at the
     given site provided in the Inputs component.

     STEP 5;  Estimate the environmental impact expected to
     result from the BATEA level of contaminant discharge,
     as in Step 3.

     STEP 6;  Evaluate the difference in the impacts esti-
     mated in Steps 5 and 3 to give a measure of the extent
     to which the BATEA regulations reduce the BPCTCA level
     of adverse environmental impacts.
                             -10-

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Estimate Baseline
- (BPCTCA) Levels of
Discharged Contaminants

Estimate Regulated
_ (BATEA) Levels of
Discharged Contaminants





Determine
Environmental Fates
of Contaminants

Determine
Environmental Fates
of Contaminants







Estimate
Environmental
Impacts

Estimate
Environmental
Impacts







Estimate
Differences
Between
BATEA and
Baseline
Levels


Assessment
of
Benefits

                         Ecological
                         Characterization
                         of Sites
Survey of
Contaminant
Effects
     Figure 2-1.   Flowchart of  procedure  for assessing  benefits of proposed
offshore oil and  gas effluent regulations.

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2.2  Details of Project Methodology

     2.2.1  Choice of Contaminants

     The contaminants chosen for quantitative impact eval-
uation in this study are listed in Table 2-1.  These sub-
stances were selected as being those of most concern from
tables of pollutants in produced water given in the EPA
Development Document.  In addition to the 12 substances
listed in Table 2-1, hypersalinity was also examined but in
a qualitative manner only, because of a lack of data relating
specified salinity levels to toxic effects, and also because
a relatively small dilution is sufficient to bring a strongly
hypersaline effluent down to levels close to that of seawater.
Two constituents were also chosen for examination on the
basis of possible human health effects if ingested in seafood
mercury and the petroleum hydrocarbon benz[a]pyrene, a
potent carcinogen.


                          TABLE 2-1

            CONTAMINANTS CONSIDERED IN THE STUDY
    ORGANICS
 TRACE
 METALS
  OTHER
TOXICANTS
   Oil Hydrocarbons
   Phenol
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Zinc
  Cyanide
     2.2.2  Site Selection

     Separate impact assessments were made at four sites
chosen for reasons of data availability, the presence of
production platforms discharging considerable volumes of
produced water, and representativeness; and in order to
include sites from each of the three location categories:
onshore, near offshore, and far offshore waters.  The two
                             -12-

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onshore coastal sites chosen were in Hackberry Bay, Louis-
iana, and in Cook Inlet, Alaska.  A near offshore site was
chosen in the Gulf of Mexico off of Grand Isle, Louisiana,
and a far offshore site was chosen in the Ship Shoal oil
field 20 miles from the Louisiana coastline.  The approxi-
mate, locations of these sites are shown in Figures 2-2 and
2-3.

     Since the sites chosen differ considerably in their
characteristics, they may also be expected to differ in the
magnitude of the impacts observed at them.  For this reason,
the analysis is necessarily site specific, taking into
account important local features at each of the four sites
which might be important in affecting the magnitude of
brine-related impacts.  The important site specific features
which are included in the analysis are listed in Table 2-2.
                          TABLE 2-2

      IMPORTANT SITE SPECIFIC FEATURES OF THE ANALYSIS
           •  Discharge rate of produced water

           •  Composition of produced water

           •  Currents (tidal, freshwater, drift)

           •  Depth of water

           •  Diffusion coefficients

           •  Biota at site



     2.2.3  Characterization of Produced Water

     Data on the rate at which produced water is discharged
at a given site are available from different sources depending
on the site.  For onshore and near offshore coastal waters
in Louisiana, discharge information was obtained from the
Louisiana Department of Conservation offices in Baton Rouge
and Houma.  Far offshore Gulf of Mexico discharge data were
obtained from the U.S. Geological Survey in Metairie,
Louisiana.  Cook Inlet discharge data were obtained from the
      Information on the ownership, exact location, and dis-
charge rates of the platforms studied is provided in Appendix D,
                             -13-

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        BARATARIA
          BAY     HACKBERRY"
                     BAY
          *GRAND
           ISLE

     GRAND
                                /
                                  ISLE
                             PLATFORM
                         10
                                                       95
 Ship Shoal Platform
/   (Far Offshore)
(SCALE FOR ENLARGED MAP)

  STATUTE MILES

   I	I	I	!_
   10
20
30
40
50
                                       AREA SHOWN:

                                         90*        85'
               GULF OF MEXICO
                     * i
is the Production Platform
      Figure 2-2.  Location of Gulf of Mexico production sites.

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Ul
I
                   ENLARGED AREA
                       Figure 2-3.   Location of Cook Inlet production sites (ARCO

                   and Marathon platforms were  studied  in  this  report).

-------
Water Permits Section, U.S. Environmental Protection Agency
in Seattle, Washington, and from U.S. Army Corps of Engineers
discharge permit applications.

     Available data on the composition of produced water are
somewhat sketchy since detailed analyses on brine composi-
tion are not performed in general as part of discharge
monitoring.  A detailed account of the sources used for data
on concentrations of contaminants in produced water is given
in Chapter Three.
     2.2.4  Fates of Contaminants in Discharged Produced
            Water

     Once discharged into the receiving waterbody, the con-
taminants present in produced water are subjected to a
variety of processes which determine their concentration
distributions.  Such processes include transport by currents,
diffusion, dilution, biodegradation, adsorption onto sus-
pended particulates, sedimentation, sediment transport, and
chemical transformation.  Because little quantitative know-
ledge is available regarding the processes of adsorption,
sedimentation, and chemical transformations in marine waters,
these processes were not included in the quantitative esti-
mation of impacts, although they are discussed in the report
(see Appendix C).

     Quantitative evaluation of contaminant dispersion due
to current transport, diffusion, and dilution was accomplished
in this study by means of a computerized dispersion model
originally developed at the Massachusetts Institute of Tech-
nology for predicting the dispersion of thermal discharges.
This model uses input data on currents, depth of water, and
diffusion coefficients in order to predict the relative
dilution of the discharged brines at various points around
the production platform.  Microbial degradation of oil
hydrocarbons can also be incorporated into the model as a
decay parameter, but was not used in model runs since little
quantitative data on aromatic biodegradation kinetics were
available.  The outputs of the computer model were used to
produce a series of isodilution contours such as the one
shown in Figure 2-4.  The areas enclosed by each of these
isopleths were measured by planimeter and used to plot a
curve showing impacted area as a function of concentration.

     Since precise quantitative data on inputs to the dis-
persion model  (e.g., the values of the diffusion coefficients)
were frequently not available, and since the model itself
incorporates certain simplifying assumptions  (e.g., constant
depth of water), sensitivity analysis was performed.  This
                             -16-

-------
10,000n
 9000-
 8000-
 7000-
 6000
 5000
 4000
 3000
 2000-
 1000
           TOO    200    300    400    500    600    700    800    900    1000
           Figure  2-4.   A typical  set  of isodilution  contours.
      Numbers on contours show percent dilution of brines.
      Distances on axes are in feet.   (Near offshore  site.)
                              -17-

-------
was done by obtaining model outputs corresponding to a range
of input parameter values.  The resulting set of concentration/
area curves for each site were then used to define a best,
worst, and most probable case, based on available knowledge
of the input parameters, and on the simplifying model
assumptions.


     2.2.5  Toxicology

     Data from the technical literature were collected on
the toxic (lethal and sublethal)  effects produced on marine
and estuarine organisms by each of the oilfield brine con-
taminants listed in Table 2-1.  The data were organized in
tables (see Chapter Six) which facilitate reference to the
kind of impact associated with a specified concentration of
a given contaminant.
     2.2.6  Ecological Characterization of Sites

     The detailed assessment of the impact produced by a
specified concentration level of a given contaminant on the
biota at a site is a highly complicated task.  The great
majority of studies on toxic effects have been conducted in
laboratories under carefully controlled conditions which
bear little resemblance to the constantly shifting features
of a real environment.  Laboratory studies cannot begin to
take into account the real world complexity of population
dynamics and the web of interconnections of species with
their physical and biological environment.  To give a simple
example, a laboratory study may determine that a particular
concentration of a pollutant may cause a 25 percent reduction
in the hatching rate of fish eggs of a certain species, but
this information is of little value in predicting the impact
on an actual field population since eggs may be produced in
such large numbers that a 25 percent reduction in egg viability
has virtually no effect on the population size.  Conversely,
a species may be poised in such a delicate competitive
balance in its actual field environment that the addition of
a certain pollutant concentration may produce a reduction in
population numbers which would not be anticipated on the
basis of laboratory experiments alone.  In view of the great
difficulty that would be involved in an attempt to incorporate
detailed ecological considerations into the prediction of
impact, these indirect effects were not considered in this
study.  The basic information used was simply a knowledge of
the species that are present at a given site and, in the
event that the life cycle of a species is divided among
different environments, which life stage is spent in the
                             -18-

-------
site under consideration.  This information was used to pro-
vide an estimate of the economic and ecological importance
of the impacted area.
     2.2.7  Impacts

     The goal of the analysis described in this report is
the prediction of the impacts which result from the discharge
of oilfield brines.  In accordance with what has been said in
Section 2.2.4 on the use of a computerized dispersion model
to predict concentration distributions, the approach adopted
focusses on delineating a set of zones of impact; that is,
zones inside of which particular adverse effects are predicted
to occur.   Each site is characterized in terms of absolute
size of the zones of impact for various classes of adverse
effects.  For enclosed bays, the percentage of the receiving
waterbody included in the zones of impact is also taken into
account in assessing impact.  Two basic classes of impacts
are included in the study:  toxic (lethal and sublethal)
effects on marine and estuarine organisms, and potential
human health impacts resulting from the bioaccumulation of
toxic brine constituents by organisms which might eventually
be used for human consumption.
                             -19-

-------
                        CHAPTER THREE
               COMPOSITION OF OILFIELD BRINES
     Oilfield brines are generally much more saline than
seawater (Mackin, for example, has reported that Louisiana
brines have salinities as high as 128 to 131 ppt, as opposed
to approximately 30 ppt for seawater^).   They also contain a
number of trace metals in concentrations several orders of
magnitude higher than their ambient seawater concentrations.
Some data are available on trace metal levels in brines from
Louisiana,  California, Texas, and Alaska oilfields, but even
within individual regions the reported values show a high
degree of variability.

     Total hydrocarbon content of oilfield brines, measured
as total freon-extractable "oil and grease," has been found
to be as high as 1,300 mg/1 prior to treatment.2  Little or
no data are available on the individual hydrocarbon compo-
nents of oilfield brines.  In general, these hydrocarbons
cannot be expected to occur in the same relative concen-
trations at which they occur in crude oil, since the more
water-soluble components will be preferentially concentrated
in the oilfield brines.  In particular,  the brines will be
relatively enriched in aromatic hydrocarbons.  This is
significant since the aromatic components of crude oil are
those which create the most significant toxicity problems.
Some inference relating to the hydrocarbon composition of
oilfield brines can be made by analogy with data on the
composition of the so-called water-soluble fraction of crude
oil.
      J.G. Mackin, A Review of Significant Papers on Effects
of Oil Spills and Oilfield Brine Discharges on Marine Biotic
Communities  (College Station, Texas:  Texas A&M Research
Foundation, Project No. 737, February 1973), pp. 4-8.
     2
      U.S. Environmental Protection Agency, Effluent Guide-
lines Division, Office of Waste and Hazardous Materials,
Development Document for Interim Final Effluent Limitations
Guidelines and New Source Performance Standards for the Off-
shore Segment of the Oil and Gas Extraction Point Source
Category, September 1975, pp. 42-43.
                             -21-

-------
3.1  Major Cations and Anions:  Salinity

     Oilfield brines contain high concentrations of three
principal cations — sodium, magnesium, and calcium — and
one principal anion — chloride.  The high levels of these
ions are responsible for the high salinity of brines rela-
tive to seawater.  The levels of these ions in brines and in
seawater are listed in Table 3-1.
3.2  Trace Heavy Metals in Oilfield Brines

     Metals commonly found in brines are silver, arsenic,
cadmium, chromium, copper, mercury, nickel, lead and zinc.
Data on concentrations of metals in produced waters are
scarce.  In general, the metals exist in brines at parts per
million levels.  The limited amount of data which are avail-
able give concentrations scattered over a wide range.  The
inconsistencies in concentration data may represent actual
ranges of concentration in different oilfield waters, or
they may be the result of the different methods of analysis
used in the various studies.  Approximate levels of trace
metals in oilfield brines are reported in Table 3-2.

     As an example of the variability of the composition of
oilfield brines even at sites within the same field, and
even at different times at the same site, Table 3-3 gives
the results of analyses performed on oilfield brines from
five sites at Baytown, Texas.  Variability is especially
noticeable for zinc (from 0.10 to 1.55 ppm), cadmium (from
0.02 to 0.21 ppm), and lead  (from 0.20 to 2.00 ppm).

     Knowledge of metal content of brines is limited.  The
ranges presented here are the results of a small sample of
oilfield waters.  No thorough investigations of the chemical
forms or properties of metals in oilfield brines have been
performed.  This represents a clear limitation to the com-
plete investigation of environmental impacts of brine and
disposal, since the impact of the metals contained in the
discharged brine will depend on both the concentrations and
the forms  (oxidation state, etc.) of those metals in the
discharge.
     3.2.1  Heavy Metals and Other Constituents in
            Louisiana Produced Waters

     Data on produced water content for offshore Louisiana
wells were obtained from analyses of effluents from 25
                            -22-

-------
                          TABLE 3-1

         MAJOR CATIONS  AND ANIONS IN OILFIELD BRINES
ION
Na+
Mg++
Ca++
aM.G.
CONCENTRATIONS
IN
SEAWATERa(mg/l)
10,500
1,350
400
19,000
Gross, Oceanography: A View
TYPICAL BRINE
CONCENTRATIONS33
(mg/1)
-50,000
500-3,000
2,000-8,000
50,000-150,000
of the Earth
(Englewood  Cliffs,  N.J.:   Prentice-Hall,  1972).
     r^
      Gene  A.  Collins,  Geochemistry of Oilfield  Waters
(New York:   Elsevier  Scientific  Publishing Co.,  1975).
                           -23-

-------
                          TABLE 3-2

            TRACE HEAVY METALS IN OILFIELD BRINES


METAL

Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Mercury (Hg)
Nickel (Ni)
Lead (Pb)
Silver (Ag)
Zinc (Zn)
aM.G. Gross,
CONCENTRATION
IN
SEAWATER3
(ppb)
3.00
0.11
0.05
3.00
0.03
5.40
0.03
0.30
10.00
Oceanography:
CONCENTRATION
IN
OILFIED BRINES
(ppb)
1-80, b 0-10,000°
<5-675,b 0-1C
10-230, b l-5d
<10-380,b <500-3,000C
0. 5-130, b 0-150°
<10-440,b 100,000°
<10-100b
50-3,200, b 0-500,000°
A View of the Earth
(Englewood Cliffs, N.J.:  Prentice Hall,  1972).

      U.S. Environmental Protection Agency, Effluent Guide-
lines Division, Office of Waste and Hazardous Materials,
Development Document for Interim Final Effluent Limitations
Guidelines and New Source Performance Standards for the
Offshore Segment of the Oil and Gas Extraction Point Source
Category, September 1975.

     °Gene A. Collins, Geochemistry of Oilfield Waters
(New York:  Elsevier Scientific Publishing Co., 1975).

      G. Rittenhouse et al.,  "Minor Elements in Oil-Field
Waters," Chemical Geology 4 (1969): 189-209.
                            -24-

-------
                                              TABLE 3-3


               RESULTS OF  ANALYSES OF  OILFIELD  BRINE DISCHARGED AT BAYTOWN, TEXAS
I
K)
Ln
I

ITEM
As
Cd
Cu
Cr
Pb
Ni
Hg
Ag
Zn
+
Oil &
Grease
1
	 *
0.21
0.12
0.10
1.80
1.70
0.0001
0.14
1.55
52,200
35
4
Bio Assay 10
(fish kill
time in
minutes)
Sample 1
2
3
4
5
6
7
8
9
Gulf Oil Corp.
Gulf Oil Corp.
Gulf Oil Corp.
Gulf Oil Corp.
Gulf Oil Corp.
Gulf Oil Corp.
Texaco, Goose
Texaco, Goose
Texaco, Goose
Analyses performed by the
2 3
<0.50
0.25 0.08
0.12 0.05
0.10 0.05
2.00 0.90
1.70 0.90
<0.0001 <0.0001
0.14 0.05
1.36 0.67
49,800 54,700
] 25
6 8
14 15
, Goose Creek Field,
, Goose Creek Field,
, Goose Creek Field,
, Goose Creek Field,
, Goose Creek Field,
, Goose Creek Field,
Creek Field, Permit
Creek Field, Permit
Creek Field, Permit
SAMPLE (Concentrations in mg/1)
45678
<0.50 — <0.50
0.24 0.21
0.10 0.12
<0.05 0.15
2.05 1.75
1.60 1.80
0.0001 0.0002
0.10 0.11
0.68 1.32
48,500 19,400
25 25
8 8
21 No kill
Permit Application No.
Permit Application No.
Permit Application No.
Permit Application No.
Permit Application No.
Permit Application No.
No. C.O.E. H000156, Main
No. C.O.E. J000156, Main
0.08
0.04
0.05
0.85
0.60
0.0001
0.02
0.26
13,900
25
5
No kill
000088,
000088,
000088,
000088,
000088,
000088 ,
outfall
outfall
No. C.O.E. K000157, Skimmer tank
Harris County Pollution Control Department,
<0. 50 <0 .50
0.08 <0.01
0.07 0.1
0.10 0.25
0.70 0.20
0.60 1.0
<0.0002 <0.0001
0.03 <0.01
0.13 0.10
60,800 25,500
35 0
10 13
8 65
Permit sample point
Permit sample point
Permit sample point
Permit sample point
Permit sample point
Permit sample point
, 3/21/72.
, 5/10/72.
bottoms, 5/10/72.
107 North Munger, Pasadena
9
<0.50
0.02
0.55
0.4
0.35
2.2
<0.0001
<0.01
0.17
63,800
0
2
10
11, 2/22/72.
11, 3/10/72.
12, South, 2/22/72.
»2, South, 3/10/72.
1(2, North, 2/22/72.
12, North, 3/10/72.



, Texas.
*Dlank indicates no analysis performed.

-------
offshore platforms.   Unfortunately, the data do not cover
all the parameters of interest.  Table 3-4 presents the
concentrations of parameters measured, with seawater concen-
trations and chemical forms of the elements of interest.
The concentrations of calcium, sodium and chloride ions are
all higher in the brine than in seawater.  Cadmium and
mercury are the only metals for which concentrations were
determined.  Cadmium, at levels up to 1.68 ppm, is about
15,000 times as concentrated in the brine as in seawater.
Mercury levels were determined to be less than 0.0005 ppm,
the limit of detection of the analytical method used.
     3.2.2  Heavy Metals and Other Constituents in Alaska
            Produced Waters

     Concentrations of brine constituents for Cook Inlet,
Alaska were obtained from Army Corps of Engineers Waste
Water Discharge Permit Application forms submitted by the
oil industry to the Corps of Engineers, and later to the
EPA.  The numbers shown in Table 3-4 are averages of numbers
from four separate permit applications, three for onshore
facilities treating production from offshore platforms, and
one for ,an onshore facility treating waters from an onshore
gas field.  All four facilities discharge to Cook Inlet.

     Most major nonmetal ions are less concentrated in these
waters than in seawater, possibly indicating the occurrence
of freshwater flushing of petroleum formations in the area.
The metals are more concentrated in the brines than in the
seawater.  Arsenic, at 1.404 ppm, is 470 times as concen-
trated as in seawater; cadmium, at 0.081 ppm, is 736 times
as concentrated.  Levels of chromium and lead are 2,000 and
1,300 times higher, respectively, than corresponding seawater
levels.  Concentration factors for the other metals are
shown in Table 3-4.
 3.3  Hydrocarbons in Oilfield Brines

     The relative proportions of various hydrocarbons in
 oilfield brines are probably not representative of the
 proportions found in the parent crude oil.  Those hydro-
 carbons which are most soluble in water — for example the
      U.S. Environmental Protection Agency, Development
 Document  for  Interim Final Effluent Limitations Guidelines
 and New Source Performance Standards, 1975.
                             -26-

-------
                                                     TABLE  3-4


                                            PRODUCED  WATER  CONSTITUENTS
i
K)
PARAMETER
Ag
As
Cd
CN
Cr
Cu
Mg
Nl
Pb
Zn
Ca
Mg
Ha
Cl
Oil & Grease
Phenols
BOD
COD
Total Solids
IDS
TSS
TOC
SEAUATERd
FORM PPM
AgCl2" .0003
As04H~~ .003
Cd** .00011

Cr04,Cr3* .00005
Cu* + .003
HgCl2,HgCl4"~ .00003
Ni** .0054
Pb**,PbCl* .00003
Zn** .01
Ca** 400
Mg** 1,350
Ha* 10,500
Cl" 19,000



34,325



BRINES
FORMb LOUISIANA0 ALASKAd CALIFORNIA0
(mg/!) (mg/1) (mg/1)
<.010
HAs02",H2As04" <.]-!. 404
CdS04,CdCl2 <.005-.675 .001
<.01-.01
<.01-.10
Org. Acid Salt .086
<.0005 <. 002-^.010
.005-. 430
Pb(HC03)2 '.01-. 39
ZnCl2,ZnS04 .277
2,4739 3,725
Mg** 7479 145.8
Na* 44.6079 7.650
Cl" 61.0009 13,953
2029 36
3.100
683
1,671
110,200 23,842
110,000 23,482
73 99
413
.03
.001-. 08
.02-. 18
0-.004
.02-. 04
.05-. 116
.0005 -.002
.1-.29
0-.28
.05-3.2



17,230-
21 ,000
56-359
.35-2.1
370-1,920
400-3,000

21 ,700-
40,400
1-60

LA. AK.
TEXAS CONCENT. CONCENT.
(mg/1) RATIO RATIO
<.01-.10 <3.3
<.01--'.02 O33-468
•-.02-. 193 <45-6136 736

<.01-.23 <200-<2000
'..01-.38 28.7
<.0001-.13 <16.7 <4-<70
--.01-. 44 .9-79.6
<-01-.22 <33. 3-1300
1- 27 27.7
6.2 9.3
.55 .11
4.2 .73
42.000- ,,
62,000 J'^ ' J
5.3
126-342
182-582
3.2 .69
806-
169,000
12-656

WATER QUALITV CRITERIA LIMITSf
MAXIMUM MINIMUM
ACCEPTABLE RISK
CONCENTRATIONS THRESHOLD
('"9/D (mg/1)
.005 .001
.05 .01
.Olh .0002
.01 .005
.1 .05'
.05h .01
.0001
.! .002
.05 .01
lh .02











      NOTE:  Footnotes are on the following page.

-------
                   FOOTNOTES TO TABLE 3-4
      M.G. Gross, Oceanography;  A View of the Earth (Engle-
wood Cliffs, N.J.:  Prentice-Hall, 1972).

      Gene A. Collins, Geochemistry of Oilfield Waters (New
York:  Elsevier Scientific Publishing Co., 1975).
     Q
      U.S. Environmental Protection Agency, Development
Document for Interim Final Effluent Limitations Guidelines
and New Source Performance Standards for the Offshore Segment
of the Oil and Gas Extraction Point Source_Category, 1975.

      Values are averages of values from four permit applica-
tion forms submitted to U.S. Army Corps of Engineers.  See
text.
     f^.
      Concentration Ratio = (mg/1 Brine)/(mg/1 Seawater).

      Water Quality Criteria Limits, October 1973, from
Environmental Studies Board, U.S. Environmental Protection
Agency - Water Quality Criteria 1973, 1973.

     ^Gene A. Collins, "Geochemistry of Some Petroleum
Associated Waters from Louisiana," U.S. Bur. Min. Rep.
Invest., No. 7326, 1970.

      Synergistic effects have been observed when cadmium,
copper, and zinc are present simultaneously.  Under those
conditions Maximum Acceptable Concentrations should be
reduced by an order of magnitude.

     1When oysters are present the Maximum Acceptable
Concentration should be reduced to 0.01 mg/1.
                             -28-

-------
aromatic hydrocarbon components — would be preferentially
concentrated in the brines, since the brines essentially
consist of a water extract of crude oil.  Little or no data
are available on the quantities of specific hydrocarbon
components in oilfield brines, but these quantities can be
estimated on the basis of composition data on artificial
"water-soluble fractions" of crude oil.
                    4
     Anderson et al.  prepared water-soluble fractions and
oil-water dispersions of two crude oils, and analyzed the
water from these two preparations for specific hydrocarbon
content.  The water-soluble fraction (WSF)  was prepared by
mixing oil and 20 ppt salinity seawater gently for 20 hours
at 20° C, and then allowing the mixture to separate for 1 to
6 hours.  The water was then analyzed for hydrocarbon con-
tent.  The results of the analysis are shown in Tables 3-5
and 3-6.  The water-soluble fractions of South Louisiana
crude and Kuwait crude contained 23.76 and 21.65 ppm of
hydrocarbons, respectively.  As shown in Table 3-6, a large
percentage of the hydrocarbons contained in water-soluble
fractions from both crudes is composed of aromatics — in
particular the low molecular weight aromatics.  The relative
abundance of aromatics versus n-paraffins in the water-
soluble fractions, as compared to the original crude, is a
result of the greater solubility of the aromatic compounds.
Table 3-6 shows Aromatic Enrichment Factors (AEF)  for the
WSF's of the ratio of the concentration of aromatics to
n-paraffins in the WSF divided by the same ratio for the
whole oil.  The AEF is an indication of the degree to which
aromatics are enriched in the WSF as compared to the whole
crude.  The AEF of 125 for Kuwait crude makes it clear that
solubility is a key factor in determining the composition of
the hydrocarbon content of oilfield waters.

     The results obtained by Anderson et al. with oil-water
dispersions  (OWD) were similar.^  The OWD's were prepared by
mixing oil and 20 ppt seawater violently for 5 minutes, and
allowing only 30 to 60 minutes for separation.  Analysis of
the water fraction of the mixtures yielded the results shown
in the "initial" columns of Table 3-7.  When a 10,000 ppm
     4
      J.W. Anderson et al., "Characteristics of Dispersions
and Water-Soluble Extracts of Crude and Refined Oils and
Their Toxicity to Estuarine Crustaceans and Fish," Marine
Biology 27 (1974): 15-88.

      Oil-water dispersions can be used to model the hydro-
carbon content of brines with high levels of suspended oil
contamination  (e.g., untreated brines).
                            -29-

-------
                          TABLE 3-5
                 HYDROCARBON CONCENTRATIONS
OF CRUDE OIL WATER-SOLUBLE FRACTIONS

rnfirnnwn SOUTH
LOUISIANA
k, \JLJir U U IN U 	
CRUDE OIL
ALKANES
Ethane
Propane
Butane
Isobutane
Pentane
Isopentane
Cyclopentane + 2-Methylpentane
Methylcyclopentane
Hexane
Methylcyclohexane
Heptane
C,, n-Paraffin
J-b
C,7 n-Paraffin
TOTAL ci2~C24 n~Para£fins
AROMATIC S
Benzene
Toluene
Ethylbenzene + m-, p-Xylenes
o-Xylene
Trimethylbenzenes

0.54
3.01
2.36
1.69
0.49
0.70
0.38
0.23
0.09
0.22
0.06
0.012
0.009
0.089

6.75
4.13
1.56
0.40
0.76
KUWAIT
CRUDE OIL

0.23
3.30
3.66
0.90
1.31
0.98
0.59
0.19
0.29
0.08
0.09
0.0006
0.0008
0.004

3.36
3.62
1.58
0.67
0.73
     Source:  J.W. Anderson et al., "Characteristics of Dis-
persions and Water-Soluble Extracts of Crude and Refined
Oils and Their Toxicity to Estuarine Crustaceans and Fish,"
Marine Biology 27 (1974): 15-88.

                             -30-

-------
                     TABLE 3-5  (CONT.)
COMPOUND
AROMATICS (CONT.)
Naphthalene
1-Methylnaphthalene
2-Methylnaphthalene
Dimethyl naphthalenes
Trimethylnaphthalenes
Biphenyl
Methylbiphenyls
Dimethylbiphenyls
Fluorene
Me thy If luorenes
Dime thy If luorenes
Dibenzothiophene
Phenanthrene
Me thy Iphenanthrenes
Dime thy Iphenanthrenes
TOTAL SATURATES
TOTAL AROMATICS
SOUTH LOUISIANA
CRUDE OIL

0.12
0.06
0.05
0.06
0.008
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.002
0.001
9.86
13.90
KUWAIT
CRUDE OIL

0.02
0.02
0.008
0.02
0.003
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
11.62
10.03
TOTAL DISSOLVED HYDROCARBONS
MEASURED                          23.76           21.65
                             -31-

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                          TABLE 3-6
            AROMATIC AND n-PARAFFIN CONTENT OF
         SOUTH LOUISIANA AND KUWAIT CRUDE OILS AND
          THEIR WATER-SOLUBLE FRACTIONS  (WSF) AND
       CALCULATED AROMATIC-ENRICHMENT FACTORS  (AEF)
  OIL
AROMATICS

Oil    WSF
(%)   (ppm)
                           n-PARAFFINS
         Oil
 WSF
(ppm)
                         AROI1ATICS/
                         n-PARAFFINS
Oil
WSF
AEF
South
Louisiana   0.94  0.305
               3.98  0.089
                         0.24  3.43
                         14.29
Kuwait
0.60  0.075    4.00  0.004
                         0.15 18.75    125.00
    NOTE:
AEF =
(Aromatics/n-paraffins)WSF

(Aromatics/n-paraffins)_.,
     Source:  J.W. Anderson  et  al.,  "Characteristics of Dis-
persions and Water-Soluble Extracts  of  Crude and Refined Oils
and Their Toxicity to Estuarine Crustaceans and Fish," Marine_
Biology 27  (1974): 15-88.
                             -32-

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                         TABLE 3-7
        HYDROCARBON COMPOSITION OF AQUEOUS PHASE OF
        1,000 ppm OF OIL-IN-WATER DISPERSIONS  (OWD)
              AND EFFECTS OF 24-HOUR AERATION
  HYDROCARBON
     KUWAIT

INITIAL   FINAL
SOUTH LOUISIANA

INITIAL   FINAL
                           1,320
            71
1,988
64
n-paraf f ins
Tri-and tetra-
methylbenzenes
Naphthalene
1-Methylnaphthalene
2-Methylnaphthalene
Dime thy Inaphthalenes
Trimethylnaphthalenes
Phenanthrene
Methylphenanthrenes
TOTAL N-PARAFFINS
PERCENT DECREASE
TOTAL AROMATICS
PERCENT DECREASE
TOTAL HYDROCARBONS
MEASURED
PERCENT DECREASE

260
19
12
16
33
19
2
2
1,320

359

1,679


70
15
1
17
4
3
2
2
71
95%
110
69%
181
89%

135
64
40
46
108
56
34
20
1,988

506

2,494


99
53
24
25
32
6
2
2
64
97%
241
52%
305
88%
     Note:  All concentrations expressed in ppb.

     Source:  J.W. Anderson et al., "Characteristics of Dis-
persions and Water-Soluble Extracts of Crude and Refined Oils
and Their Toxicity to Estuarine Crustaceans and Fish," Marine
Biology 27  (1974): 15-18.
                            -33-

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OWD prepared from South Louisiana crude was aerated after
mixing for 1 to 72 hours, hydrocarbon concentration dropped
off from an initial 60 ppm to 4.7 ppm at 24 hours, and
remained stable for the rest of the aeration period.  Eighty
to 90 percent of the initial hydrocarbon burden was lost in
the first 24 hours.  There was a 95 percent decrease in
n-paraffins, and 69 percent decrease in aromatics in a
1,000 ppm OWD of Kuwait crude due to aeration (Table 3-7).
A 1,000 ppm OWD of South Louisiana crude lost 97 percent of
its n-paraffins and 52 percent of its aromatics as a result
of the aeration.  The aeration of oil-water dispersions
appears to remove the bulk of the n-paraffins present,
leaving a greater proportion of aromatics in the aerated OWD
than in the original crude.

     Aromatics are much more soluble than other oil fractions.
They enter solutions more readily, and are retained in
solution in both water-oil dispersions and oil-water solu-
tions.  Furthermore, most treatment processes which are used
for brines prior to their discharge (see following section)
will preferentially remove non-aromatic hydrocarbon compo-
nents.  The majority of these processes only remove suspended
contamination, and so leave behind the dissolved, and pre-
dominantly aromatic, hydrocarbons.  Treatment by gas flotation
probably serves to oxidize a significant portion of brine
hydrocarbons, but the aromatics are relatively resistant to
oxidation compared to the non-aromatic oil hydrocarbons  (see
Table 3-7) .

     The factors considered here, then, point to the con-
clusion that aromatics, both mono- and polycyclic, are the
hydrocarbons expected to be present in appreciable quantities
in the produced water both before and after treatment.
These are the compounds that must be considered then in the
analysis of possible adverse environmental effects of the
discharge of produced waters into the marine environment.
3.4  Treatment Processes for Oilfield Brines

     Oilfield brines are frequently subjected to primary or
secondary treatment processes prior to being discharged into
the ocean.  These processes can significantly affect some,
but not all, of the pollutant content of the brine.

     The combined oil and water first go through primary
separation processes, which yield relatively pure oil and
contaminated water.  This water is then treated more exten-
sively to bring oil and grease levels down to an acceptable
                            -34-

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level.  Several methods are used for this treatment.  The
simplest method is gravity separation.  Production waters
are allowed to sit in tanks or settling ponds for a time to
allow the lower density oil to rise to the surface, where it
can be skimmed off.  Some of the suspended particles settle
to the bottom of the tank or pit during this process.

     Parallel plate coalescers are based on the principle of
gravity separation.  They are equipped with a series of
slanted plates which collect rising oil droplets and channel
them to the top of the separators.  Similarly, suspended
particles sink until coming in contact with a plate, then
slide down the plate to be collected in the bottom of the
separator.

     Filter systems operate by filtering the brine through
either a fibrous medium such as fiberglass or a loose medium
such as sand, thereby removing oil droplets and suspended
particulates.

     The gas flotation method of oil-water separation is
slightly more sophisticated than the other techniques.  Air
is bubbled through the untreated water.  As the bubbles rise
to the surface, they collect oil droplets in their path, and
carry them to the surface where they can be skimmed off.

     Chemicals are often used in conjunction with other
methods to enhance the effectiveness of those methods.
Surfactants are used to break up oil-water emulsions.
Coagulants promote aggregation of suspended materials, and
thus enhance their natural tendencies to rise or to sink.
Polyelectrolytes are used to facilitate the removal of
colloidal and extremely fine suspended particles.

     The results of an Environmental Protection Agency
survey of oil and grease content of produced waters after
treatment by various methods are shown in Table 3-8.
According to this study, loose media filters and gas flota-
tion processors yield lower oil and grease levels than the
other commonly used methods.

     These treatment processes will generally not affect
trace metal levels in brines.  It is also clear that all of
these separation methods are directed at the removal of
suspended oil droplets and particles.  None of the methods
remove dissolved hydrocarbons from solutions.  Therefore,
most of the oil and grease which remains in the produced
water after treatment is composed of soluble hydrocarbons.
                            -35-

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                           TABLE 3-8


               PERFORMANCE OF TREATMENT SYSTEMS

                      LOUISIANA COASTAL
                          OTT  &
  TYPE TREATMENT SYSTEM     (mg/l)         NUMBER OF SAMPLES
  Gas  Floatation              27                 27

  Parallel Plate              .„                 ,,
   Coalescers
Filters
Loose Media
Fibrous Media
Gravity Separation
Pits
Tanks

21
38

35
42

15
7

31
48
     Source:  U.S. Environmental Protection Agency, Effluent
Guidelines Division, Office of Waste and Hazardous Materials,
Development Document for Interim Final Effluent Limitations
Guidelines and New Source Performance Standards for the
Offshore Segment of the Oil and Gas Extraction Point Source
Category, September 1975, p. 81.
                             -36-

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     On the basis of this fact and of several other consider-
ations, the decision was made in this study to restrict
attention to the dissolved portion of the oil hydrocarbons
in the produced water and to omit a detailed and separate
treatment of the impacts of the emulsified portion of the
hydrocarbons.  The reasons for emphasizing the dissolved
portion can be summarized as follows:

     1.   As has been discussed above in this section,
          standard treatment methods are capable of removing
          a considerable part of the emulsified portion of
          the hydrocarbons in produced water but are ineffec-
          tive in removing the dissolved portion.

     2.   The dissolved part of the hydrocarbons is, as dis-
          cussed in Section 3.3, especially rich in aromatic
          hydrocarbons.  It is precisely the dissolved aro-
          matic hydrocarbons that are also the most toxic to
          marine organisms.6

     3.   There is evidence  that bacteria are more effective
          in degrading emulsified oil than they are in de-
          grading dissolved oil, since emulsified oil pro-
          vides a more substantial substrate for bacterial
          colonization.  Dissolved hydrocarbons may there-
          fore be expected to persist longer in marine
          environments.

Thus the dissolved aromatics not only comprise the largest
part of hydrocarbons remaining after effective treatment of
produced water, but they are the most toxic, and may be the
most persistent as well.  Since the impacts of the hydro-
carbons in produced water can therefore be expected to be
      Stephen F. Moore, "Towards a Model of the Effects of
Oil on Marine Organisms," in National Academy of Sciences,
Background Papers for a Workshop on Inputs, Fates, and
Effects of Petroleum in the Marine Environment, Vol. II,
1973.

      National Academy of Sciences, Petroleum in the Marine
Environment,  1975, p. 59; P.J. Kinney, D.K. Button, and D.M.
Schell, "Kinetics of Dissipation and Biodegradation of Crude
Oil in Alaska's Cook Inlet," in Proceedings Joint Conference
on Prevention and Control of Oil Spills, American Petroleum
Institute, 1969; and C.E. Zobell, "Microbial Modification of
Crude Oil in the Sea," in Proceedings Joint Conference on
Prevention and Control of Oil Spills, American Petroleum
Institute, 1969.
                            -37-

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dominated by the dissolved aromatics, it was felt that the
emulsified part could be neglected without significantly
affecting the conclusions of this study.  It should also be
noted that the computer dispersion model, described in
detail in Chapter Four and Appendix B, used to calculate the
concentration distributions of produced water constituents
in the receiving waters, is restricted to working with
dissolved substances only.  Adequate treatment of the
dispersion of the emulsified portion of the hydrocarbons
would involve a modeling effort additional to the one used
as the basis for this study.
                              -38-

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                        CHAPTER FOUR
                     DISPERSION MODELING
4.1  Introduction

     Oilfield brines, once discharged into a receiving
waterbody, are subject to the processes of transport, dif-
fusion and dilution which determine the distributions
through time and space of pollutant concentrations.  Since
the impact exerted on the marine environment by the brine
discharge depends in large part on the concentration distri-
butions of the discharged contaminants in the receiving
waterbody, it is of great importance to understand and
predict the physical dispersion processes which determine
these distribution patterns.  The heart of the analysis
described in this report is a set of dispersion models which
are used to predict the quasi-steady state distributions of
brine concentrations resulting from the combined influence
of natural decay processes, steady and tidal current flow,
and diffusion.

     Two types of models are discussed in this chapter.  The
simplest type of calculation, a tidal prism flushing model,
is discussed in Section 4.2.  This model is useful for
giving the average concentration of a pollutant in a small
bay area but cannot give any information regarding concen-
tration contours.  In this analysis, this simple tidal prism
calculation is used to set a "background" concentration of
brine levels in small enclosed bays such as Hackberry Bay.
The more detailed diffusion model used in this report is
discussed in Section 4.3.  It should be emphasized that the
discussion given the model in this chapter is only cursory,
and designed to highlight the physical assumptions upon
which the model is based.  A more detailed discussion of the
model, including a description of the differential equations
which are used to represent physical dispersion processes,
is presented in Appendix B to this report.  The model used
in this analysis is capable of incorporating three-dimensional
diffusion as well as the time varying tidal currents which
play a key role in estuarine dispersion.
4.2  Simple Tidal Flushing Calculations for Shallow,
     Enclosed Bays

     Pollutants introduced into an estuary are flushed out
over a period of time by the combined actions of seaward
river flow and mixing at high tides followed by tidal
                            -39-

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outflow.  The residence time of estuarine pollutants is
dependent on the overall rate at which this flushing occurs.
Therefore, one important indicator of the ability of an
estuary to rid itself of pollutant discharges — especially
if they are conservative! -- is the flushing time, or the
length of time required for the river flow and tides to
flush an amount of water equal to the low tide volume of the
estuary.  For very large estuaries or those which have
complicated geometries, the flushing time is quite difficult
to compute; however, for small estuaries a relatively simple
method has been developed to make reasonable estimates of
the length of time, measured in units to tidal periods,
needed to replace the estuary volume.

     Such calculations are useful for two reasons.  First,
they can be used to gain a rough idea of the length of time
it takes an estuary to rid itself of oilfield brine pollu-
tants dissolved in the water column.  Second, in the case of
continuous discharges, they can be used to determine the
steady state concentrations of those pollutants. The tidal
flushing calculations described below in this section can be
used to supplement the predictions of the more sophisticated
computer model in small, enclosed bays by supplying order-
of-magnitude estimates of the average background levels of
discharged pollutants.  These estimates are not only useful
in their own right but can also serve as checks on the
reasonableness of the results obtained from the computer
mode1.

     The simplest version of the method to be discussed is
based on the fairly crude assumption that the total volume
of water entering the estuary between low and high tides
 (incoming river water plus incoming seawater) becomes
thoroughly mixed with the low tide volume before the ebb
tide begins.  On the basis of this assumption, the fraction
of the  low tide estuary volume  ("old water") flowing seaward
during  the ebb tide can be computed.  In particular, if V is
the low tide volume of the estuary and P is the volume
entering between low and high tides  (called the tidal
prism), then V + P is the volume of the estuary at high
tide.   Since the tidal prism P is carried away on the next
ebb flow and since the total high tide volume is assumed to
be thoroughly mixed, the fraction of the volume V of old
water carried away per tidal period is P/(V + P).  The
      A pollutant discharge is conservative  if  the pollu-
 tants do not decay with time; i.e.,  if  total pollutant mass
 is conserved.
                             -40-

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number T of tidal periods needed to flush out all of the old
water is just the inverse of this fraction:

                    T = V + P
                          P
                                                     2
This number is a first estimate of the flushing time.

     As ought to be expected, this simple-minded method
generally yields shorter-than-realistic flushing times for
most types of estuaries.-*  For most real estuaries, complete
mixing during high tide does not occur, and the ebb tide
does not always carry waters near the head of the estuary
all the way past the mouth and into the open sea.

     Despite this drawback, the approach leads to an equa-
tion relating the low-tide, steady-state concentration of a
given contaminant to the amount of pollutant discharged into
an estuary.  For simplicity it can be assumed that all of
the discharge occurs between low tide and the following high
tide.  Let the concentration of the contaminant at low tide
(ambient concentration) be CL and its concentration in the
discharge stream be CD in a total volume VQ of discharge in
one tidal cycle.  A simple calculation (Figure 4-1) then
yields:

                    C  = C  -—                         (4-1)
                    CL   CD P                          (  lj

     Hackberry Bay, 29°4', 90°15' (see Figure 4-2) in the
northwest corner of Barataria Bay, Louisiana, provides a
good example of the kind of bay for which this approach can
be useful.  It harbors Texaco's Bay de Chene oilfield, the
site of the largest brine discharge (VD = 9,747 m3 per
tidal period) in Barataria Bay.  The average tidal height in
Barataria Bay4 is 0.3 m; if we assume this datum for Hackberry
     2
      F.F. Wright, Estuarine Oceanography, Council Education
in the Geological Sciences Publication No. 18  (New York:
McGraw-Hill Inc., 1974), pp. 28-33; and K.R. Dyer, Estuaries:
A Physical Introduction  (London:  John Wiley and Sons, 1973),
pp. 109-114.

      Dyer, Estuaries;  A Physical Introduction.
     4
      Barney Barrett, Cooperative Gulf of Mexico Estuarine
Inventory and Study, Louisiana, Phase II Hydrology and Phase
III Sedimentology (New Orleans:  Louisiana Wildlife and
Fisheries Commission, 1971), p. 55.
                             -41-

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     Low Tide

           high tide volume of bay

           water entering between
           low and high tide
TOTAL VOL
  = V + P
TOTAL AMT
    OF
POLLUTANT
  D
      VC
          (tidal prism; vol = P)


          low tide vol. of bay  (V)
          (ambient concentration
          of pollutant = CT )
                          ij

          discharge introduces vol V
          of effluent  (VD «.<. V+P)
          (cone, of pollutant = C )
     High Tide
     Bay Becomes Well-Mixed

           New cone, of Pollutant
            _ Amount of Pollutant
              Volume of Bay

                   + VC
                 V + P
©
C.)  Low Tide
    Volume P Carried Out of Bay

          Amount of Pollutant Lost
           = (cone.)(vol.)
                      vc
            = P
                VDCD
                   V + P
 Steady State Assumption: Amount of Pollutant Introduced
 in One Tidal Cycle = Amount Lost During One Tidal Cycle
           Therefore:
                        VDCD
                                  V_C_ + VCT
                                   P D	L
                                     V + P
           Solving for C   (steady state concentration)

                                C V

                           CL =   P~~

        Figure 4-1.  Tidal flushing calculation.
                           -42-

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  HACKBERRY BAY
                                             FRESH MARSH
                                              (0-5 ppt.)
                                             SALT MARSH
                                             (14-30 ppt.)
Figure 4-2.  Location  of Hackberry  Bay study area.
                         -43-

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Bay our estimate of CL is likely to be slightly low, since
the smaller bay probably experiences less extreme tides than
the larger one.  This tide height multiplied by the surface
area of Hackberry Bay of 1.77 x 10"? square meters5 gives
P = 5.33 x 106 m3; if the tide height is 0.1 m, P =
1.78 x 1()6.  By (4-1), assuming 0.3 m tides gives


                    CT = 1.8 x 10~3 Cn = 0.18% Cn
                     Jj               u          L)

Assuming 0.1 m tides gives


                    CT = 5.5 x 10~3 Cn = 0.55% Cn
                     .Lj               D          LJ

     It is important to emphasize that these results have
considerable limitations.  To begin with, the methodology is
based on the assumption that complete mixing occurs during
the flood tide, an approximation which can be used reason-
ably only for relatively small, shallow bays like the
Hackberry Bay.  Thus no attempt is made to reproduce the
concentration isopleths, in direct contrast to the computer
model.  The implicit assumption that the surface area of a
natural body of water remains constant over a tidal cycle
introduces yet another source of error.  Another underlying
assumption in these calculations is that the concentrations
of pollutants are at a steady state.  While this may be true
over short time intervals or in a time-averaged sense,
seasonal and even weekly variations in the tides and river
inflow may cause significant discrepancies between the
computed concentrations and observed values of background
concentrations.  The method is valid as a means of arriving
at an order of magnitude approximation to the average
background concentrations of contaminants in relatively
small, shallow estuarine bays.
4.3  Description of the Dispersion Model

     The rough tidal prism calculations described in the
previous section are only applicable  to enclosed areas  such
as Hackberry Bay, and even then only  indicate one summary
statistic:  the well-mixed "background" concentration of a
continuously discharged pollutant flushed by tidal mixing.
      Barney Barrett, Water Measurements of  Coastal  Loui-
 siana  (New Orleans:  Louisiana Wildlife and  Fisheries Com-
 mission, Division of Oysters, Water Bottom and  Seafood,
 1970) .
                             -44-

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A much more detailed analysis is, of course, necessary to
predict detailed concentration distributions for the pol-
lutant as it disperses under the influence of currents and
diffusion forces.  A very useful approach to the problem of
predicting pollutant concentrations in the receiving water-
body is to apply the fluid dynamics to modeling the actual
diffusion process responsible for the dispersion of concen-
trated effluents.  This kind of analysis yields concentra-
tion distributions instead of averages.  The mathematical
background of such an analysis is developed in detail in
Appendix B, and has been implemented as a computer program
which was used for this project.6  This section will describe
the physical assumptions relating to pollutant dispersion
upon which the model is based.  Readers interested in
further information on the nature of the model should
consult Appendix B.

     There is an interest in analyzing the movement of
pollutants in a current field.  An important factor influ-
encing the nature of pollutant movement in such a field is
the relationship between the scale of the pollutant concen-
tration distribution and the curvature of the streamlines,
or directions of fluid flow.

     If the scale is small compared to the streamline curva-
ture, i.e., if the pollution stream is small compared to the
distance over which the current remains relatively uniform,
then the current will not disperse the pollutants very much.
Rather, it will tend to carry them more or less intact along
the overall direction of flow.  This situation, illustrated
in Figure 4-3, is often described by saying that the charac-
teristic eddy of the current is much larger than the pollu-
tant stream,and the resulting transport is called advec-
tion.

     On the other hand, if the characteristic eddy is
smaller than the pollutant stream, the pollutants will be
subject to several different directions of flow over any
small period of time.  The resulting transport pattern,
illustrated in Figure 4-4, tends to disperse the pollutant
      The dispersion model used for this project was
developed at the Massachusetts Institute of Technology by
E. Adams and K.D. Stolzenbach.  See E.E. Adams et al., Near
and Far Field Analysis of Buoyant Surface Discharges  into
Large Bodies of Water, Ralph Parsons Lab, for Water Re-
sources , Report No. 205  (Cambridge, Mass.:  Massachusetts
Institute of Technology, 1975).
                             -45-

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CTl
I
                               !
                             \
\	\
                                                \
           \
                                                            X
                                                       current streamlines
                        Figure  4-3.  Advection  due  to uniform,  steady flow.

-------
I
.fc.
                     I
                                                                  current streamlines
                     Figure  4-4.   Diffusion  due to turbulent flow.

-------
parcel.  This situation is often described by saying that
turbulent flow causes more pronounced diffusion of the
pollutant stream.  (The reason for the adjectives "more
pronounced" is that diffusion also occurs on a molecular
scale, independent of any observable fluid flow.  The
component of diffusion attributable to turbulence is usually
called "eddy diffusion.")

     There is an interest, then, in the extent to which
diffusive and advective forces will influence the movement
of pollutants.  The extent to which the pollutant distri-
bution is "spread out" in any particular direction (say the
y direction) can be described by the variance of this
distribution.^

     If the diffusion processes operate, this variance will
be taken as a measure of the rate of diffusion, so that a
very large part of the task of characterizing a diffusion
process is accomplished by defining a diffusion coefficient E
in terms of the time rate of change in the variance  (spatial
spreading) of the pollutant stream.8

     The analysis is complicated by the experimental fact
that the spreading rate, E, of pollutant streams in natural
waters increases as the diffusion process progresses.  In
other words, as the scale of the pollutant stream increases
because of diffusion, the rate at which further diffusion
occurs also increases, causing increasingly rapid dispersal.
This observation can be explained in terms of the turbulent
effects discussed above.  When a pollutant stream is small
      Mathematically, the variance in the y direction is
given by :


                   2    C 2
                  a .  =  /  y c (x,y ,z) dy
                        — 00

where c(x,y,z) is the spatial concentration distribution.
     P
      E  is defined as:
                          7
                          2 dt

See Frank D. Masch,  "Mixing and Dispersion of Wastes by
Wind and Wave Action," in Advances in Water Pollution  Re-
search, ed. by E.A.  Pearson  (Oxford:  Pergamon Press,  1964),
p. 146.
                             -48-

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in scale, only currents with comparatively small character-
istic eddies can be considered turbulent with respect to the
stream.  Two representative pollutant particles will there-
fore tend to have very similar trajectories because of their
proximity to each other, so that they will not be separated
quickly at this small scale.  As the scale increases, the
degree to which the motion of two representative pollutant
particles are correlated diminishes, resulting in a more
rapid overall rate of separation.   Therefore, the eddy
diffusion coefficient E is a function of the scale (i.e.,
the largest dimension) a of the parcel formed by the pollu-
tant stream.  Empirical studies have found that a reasonably
accurate expression for the dependence of E on o is fre-
quently given by a power law such as:

                    E = aa4/3                            (4-2)


where a is an empirically determined constant.    This
relation is generally known as the "four-thirds law".
     9
      Henry Stommel, "Horizontal Diffusion Due to Ocean
Turbulence," Journal of flarine Research 8  (1949): 199-225.

       It is important to realize that eddy diffusion, as
described by (4-2), is nothing more than a sort of statis-
tical construct devised to alleviate the difficulties
encountered in solving differential equations for compli-
cated velocity fields.  Analysis at the microscopic scale
would involve a set of equations of motion tracing the path
of each minute parcel of the pollutant as it moved through a
current field, which varied both spatially and temporally in
a complicated and irregular way.  Such problems are hope-
lessly intractable.  The saner approach normally taken for
eddy diffusion is to view the background current field from
a macroscopic standpoint, taking into explicit account only
the major features of speed and direction of the flow.  So
that the important dispersing effect of the irregular
details (turbulence) of the current fields is not thereby
ignored, it is modeled by lumping all of the eddy-diffusive
flow characteristics into a single factor representing, in a
sense, their aggregate effect on the pollutant stream.  This
factor is the non-molecular diffusion coefficient E described
by (4-2).   The justification for the form of such a simpli-
fying assumption must be provided by actual empirical
studies verifying that the hypothetical law accurately
models the measurable behavior of dispersing pollutant
particles in real bodies of water.
                             -49-

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     There remains considerable controversy over the accuracy
with which eddy diffusion coefficients can be evaluated.  It
is likely that different flow and depth regimes are best
characterized by different diffusion laws.  The 4/3 law in
(4-2) best fits data for ocean regimes as summarized by
Pearson11 and has been used in many investigations of ocean
diffusion.  The model used for this report incorporates a
more general form of the diffusion coefficients (diffusion
must be described by three coefficients, one for each
mutually perpendicular direction) to take into account cases
in which the 4/3 law may not be valid  (an example is Hack-
berry Bay — see Chapter Five).  The horizontal diffusion
coefficients are assumed to be of the  following form:


                  E = Aan    aa                     (4-4)
                        (—       t—

where A is constant, a is the scale of the pollution distri-
bution, and a  is some limiting scale.  The form of the
equations suggest that over a certain  range of length
scales  (oac) diffusion is more accurately  (or conserva-
tively in the absence of data) described by constant diffu-
sion coefficients. Based on empirical  results, vertical
diffusion in the model does not depend on scale, but instead
has a value which varies only with depth, and is constant at
any given depth.

     The model described in Appendix B was used to predict
the quasi-steady state1^ distributions of pollutant concen-
trations in the neighborhood of a brine discharge point.
The nature of the system being analyzed is summarized in
Figure 4-5.  Pollutant is discharged from an orifice in a
particular direction.  For a small time it moves under the
       N.H. Pearson, An Investigation of the Efficacy of
Submarine Outfall Disposal of Sewage and Sludge, State Water
Pollution Control Board Publication No. 14, Sacramento,
California, 1956.
     12
       The distributions are quasi-steady state in that
although they vary through the course of the tidal cycle,
the distribution at any particular time in a cycle is the
same as that at the equivalent time in the next cycle.
                            -50-

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i
en
                  FARFIELD
        DISCHARGE POINT
                        \
                         \
                           \
                             \
                                           INITIAL
                                          DILUTION   »
                                                                   NEARFIELD MIXING
                                                                   ZONE
'VIRTUAL ORIGIN"
 OF  DISCHARGE
                                                           CURRENT.
                                                      VELOCITY V
                     TIDAL COMPONENT
                     OF CURRENT*
                      (SINUSOIDALLY VARYING)
                                                                   STEADY  CURRENT
                                                                   COMPONENT*
                *  CURRENTS ARE ASSUMED  TO  BE SPATIALLY HOMOGENEOUS
            Figure 4-5.  Dispersion of  brine  discharges.

-------
influence both of its discharge momentum and of an external
current, but outside of a relatively small nearfield mixing
zone it is pushed along primarily by the current.  Once
beyond a characteristic distance RTRANS from its source the
pollutant moves under the influence only of current, decay,
and diffusion forces.  The current is the vector sum of a
steady current component  (due, for example, to freshwater
flow in an estuary or drift current in the ocean) and a
sinusoidally varying tidal component.  The pollutant plume
absorbs some water in the nearfield mixing zone  (inside
RTRANS), so another important input parameter to the model
is the initial dilution, which can be predicted roughly on
the basis of previous empirical work (see Chapter Five).

     The dispersion of pollutants afer their discharge is
assumed to be influenced primarily by three forces:  advec-
tive transport by currents, diffusion (described by a set of
diffusion coefficients for the x, y, and z directions), and
decay  (see Figure 4-6).

     The movement of the pollutant under the influence of
these  three forces can be modeled by a set of differential
equations and associated boundary conditions as described in
Appendix B.  These in turn are solved numerically by a
computer program which predicts quasi-steady state pollutant
distributions and then averages them over an entire tidal
cycle  to produce a matrix showing the spatial distributions
of average pollutant concentrations near the discharge site.
The program then uses this concentration matrix to calculate
the positions of a series of  isopleths, or lines of equal
pollutant concentration  (or equivalently, lines of equal
brine  dilution).

     The model used is also able to simulate the presence of
a single straight shoreline.  When the discharge is located
near a straight shoreline, two constraints are imposed.
First,  the currents are assumed to flow parallel to the
shoreline to prevent advection of the pollutant mass across
the boundary.  Secondly,  to prevent effective diffusion
across the boundary, an image source corresponding to each
real source is assumed to be  located on the opposite side of
the shoreline.
 4.4   Summary of Model Parameters

      The model described  in  this  chapter  requires  the  spe-
 cifications of the  following parameters:
                             -52-

-------
                                    BRINE

                                    PLUME
                                                                              DIFFUSION
I
ui
u>
I
                                                             «•:•:•:.«

              Figure 4-6.   Forces affecting brine  dispersion

-------
                    Q  = initial brine discharge flow
                         (ft3/sec)

                   Ac  = initial discharge excess concen-
                         tration (= 100 percent)

                     D = initial dilution (in near field)

                    x, = initial fixed mixing distance (see
                         Figure 4-5)

                    H~ = initial depth of source

                RTRANS = initial variable mixing distance
                         (see Figure  4-5)

                     H = total water  depth (assumed to be
                         constant)

                XSHORE = distance to  shoreline  (if appli-
                         cable)

              k,,k ,k.  = internal,  surface,  and bottom decay
                         coefficients

                    E^ = vertical diffusion coefficient
                     4_J

   A ,A ,n ,n ,a  ,a   = parameters describing the hori-
                         zontal diffusion coefficients^

                 U,,V, = components of amplitude of tidal
                         current

                 U ,V  = components of steady current
                         velocity
     13
       The horizontal diffusion coefficients  (E  and E )  are
given by:                                      ^


     E  = A anx   (a a  )          E  = A anY    (a >a  )
      x    x xc     x  xc           y    Y yc     y  yc
                             -54-

-------
                        CHAPTER FIVE
        RESULTS OF CALCULATIONS WITH DISPERSION MODEL
5.1  Introduction

     In this chapter the results of the calculations per-
formed to estimate the physical dispersion of discharged
brines are presented.  The calculations were made using the
computer dispersion model described in Chapter Four.  For
each of the four site areas -- Hackberry Bay, Louisiana;
Cook Inlet, Alaska; near offshore Gulf of Mexico (Grand
Isle, Louisiana); and far offshore Gulf of Mexico -- a
series of computer runs was made to predict the patterns of
concentration resulting from brine discharges.  The key
variables incorporated in the model influencing the concen-
tration contours are (1)  rate of discharge,  (2) depth of
water, (3) initial mixing dilution, (4) currents in the
receiving waterbody, and (5)  diffusion coefficients.  The
results of the computations are given in the form of plots
of normalized concentration contours (isopleths) and plots
of the areas enclosed by the concentration contours.

     Section 5.2 discusses the calculation methodology, and
Sections 5.3, 5.4, 5.5 and 5.6 present the computed results
for Hackberry Bay, Cook Inlet, near offshore Gulf of Mexico,
and far offshore Gulf of Mexico, respectively.
5.2  Calculation Methodology

     The dispersion model described in Chapter Four, Section
4.3, was used to calculate concentration distributions for
four sites:  Hackberry Bay, Louisiana; Cook Inlet, Alaska;
near offshore Gulf of Mexico waters (Grand Isle, Louisiana);
and far offshore Gulf of Mexico.  The input parameters to
the dispersion model have been summarized in Chapter Four
and will be given here as well for convenience:
     Qn   =    rate of brine discharge

     Ac   =    excess concentration (compared with ambient
               level)  of contaminants in discharged brine

  RTRANS  =    initial mixing distance (length of near and
               intermediate mixing zones:   the zones in
               which initial discharge velocity of effluent
                             -55-

-------
               plays an important role;  in addition to
               currents,  in determining  the movement of the
               effluent)

     D    =    initial dilution of discharge resulting from
               mixing of  discharge with  receiving waters in
               near and intermediate mixing zones

     H    =    total water depth (assumed constant)

     H2   =    depth of source at beginning of far mixing
               field (zone in which effluent can be con-
               sidered to be moved passively by currents and
               diffusion  forces)

  XSHORE  =    distance to shoreline if  applicable (the
               model can  incorporate the effects of only one
               straight shoreline)

   E , E  =    horizontal diffusion coefficients; these are
               given in terms of Ax, Ay, nx, n , o  ,  and
               a   (see Equations 4-3 and 4-4)y   xc

Un,U,,V ,V, =  current parameters.  The  current is assumed
               to be spatially homogenous.  Given an x-y
               cartesian coordinate system chosen on the
               basis of site geography,  UQ and VQ are the
               non-time-varying current  components in the x
               and y direction respectively, and U]_ and Vj_
               are the amplitudes of sinusoidally varying
               current components in the x and y direction.
               The total currents in the x and y direction
               respectively, U(t) and V(t), are given by

                    U(t)   =  U0 + u]_ sin  (2Trt/T)

                    V(t)   =  V0 + vi cos  (2irt/T)

               where T is the tidal period.

     For each set of input parameters, the output of the
computer dispersion model is a set of predicted concentration
values averaged over a tidal cycle, at points on a cartesian
grid whose origin corresponds to the discharge point.   In
the computations performed, the  initial excess concentration,
AcQ, was always set equal to 100.00 so that the output con-
centration values can be interpreted as indicating percent
dilution of the discharged produced water itself, or percent
dilution of the initial concentration of any contaminant
contained  in the discharged brine.  A value of 1.00, for
                             -56-

-------
example, at a certain point means that the contaminant
concentrations at this point are predicted to be I percent
of their level in the discharged brine at the point of
discharge.  The actual concentration of a particular brine
constituent can then be found simply by multiplying its
concentration in the produced water (as known from laboratory
analyses)  by the dilution percentage given by the computer
program.

     The basic computer output, an array of concentration
factors or dilution percentages, can be converted to a form
which is much more accessible to analysis and interpretation
by connecting points with the same concentration values.
The curves thus formed are called concentration isopleths or
contours  (or more accurately, concentration factor isopleths,
because of the normalized value of 100.00 used for Aco) and
were obtained by estimating concentrations between output
grid points using linear interpolation.  Since a principal ^
aim of the study is to assess the impact of pollutants dis-
charged into the marine environment, and since impact depends
in large part on the size of the areas subjected to particular
levels of concentration, the areas enclosed by the concentra-
tion isopleths were calculated, by use of a planimeter, to
give estimates of the areas of the receiving waterbodies for
which concentrations can be expected to be equal to or
greater than any particular level.

     As an example, Figure 5-1 shows a set of concentration
isopleths obtained from one of the near offshore Gulf of
Mexico calculations.  The origin of the coordinate system is
the location of the discharge.  The concentration distri-
bution is symmetrical with respect to the y-axis so that
only one-half of the pattern is shown.  Points between the
y-axis and the 2 percent isopleth have contaminant concen-
trations greater than 2 percent of their concentration in
the discharge, points between the 2 percent isopleth and the
1 percent isopleth have concentrations between 2 percent and
1 percent of the discharge concentrations, and so on.  The
decrease of concentration with increasing distance from the
source is shown by the location of the isopleths for smaller
concentrations at greater distances from the origin.  A plot
of the areas enclosed by the concentration isopleths in Figure
5-1 is shown in Figure 5-2.  The area of 184 x 104 square
feet corresponding to a concentration level of 0.1 percent,
for example, is obtained by measuring  (by planimeter) the
area enclosed between the 0.1 percent isopleth and the y-
axis in Figure 5-1  (and doubling this value to incorporate
the symmetry of the concentration distribution).  This area
is shaded in Figure 5-1.  Similarly, values for the areas
enclosed by the other concentration isopleths are measured,
                             -57-

-------
I
Ul
CO
I
                   )0,000n
                    9000
                             100    200   300   400
                    -1000
500    600   700    800   900


  FEET
1000
                        Figure  5-1.   Isopleths for  near offshore  site.
                   Concentrations  are in percent, and distances in  feet.
                   Shaded area  shows region in which  brine concentration
                   is 0.1 percent  or greater.

-------
 184.0
 o
OJ
 CM
     10
      001
                           CONCENTRATION  (%)

    Figure 5-2.  Area/concentration curve for  same site as used in
Figure 5-1.  Dotted lines show that brine concentration is ->0.1 percent
over 184 x 10^ ft^  (shaded area in Figure 5-1).

-------
the areas plotted versus the corresponding concentrations,
and the resulting set of five points connected to give the
curve shown in Figure 5-2.

     In general, the values of the input parameters are not
known exactly.  In the absence of detailed field measure-
ments at the discharge sites, values for the diffusion
coefficients, currents, and initial mixing depth all have to
be estimated using whatever information and knowledge is
available.  Details on how these parameter values were
estimated are given below in Sections 5.3 through 5.6.  In
addition, certain simplifying assumptions are built into the
model (as indeed they are in any model)  such as, for example,
the assumption here of spatially homogeneous currents.  It
is, therefore, important to perform sensitivity analyses
consisting of a series of computer runs in which input
parameters are given a range of values to allow for the
degree of uncertainty with which they are known, or to allow
for simplifying model assumptions.  The concentration
factor isopleths for each such calculation can be plotted
and compared with the isopleths of calculations performed
with different choices of the input parameter values. In
this study impacts are measured in terms of receiving
waterbody areas that are subjected to particular levels of
contaminant concentrations.  Hence, comparison of the com-
puter outputs for different sensitivity analyses are most
easily performed by plotting the area versus concentration
curves, one for each sensitivity analysis, together on one
graph.  An example of this is shown in Figure 5-3.  The base
case is the curve corresponding to the set of input parameters
regarded as the most probable.  A "best"  (least impacted
area) and "worst"  (greatest impacted area) case can be
constructed as shown in Figure 5-3 by forming the two enve-
lopes of the set of area/concentration curves.  These do
not, in general, correspond to any one set of input param-
eters but are best and worst in the collective sense that
particular points on these curves correspond to some choice
of possible input parameter values.

     Although the dependence of the distribution of concen-
tration factors on the input parameters is not a simple one
 (as is evidenced by the involved structure of the dispersion
model), it may be useful here to indicate in qualitative
terms the influence of the input parameters on the output
distribution of concentrations  (see Table 5-1).  Concentra-
tions naturally vary directly with the rate of brine discharge,
Qo-  The greater QQ, the greater will be the value of the
concentration at a given point if all other parameters are
held constant.  The variation of concentration with QQ is,
however, not  linear as demonstrated by the fact that in the
                              -60-

-------
  XXX) C-
CN
 w
   10 CM
     1
     j
     I
     J
     j
    I.Ci	
     o.oi
                    H2,!(4,H5
                       H7
                 BASE CASE HI
                       H3
                          CONCENTRATION (%)
         Figure 5-3.  Plots  of  area/concentration curves  for
    sensitivity analyses performed for Hackberry Bay  site.
    Base Case assumes most probable values of input parameters;
    for other cases, input parameters are individually  varied
    over their range of plausible values.
                           -61-

-------
                       TABLE 5-1
  QUALITATIVE  INFLUENCE OF  INPUT  PARAMETERS
             ON CONCENTRATION  DISTRIBUTION
    PARAMETER
                                             EFFECT
Q.  =  discharge  rate


AcQ = excess  contaminant
      concentration

RTRANS = radius of initial
         mixing zone

D = initial mixing
    dilution
H
H2
U./V.
VEy
       total  water depth
       thickness of pollutant
       plume  layer
       = steady current
         tidal  current
         components
       diffusion
       coefficients
                                   Larger discharge  rate results
                                   in larger concentrations.

                                   Set equal to  normalized value
                                   100.00 for all  computations.

                                   No effect on  shape of pattern.
Most strongly influences concen-
trations close to  source.
Larger values of D result in
smaller concentration  values.

Larger values of H and H2 result
in larger initial  mixing dilution.


Steady currents remove pollutant
from vicinity of discharge.
Larger values result in more
rapid rate of pollutant dilution.

Tidal currents produce periodic
circulation of pollutants but no
net removal.   Larger values result
in larger effluent dilutions
because mixing occurs  over a
larger area.
Larger values of coefficients
result in more rapid rate of
pollutant diffusion.   Shape of
pollutant plume strongly
influenced by diffusion in
direction transverse to
principal current  flow.
                            -62-

-------
receiving waters the effluent discharge contaminant concentra-
tions cannot be larger than they are in the effluent itself,
no matter how great the effluent discharge rate is.  The
parameter ACQ/ the excess concentration of a contaminant in
the discharged brine, does not directly influence the computed
concentrations here since, as mentioned above, it is set
equal to a normalized value of 100.00 for all computations.
The output values of the computer program are thus percentage
concentrations of the discharged produced water.  Data on
the actual concentrations of particular contaminants in the
receiving water can be obtained by multiplying the concen-
tration of a brine constituent in produced water by the
percent dilution of the produced water as given by the
computer program.

     The parameter RTRANS, as used here, influences only the
location of the effective far field source (see Figure
4-5).  It serves to indicate that the concentration distri-
butions are computed starting from an effective origin whose
distance from the actual point of discharge varies with the
initial effluent discharge velocity.  In all computations
performed in this study RTRANS is small and has an insignifi-
cant effect on the output concentration distribution, pro-
ducing only a slight displacement of the concentration
distribution away from the actual point of discharge.

     The parameter D, the initial dilution of the discharge
resulting from mixing in the near and intermediate mixing
zones,! has a marked influence on concentrations at points
relatively close to the discharge point, but its influence
tends to diminish with increasing distance from the discharge
point.  For distances close to the discharge point, the
greater the value of D the smaller are the resulting receiving
water concentrations.  The parameters H and H2, total depth
of water and initial mixing depth, respectively, are used in
computing D.  In general, the greater the water depth the
greater will be the dilution of the discharged brine.
Because of the fact that produced water is generally more
saline, and therefore denser than seawater, the discharge
will tend to form a layer at the bottom of the water column.
The thickness of this layer is H2 and it is generally pro-
portional to the total depth of water.  Larger values of H
and H2 are reflected in larger values of the initial mixing
dilution D.

     The current parameters, as might be expected, have an
important influence on the concentration distribution.  The
      These are the zones in which the initial discharge
momentum of the brine still affects its movement.
                             -63-

-------
                          2
steady current components,  Ug and VQ, control the net
movement of the discharge away from the discharge point.
The greater UQ and VQ,  the more rapidly the effluent will be
carried away from the discharge point and hence the faster
that concentrations will decrease with increasing distance
from the source location.  The tidal current components, U]_
and V]_, do not produce any net movement of effluent.  In
fact, if there were no steady current components, the tidal
current components alone would result in a periodic circula-
tion of effluent but no net movement, with the result that
concentrations would tend to increase with time.  The magni-
tude of the tidal current parameters influences the size of
the region in which the discharge is circulated  (the tidal
excursion).  The larger the tidal current the more mixing of
the discharge with receiving waters can occur in each tidal
cycle, and hence the more rapidly concentrations will tend
to decrease farther from the source.

     The diffusion coefficients control the rate at which
the discharge plume spreads out in the receiving waters.
The greater the diffusion coefficients, the more rapidly
diffusion occurs.  In open waters diffusion has been found
to increase with the scale of the diffusing patch  (this is
discussed in more detail in Appendix B) so that the rate of
diffusion increases with increasing distance from the source.
There is also an interplay between the diffusion coefficients
and the shape of the discharge plume.  If currents are
assumed to flow along one axis only  (the longitudinal or y
axis) the smaller the transverse diffusion coefficient, Ex,
the more long and narrow the plume tends to be.  Conversely,
large values of Ex result in a more rapid diffusion of
effluent in the transverse direction with the result that
the plume tends to be wider and shorter.  The influence of
the transverse diffusion coefficient on plume shape is a
direct consequence of the law of conservation of mass.
Since the quantity of discharged contaminant is fixed by the
discharge rate, it follows that if more contaminant spreads
out in the transverse direction then less contaminant is
available at large distances in the longitudinal direction,
and conversely.

     The above remarks on the influence of the input param-
eters are rough and qualitative only, but they do serve to
give some insight into the kinds of changes in the concen-
tration distributions that can be expected to accompany
changes in the values of the input parameters.
      2
      Current components in the x and y direction are repre-
 sented by U and V, respectively.
                             -64-

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5.3  Hackberry Bay, Louisiana

     Table 5-2 lists the various sets of input parameters
which were used in computer calculations of concentration
factors at the Hackberry Bay site.  Case HI can be considered
the base (most probable) case; H2 and H3 examine the effect
of varying the horizontal diffusion coefficients; in H4 and
H5 the initial dilution is varied; in H6 the tidal velocity
is varied;  in H7 and H8 the nontidal current component is
varied; and in H9 a rotational current component^ is intro-
duced .

     Table 5-3 gives for each input parameter its base case
value, the range within which it was varied, and comments
about the choice of values.  For all calculations Qg was
set equal to 3.98 cubic feet per second, the average rate of
oilfield brine disposal from the Bay de Chene oil field in
Hackberry Bay (see Appendix D).  On the basis of what was
known about the mode of disposal  (release of effluent into a
large cylinder extending below the surface of the water)
RTRANS was set equal to 1 foot.  The value of RTRANS is in
any event unimportant for the purpose of this study since it
influences only a small zone immediately adjacent to the
point of disposal.  In all calculations XSHORE was set equal
to infinity and the effect of the shoreline was incorporated
by computing a background concentration level of the order
of 0.1 percent (see Chapter Four, Section 4.2) and using the
computer model to predict concentration factors only down to
this level of dilution.  The base case value of D equal to 2
is a conservative minimum as any form of discharge is likely
to achieve at least this level of initial dilution.  The
base case value of H of 3 feet was obtained by calculating
the mean low water depth of Hackberry Bay to be 2.4 feet on
the basis of known volume and surface area,4 and adding to
this an amount equal to one-half the average tidal range of
approximately 1 foot.5
      If there are nonzero tidal current components in both
the x and y directions, then the tidal current vector will
rotate through an ellipse during each tidal period.
     4
      Barney Barrett, Water Measurements of Coastal Louisiana,
(New Orleans:  Louisiana Wildlife and Fisheries Commission,
Division of Oysters, Water Bottoms and Seafoods, 1970), p. 97.

      Barney Barrett, Cooperative Gulf of Mexico Estuarine
Inventory and Study, Phase II, Hydrology and Phase III,
Sedimentology (New Orleans:  Louisiana Wildlife and Fisheries
Commission, 1971), p. 55.
                             -65-

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                 TABLE 5-2
LISTING OF COMPUTER CALCULATIONS PERFORMED
FOR THE HACKBERRY BAY SITE



o

CALCULATION
HI
112

H3
1 114
cn

-------
                                             TABLE 5-3



                         PARAMETER VALUES  FOR HACKBERRY BAY CALCULATIONS
I
cr\

VALUES
PARAMETER BASE CASE RANGE
QQ 3.98 ft3/sec
RTRANS 1 ft

D 2 2-10
H 3 ft 2.5-3 ft
H2 3 ft 2.5-3 ft

V 0.035 ft/ 0.01-0.1
sec ft/sec

COMMENTS
Based on discharge data.
Conservatively small. Insignificant effect on
concentration distribution.
Two is conservative minimum.
Real mean depth. Varies with tidal height.
Realistic value considering shallow water depth.
Complete mixing assumed.
Based on net flow values.

V, 0.22 ft/sec 0.065-0.22 Consistent with tidal volumes.
ft/sec
U 0

U, 0 0.05
_L
XSHORE

E 0.1 ft2/sec 0.1-1.0
x ft2/sec
E 1.0 ft2/sec 0.1-1.0
" ftVsec
Ez 0
Hugo B. Fischer, "Longitudinal

Reasonable and conservative assumption in
absence of detailed current data.
Arbitrarily assumed to examine sensitivity
to rotational velocity component.
Account for boundaries by computing background
concentration with tidal flushing calculation.

Values of E /Hu* and E /HuA
ra
consistent with Fischer.

Complete mixing in water column assumed.
Dispersion and Turbulent Mixing in Open-Channel Flow,
Annual Review of Fluid Mechanics, Vol. V, ed . by Van Dyke (Palo Alto: Annual Reviews, Tnr
   1973).

-------
     A simplified current scheme was adopted in the calcula-
tions in which tidal and nontidal (i.e., freshwater)  currents
were assumed to flow along the y-axis.  Values for these
current velocity components were then estimated on the basis
of tidal volume information" using the somewhat involved
calculations described in Appendix E.

     Values for the diffusion coefficients were estimated by
combining values of depth and current velocities with values
given by Fischer7 for the dimensionless quantity E/Hu*
where u^ is the friction velocity.  This procedure is discussed
in more detail in Appendix E.

     The concentration factor isopleths for the calculations
Hi through H9 enumerated in Table 5-2 are shown in Figures
5-7a through 5-7i, respectively, and plots of areas enclosed
by the isopleths versus dilution level are given in Figure
5-3  (above).  The concentration factor isopleths are symmetric
with respect to the y axis.
5.4  Cook Inlet, Alaska

     Table 5-4 presents a listing of the sets of input
parameters for which computer calculations were performed to
predict concentration factors for the Cook Inlet oilfied
area, and Table 5-5 gives for each parameter its base value,
range when varied, and comments about choice of values.

     Of the seven known sources of brine discharge into Cook
Inlet waters  (see Appendix D), two were selected for compu-
tations:  the Trading Bay Production Facility with an average
daily discharge of 12,500 barrels brine (0.81 cubic feet per
second), and the Granite Point Production Facility with an
average discharge of 5,000 barrels brine per day (0.32 cubic
feet per second).  Both of these are onshore facilities
which discharge brine into Cook Inlet close to the shore.
These facilities were selected on the grounds that the
impacted areas for these facilities would be considerably
larger  than those corresponding to offshore platforms dis-
charging produced water into the much deeper waters of Cook
Inlet far from the shoreline.
      Barrett, Cooperative Gulf of Mexico Estuarine Inventory
and Study, p. 57.

      Hugo B. Fischer, "Longitudinal Dispersion and Turbulent
Mixing in Open-Channel Flow,"  Annual Review of Fluid Mechanics,
Vol. V, ed. by Van Dyke  (Palo Alto:  Annual Reviews Inc., 1973).
                              -68-

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            TABLE 5-4
LISTING OF COMPUTER CALCULATIONS
PERFORMED








I
cr\

1








CALCULATION
Cl

C2

C3



C4

C5





(ft
0

0

0



0

0



Qn D
0
3/sec)
.81 2

.81 2

.81 2



.32 2

.32 2



RTRANS H

(ft)
1 8

1 8

1 8



1 8

1 8



H2

(ft)
8

8

8



8

8





Ax
0.005

0.005

0.005



0.005

0.005


FOR COOK INLET,

E
X
nx °xc
4/3 250

4/3 250

4/3 250



4/3 50

4/3 50



E
Y
(ft2/sec)
1,250

7,500

250



1,250

250


ALASKA

un
0
(ft/sec)
0

0

0



0

0




0
1
(ft/sec)
0

0

0



0

0




Vn V,
0 1
(ft/sec) (ft/sec) COMMENTS
0.014 n.a. Trading bay

0.014 n.a.

0.014 n.a.


production
facility .
Variation of
tidally averaged
diffusion
coefficient, E .
' Y
0.014 n.a.

0.014 n.a.

Granite point
production
facility.
Variation of E .
1 Y

-------
                                       TABLE 5-5

                      PARAMETER VALUES FOR COOK INLET CALCULATIONS
o
I
   PARAMETER
     E
     E
                           VALUES
 BASE CASE
RANGE
COMMENTS
QQ 0.81, 0.32
RTRANS 1 )
D 2 f
H 8 )
H2 8[
V0 0.014

Based on discharge data.
Conservative minimum value.

Based on actual water depth.
Total mixing assumed.
Estimated from freshwater flow
data.
Un
0
u.
1
E ""
x
1




1 A
x
> nx
1 **
axc
0

0

0.005
4/3
250,
                       50 ft
                                 Not  input parameter.   Maximum observed
                                 value of  6.4  ft/sec used in computing
                                 base case value of E .

                                 Currents  assumed to be
                                 along shore only.

                                 "4/3" diffusion law in direction
                                 perpendicular to shoreline.
                                 Eddy size bounded by distance to shore.
1,250 ft /sec  250-7,500 ft /sec  Estimated by tidally averaged computation,

                                 No vertical diffusion.   Uniform mixing
                                 assumed.

-------
     The extremely fast tidal currents in Cook Inlet (see
Appendix A)  with speeds up to 6.5 feet per second in the
region of the oil fields, and the consequently large tidal
excursions,  result in a situation in which discharged con-
taminants tend to be sloshed back and forth over large
distances for a considerable length of time.  The contaminants
are moved seaward only gradually by the relatively small
freshwater flow.  In the computer model, concentrations are
calculated by summing over the contributions of a series of
contaminant "puffs" released at discrete time intervals.  To
calculate a steady state concentration distribution, the
model must follow the course of the discharge puffs over the
period of time that the initial puff in the series remains
in the zone of interest.  It follows that in the case of
Cook Inlet with its long flushing times, a lengthy computa-
tion is required if the model is to incorporate tidal currents
directly.  In order to circumvent this problem, it was
decided to account for the effects of the tidal currents by
incorporating them into the alongshore diffusion coefficient,
Ey.  The procedure for doing this is given in Appendix E
along the the associated calculation required to estimate
V_, the downstream freshwater flow velocity.

     The concentration factor isopleths for the calculations
Cl through C5 enumerated in Table 5-4 are shown in Figures
5-8a through 5-8e respectively, and area vs. dilution plots
are given in Figure 5-4.
5.5  Near Offshore Gulf Waters

     For Gulf of Mexico waters offshore from the barrier
islands and within the 3-mile limit, a site was selected in
Block 16 of the Grand Isle oilfield area offshore of Grand
Isle, Louisiana.  Table 5-6 presents a listing of the"various
sets of input parameters for which calculations were per-
formed, and Table 5-7 gives base values, ranges when varied,
and comments about choice of values for each parameter.

     The value of Q0 = 1 cubic foot per second used for the
base case (approximately 15,000 barrels produced water
discharged per day)  is somewhat higher than the figure
obtained from the Louisiana Department of Conservation in
Houma, Louisiana, for 1975 produced water discharge in
Block 16 (approximately 9,000 barrels produced water discharged
per day).  However,  an average brine discharge of 15,000
barrels is known to occur in offshore waters (as can be seen
from USGS records for far offshore Gulf of Mexico brine
discharges), and since only one near offshore site was con-
sidered in this study it was decided that potential benefits
                             -71-

-------
  100,000^
   10,000-
  i,ooo.o:
o
rH
JJ
fc.
<

<
    100.0:
     10.0-
      1.0-
      0.1
                                     COOK INLET
                             WORST CASE
               BEST
                 CASE
         .01
                       ,10             1.0

                        CONCENTRATION (%)
10.0
     Figure 5-4.   Area/concentration curves for  Cook Inlet.
                         -72-

-------
                TABLE  5-6
LISTING OF COMPUTER CALCULATIONS  PERFORMED

CALCULATION
N1A
NIB
, NIC
U) N1D
1
N1E
N2A
N2B
N2C


Q0 D
(ft3/sec)
1
1
1
.5
1
1
1
1
25
10
25
25
25
5
5
5

FOR

RTRANS XSHORE
(ft) (ft)
20
20
20
20
20
20
20
20
15,000
15,000
15,000
15,000
15,000
2,500
2,500
2,500
THE

"l
(ft)
33
33
33
33
33
15
15
15
NEAR

112
(ft)
5.5
5.5
5.5
5.5
5.5
3.5
3.5
3.5
OFFSHORE GULF OF


Ax
.00524
.00524
.00524
.00524
.002
.00524
.00524
.002

Ex
n
X
4/3
4/3
4/3
4/3
4/3
4/3
4/3
4/3


°XC
(ft)
7,500
7,500
7,500
7,500
7,500
1,250
1,250
1,250


N
.00524
.00524
.00524
.00524
.002
.00524
.00524
.002
MEXICO SITE

Ey
ny V
(ft) i
4/3
4/3
4/3
4/3
4/3
4/3
4/3
4/3

U0
[ft/sec)
0
0
0
0
0
0
0
0


ul V0
(ft/sec) (ft/sec)
0
0
0
0
0
0
0
0
.37
.37
.18
.37
.37
.37
,18
.37

Vl
(ft/sec)
.25
.25
.12
.25
.25
.25
.12
.25

COMMENTS
Base Case:
XSHORE=3 miles
Variation of D
Variation of
Current Velocity
Variation of Qo
Variation of A-,
Ay
Base Case:
XSHORE=l/2 mile
Variation of
Current Velocity
Variation of Ax,

-------
                                        TABLE 5-7
                         PARAMETER  VALUES  FOR NEAR OFFSHORE
GULF OF MEXICO CALCULATIONS


PARAMETER BASE CASE RANGE
Q0 (ft3/sec) 1 .5-1
D 25 5-25
XSHORE (ft) 15,000 2,500-15,000
H (ft) 33 15-33
H2 (ft) 5.5 3.5-5.5
A .00524 .002-. 00524
Ex -I «/3
a 7,500 1,250-7,500
xc
A .00524 .002-. 00524
Ey n* 4/3
o °°
yc
DO (ft/sec) 0
U, (ft/sec) 0
VQ (ft/sec)
Vj (ft/sec) ;

37 .18-. 37
25 .12-. 25

COMMENTS
Value of 1 chosen to given conservative estimate.
Value of D computed using EPA plume theory.3 Results not
sensitive to varying D by factor of 2.
15,000 is actual distance to shore. 2,500 used to test
sensitivity of results to variation of XSHORE.
Actual depth at site. 15 is approximate depth at XSHORE = 1/2 mile
H2 = l/6Hb
"4/3" diffusion law for horizontal diffusion in
ocean waters.0 Scale limited by distance
to shore. Value of .002 for A and A
x y
conservative estimate consistent with
published data. Results insensitive
to Ey.
Transverse (onshore) currents set equal to
zero. Conservative assumption.
Base Case values consistent with published
e f
studies. ' Lower values used to obtain more
conservative estimates.
Note:  See  references on following page.

-------
                REFERENCES FOR TABLE 5-7
     aM.A. Shirazi and L.R. Davis, Workshop of Thermal
Plume Prediction, Volume 1:  Submerged Discharge, EPA-R2-
72-005a  (Corvallis, Oregon:  National Environmental
Research Center, U.S. Environmental Protection Agency,
August 1972).


      G. Abraham, Jet Diffusion in Stagnant Ambient Fluid,
Delft Hydraulics Laboratory, Publication No. 29, 1963.

      N. Brooks, "Diffusion of Sewage Effluent in an Ocean-
Current," in Proceedings of the First International Con-
ference on Waste Disposal in the'Marine Environment, Univer-
sity of California, Berkeley, July 22-25, 1959, ed. by
E.A. Pearson (Oxford:  Pergamon Press, 1960).

      R. Koh and L. Fan, Mathematical Models for the
Prediction of Temperature Distributions Resulting from
the Discharge of Heated Water into Large Bodies of Water,
for the U.S.Environmental Protection Agency, Water Quality
Office, Water Pollution Control Research Series Report
16130 DWO 10/70, October 1970.

     0
      P. Oetking et al., Currents on the Nearshore Continental
Shelf of South Central Louisiana,Report No.17,Offshore
Ecology Investigation, Gulf Universities Research Consortium,
May 1, 1974.

      Louisiana Offshore Oil Port Environmental Baseline
Study, Volume II, Technical Appendices 1-5  (New Orleans:
LOOP, Inc.).
                           -75-

-------
of the EPA regulations could be more usefully estimated by
choosing a relatively high value for the rate of discharge.
A sensitivity run was made with the value of QQ equal to 0.5
cubic feet per second so that the impact associated with a
rate of discharge more closely approximating the actual
Block 16 discharge rate could be estimated.  Several compu-
tations were made with a value of XSHORE (i.e., distance to
shore) of 0.5 miles instead of the actual distance of 3
miles offshore of Block 16.  The results of these computations
can be used to indicate the predicted impacts of discharge
from platforms located one-half mile offshore.

     Data on the depth of water, H, was obtained from the
NOAA National Ocean Survey 1:80,000 scale map of Barataria
Bay and approaches.  The values for the thickness of the
initial mixing layer H2 were obtained from H by using the
relation H2 = H/6.  The source for this relationship is
Abraham8 who gives a range for H2 of from H/12 to H/6.  The
larger value of H2 (i.e., H2 = H/6) was used in the computa-
tions since vertical diffusion was not explicitly incorporated
into the computations, and the assumption of a thick mixing
layer without vertical diffusion is roughly equivalent to
assuming a thin initial mixing layer with vertical diffusion.

     The values of D were computed on the basis of values of
H, H2, and QQ using charts given in the EPA Workbook of
Thermal Plume Prediction^  (see Appendix E).  Diffusion
coefficients were computed using the "4/3" diffusion law
discussed in Appendix B.  The base case value of Ax = Ay =
0.00524 is taken from Brooks.1°  The sensitivity test value
of Ax = Ay = 0.002 is consistent with a range of 0.001 to
0.06 reported by Koh and Fan.H
     g
      G. Abraham, Jet Diffusion in Stagnant Ambient Fluid,
Delft Hydraulics Laboratory Publication No. 29, 1963.
     9
      M.A. Shirazi and L.R. Davis, Workbook of Thermal Plume
Prediction, Volume 1:  Submerged Discharge, EPA-R2-72-005a
 (Corvallis, Oregon:  National Environmental Research Center,
U.S. Environmental Protection Agency, August 1972).

       N. Brooks, "Diffusion of Sewage Effluent in an Ocean-
Current," in Proceedings of the First International Conference
on Waste Disposal in the Marine Environment, University of
California, Berkeley, July 1959, ed. by E.A. Pearson  (Oxford:
Pergamon Press, 1960).

       R. Koh and L. Fan, Mathematical Models for the Prediction
of Temperature Distributions Resulting from the Discharge of
Heated Water into Large Bodies of Water, for the U.S. Environ-
mental Protection Agency, Water Quality Office, Water Pollution
Control Research Series Report 16130 DWO 10/70, October 1970.

                            -76-

-------
     The base case drift current velocity of 0.37 feet per
second was obtained from the GURC study. ^-2  The tidal current
velocity value of 0.25 feet per second is in accord with
studies of the tidal current made for the proposed Louisiana
Offshore Oil Port (LOOP).13  The assumption that all currents
are in the alongshore direction (UQ=U]_=0) is a conservative
one since the tidal current component then transports the
discharge back and forth in the same line.

     The concentration factor isopleths for the calculations
NlA through N2C listed in Table 5-6 are shown in Figures 5-9a
through 5-9h, respectively, and plots of the areas enclosed
by the isopleths are given in Figure 5-5.
5. 6  Far Offshore Gulf of Mexico Waters

     For Gulf of Mexico waters beyond the 3-mile limit, a
site was selected in Block 108 of the Ship Shoal oilfield
area.  Block 108 is located approximately 27 miles offshore
with a depth of water of only 20 feet.14  Table 5-8 presents
a list of the various sets of input parameters for which
calculations were performed to obtain concentration factors
for far offshore Gulf waters, and Table 5-9 gives for each
input parameter its base case value, other values used, and
comments about choice of these values.

     As in the case of the near offshore calculations,  a
value of QQ = one cubic foot per second (15,000 barrels per
day)  was used.  This value is reasonable considering that
the average 1975 produced water discharge rates of Chevron
platforms S-93 and S-94 in Block 108 were 9,000 and 12,000
barrels per day, respectively.  Values of the mixing layer
thickness, H2, the initial dilution, D, and the diffusion
coefficients were obtained as described in Section 5.5.
Estimates of the current magnitudes were obtained from the
       P. Oetking et al., Currents on the Nearshore Continental
Shelf of South Central Louisiana, Report No. 7, Offshore
Ecology Investigation,Gulf Universities Research Consortium,
May 1, 1974.

     13Louisiana Offshore Oil Port Environmental Baseline Study
Volume II, Technical Appendices 1-5 (New Orleans:  LOOP, Inc.).

     "^Transcontinental Gas Pipe Line Corporation iMap of South
Louisiana and Louisiana Continental Shelf Showing Natural Gas
Pipe Lines, Transcontinental Gas Pipeline Corporation, 1974.
                              -77-

-------
  1000.0
   100.0:
(N
 <
 <
    lo.o:
       o.oi
                                    GRAND ISLE
0.1                1.0
    CONCENTRATION (%)
10.0
     Figure 5-5.   Area/concentration curve for Grand Isle
site in near offshore Gulf of Mexico.
                              -78-

-------
                 TABLE 5-8
LISTING OF COMPUTER CALCULATIONS PERFORMED
FOR THE FAR OFFSHORE GULF
OF MEXICO SITE




"° " "'" 'Tf'tP ('ft) (ft) Ax
FX 1 11 20 » 20 3.3 .00524
F0 1 11 20 «» 20 3.3 .00524
1 2
— 1
10 F, 1 11 20 20 3.3 .002
i J

F4 1 5 20 <» 20 3.3 .00524

E
X
nx
4/3
4/3


4/3

4/3

E
y
a A n n
xc y y °yc
.00524 4/3
°° .00524 4/3


.002 4/3

» .00524 4/1


U0 Ul V0 Vl COMMENTS
0 0 . 37 . 37 Base Case
0 0 .18 .18 Current
Sensitivity

0 0 .37 .37 Diffusion
Coefficient
Sensitivity
0 0 .37 .37 Initial
Dilution
Sensitivity

-------
                                                   TABLE 5-9
                                     PARAMETER  VALUES FOR  FAR OFFSHORE

                                         GULF OF MEXICO CALCULATIONS
I
oo
o
I
PARAMETER BASE CASE RANGE COMMENTS
Q (ft /sec) 1 Value of 1 consistent with discharge data.
D 11 5-11 Computed using EPA plume theory. a
H 20 Actual depth of water in block IDS, ship shoal oilfield area.
H2 3.3 H2 = H/6b.
AX, A .00524 .002
Ex'Ey "V ny 4/3
o o
xc, yc
U0 °
u1 o
VQ .37 .18-. 37
Vx .37 .18-. 37
"4/3" diffusion law for horizontal diffusion
in ocean waters,0 Value of .002 for AX, A
conservative estimate consistent with published data.
Transverse currents set equal to zero.
Conservative assumption.
Base case values consistent with published study. Lower
values used to obtain more conservative estimate.
            Note:  References a-e are identical to references a-e in Table 5-7.

-------
GURC Study report.    The conservative assumption was made
that both drift and tidal currents flow along the same axis.

     The concentration factor isopleths for the calculations
Fl through F4 listed in Table 5-8 are shown in Figures
5-10a through 5-10d, respectively, and plots of the areas
enclosed by these isopleths are given in Figure 5-6.
       Oetking et al., Currents on Nearshore Continental
Shelf of South Central Louisiana.
                             Q 1
                            "~ O -1.

-------
 XJCO.CH
  tooo.
o
.-I
<
w
«
<
   W.O-
                                        FAR OFFSHORE

                                            GULF OF MEXICO
                                                     ,\ WORST
                                                        F2.F4
    001
                          ' r
                          0.1
1.0
                            CONCENTRATION  (%)
                      10.0
         Figure 5-6.   Area/concentration curves  for far  offshore

   Gulf  of Mexico site.
                                 -82-

-------
  5000 -
  4000 _
-4000
                                     800
                                  FEET
                                                      j	I    _L
                                             1000      1200
                                                             1400
-5000  _
      Figure 5-1 a.
   HI:   Base case.
Percent  dilution isopleths, Hackberry Bay,  La
                               -83-

-------
 • 5000 -'
    Figure 5-7b.  Percent dilution isopleths, Hackberry Bay, La
H2:  Diffusion coefficient sensitivity, E =E =1.0
                          -84-

-------
  5000 -
  4500 ~
      UJ-LL
                        1	I	!_
                             800
                          FEET
j	j	
   iOOO
	J	
1200
                   -I-.-
                                                140u
X
  -4500 -
  -500C-
    Figure 5-7c.  Percent diffusion isopleths, Hackberry Bay, La.
H3: Diffusion coefficient sensitivity, E =E =1.0
                      -85-

-------
  5000 -
  4000 -
 -4CQO
                                                                    X
 -5000 -
    Figure 5-7d.   Percent dilution isopleths,  Hackberry Bay, La,

H4: Initial dilution sensitivity, D=5,(E =1.0)
                                         X
                           -86-

-------
 5000 -
 4000
 3000 -
 2000 -
 1000 r
-3.000 K
-2000 -
-3000
-4000
-5000 -
                                                                  	___  -*r
         Figure 5-7e.   Percent  dilution  isopleths,  Hackberry Bay,  La,

   H5:   Initial dilution sensitivity, D=10,(E =1.0)
                                                 X
                             -87-

-------
  5000 -
  4000 -
 -3000
 -4000
                                                                 X
    Figure 5-7f.   Percent dilution isopleths,  Hackberry Bay, La

H6:   Tidal velocity sensitivity, V =0.065,  (E  =1.0)
                                   J_           X
                            -88-

-------
En
K
  -1000 -
  -1500 -
  -3000
  -3SOO -
  -OOO -
  -4500 -
  -5000 -
                                             1000
                                                     1200
                                                              1400
                                                                       X
     Figure 5-7g.   Percent dilution isopleths Hackberry  Bay, La.
 H7:  Freshwater  current velocity sensitivity, V =0.1  (E =1.0)
                           -09-

-------
   5000 -
   4500 '
   4000 -
  3500 -
  3000 -
  2500 -
   2000 -
   1500
   1000 -
   500
K)
w
fa
  -500 -
  -1000 -
  -1500 -
  -2000 -
  -2500 -
  -3000 -
  -3500 -
  -«000 -
  -4500-
  -5000-
                                                                           X
      Figure  5-7h.   Percent  dilution  isopleths, Hackberry Bay, La

  H8:   Freshwater current velocity sensitivity, V =0.01  (E  =1.0)
                                                       O         X
                                  -90-

-------
 -4500
 -5000
     Figure 5-7i.  Percent dilution  isopleths, Hackberry Bay, La

H9:  Rotational tidal current  sensitivity,  U =0.05 (E =1.0)
                                             1        X-
                             -91-

-------
SHOPZI.INE
                         200   310   41)0   MO  300  700  SOO  900   1000
             -10,001
        Figure 5-8a.   Percent dilution isopleths,  Trading Bay
  Facility, Cook  Inlet,  Alaska.
  Cl:   Base Case, E  =1250.
                                 -92-

-------
S'-iORELINE-J
             -5,000





             -6.COO




             -7,000





             -8,000




             -9.000





            IC.oCO
                         200  300  400  5nO  600   700   800  900  1000


                                  FEET
       Figure  5-8b.  Percent dilution isopleths, Trading Bay
Facility, Cook Inlet,  Alaska.
C2:   Diffusion coefficient sensitivity,  E =7500.
                                              Y
                                -93-

-------
•b.
I
                         6,000
                         5,000





                         4,oon




                         3,000





                         2.000
                        -2.000
.05
                                0  200   300  40C  SOO 600/ 700  800   900  1000  1100 1200  1300 1400  1500 1600  1/00  1800 1900  2000
                        -10.000
                   Figure 5-8c.   Percent dilution  isopleths,Trading  Bay Facility,
            Alaska.

            C3:   Diffusion coefficient sensitivity, E  =250.

-------
 SHC-FELi.TE
         -4,
         -5,
         -e.ioo
         -7,
         -8,i
         -9,
            00
            0?
            00
            oo •
            00
            00
                     20G  30
                             40C   500  600  700  SOJ   900  1000

                               FEET
        -10.0301-
      Figure  5-8d.  Percent dilution  isopleths,  Granite
Point Facility,  Cook  Inlet, Alaska.
C4:   Base Case,  E =1250.
                          -95-

-------
                                           .05
SI! jrELIKE
                    200  300 I 40C  500

                               FEET
                                             300  900  1000
         -10,300
       Figure 5-8e.  Percent dilution isopleths, Granite
  Point Facility,  Cook Inlet,  Alaska.
  C5:  Diffusion coefficient sensitivity,E  =250.

                           -96-

-------
       Y


   10,000-



    9000



    8000



    7000



    6000



    5000
W   4000
W
    3000-
    2000
     1000

      1,
      2.
       0
    -1000
             100    200    300   400   500   600   700    800    900    1000

                                     FEET
X
       Figure  5-9a.  Near offshore dilution percentage isopleths.
  N1A:   Base case,  XSHORE=3 miles.

-------
00
I
                      Y


                  10,000-



                  9000



                  8000



                  7000



                  6000



                  5000
EH
W  4000
W
                  3000
                  2000
                   1000
                    1.
                    2.
                     0
                  -1000
                        .5
                           100    200   300   400    .>00    600

                                                 FEET
                                               700    800   900   1000
                                                                      X
                      Figure  5-9b.  Near  offshore dilution percentage isopleths.
                NIB:   Dilution sensitivity, D=10 (XSHORE=3 miles)

-------
W
w
c-4
10,000-





 9000





 8000





 7000





 6000





 5000





 4000





 3000





 2000





 1000


   1.


   2t





 -1000-
            —i	1	1	1	1 -  •  i—
             100   200   300    400    500   600


                                     FEET
700
—1	1	1	

 800   900   1000
                                                                     X
       Figure 5-9c.   Near offshore dilution percentage  isopleths.

   NIC:   Current velocity sensitivity,  V =.18,  V = .12  (XSHORE=3  miles)

-------
o
o
I
EH
W
W
Pn
                  10,000-
                   9000
                   8000
                   7000
                   6000
                   5000
                   4000
                   3000
                   2000
                   1000
                     1.
                      0
                   -1000-
                         .05
                            100   200   300    400
                                    500    600


                                     FEET
700    800    900   1000
                                                                       X
                       Figure  5-9d.  Near offshore dilution percentage isolpleths
                 N1D:   Discharge rate  sensitivity, Q =.05  (XSHORE=3 miles)

-------
I
M
O
M
I
                  10,000
                   9000
                   0000
                   7000
                   6000
                   5000
W
W   4000
                   3000
                   2000


                    1.

                   1000

                    2.
                  -1000
                        .5
                                  .05
                           100    200   300   400    500    600   700   800    900    1000
                                    FEET
                                                                                     X
                      Figure 5-9e.   Near offshore dilution percentage isopleths.
                 N1E:  Diffusion coefficient  sensitivity, A =A  =0.002  (XSHORE-3 miles)

-------
I
M
O

I
W
Cn
10,000-



 9000



 8000



 7000



 6000



 5000



 4000



 3000



 2000



 1000

   2.
    -1000
              100   200    300   400
                                 500    600

                                   FEET
                                                              700    800    900    1COO
                                                                       X
        Figure 5-9f.   Near  offshore  dilution percentage isopleths
  N2A:  Base case, XSHORE=%  mile.

-------
   10,000-
    9000
t
M
O

I
W
W
    8000
    7000
    6000
    5000
    4000
    -1000
                                   500    600


                                    FEET
                                                             700   800    900   1000
                                                                     X
       Figure 5-9g.  Near offshore  dilution percentage  isopleths.
 N2B:  Current velocity  sensitivity,  V =.18,  V =.12  (XSHORE=Jj mile)

-------
o
£*
               Pn
10,000-




 9000




 8000




 7000




 6000




 5000




 4000




 3000


  1.

 2000


  2.

 1000
                   -1000-J
                                         .05
                             100   200    300   400   500    600    700    800   900   1000


                                                     FEET
                       Figure 5-9h.  Near offshore dilution percentage isopleths.
                N2C:   Diffusion coefficient sensitivity,  A =A =0.002  (XSEORE=h rcile)

-------
o
Ul
I
               W
               W
                   10,000-
                    9000
                   8000
                    7000
                    6000
                    5000
4000
                    3000
                    2000
                    1000
                   -1000
                             100   200   300   400    WO   600    700    600   900   1000
                                   FEET
                                                                                        X
                       Figure  5-10a,
                  Fl:  Base case.
                     Far  offshore dilution percentage isopleths

-------
    10,000
    9000
    8000


      \
    7000
I
H-1
O

I
EH
W
W
    6000
     5000
4000
     3000
     2000
     WOO
    -1000
                   200    300   400   500    600    700    800   900   1000
                                  FEET
                                                                       X
        Figure  5-10b.  Far  offshore  dilution  percentage isopleths.
   F2:   Current  velocity sensitivity, V =V =0.18.

-------
I
M
O

I
                10,000
                 9000
                 8000
                 7000
                 6000
                 5000
W     4000
W
                 3000
                 2000
                 1000
                                  .05
                 -1000
                          100   200   300    400    500   600   700    800    900    1000


                                                    FEET
                                                                                   X
                     Figure 5-10c.   Far  offshore  dilution  percentage isopleths,
              F3:   Diffusion  coefficient sensitivity, A =A =0.002.

-------
o
CO
I
                  10,000-
                   9000
                   8000
                   7000
                   6000
                   5000
              W
              W
                                 200    300   400
                  -1000
500    600


  FEET
700    800   900   1000
                                                                                    X
                      Figure 5-10d.   Far offshore dilution percentage  isopleths,

                 F4:  Initial dilution sensitivity,D=5.

-------
                         CHAPTER SIX
              METHODOLOGY FOR IMPACT ASSESSMENT
6.1  Introduction

     This chapter is concerned with the data and analytical
methods which were used for predicting the toxic impacts
which would result from the altered toxicant and salinity
distributions in the waters surrounding an offshore oil
drilling site as a result of brine discharges.  Two classes
of brine-related impacts are considered here:  toxic effects,
including direct mortality and a variety of sublethal effects
on resident organisms; and potential human health effects
resulting from the consumption of oysters or other organisms
which can accumulate in their body tissues high levels of
toxic metals and hydrocarbons.  Because of the highly
variable and nonsystematic nature of the available data on
the toxic effects of pollutants, the analysis described here
is necessarily only semi-quantitative, and based on simpli-
fying assumptions derived from general toxicological consi-
derations and from recent field studies of biological
communities in the vicinity of offshore drilling sites in
Louisiana and Texas.  It is believed that the approximations
which are introduced have at least order-of-magnitude validity;
and the results, which are described in a subsequent chapter
of the report, should be considered in that light.

     The material in this chapter is of two types.  The
first consists of toxicity data directly used in the impacts
analysis of the next chapter, and the second deals with a
variety of issues (e.g., synergisms, adaptation responses,
etc.) which although not used directly in the analysis due
to the lack of quantitative data, are nonetheless secondary
considerations which should be kept in mind in interpreting
the conclusions reached in this report.


6.2  Methodology

     The assessment of impacts, outlined in Figure 6-1,
consists basically of delineating a "zone of impact" outside
of which only insignificant impacts would be predicted on
ecological communities and on contaminant levels in human
food organisms.  Determining the area of this zone of impact
involves three steps:
                             -109-

-------
Criteria
LC50 Data
    Sublethal Effects
           Data
   Estimation of "Safe"
      Concentrations
                     Levels in Brines
            Calculation of Necessary
               Dilution Factors
            Determine Dominant
             (Longest Range)
                 Effect
                         Data on Human
                         Health Effects
                                                  Bioaccumulation
                                                    Data (Hg,BaP)
                                Dispersion Model
                                     Outputs
                                          Determine Impacted
                                        Areas(Best,Worst Cases)
       Figure 6-1.  Outline of the analysis.
                              -110-

-------
     1.   For a particular class of impact, a set of "safe"
          levels must be defined for each toxic contaminant
          in oilfield brines.

     2.   The safe levels of each constituent must then be
          compared with the levels actually found in oil-
          field brines to produce a Necessary Dilution
          Factor (NDF) for each constituent; i.e., the
          dilution necessary to bring that constituent down
          to a "safe" level.

     3.   The dispersion model output described in the
          previous chapter can then be used to determine the
          area around the production platform in which the
          dilution of each constituent is less than or equal
          to its NDF.  The maximum area for any of these
          constituents will then be used as an estimate of
          total impacted area.
     Similar analyses can be done for specific classes of
effects which are known to be associated with the pollutants
found in oilfield brines.  For example, the band between two
adjacent isopleths produced by the dispersion model repre-
sents a region of predicted pollutant concentration in the
range x to x + Ax, for some particular x, and the tables of
effects given later in this chapter can then be consulted to
see if any significant effects have been noted on organisms
in that range of concentrations.  Thus, the type of effect,
and in some cases, the absolute magnitude of the effect (in
terms of number of organisms affected)  can be estimated for
each band.  This information is complemented by the calcu-
lations of the areas of impacted zones, which provide a
useful summary statistic for the whole site.

     Three separate estimates of "safe" (no effects)  concen-
trations are made for each brine constituent based upon the
toxicological data presented later in this chapter.  The
first is based on the EPA marine water quality criterion for
each constituent  (see Table 6-1); a second is based on the
minimum concentration at which any adverse effect has been
noted in the literature; and a third is based on the use of
an application factor of 0.01 in conjunction with 96 hr LC50
data.  (The use of an "application factor" of 0.01 together
with 96 hr LC50 data in predicting safe levels is supported
                            -111-

-------
                         TABLE 6-1

     EPA WATER QUALITY CRITERIA FOR BRINE CONSTITUENTS
                        MAXIMUM             RECOMMENDED
 SUBSTANCE               LEVEL3         APPLICATION FACTOR3
                         (mg/1)
 Arsenic                0.05b          0.01 x 96 hr LC50b
 Cadmium                0.005°         0.01 x 96 hr LC50b
 Chromium               0.1 (0.01 in   0.01 x 96 hr LC50
                        oyster-producing
                        areas) *-*
 Copper                 0.05b          0.1  x 96 hr LC50°
 Cyanide                0.005°         0.1  x 96 hr I,C50b
 Lead                   0.05b          0.01 x 96 hr LC5QC
 Mercury                0.0001C
 Nickel                 O.lb           0.01 x 96 hr LC50°
 Oil & Grease            --            0.01 x 96 hr LC50C
 Silver                 0.005b         0.01 x 96 hr LC50°
 Zinc                   O.lb           0.01 x 96 hr LC50b
     aCriterion is lower of the numbers in these two columns,
      Committee on Water Quality Criteria, Water Quality
Criteria 1972, National Academy of Sciences and National
Academy of Engineering, 1972.
     °U.S. Environmental Protection Agency, Quality Criteria
for Water, 1976, Washington, D.C.
                              -112-

-------
both in recent EPA water quality criteria documents  and in
the technical literature.2  it is believed to represent a
margin of safety adequate to protect marine communities from
significant acute and chronic deleterious effects.  The use
of application factors in interpreting lethal concentration
data is discussed later in this chapter.)

     Accurate numerical estimates of the degree of risk
associated with the human consumption of fish or shellfish
which have accumulated quantities of trace metals or hydro-
carbons are, of course, impossible to obtain, so the follow-
ing highly qualitative approach is adopted.  The analysis
will concentrate on a two components of oilfield brines
which are known to be bioaccumulated and to pose a signifi-
cant human health risk:  benz[a]pyrene and mercury.  For
benzpyrene, an important hydrocarbon carcinogen in crude
oil, extrapolations from concentrations in water to concen-
trations in sessile food organisms such as shellfish will be
estimated based on available data on the bioaccumulation of
aromatic hydrocarbons.  Although reliable dose response data
for this chemical are not available, the estimated concentra-
tion in fish will be considered unacceptable if it exceeds
the background level of benzpyrene exposure in other food
sources, as estimated in previous studies.  Mercury bio-
accumulation will be estimated from available data on
mercury accumulation rates for various organisms, and the
final levels in organisms will be considered unacceptable if
they exceed the 0.5 ppm standard currently prevailing in the
United States and Canada.  Each site can then be charac-
terized by the area of its "unacceptable" or "unsafe" region.

     Two important assumptions of the impact analysis are:

     1.   That there is no significant toxicity modification
          due to complexation of metal ions, oxidation or
          reduction, microbial degradation of hydrocarbons,
          and other environmental interactions (in other
          words, it is assumed that these effects are small
      For example:  "The maximum acceptable concentration of
mercury in marine or estuarine waters is 1/100  (0.01) of the
96 hr LC50 value determined using the receiving water in
question and the most important sensitive species in the
locality as the test organism."  U.S. Environmental Protection
Agency, Water Quality Criteria, 1973, p. 275.  Similar criteria
are set for other metals.
     2
      See the data reviewed in J.B. Sprague, "Measurement of
Pollutant Toxicity to Fish--III.  Sublethal Effects and
'Safe1 Concentration," Water Research 5  (1971): 257.
                             -113-

-------
          in magnitude compared with concentration effects
          which depend only on the rate of dilution of the
          brine).

     2.    That the effects of the pollutants are purely
          additive, and do not depend in a synergistic or
          antagonistic fashion on the levels of other
          pollutants.  In general, this second assumption is
          not valid, since synergisms have been noted for
          trace metals, but it has been shown to hold for at
          least some pollutants at low concentrations (on .,
          the order of only a few tenths of their LC50's).
     These assumptions are made necessary by the absence of
quantitative data on the extent to which environmental
interactions or synergisms with other pollutants will effect
toxicity at a particular site.
6.3  Toxicity Data

     6.3.1  Introduction

     Tables 6-2 through 6-12 summarize currently available
data on the toxicity of crude oil, phenol, and trace metals
(silver, copper, mercury, cadmium, chromium, zinc, nickel,
arsenic, and lead) to organisms in marine and estuarine
environments.   (See Figure 6-2 for an explanation of the
format of these tables.)  In addition, supplementary data
are presented in Table 6-13 relating to the toxicity of
specific crude oil fractions and components.  This section
will deal briefly with some of the factors which must be
taken into account in interpreting and applying the data
contained in these tables.
      See, for example, J.B. Sprague and Ramsay, "Lethal
Levels of Mixed Copper-Zinc Solutions for Juvenile Salmon,"
Journal of the Fisheries Research Board of Canada 22(2)  (1965):
425-432, who found an additive interaction between copper and
zinc for the juvenile Atlantic salmon in the range of one toxic
unit, and a superadditive interaction only at much higher levels.
                             -114-

-------
    Typical Data Point:   0.32  ppm -  Incipient lethal level of  copper for
                                     juvenile Atlantic salmon  (J.B.  Sprague
                                     and B.A. Ramsay, Journal of  the Fisheries
                                     Research Board of Canada 22/2)  (1965) :
                                     425-432)

    is entered in Table  6-3  as follows:
        CONCENTRATION  (mg/1)*
                                                    LOCATION      REFERENCE
       1.000
          •1 mg/1 - 1 ppm
     Tables use the approximation  1  ppm =  1 rag/1.   Location code indicates whether  tested
species is found in Alaska  (A)  or  Louisiana (L)  waters.  Superscript s indicates  that test
species is found in location;  superscript  g indicates that other species of  the same genus
as the test species are found  in the location.
            Figure  6-2.  Explanation of toxicity tables.

-------
                                                                TABLE  6-2
                                                     TOXICITY  TABLE  - COPPER
 CONCENTRATION  (mg/1)*
                                                           EFFECT
                                                                                                  LOCATION
                                                                                                                          REFERENCE
1  ,000
                                           92 hr.  LC50 for Artemia
                                              centration which  produces Sot  reduction within 1 h
                                           hronlc exposure of flounder Pseudopleuronectes at thl
                                            hr. LC50  for Haterslporia
                                            he. ICiO  (or Splrot,
                                          11
                                          LCD r
                                          Caused  11.3* mortality  in 2* nra.  in HUgcr
                                          Reduced On Consumption  591 in mud  snail Haasariur obsolet
                                          6 h
                                          Causes greening  of oysters within 3 wkt
  o.i  ---
 o.oi  "irrr::1
                                                                                                                         Raymont and Shields (1962)
                                                                                                                        Wiiely And BUck 1196?)
                                                                                                                        Jackim !191Di

                                                                                                                        jackim U9'0}
                                                                                                                        Jackim (1970)
                                                                                                                        Jackim (1970)
                                                                                                                        Payment and Shields (1962)
                                                                                                                        Eisler and Gardner  (1973)
                                                                                                                        Bryan  and Humnverstone  (1971}
                                                                                                                        Hiaely and Slick (1967)
                                                                                                                        Pyofinch and Mott
                                                                                                                        Pyefinch and Mott
                                                                                                                                             6)
                                                                                                                        Bryan and Hummeratone (1*71

                                                                                                                        Rayront and Shields  (1961)
                                                                                                                                     ott
                                                                                                                        Pyefinch and Mott
                                                                                                                        Rjymont and Shields (196:)
                                                                                                                        laymont and Shields (1962)
                                                                                                                       Calabreae (1973)
                                                                                                                       Raymont and Shield* [19631
                                                                                                                       Stephenaon  and Taylor (1975)

                                                                                                                       Stephenson  and Taylor (Z975J
     *1  mg/1  =  1  ppm

-------
                                                 TABLE 6-2  (CONT.)




                                            TOXICITY  TABLE -  COPPER
CONCENTRATION  (mg/1)*
                                                  EFFECT
                                                                                   LOCATION
                                                                                                        REFERENCE
1,000
                                      72 hr. LC100 for Acmaea and Haliotla
 0.01
0.001
EPA (1973)




EPA (1973)




Calabrese (1973)








EPA (1973)






Sprague  (1964)
                                                                                                       Bornos and Stanbory 1191




                                                                                                       JUiymont «nd Shields (I9fi
                                                                                                             et al. (19^1
    *1 mg/1  = 1  ppm

-------
                                                          TABLE  6-3




                                                 TOXICITY TABLE -  ZINC
  CONCENTRATION  (mg/1)*
                                                      EFFECT
                                                                                          LOCATION
  REFERENCE
     100
  0.001
 0.0001
0.00001
                                                        dulu




                                         2 hr,  LC50 for Hat




                                         Interpolated 24 hr  LC50 for Atlantic salmon amolta
   o.oi  -  —-\~-
Eifller and Gardner  (1973)




Wisely and Bliek (1967)



Herbert and Wakeford (196*)




EPA (1973)
                                                                                                                               7)
                                                                                                              Wisely and Blick 11967)
                                                                                                              Sprague (1964)
                                                                                                              Calabrese (1973)
                                                                                                              Venlilla (1973}



                                                                                                              EPA (1973)
     *1  mg/1  = 1  ppm

-------
                                                   TABLE  6-4




                                         TOXICITY TABLE - CHROMIUM
 CONCENTRATION  (mg/1)*
                                                EFFECT
LOCATION
                    REFERENCE
1,000
  100
   10
    1   •-
  0.1
                                                                                                  Raymont and Shields (1962)








                                                                                                  Calabrase (197])



                                                                                                  Raymont and Shields (1962)




                                                                                                  Raymont and Shields (1962)




                                                                                                  Raymont and Shields (19C2)




                                                                                                  EPA (1973)
   *i mg/1 «  1 ppm

-------
                                         TABLE  6-5


                                   TOXICITY TABLE - LEAD
CONCENTRATION  (mg/1)*
                                          EFFECT
                                                                       LOCATION
                                                                                        REFERENCE
1 ,000
  100
   10  -
   1  -
 0.1
0.01
                                                                                       JacXLm (1970)
                   - concentration
                     in seawater
                                                                                       EPA (1973)
                                                                                       EPA (1973)
    *1 mg/1 =  1 ppm

-------
                                                                 TABLE 6-6

                                                     TOXICITY  TABLE  -  MERCURY
  CONCENTRATION  (mg/1)*
EFFECT
                                        LOCATION
                                                                 REFERENCE
 1000.0
                                              2.5 hr. LC50 for Aytemia
                                              population)

                                             .2  hr. LCSQ for Mytllus
                                                            CH3HgCl)

                                             24 hr.  exposure produced  B0% mortality in  Vustralorbia
                                               use.1 104  24 hr. mortality in Hitocy
                                             2,5 hr.  LC50  for Elminius
                                             96 hr  exposure  (Fundulus) caused 19,1% reluctio
                                                 bovo,  31.94 reduction in xanthine oxLdase level
                                              6 hr.  TLm for Fundulua
                                                          gill filaments witnin  a  28 day expounre
                                              4  hr. exposure caused 53* reduction in efficiency of
                                             Caustd 100% reduction ir settlement by ciprida  of
                                             barnacle Dal anna  balanoidoa (19 day exposure)
                                               hr. exposure  caused 22 2%  reduction in  efficiency
                                            Gambuaia in  escaping predation by Hicropterus
                                                                                                                            Wisely and Ulick  (1967)
                                                                                                                            Barnes and StanUuiy  (1'J48)



                                                                                                                            Barnes and Stanbury  (1948)

                                                                                                                            Hiaely and Dlick  (1967)

                                                                                                                            LPA (1973)
                                                                                                                           Barnes and Stanbury (1948)

                                                                                                                           Pyefinch and Mott
                                                              Jackim (1970)


                                                              Jacnim (1970)

                                                              Jacttim (1970)

                                                              Jackim (1970)
                                                                                                                           Pyefinch and Kott

                                                                                                                           Darnes  and Stanbury  (1948)
                                                              Wisely and Dlick  (19671

                                                              Kania and O'Hara  (1974}


                                                              Wisely and Blick  (1967)
                                                                                                                           Pyefinch and Mott
                                                                                                                           Kama and O'Hara  (1974)
                                                              Kama and O'Hara  (1974)


                                                              C^labres-e (19131

                                                              Calabrese (1973)

                                                              Ventilla (1973)


                                                              EPA U9131

                                                              EPA (1973)


                                                              Calabrese (1973)
0.001
     *1 mg/1  =  1 ppm

-------
                                                              TABLE  6-7


                                                               SILVER
   CONCENTRATION  (mg/1)*
EFFECT
                                     LOCATION
                                                            REFERENCE
     10
    0.1
  0.01
 0.001
                                            Approximately double O. consumption in H.'tllua
                                             :au< ed approximately 141 increase in 0., >:onBumption
0.0001
                                             lowed development  and induced abnormal  iltitei in
                                             mb.
                                                                                                                    EPA (1973)

                                                                                                                    Maclnnen an
                                                                                                                    Jackim (1970)



                                                                                                                    Jackim (1970)



                                                                                                                    Jackim (1970)



                                                                                                                    Jackim (1970)

                                                                                                                    Calabrete (1973)

                                                                                                                    Calabrese (1973)

                                                                                                                    EPA (1973)

                                                                                                                    Calabtesa (1973)
                                                                                                                    EPA (1373)

                                                                                                                    EPA (1973)
       *1 mg/1  =  1 ppm

-------
                                                                   TABLE  6-!

                                                                    CADMIUM
CONCENTRATION  (mg/1)*
                                                             EFFECT
                                                                                                       LOCATION
                                                                                                                                 REFERENCE
1,000
    10
   0.1
  0.01
0.001
                                           ,48 hr.  TL25 blue  mussel,  Hytilua edulia
/96 hr. TL25 blue mussel,  Hytilua  edulia                            A9

    hr. TLSO blue mussel,  Hytilua  edulis                            A9

-24 hr. killifish. Fundulua majalls                                 L9

. 48 hr, TL25 soft shell clam.  My a  arenajrla.

-24 hr, TL50 Atlantic oyster drill,  Urosalpinx cinerea              L9




-24 hr, TL50 killiiish,  Fundulus majalls                            L9

-48 hr. TLSO mud snail,  N a s s ar i u s  gb_s_p_letu_s                         L9

 24 hr, TL75 Atlantic oyster drill,  Urosalplnx ein_ere_a              L9

 46 hr, TL25 green crab, Carclous  maenus



 24 hr.

 48 hr, TL75 blue mussel, Mytilus  edulis                            A9

 24 hr, TL75 klllifish,  Fundulus majalis                            L9



 48 hr. TL25 killifish,  Fundulus maj^ljlj                            L9






 96 hr. TL25 shecpshead  minnow, Cyprinodon, va r iggatua               A5



X24 hr. TL75 sheepshead  minnow, Cyprinodon variegatus               A*

    hr, TLSO klllifish,  Funduluj ma]alis                            L

'168 hr.  TL25 mummichog, Fundulua  heterocUtus                      L9

    hr. TLSO mummichog,  Fund_ulus heterOcl^ttua                       L9



 24 hr. TL25 grass  shrimp,  Palacmqnetcs vulgarIs                     L*

L96 hr. TLSO ahr>epaheaa  minnow, Cyprinodon va r i .egatua               L*






 20 hrs.
                                          L 24
                                             I hr. TL25 sandworm, Ne^eJ^ yirens

                                             : hr, TL7S shecpshc.sJ -"i' now,  Cyprinodon  varlegatua
                                           Veduction in acid phosplmtase levels;  10.61  reduction in
                                             anthinc oxidase levels, and 17 31  reduction in caLalata
                                           ilevels in surviving Fundulus
                                          V96 hr. TL50 blua musael, Mytilus edulia
 Eialor  (1971)

 Elaler  (1971)

 Eisler  (1571)

 Eisler  (1971)

 Eisler  (1971)

 Eisler  (1971)

 Elaler  (1971!

 Clsler  (1971)

 Eisler  (1971)

 Eisler  (197U

 Eisler  (1971)

 Eisler  (1971)

 Eisler  (1971)

 Elaler  (1971)

 Eisler  (1971)

 Eisler  (1971)

 Eisler  (1971)

 Eisler  (1971)

 Eisler  (1971)

 Eialer  (1971)

 Eisler  (1971)

 Eisler  [1971)

 Elaler  (1971)

 Elsler  (1971)

 Eisler  11971)

 Eisler  (1971)

 Eisler  (1971)

Eisler  (1371)

Elsler  11971)

Eialer  11971)

Eisler  (1971)

Gardner  and Yevich  (1970)



Eialer (1971)

Eisler (1971)

Eialer (1971)

Eisler  (1971)

Eisler  (1971)

Eialer (1971)

Eislej (1971)

Eisler (1971)

Eialer  (1971)

Eisler  (1971)

Eialer {19711

Eisler  11971)

Eisler  11971)
Eisler (1971)

EiBlar (1971)

Eisler (1971)

Eial^r (1971)

Eioler (1971)

Elsler (1971)

Eialer M971)
      *1  mg/1  =   1  ppm

-------
                                                          TABLE  6-8   (CONT.)





                                                                  CADMIUM
CONCENTRATION  (mg/1)*
                                                           EFFECT
                                                                                                  LOCATION
                                                                                                                           REFERENCE
1,000
                                           tl  ht. TI.75 sanduorm, Herein vlren



                                          y96  hr. TL25 sandworm, Nereis virpn
   100
 0.01
0.001
 Eliler  (1971)



 Eisler  (1971)



 Eial«r  (1971)




 Eisler  (1571)




 Eisler  (1971)




 Eisler  (1971)




 Eisler  (1971)




 EisUc  (19711




 Eisler  (1971)




 Eisler  (1971!



 Eisler  (1971)



 EisJer  (197U



 Collier ot al  (1973)




 Eialec  (1971)




 Eialcr  (1971)



 Eialer and Gardner  (19




 Eislgr  (1971)



 Eisler  (1971)




 Eisler  (1971)



 Eisler  (19711




 Eialcr  (1971)




 Eisler  [19711




 Eisler  (1971)




 Eisler  (1971)




 Collier i t al  (1973)






 Eisler  (1971)



 Eialer ( 1971 )




 Eiil«r (1971)








 Eisler (1971)



 Eislor (1971)



 Eislsr (1971?



 EUler (1971)




 Eisler (1971)
                                                                                                                                       (1973)
Collier



EUler (1971)




Eislec (1971)




Eisler (1971)




Elaler [1971]



Calabrese  {1973)




Eisler U971I



Collier et si.  (1973)




Eisler (1971)




Elsler (1971)




Eialer (1971)



Eisler (1971)




Eisler (1971)



Eisler (1971)




Elsler (1971)




Collier et «1.  (1973)






Eisler (1971)




Einlrr 11971)



Cfllflbrese  [1973)




Collier at al.  (1973)
     *1  mg/1  =  1 ppm

-------
                                                     TABLE 6-8  (CONT.)
                                                          CADMIUM
 CONCENTRATION  (mg/1)'
EFFECT
                                    LOCATION
                                                          REFERENCE
 1,000
    10
 0.01
0.001
                                                                                                             Eiller (1971)
                                                                                                                     71)
                                                                                                             Eisler (1971)
                                                                                                             Eisler (1971)
                                                                                                             Eisler (1971)
                                                                                                             Elsler (19711
                                                                                                             Eisler (1971)
                                                                                                             Eisler (1971)
                                                                                                             Elilcr 11971)
                                       J8 hr. TL75 sand shrimp, Ctangon  sortemspinoaa
                                                                                                                      II
                                                                                                                     71)
                                                       Eisler (1971)
                                                       Eisler (1971)
                                                       EisUr [19711
                                                       Eisler (1971)
                                                       EPA  (1973)
                                                       tPA  (1S73)
    *1 mg/1  =  1  ppm

-------
                                                                 TABLE  6-9
                                                  TOXICITY TABLE -  CRUDE OILS
 CONCENTRATION  {mg/1)*
EFFECT
                                        LOCATION
                                                                                                                              REFERENCE
.  100,000
  10,000
   1,000

                                                    f equilibrium in codfish
                                               4 hr, TLm for Oncorhynchua  gorbuscha (pink salmon)  fry
                                                thai to Ch 1 Qre 1 l_a a u t o t coph lea (green  algae)
                                                   urchins)  wTuTVfi "6~ ~hT,  exp
                                                                 delayed cull division in CoacinodlB:ua
                                                  hr  LCSO for cypitnodon variegatua (sbeepshBdfl minno*)




                                                  hr  LC50 fnr Funclulua aimul
                                                                                                                                       3)
                                                                                                                              alcr 11973)






                                                                                                                              rhina (197<)
                                                                                                                            Eialer 11975)
                                                               Sturdevant  (1972)






                                                               Rice (1^73)






                                                               Rice (1973)






                                                               Rice (1973)






                                                               Elaler (1975






                                                               Eiolet (1975)



                                                               Eialer (1975)



                                                               Kaiinen and Rica (1974)




                                                               Rice [1973)






                                                               Rice (1973)






                                                               Rice (1973)










                                                               Pulich at  al.  U974J




                                                               Rice (1973)






                                                               Rice (1973)






                                                               Rice (1973)






                                                               Eifller (1975






                                                               Rice (1973)
                                                                                                                                       •?*>
                                                                                                                             Petkina (1974)






                                                                                                                             Wells  (1972)








                                                                                                                             Wells  (1972)



                                                                                                                             Spoonar (196B)






                                                                                                                             Mirohov (1970)










                                                                                                                             Malacea (1964)




                                                                                                                             Rice  (1973)
                                                                                                                             Anderson et. al.  (1974)
                                                                                                                                     et al  (1974)
                                                                                                                             Morwnaerts-VlUiet (1973)
        *1  mg/1=   1  ppm

-------
                                                          TABLE  6-9  (CONT.)
                                                   TOXICITY TABLE  -  CRUDE  OILS
CONCENTRATION   (mg/1)*
                                                            EFFECT
                                                                                                     LOCATION
                                                                                                                              REFERENCE
100,000
                                              to 501 in  phytoplanKton


                                               dulus simulu
                                              51 reduction in photosynthesis of Enteromorpha intestine]la

                                             (pink  salmon) fry at 1. 5° C
                                                hr  TL50 for Mysidc Jsis almyrg (mysid)
                                             Photosynthesis reduo-ed  in ulva fenestia.  Latninaria
                                             96 hr.  1Ui  for Henjdu beryllina (silveraide)
                                             96 hr.  TLm  for pink salmon  eggs
Gordon and Prouso 11973)

Anderson et al. (19741
Anderson et al. (1974)
                                                                                                                           Andi
                                                                                                                                              4)
                                                                                                                           Malacca et al.  (19641
                                                                                                                           Anderson et il.  (19741
                                                                                                                           Rice et al. 11975)
                                                                                                                                             2)
                                                                                                                            Xnoeraon et al.  11914)
                                                                                                                           Anderson et al.  (19741
                                                                                                                           Andi
                                                                                                                            Rice  11973)
                                                                                                                            Rice et al.  (197<)

                                                                                                                            Anderson et  al.  (1974)
                                                                                                                            Anderson et  al.  (1974)
                                                                                                                            Shiela  11973)

                                                                                                                            Shiels  (1973)
                                                                                                                            Walsh and Kttchell  (1973)
                                                                                                                            Atema and stein  11974}
Shiels 11973)
Shiela (1973)
Hells 1197!)
Eisler (19751
Perkins (1974)

Perkins (1974)
                                                                                                                                              '41
                                                                                                                                       4)
                                                                                                                            Pcikin»  (197J)
                                                                                                                            Mironov  (1970)
                                                                                                                            Moore et al.  (1974)
                                                                                                                            Moore el al.  119741
                                                                                                                            And.
                                                                                                                                 (1973)
 Anderson ot al.  (19741
 Anderson et al.  (1974)
 Shiels  11973)

 Shiels  (1973)
 Anderson et al.  (1974)
 Anderson et al.  (1974)
 Rice  et al. (1075)

 Cairns  and Scheier (1962)
 Anderson et al.  (1974)
 Thomas  and Rica 11975)
 Anderson et al.  11974)
      *  I rag/1 = 1  ppm

-------
                                                          TABLE 6-9   (CONT.)

                                                   TOXICITY TABLE - CRUDE OILS
CONCENTRATION   (mg/1)*
                                                            EFFECT
LOCATION
                         REFERENCE
100,000
                                            10 day  etfpQ&ure had no effect on Chlorocuccum Sp.
                                            (t-hytuplankton)
                                            I day

                                            631  Gadus rr.orrhua (cod)  killed during  100 hr. exposure
                                            (grass  shrimp)
                                                                                         i pug 11o
                                            wuj_f_i

                                            Ho effect on tjrre to d^ath of larvae  of Gadus^ morrhu.
                                            trgchpiJemn (dinof I


                                            of phytoplankton
                      JHPCF  (1972)

                      Thomas and Rice  (1975)


                      Shiela (1973)


                      Moore et al.  (1974)

                      JHPCF (1»7J)

                      Shiels (1973)


                      Anderson et al.  (1974)


                      Rice (1973)

                      Thomas and Rice  (1975)

                      Moore et al.  (1974)


                      Moore et al.  (19741


                      Mciora et nl.  (1974)


                      Perkins (1974)


                      Perkins (1974)

                      Moore ct al.  (1974)


                      Mooro et al.  (1974)

                      Environmental Studies
                      Board (1972)

                      Environmental Studies
                      Board (1972)

                      Mironov (1968)
                      Amlfrflon et  al.  (1974)


                      Rice (1973)

                      Pice (1975)


                      Shiala (1973)

                      Perkins (1574)

                      Perkins 11914)

                      Perkins (1974)


                      Perkins (1974)


                      Perkins (1974)


                      Moots et al.  (1974)


                      Moore et al.  (10741


                      Moore et al.  (1974)


                      Moore et at,  (1974)


                      Perkins (1974J



                      Perkins (1974)

                      Perkins (1974)
                                                                                                                           Moore et al.  (1974)

                                                                                                                           Mironov (1971)   (WQC 1972 342)
                                                                                                                           Perkins (1974)

                                                                                                                           Perkins (1974)
     *1  mg/1  =  1  pptu

-------
                                                        TABLE  6-9   (CONT.)

                                                 TOXICITY  TABLE  -  CRUDE OILS
 CONCENTRATION  (mg/1)'
                                                        EFFECT
                                                                                             LOCATION
                                                                                                                    REFERENCE
 100,000
I  10,000
  1,000
               isb
                 T



         Ttfet*
                                                                 iTed
                                        —Abnormal development of flounder spawn
-100%  increase in photosynthefcic rate of Port Vald-z plankton

 Inhibited attraction to food source of HaB_p_a_tiua_ abacietus
 (mud  mail)

-Stimulates plankton growth

_IntubiteJ feeding and mating responses of male Pashygrapsua


-Increase of carbon uptake in phytoplankton
Mironov (1967)  (WQC 1972  3«1)

Menzel (1948)

Mironov (1968)

Shiela (1973)

Shiela (1973)

Atema et fll.  (1973)
                                                                                                                  Gordon  11973)
      *1  mg/1  -  1  ppm

-------
                                                               TABLE  -i  10

                                                      TOXICITY TABLE  -  NICKEL
CONCENTRATION   (mg/1)*
                 EFFECT
                                                                                                LOCATION
                                                                                                                        REFERENCE
10,000
 1,000
   100
    10
                                         ,36 hr. LC100  to Fundulua heteroclitus fertilized eggi

                                          Prevented gastrulntion  in embryos of BCO  urchin
                                         ' Lytechinua El?_tu^

                                          Tolerated by  fish for 1-2 wka
                                         /urchin Lytechinua
                                                stia  pycifera after 96 hr. expo:
                                          48 hr. LC100 for Crasscg;

                                         '2 day LC50, stickleback

                                           day LC50, Stickleback
                                         yLytechinua  pictus


                                         'embryOB
                                          4S  1
 1973 Marine Water  Quality Criterion

'_4fl hr.  LCD for Herctinarla mcrccnaria embryos

'.Arrested development of skeleton at prism stage in developing
                                                                                                                     Murdock  (1953)
                                                                                                                                 I Watchmaker
                                                                             Murdock [ 19531

                                                                             Murdock (1953)
                                                                                                                     Murdock  (1953)

                                                                                                                     Murdack  (1953}
    *1  mg/1  =  1 ppm

-------
                                                            TABLE  6-11

                                                    TOXICITY  TABLE  - PHENOL
 CONCENTRATION  (mg/1)'
EFFECT
                                       LOCATION
                                                              REFERENCE
1,000
   100
    10  -
   0.1
                                          Caused  95% mortality in developing Craiaoatrea egg*
                                          after 48 hr.  exposure
                                          .Caused 1001 mortality in Mercenaria mercenaria eggs
                                          after 48 hr. exposure and larvae  after 10 day exposure
                                          48 hr. TLm, Artercia salin
                                          48 hr. TLra, Hercenana eggs
                                             hr. LC50,  Crangg!
                                          No effect on growth of Harcen^ria mercanari* larvae


                                            riicra after 96 hr.  exposure              '
                                                                                                                     Price et al.  (19741

                                                                                                                     Davis and Hldu  (1967)
                                                                                                                                      71
                                                            Davis and Hidu  (1967}

                                                            Price et al.  (1974)

                                                            Davis and Hidu  (1967)

                                                            DaviB and Hidu  (1967)

                                                            Portmann

                                                            Portmann




                                                            Davis and Hidu  (1967)


                                                            McKee and fcoLf  (19G3)


                                                            HcKee and Wolf  (19631

                                                            EPA (1975)

                                                            Davin and Hidu  (1967)

                                                            HCKee and Wolf  (1963)


                                                            HcKee and Wolf  (1963)
     *1  mg/1  =  1  ppm

-------
                                                          TABLE  6-12

                                                TOXICITY  TABLE  - ARSENIC
CONCENTRATION  (mg/1)'
EFFECT
                                    LOCATION
                                                          REFERENCE
 100
  10
 .01
                                       Estuary, England
                                          hr. LC100, erobr

                                       48 hr. LC5U, young
                                      .72  hr. exposure caused "distressed" behavior and 72.31
                                      'decrease in Oj consumption in mud snail, Haasati.ua  gbgoletu
                                       1973 Marina Water Quality Criteria
                                                        Vernberg and Vernberg  (1974)


                                                        Perkins (1974)
                                                                                                                              73]
                                                                                                             Vernberg and Vcrnberg (1974)
                                                                                                             Haclnnes and Thurberg (197J)
   *1 n\g/l =  1  ppm

-------
                                                            TABLE   6-13
                                             EFFECTS OF CRUDE  OIL  FRACTIONS
     CONCENTRATION
         (ppm)
HYDROCARBON
                                      EFFECT
                                                                                  REFERENCE
LO
I
        0.0008      Kerosene:  water-soluble
                    fraction

        0.001       Kerosene:  water-soluble
                    fraction

        0.004       Kerosene:  water-soluble
                    fraction

        0.06        Aromatic fraction of
                    kerosene
        0.08        Water-soluble fraction
                    dimethylnaphthalenes

        0.180       #2 fuel oil
        0.7         Dimethylnaphthlenes


        0.7         2-methylnaphthlene

     0.75-0.8       Bunker C.


     1.00-100       Diesel fuel, emulsion
                        No effect  on  attraction  to  scallop  homogenates
                        of Nassc\rius  ojsolotus  (marine  snail

                        No effect  on  attraction  to  oyster extract  of
                        Nassarius  obso Ictus  (marine snail

                        Reduced  attraction to scallop homogenate of
                        Nassarius  obsoletus  (marine snail)

                        Induced  searching  behavior  in Homerus
                        americanus (loaster) at  distance; repulsed
                        H.  americanus at close range

                        24-hour  LC50  f 51 Penae-us aztecus  (Brown shrimp)
                        Interference  with phospholipid  metabolism in
                        marine fish after 180  day  exposure  suggesting
                        altered membra le  structure

                        24-hour LC50  for  Palaemonetes puglio (Grass
                        shrimp)

                        24-hour LC50  for  Penaeus aztecus  (Brown  shrimp)

                        Increase in crivling and respiration rates of
                        Littorina littnea (snail)

                        Loss  of photosfnthetic ability  by Macrocystis
                        augustifolia  {telp)  after  7-day exposure
Jacobson and Boylan
(1973)

Jacobson and Boylan
(1973)

Jacobson and Boylan
(1973)

Atema et al. (1973)
Anderson et al. (1974)
Sabo and Stegeman (in
press) 1975
Anderson et al. (1974)


Anderson et al. (1974)

Hargrave et al. (1973)


Moore et al. (1974)

-------
                                                TABLE  6-13  (CON1?.)
CONCENTRATION
    (ppra)
HYDROCARBON
                                       EFFECT
                                                                                   REFERENCE
 I
M
OJ
 I
     1.0         Toluene, naphthalene, 3,4
                benxpyrene

     2.0         2-methylnaphthlene
     1.7         2-methylnaphthalene

     2.4         Naphthalene


     2.5         Naphthalene

     2.6         Naphthalene
    •

     3.4         1-methylnaphthalene


 4.5-5.0        Phenanthrene

 4.0-5.0        Naphthalene

 4.0-15.0       Benzene



 4.0-25.0       Benzene



 4.0-25.0       Benzene


     4.7         Benzene
                         Not toxic to Hytilus edulis (mussel) after
                         6-day exposure

                         24-hour LC50 for Cyprinodon variegatus
                         (Sheepshead minnow)

                         24-hour LC50 for Palaemonetes puglio (Grass shrimp)

                         24 hour LCBO for Cyprinodon variegatus
                         (Sheepshead minnow)

                         24 hour LC50 Panaeus aztecus (Brown shrimp)

                         24 hour LC50 for Palaemonetes puglio (Grass shrimp)

                         24 hour LC50 for Cyprinodon variegatus
                         (Sheepshead minnow)

                         1 hour exposure fatal to sunfish

                         1 hour exposure fatal to sunfish

                         10 percent decrease in survival of Engraulis
                         mordax (Nortnern anchovy) larvae with 48 hour
                         exposure

                         20 to 50 percent increase in abnormal Engraulis
                         mordax (Nort iern anchovy) T day larvae as a
                         result of 48 hour exposure

                         Larvae of Engraulis mordax (Nothern anchovy.
                         larger at da'' 6

                         10 percent decrease in 3 day survival of
                         Engraulis mo :da_x (Northern anchovy) larvae
                         following 24 hour exposure
Moore et al.  (1974)


Anderson et al.  (1974)


Anderson et al.  (1974)

Anderson et al.  (1974)


Anderson et al.  (1974)

Anderson et al.  (1974)

Anderson et al.  (1974)


Moore et al.  (1974)

Moore et al.  (1974)

Struhsaker et al.  (1974)



Struhsaker et al.  (1974)



Struhsaker et al.  (1974)


Struhsaker et al.  (1974)

-------
                                                      TABLE   6-13  (CONT. )
      CONCENTRATION
          (ppm)
                   HYDROCARBON
                                                          EFFECT
                                                                                       REFERENCE
U)
Ui
 I
4.7-55.0



   5.0

   5.0




   5.0



   5.1


   6.7


  10.0




  10.0



  10.0


  10.0
Benzene



Kerosene

Benzene




Benzene



Dimethylnaphthalene


Benzene


Benzene




Benzene



Benzene


Methylcyclohexane
20 percent increase in abnormal Engraulis
mordax (Northern anchovy) larvae at day 6
following 24 hour exposure

Tainting of Mugil cephalus (mullet) tissue

80 percent increase in oxygen consumption rate
of Oncorhynchus tshawytscha (Chinook salmon) after
48 hours of exposure; subsequent decrease to 130
percent of noimal value at 96 hours

Increased oxygen consumption in Morone saxa :ilis
(Striped bass) to 24 hour peak of 130 to 145 percent
of the normal value, with subsequent return to normal

24 hour LC50 for Cyprinodon variegatus (Sheepshead
minnow)

Growth rate of Clupea pallasi  (Herring) larvae
decreased by 48 hour exposure

48 hour exposure produced 120 percent increase
in oxygen consumption in Oncorhynchus tshawytscha
(Chinook salmon), with a return to normal consump-
tion at 96 hours

Decreased oxyqen consumption in Morone saxatilis
(Striped bass) after 24 to 48 hours of exposure,
with a return to normal by 96 hours

3 to 4 hour exposure produced lethal toxicicy
in Rutilis sp.  (Roach)

3 to 4 hour exposure produced lethal toxicity
in Rutilis sp.  (Roach)
                                                                                                           Struhsaker  et al.  (1974)
                                                                                                           Connel (1971)

                                                                                                           Brocksen and Bailey
                                                                                                           (1973)
                                                                                                           Brocksen and Bailey
                                                                                                           (1973)
Anderson et al. (1974)
                                                                                                           Struhsaker et al.  (1974)
                                                                                                           Brocksen and Bailey
                                                                                                           (1973)
                                                                                                           Brocksen and Bailey
                                                                                                           (1973)
                                                                                                           Moore et al.  (1974)
                                                                                                           Moore et al.  (1974)

-------
                                                      TABLE  6-13 (CONT.)
      CONCENTRATION
          (ppm)
                  HYDROCARBON
                                                         EFFECT
                                                                                                     REFERENCE
U)
CTi
 I
           10.0
           10.0
           10.0
           10.0
           12.1
22.0-65.0
        25.0-50.0
          38.0
                        Benzene
                        n-hexane
               Toluene
                        Cyclohexane
                        Benzene
Xylene, toluene,
benzene, ethylene

O-xylene
        25.0-250.0     Toluene
        25.0-500.0     Benzene
                       Kerosene
        40.0-400.0     #2 fuel oil

        40.0-55.0      Benzene
Slight photasynthesis inhibition in Macrocystic
augustifolia (Kelp) caused by 96 hour exposure

No effect of Macrocystic augustifolia (Kelp)
seen with 9 > hour exposure

96 hour expssure resulted in visible injury,
75 percent "eduction in photosynthesis of
Macrocystic augustifolia Kelp)

3 to 4 hour exposure produced lethal toxicity
in Rutilis sp.  (Roach)

25 percent mortality of Clupea pallasi (Herring)
larvae after 48 hour exposure

Lethal toxicity to sunfish
                                             Slight  inhibition  of  growth  of  Chlorella  vulgaris
                                             (Phytoplankt-.cn) , 10 day  exposure

                                             Slight  inhibition  of  growth  of  Chlorella  vulgaris
                                             (PhytoplankLon), 10 day  exposure

                                             Initial  inh: bition for 2 days,  then growth of
                                             Chlorella vulgaris during  10 day exposure

                                             Depresses gi owth rate of Asterionella  japonica
                                             (diatom)

                                             Lethal to Thalassiosira  pseudonana  (diatom)

                                             Larvae of Ei.gcaulis mordax  (Northern anchovy)
                                             smaller  at ciays 3  and 6  after 24 hour  exposure
Moore et  al.  (1974)


Moore et  al.  (1974)


Moore et  al.  (1974)



Moore et  al.  (1974)


Struhsaker et al.  (1974)


Moore et  al.  (1974)


Moore et  al.  (1974)


Moore et  al.  (1974)


Moore et  al.  (1974)


Aubert et al. (1969)


Pulich et al. (1974)

Struhsaker et al. (1974)

-------
                                                      TABLE  6-13   (CONT.)
u>
     CONCENTRATION
         (ppm)
         45.0



         45.0


         57.0

        100.0


        500.0
    HYDROCARBON
Benzene



Benzene


Kerosene

Tetralin


Toluene
       500-1,744      Benzene
                                          EFFECT
20 percent increase in abnormalities, 10 percent
decrease in survival in Clupea pallasi (Herring)
eggs as a result of 24 hour exposure

50 percent mortality of Clupea pallasi (Herring)
eggs

Toxic to Astt r Lonella japonica (diatom)

Exposure up to 6 days toxic to Mytilus edulis
(Mussel)

Lethal toxicity to Chlorella vulgaris (Phytc-
plankton) with 10 day exposure

Lethal toxici ty to Chlorella vulgaris^ (Phyto-
plankton) wit h 10 day exposure
                                                                                      REFERENCE
Struhsaker et al. (1974)



Struhsaker et al. (1974)


Aubert et al. (1969)

Moore et al. (1974)


Moore et al. (1974)


Moore et al. (1974)

-------
              REFERENCES FOR TABLES 6-2 to 6-
Barnes and Stanbury.  "The Toxic Action of Copper and Mercury
     Salts Both Separately and When Mixed on the Harpacticid
     Copepod Nitocra."  Journal of Experimental Biology
     25(3) (1948):  270-275.

Bryan and Hummerstone.  "Adaptation of the Polychaete Nereis
     diversicolor to Estuarine Sediments Containing High
     Concentrations of Heavy Metals."  Journal of the Marine
     Biological Association of the United Kingdom 51  (1971):
     845-863.

Calabrese, A. et al.  "The Toxicity of Heavy Metals to Embryos
     of the American Oyster Crassostrea 'virginica."  Marine
     Biology 18 (1973): 162-166.

Collier, R.S. et al.  "Physiological Response of Mud Crab
     Eurgpanopeus depressus to Cd."  Bulletin of Environmental
     Contamination Toxicology 10  (1973): 378-382.

Corner, E.D.S. and Sparrow, B.W.  "The Modes of Action of
     Toxic Agents.   I.  Observations on the Poisoning of
     Certain Crustaceans by Copper and Mercury."  Journal
     of the Marine Biological Association of the United
     Kingdom 35 (1956): 531-548.

DeCoursey and W.P.  Verberg.   "Effect of Mercury on Survival,
     Metabolism and Behavior  of Larvae Uca pugilator."
     Oikos 23  (1972): 241-247.

Eisler, R.   "Cadmium Poisoning in Fundulus heteroclitus
      (Pisces:  Cyprinodontidae) and Other Marine Organisms."
      Journal of the Fisheries Research Board of Canada
      28 (9)  (1971) :  1225-1234.

Eisler, R. and Gardner, G.R.  "Acute Toxicology to an Estuarine
     Teleost of Mixtures of Cadmium, Copper and Zinc Salts."
     Journal of Fish Biology  5  (1973):  131-142.

Gardner,  G.R. and Yevich,  P.P.  "Histological and Hermatologi-
     cal  Responses  of an Estuarine Teleost to Cadmium."
     Journal of the Fisheries Research Board of Canada
      27(52)  (1970):  2185-2196.

Herbert and Wakeford.   "The Susceptibility of Salmoned Fish
      to Poisons Under Estuarine Conditions.  I. Zinc Sulfate."
     Air  and Water  Pollution  8  (1964):  251-256.

Hunter, W.R.   "The  Poisoning  of Marino  gammarus marinus by
      Cupric  Sulfate  and Mercuric  Chloride."  Journal  of
      Experimental Biology  26(2):  113~124.

                           -138-

-------
            REFERENCES FOR TABLES 6-2 to 6-7 (CONT.)
Jackim et al.  "Effects of Metal Poisoning on Five Liver
     Enzymes in the Killifish Fundulus heteroclitus."
     Journal of the Fisheries Research Board of Canada
     27 (2)  (1970) :  333-391.

Jones.  "The relative toxicity of the salts of Pb, Zn and
     Cu to the Stickleback (Gasterosteus aculeatus L.).
     Journal of Experimental Biology 15 (1938):  394-407.

Kania and O'Hara.   "Behavioral Alterations in a Simple
     Predator-Prey System Due to Sublethal Exposure to
     Mercury."  Trans. Am. Fish Soc. 103(1) (1974): 134-136.

Maclnnes and Thurberg.  "Effects of Metals on the Behavior
     and Oz Consumption of the Mud Snail."  Marine Pollution
     Bulletin 4 (1973): 185-186.

Pyefinch and Mott.   "The Sensitivity of Barnacles and Their
     Larvae to Cu  and Hg."  Journal of Experimental Biology
     25 (1948): 276-298.

Raymont and Shields.   "Advances in Water Pollution Research."
     Proc. Int. Conf., London, 1962.

Sprague,  J.B.  "Lethal Concentrations of Copper and Zinc
     for Young Atlantic Salmon."  Journal of the Fisheries
     Research Board of Canada 21(1) (1964): 17-26.

Sprague,  J.B. and  Ramsay, B.A.  "Lethal Levels of Mixed
     Copper-Zinc Solutions for Juvenile Salmon."  Journal
     of the Fisheries Research Board of Canada 22(2)  (1965):
     425-432.

Sprague,  J.B. et al.   "Sublethal Copper-Zinc Pollution in a
     Salmon River:   A Field and Laboratory Study."  Inter-
     National Journal of Air and Water Pollution 9 (1965):
     531-543.

Stephenson, R.R. and Taylor, D.  "Influence of EDIA on
     Mortality and Burrowing Activity of Clam (Venerupsis
     decussata Exposed to Sublethal Concentrations of Copper."
     Bulletin of Environmental Contamination Toxicology 14(3)
     (1975): 304-308.

U.S. Environmental Protection Agency.   Water Quality Criteria
     1973>
                           -139-

-------
          REFERENCES FOR TABLES 6-2 to 6-7  (CONT.)
Ventilla, R.J. and Gray, J.S.  "Growth Rates of a Sediment-
     Living Marine Protozoon as a Toxicity Indicator for
     Heavy Metals."  Ambio 2(4) (1973): 118-121.

Wisely, B. and Blick, R.A.P.  "Mortality of Marine Inverte-
     brate Larvae in Mercury, Copper and Zinc Solutions."
     Austr. J. Mar. Fresh Res. 18(1) (1967): 63-72.
                           -140-

-------
             REFERENCES FOR TABLES 6-8 to 6-13
Pulich, W.M. et al.  "The Effects of a No. 2 Fuel Oil and
     2 Crude Oils on the Growth and Photosynthesis of
     Microalgae."  Marine Biology 28 (1974): 87-94.

Nuzzi, Robert.   "Effects of Water Soluble Extracts of Oil
     on Phytoplankton."  API Proceedings Joint Conference
     on Prevention and Control of Oil Spills.  Washington,
     D.C., 1973.

Dunning, A., and Major, C.W.  "The Effect of Cold Seawater
     Extracts of Oil Fractions upon the Blue Mussel, Mytilus
     Edulis."  Pollution and Physiology of Marine Organisms.
     Ed. by F.  Vernberg and W. Vernberg.  New York:  Academic
     Press, 1974.

Moore, S.F., Chirlin, G.R., Puccia, C.J., and Schrader, B.P.
     Potential  Biological Effects of Hypothetical Oil
     Discharges in the Atlantic Coast and Gulf of Alaska.
     Cambridge:  Massachusetts Institute of Technology, 1974.

U.S. Environmental Protection Agency.  Environmental Studies
     Board.  Water Quality Criteria 1973.

Eisler, R.  "Latent Effects of Iranian Crude Oil and a
     Chemical Oil Dispensant on Red Sea Mollusks."  Israel
     Journal of Zoology 22  (1973) :  97.

Rice, Stanley et al.  "The Effect of Prudhoe Bay Crude Oil
     on Survival and Growth of Eggs, Alevins, and Fry of
     Pink Salmon, Oncorhynchus gorbuscha."  API Proceedings
     Joint Conference on the Prevention and Control of Oil
     Spills.  Washington, D.C., 1975, p. 503.

Brocksen, R.W.  and Bailey, H.  "Respiratory Response of
     Juvenile Chiwook Salmon and Striped Bass Exposed to
     Benzene, A Water Soluble Component of Crude Oil."
     API Proceedings Joint Conference on the Prevention
     and Control of Oil Spills.  Washington, D.C., 1973.

Anderson, J.W.  et al.  "The Effects of Oil on Estuarine
     Animals:  Toxicity, Uptake and Depuration, Respiration."
     Pollution and Physiology of Marine Organisms.  Ed. by
     F. Vernberg and W. Vernberg.   New York:  Academic
     Press, 1974.
                           -141-

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           REFERENCES FOR TABLES 6-8 to 6-13  (CONT.)
Jacobson, S.M.  and Boylan,  D.B.   "Seawater Soluble Fraction
     of Kerosene:  Effects  on Chemotaxis in a Marine Snail,
     Nassarius  Obsoletus."   Nature 241 (1973):  213.

Stegeman, John. "Hydrocarbons in Shellfish Chronically
     Exposed to Low Levels  of Fuel Oil."  Pollution and
     Physiology of Marine Organisms.   Ed.  by F.  Vernberg
     and W. Vernberg.  New York:  Academic Press,  1974.

Brown, D.H.  "The Effect of Kuwait Crude Oil and a Solvent
     Emulsifier on the Metabolism of  the Marine Lichen
     Lichina Pygmaea."  Marine Biology 12 (1972) :  309-315.

Galtsoff, Paul  S.  "Experimental Studies of the Effect of
     Oil on Oysters:  Review of the Lit."  Bulletin Bureau
     Fish.  48  (1935): 158.

Anderson, J.W.  et al.  "Characteristics of Dispersions and
     Water-Soluble Extracts of Crude and Refined Oils  and
     Their Toxicity  to Estuarine Crustaceans and Fish."
     Marine Biology  27  (1974): 75-88.

Struhsaker, J.W., Eldridge, M.B., and Echeverria,  T.
     "Effects of Benzene (A Water-Soluble Component of
     Crude Oil) on Eggs and Caruae of Pacific Herring and
     Northern Anchovy."  Pollution and Physiology of Marine
     Organisms.  Ed. by Vernberg & Vernberg.  New York:
     Academic Press, 1974.

Perkins, E.J.  The Biology of Estuaries and Coastal Waters.
     New York:   Academic Press, 1974.

Shiels, W.E.   "Effects of Crude Oil Treated Seawater on the
     Metabolism of Phytoplankton and Seaweeds."  Thesis
      (M.S.), University of Alaska, 1973.

Neff, J.  "Oil  Pollution and Shellfish."  Proceedings of
     8th National Shellfish Sanitation Workshop, 1974,
     pp. 72-76.

Rice, Stanley.   "Toxicity and Avoidable Tests of Prudhoe Bay
     Oil and Pink Salmon Fry."  API/EPA/USCG Proceedings.
     Joint Conference on the Prevention and Control of Oil
     Spills.  Washington, D.C., 1973.
                            -142-

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          REFERENCES FOR TABLES  6-8  to  6-13  (CONT.)
Gordon, D.C. and Prouse, N.J.  "The Effects of 3 Oils on
     Marine Phytoplankton Protosynthesis."  Marine Biology
     22 (1973) :  329-333.

Takahashi, F.T.  and Kittredge,  J.S.  "Sublethal Effects of
     the Water Soluble Component of Oil:  Chemical Communi-
     cation in the Marine Environment."  Microbial Degradation
     of Oil Pollutants.  Ed. by D.G. Ahearn and S.P. Meyers.
     Baton Rouge:   LSU Center for Wetland Resources.
     LSU-SG-73-01, 1973, pp. 259-264.

Hargrave,  B.T.  and Newcombe, C.P.  Journal of the Fisheries
     Research Board of Canada 30(12) (1973): 1789-1792.

Sabo,  D. and Stegeman, J.   "Some Metabolic Effects of
     Petroleum Hydrocarbons in Marine Fish." (in press) 1975.

Shiells III, W.E.   "Effects of Crude Oil Treated Seawater on
     the Metabolism of Phytoplankton and Seaweeds."  Masters
     Thesis, University of Alaska, 1973.

Rice,  S.D., Moles, D.A., and Short, J.W.  "The Effect of
     Prudhoe Bay Crude Oil on Survival and Growth of Eggs,
     Alevins and Fry of Pink Salmon Oncorhynchus gorbuscha.
     Proceedings of Joint Conference on Prevention and
     Control of  Oil Pollution,  1975, pp. 503-507.

Stegeman,  J.J.  and Teal, J.M.,  "Accumulation, Release and
     Retention of Petroleum Hydrocarbons by the Oyster
     Crassostrea virginica."  Marine Biology 22  (1973) :
     37-44.

Atema, J., Jacobson, S., Todd,  J., BoyIan, D.  "The Importance
     of Chemical Signals in Stimulating Behavior of Marine
     Organisms:   Effects of Altered Environmental Chemistry
     on Animal Communications."  Chapter 9, Bioassay
     Techniques  and Environmental Chemistry  (1973): 177-197.

Menzel, R.W.  Report on Two Cases of Oily Tasting Oysters at
     Bale  Sainte Elaine Oilfield.  Texas A&M Research Founda-
     tion.  College Station, 1948.

Thomas, R.E. and Rice, S.D. "Increased Opercular Rates of
     Pink  Salmon  (Oncorhynchus  gorbuscha)  Fry after Exposure
     to Water-Soluble Fraction of Prudhoe Bay Oil."  Journal
     of the Fisheries Research Board of Canada 32 (11)   (1975) :
     2221-2224.
                           -143-

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         REFERENCES FOR TABLES 6-8 to 6-13  (CONT.)
Mironov, O.G.  "The Effect of Oil Pollution on the Flora and
     Acartia of the Black Sea."  FAO Tech. Conference on
     Marine Pollution, Rome, 1970, pp. i-92.
                             -144-

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     6.3.2  Sublethal Effects

     Tables 6-2 through 6-13 deal with a number of different
toxic effects, primarily lethality, but including a number
of important sublethal effects.  Although sublethal effects
might not result in direct mortality, they can nevertheless
have severe ecological consequences if they decrease the
rate at which organisms can find food, escape predation, or
produce offspring.   Although the majority of past work has
dealt with parameters of lethality, the direction of current
research is towards further exploration of important sub-
lethal interactions.   Among the important sublethal effects
of brine pollutants are:

     1.   "Economic effects," i.e., effects which reduce
          the marketability of economically important marine
          organisms.   An example is the "greening" of oysters
          in solutions containing moderate concentrations of
          copper, due to the bioaccumulation of copper by
          the organism.

     2.   Histo- and cytopathology -- Exposure to sublethal
          concentrations of trace metals and hydrocarbons
          has been shown to produce extensive tissue damage,
          at the light or electron microscope levels, in
          gill, kidney, and liver tissue.  Such damage can
          reduce life expectancy and productivity, and,  if
          it occurs in lateral line or taste bud tissues,
          can reduce the extent to which a fish can find
          food or avoid predation.

     3.   Biochemical alterations -- Some studies are
          reported in the tables of the effect of trace
          metals on the assay levels of certain key enzymes
          in fish,  and other studies have tried to determine
          by electrophoresis the effect of sublethal expo-
          sures on the concentrations of various serum
          proteins.  The use of acetylcholinesterase levels
          as an indicator of exposure to certain organo-
          phosphorus pesticides has received particular
          attention.   Although such biochemical parameters
          are hard to interpret in terms of effects on
          ecosystems, they seem to indicate pathological
          conditions which have the potential of reducing
          the survival rates, fertility, or adaptability of
          a species.

     4.   Physiological parameters -- Included in this
          category are effects on blood ion concentration,
          EKG rates,  blood cholesterol levels, or hematocrit
                           -145-

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          levels of affected fish populations.  A  small
          number of studies have been conducted on the
          effects of pollutants on  these parameters, par-
          ticularly on  freshwater fish; an excellent review
          is provided by Sprague.^  Again, data such as
          these are hard to interpret directly, but they can
          be used as "early warning signs" of potentially
          dangerous toxic conditions.

     5.    Effects on growth and productivity.

     6.    Effects on viability, as  indicated by rates of C>2
          consumption,  particularly in  gill tissue.

     7.    A toxic substance, even if it creates no notice-
          able toxic effects by itself, can significantly
          reduce the resistance of  an organism to  other
          environmental stressors,  including DO stress,
          salinity  stress, and thermal  stress.

     8.    Behavioral effects -- Included in this category
          are effects on mating or  swimming behavior which
          might affect  survival and growth rates of the
          organism  and  species.  Another important sublethal
          behavioral response to pollutants is the avoidance
          response; that is, the avoidance by fish of waters
          which contain particular  levels of a trace metal.
          Such an effect is important because it can prevent
          spawning  migrations of fish.  Sprague et al.^
          note that "in the laboratory, avoidance  responses
          can be obtained at less than  one-tenth of the
          incipient lethal level  (i.e., threshold) concen-
          trations."  Such behavioral effects are  most
          important if  they affect  behavioral patterns
          important for survival.   Stephenson and  Taylor,
          for example,  have noted a decrease in burrowing
          activity  of clams associated  v/ith sublethal copper
          toxicosis^ and in an elegant  experimental system
          involving the use of a radioactive mercury tracer,
     4
      Sprague, "Measurement of Pollutant Toxicity of Fish,"
p. 257.

     bJ.B. Sprague et al., "Sublethal Copper-Zinc Pollution
in a Salmon River:  A Field and Laboratory Study," International
Journal of Air and Water Pollution 9 (1965) :  531-545.

      Stephenson and Taylor, "Influence of ETDA on Mortality
and Burrowing Activity of Clams."


                             -146-

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          Kania and O'Hara demonstrated that sublethal
          exposures to mercury(II) reduced the efficiency
          of the mosquitofish Gambusia in escaping predation
          by the bass Micropterus.7

     9.   Reproductive effects -- Data in the tables include
          some effects of trace metals on development.  Such
          effects can range from lethality of eggs and
          embryos to minor developmental defect initiation
          (teratogenesis) which could reduce the survival
          rate of the hatched young.  Generally, such
          effects occur at levels far below the lethal
          concentrations for the organisms.

    10.   Aggregate effects on production in communities --
          A few experiments have been done on the effects of
          pollutants on harvestable crops, productivity, and
          diversity in natural freshwater ecosystems; pre-
          sumably, in the near future similar studies will
          be initiated in marine or estuarine systems.

    11.   Effects on performance  (e.g., swimming ability).

    12.   Effects on disease resistance.

     Each of the effects discussed above is  important in
that it can produce gross alternations in the populations,
productivity, and diversity of a community without producing
any significant mortality effect in a laboratory bioassay
system.  For this reason, it is important that available
data on sublethal effects can be taken into  account in
setting standards, and that such standards not be designed
to simply prevent significant direct mortality as a result
of exposure to a pollutant.
     6.3.3  Restrictions of the Data Base

     Ideally, toxicological data would provide us with
precise qualitative and quantitative descriptions of the
effects which can be expected in particular organisms in the
presence of specific levels of pollutants.  In practice,
this is made impossible by the highly complex nature of the
pollutant toxicity problem.  Consider, for example, the
problems associated with the assessment of oil toxicity.
      Kania and O'Hara, "Behavorial Alterations in a Simple
Predator-Prey System Due to Sublethal Exposure to Mercury,"
Transactions of the American Fisheries Society (1)  (1974):
134-136.
                             -147-

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First, oil itself is not a chemically well-defined substance,
but a complex mixture of literally 'hundreds of organic and
inorganic compounds, each with its own specific toxicological
properties.  Since oils from various parts of the world
differ widely in their content of specific substances, "oil"
per se can have no well-defined toxicity.  Furthermore, even
though extensive data are available on the toxicity of some
of the individual components of crude oils, their effects
when mixed together can be complicated by a variety of
synergistic or antagonistic interactions.  An additional
problem arises from the fact that none of the components of
oil are stable through time, either with respect to their
physical form, their chemical composition, or their distri-
bution over sediments and the dissolved and suspended
fractions of the region being considered  (as is discussed in
Appendix C).

     The reaction of an organism to toxic pollutants will be
modified by a number of environmental factors; so that the
wide diversity of possible environments, combined with the
even greater difference between any natural marine environ-
ment and a laboratory bioassay system, make it practically
impossible to extrapolate toxicity data obtained in one
experimental system under a highly specific set of condi-
tions to any other system or any other set of conditions.
According to Evans and Rice:8

     Within these environments are several...physical
     conditions such as temperature, salinity, oxygen, and
     nutrient concentration, as well as biological differ-
     ences such as species composition, diversity and
     density, and community metabolic rate.  The prediction
     or assessment of pollution effects on the basis of
     observations extrapolated from one environment to
     another is seldom supported by adequate data.  Unfor-
     tunately, however, few data on pollution effects exist
     for most areas and species, which has led to the use of
     information from areas that may be dissimilar in
     critical ways.

     Another problem involved in the application of pub-
lished laboratory or field data to the assessment of pollu-
tant effects was recently discussed by Smith:9
      D.R. Evans and S.D. Rice, "Effects of Oil on Marine
Ecosystems:  A Review for Administrators and Policy Makers,"
Fishery Bulletin 72 (1974):  625.
     9
      A.N. Smith, Oil Pollution and Marine Ecology (London:
Plenum Press, 1973) , p. 99~I

                              -148-

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     Data about the effects of oil pollution on marine
     plants and animals have been obtained from experiments
     in the field or laboratory and from observations of
     actual incidents or chronically polluted habitats...
     Toxicity tests in the laboratory are usually designed
     to result in death in a few days,  so they cannot be
     expected to reveal long-term effects.  They are often
     made on organisms which are convenient for experimen-
     tation rather than important in a threatened environ-
     ment; different results are obtained according to they
     way in which the pollutant is applied, the life-stage
     of the organism used or the season in which it is
     collected and tested, so that tests made in different
     laboratories may be far from comparable.  Often the
     importance of these factors was not realized when the
     tests were made, so that many of the circumstances
     surrounding them were not recorded.  In the field,
     factors other than the pollutant may also be at work
     and are rarely under the control of the observer, if
     they are even known to him; adequate measurement of
     those contributory factors which are recognized cannot
     usually be made, so that reports are often incomplete
     and anecdotal.

     Because of these factors, toxicity data reported even
for a single compound and a single organism may exhibit wide
variation; it has been reported, for example, that LC50 data
collected at different laboratories for a single substance
may show a standard deviation of close to one-quarter of the
mean.10  These factors must be kept in mind in applying the
data given on the toxicity tables.

     Available data permit neither valid quantitative
extrapolation of data from one environment to another, nor
the accurate prediction of the effect of such factors as
weathering and emulsification on the toxicity of crude oil
to individual organisms and its overall effect on ecosys-
tems.  Nevertheless, any consideration of the analysis
performed in this report should be done with at least a
qualitative understanding of the important factors modifying
toxicity in the marine environment.  This discussion is
intended to emphasize these factors.

     Of course, one of the principal factors affecting the
long-term toxicity of pollutants is the existence of envi-
ronmental processes which can degrade or transform them, or
result in their transfer between different compartments of
       W.R.  Hunter, "The Poisoning of Marinogammarus marinus
by Cupric Sulphate and Mercuric Chloride,"  Journal of
Experimental Biology 26(2)  (1949): 113-124.


                              -149-

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the marine environment (water, bottom sediments, suspended
particulates, etc.).  These processes are discussed in
Appendix C, and they can have a significant effect on the
toxicity of the compound involved.  Microbial or photo-
chemical degradation processes, for example, will ultimately
eliminate hydrocarbon toxicants from the marine environment
and therefore reduce the toxicity problem created by them.
Nevertheless, some of the intermediates in the degradation
process can be even more toxic than their precursors.

     The toxicity of trace metals in particular will be
affected by sedimentation, but the data on the relative
toxicities of the dissolved and precipitated forms of
various metals are sparse and occasionally contradictory.
Generally, dissolved metals can be expected to be more
accessible to living organisms than suspended ones, except
for filter feeders or benthic burrowing organisms  (e.g.,
Nereis sp.).   These observations should be considered in the
light of the general rule, enunciated by Bryan, that "in the
absence of much evidence to the contrary, it seems reasonable
to suppose that most of the factors affecting toxicity owe
their influence to changing the rates at which metals are
absorbed" or the extent to which they are available for
biological absorption.-1--1-

     Other transformations to which hydrocarbons and trace
metals are subject in the marine environment, such as
adsorption, complexation, oxidation and reduction, and
biological transformation can also affect their toxicity.
Some examples are:

                                               12
     1.   Chelation -- Experiments with oysters   have shown
          that toxic effects of high levels of copper are
          reduced or eliminated in the presence of chelating
          agents such as EDTA.  Presumably, the organometal
          complex is less readily absorbed by the organism
          than is the metal ion itself.  Similar effects may
          be observed in the marine environment with natural
          complexing agents.  Some experiments have been
          performed with cyanide and ammonium complexes of
          copper, with the result that complexation gener-
          ally lowers the toxicity of a particular metal.
     11G.W. Bryan, "The Effect of Heavy Metals  (Other than
Mercury) on Marine and Estuarine Organisms," Proceedings of
the  Royal  Society of London 177  (1971): 389.

     12Stephenson and Taylor, "Influence of EDTA on Mortality
and  Burrowing Activity of Clams."
                             -150-

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     2.   Biological transformations -- In situ biological
          transformations may drastically affect the availa-
          bility or toxicity of a trace metal.  One example
          of this which has received particularly intensive
          study is the microbial transformation of Hg  ions
          into highly toxic methylmercury compounds.  A
          number of recent reviews have dealt with the rate
          of this process and its implications for the
          environmental toxicology of mercury.13

     3.   Oxidation -- Cuprous antifouling compounds have
          been found to undergo slow but spontaneous oxida-
          tion to the cupric form in seawater, and similar
          oxidations may occur for other transition elements
          in seawater, for example, mercury (Hg+ to Hg++)
          and chromium (Cr+++ to Cr +6).   In many cases, the
          toxicity of the oxidized species can differ greatly
          from that of the reduced form.   For example,
          trivalent chromium compounds are known to be much
          less toxic than the corresponding hexavalent
          forms.

     Such effects are often not simulated in laboratory
bioassay systems, but are nonetheless important in modifying
the toxicity of a trace metal to a test organism. Further-
more, the bioassay procedure itself may produce a variety of
artifacts not representative of interactions in the marine
environment.  For example, Collier et al.^-4 note that in
static bioassay systems,  scavenging of pollutants from
solution by some of these processes may exceed the rates at
which such scavenging occurs in a natural environment:
"There are certain disadvantages inherent in tests performed
in static water.  Among these are possible loss of toxicant
       See S. Jensen and A. Jernelov, "Biological Methylation
of Mercury in Aquatic Organisms," Nature 223 (1969):  753;
and S. Skerfving, "Mercury in Fish -- Some Toxicological
Considerations,"  Food and Cosmetic Toxicology 10 (1972) :
545-556.

     14
       R.S. Collier et al., "Physiological Response of the
Mud Crab, Euypanopeus depressus,  to Cadmium," Bulletin of
Environmental Contamination and Toxicology 10(6)  (1973) :
380.
                             -151-

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via aeration, adsorption of the toxicant by the container,
and uptake of the toxicant by the test animal."15

     Other factors, including the existence of other environ-
mental stresses (such as thermal or dissolved oxygen stress),
and the conditions or life-cycle stage of the affected
organism, can also influence the toxicity of pollutants in
the marine environment.  Table 6-14 summarizes some of the
important factors influencing trace metal toxicity in the
marine environment.  Factors influencing hydrocarbon toxicity
are summarized in Table 6-15.
     6.3.4  Interpretation of Data

     Data on lethality, which is still the most abundant
form of toxicological data for marine organisms, are reported
in three key ways:

     1.   Measures of average percent mortality at a given
          level of exposure to a toxic substance (other
          factors held constant) for various lengths of
          time.  The measure used here is known as the LT
          (lethal time)- n, where n is the percent mortality
          observed in a population.  This statistic is only
          meaningful if a particular concentration or dose
          of a toxic substance is specified.  A 50 ppm LT50,
          then, refers to the mean exposure time necessary
          to cause 50 percent mortality in a population
          exposed to 50 ppm of a toxic substance.  Needless
          to say, this statistic, like the ones below, is
          both substance- and organism-specific.

     2.   Measures of average percent mortality at a given
          time of exposure to a toxic substance (other
          factors held constant) for various levels of
          exposure.  The measure is known as LC (lethal
       In other words, the metal may be absorbed on the
cuticle of the animal or on other body surfaces where it
would have essentially no physiological effect.  This pro-
cess would result in a decrease in the effective metal
concentration to which the organism is exposed, and could
only be prevented in some sort of flow-through  (non-static)
bioassay system.  This absorption of metal ions on external
body surfaces is also important to keep in mind in inter-
preting bioaccumulation data:  if accumulation in the whole
organism is measured, substantial artifacts are created by
the high, but physiologically irrelevant amounts of metal on
the external cuticle.
                              -152-

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                                       TABLE  6-14
                           FACTORS INFLUENCING THE TOXICITY OF
                            HEAVY METALS TO AQUATIC ORGANISMS
I
H1
t_n
U)
I
FACTORS
ion


FORM OF METAL IN WATER


complex
Soluble chelate
compound

Particulate / ?«<*?**«*«
^ adsorbed

PRESENCE OF OTHER
METALS OR POISONS

FACTORS INFLUENCING
PHYSIOLOGY OF ORGANISM
AND POSSIBLY FORM OF
METAL IN WATER


CONDITION OF
THE ORGANISM


Antagonistic Effects
Additive Effects
Synergistic Effects
Salinity
Temperature
Dissolved Oxygen
pH
Light?
Stage in Life-history
Changes in Life-cycle
(e.g. Moulting)
Size of Organism
Activity of Organism
Acclimatization to Metals
REFERENCES3
Clarke (1947)
Doudoroff (1956)
Grande (1967)
Corner & Sparrow (1957);
Clarke (1947)
Herbert & Wakeford (1964)

Lloyd & Herbert (1962)
Brown (1968)
Corner (. Sparrow (1956)
Herbert & Wakeford (1964)
Lloyd & Herbert (1962)
Lloyd (1961)
Sprague (1964a)
Gutnecht (1963)
fyefinch & Mott (1948)
	

.'Jkidmore (1967)
Herbert & Shurben (1963)
Edwards S Brown (1967)
METALS
Cu
Cu, Zn, Cd, Ni
Cu, Zn
Hg, Cu

Zn

Ca on Zn, Cu, Pb
Zn, Cu, Phenol,
Cyanide, Ammonia
Cu, Hg
Zn
Zn
Zn , Cu , Pb
Zn
Zn
Cu
	

Zn
Zn
Zn
ORGANISMS
Crustaceans
Fish
Fish
Crustaceans

Fish

Fish
Fish
Crustaceans
Fish
Fish
Fish
Fish
Seaweed
Crustaceans
	

Fish
Fish
Fish
          Complete references for this table may be found on  the  following two pages.

          Source:  G.W. Bryan, "The Effects of Heavy Metals  (Other  Than  Mercury)  on Marine
    and Estuarine Organisms," Proceedings of the Royal Society of London 177  (1971): 389-410

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                REFERENCES FOR TABLE 6-14
Clarke, G.L. "Poisoning and Recovery in Barnacles and Mussels."
     Biological Bulletin 92 (1947):  73-91.

Doudoroff, P. "Some Experiments on the Toxicity of Complex
     Cyanides to Fish." Sewage and Industrial Wastes 28 (1956):
     1020-1040.

Grande, M. "Effect of Copper and Zinc on Salmonid Fishes."
     Advances in Water Pollution Research 1  (1967) :  97-111.

Corner, E.D.S., and Sparrow, B.W. "The Modes of Action of
     Toxic Agents. II. Factors Influencing the Toxicities of
     Mercury Compounds to Certain Crustacea." Journal of the
     Marine Biological Association of the United Kingdom 36
     (1957): 459-472.

Herbert, D.W.M., and Wakeford, A.C.  "The Susceptibility of
     Salmonid Fish to Poisons Under Estuarine Conditions.
     I. Zinc Sulphate." International Journal of Air and
     Water Pollution 8  (1964)  : 251-256.

Lloyd, R., and Herbert, D.W.M. "The Effect of the Environment
     on the Toxicity of Poisons to Fish." Institution of
     Public Health Engineers Journal 61  (1962) : 132-145.

Brown, V.M.  "The Calculation of the Acute Toxicity of Mixtures
     of Poisons to Rainbow Trout." Water Research 2  (1968):
     723-733.

Corner, E.D.S., and Sparrow, B.W. "The Modes of Action of Toxic
     Agents. I. Observations on the Poisoning of Certain
     Crustaceans by Copper and Mercury." Journal of the Marine
     Biological Association of the United Kingdom 35  (1956):
     531-548.

Lloyd, R.  "Effect of Dissolved Oxygen Concentrations on the
     Toxicity of Several Poisons to Rainbow  Trout (Salmo
     gairdnerii Richardson)." Journal of Experimental Biology
     38  (1961) 447-455.

Sprague,  J.B.  "Lethal Concentrations of Copper and Zinc for
     Young Atlantic Salmon."  Journal of the  Fisheries Research
     Board  of Canada 21  (1964) : 17-26.
                              -154-

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            REFERENCES FOR TABLE  6-14  (CONT.)
Gutnecht, J. "An Uptake by Benthic Marine Algae." Limnology
     and Oceanography 8 (1963): 31-38.

Pyefinch, K.A. and Mott, J.C. "The Sensitivity of Barnacles and
     Their Larvae to Copper and Mercury." Journal of Experi-
     mental Biology 25  (1948): 276-298.

Skidmore, J.F. "Oxygen Uptake by Zebrafish (Brachydanio rerio)
     of Different Ages in Relation to Zinc Sulphate Resistance."
     Journal of the Fisheries Research Board of Canada 24
     (1967) : 1253-1267) .

Herbert, D.W.M., and Shurben, D.S. "A Preliminary Study of the
     Effect of Physical Activity on the Resistance of Rainbow
     Trout (Salmo gairdnerii Richardson) to Two Poisons."
     Annals of Applied Biolo'gy 53 (1963): 321-326.

Edwards, R.W., and Brown,  V.M. "Pollution and Fisheries: A
     Progress Report." Water Pollution Control 66  (1967):
     63-78.
                            -155-

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                                         TABLE  6-15
                           FACTORS AFFECTING PETROLEUM TOXICITY
         FACTOR
                 EXAMPLE
  REFERENCE
        Oil Type


        Turbidity
en
CTl
i
        Season
        Nature of
        Substrate
        Synergisms
Oils high in aromatic hydrocarbon content
tend to have high toxicity.
Suspended particulates adsorb hydrocarbons
and accelerate oil sedimentation.  The
transfer of hydrocarbons to the sediment
is generally advantageous to tidal life
and detrimental to benthic life.

Sensitivity to toxicants can vary on a
seasonal basis or between different
lifecycle stages.  Juvenile forms may
be particularly sensitive.

Oil will tend to percolate into coarse,
sandy sediments, allowing closer contact
with infauna.  Nature of sediment affects
rate and degree of hydrocarbon adsorption.
Adsorption affects availability to biota
and rate of microbial degradation.
Environmental stressors such as salinity
and DO extremes may increase oil toxicity.
Ottway  (1970)


Blumer et al.
  (1971)
Mironov  (1969)
NAS  (1975)
NAS  (1975)
  p. 86
          References are on following  page.

-------
                  REFERENCES FOR TABLE 6-15
Ottway,  S.M.   Proceedings, Symposium on the Effects of Oil
     Pollution on Littoral Communities, ed. by E.B. Cowell,
     Petroleum Institute, London (1970).

Blumer,  et al.  "A Small Oil Spill."  Environment 13(2)
      (1971):  2-12.

Mironov, O.G.  "Viability of Some Crustacea in Seawater
     Polluted with Oil Products."  Zool. Zh. 68(1): 1731.

National Academy of Sciences (Ocean Affairs Board, Commission
     on Natural Resources), Petroleum in the Marine
     Environment:  Workshop on Inputs, Fates, and Effects
     of Petroleum in the Marine Environment, 1975, p. 85.
                            -157-

-------
          concentration)  n,  where  n is  the  percent  mortality
          observed  in the population.   For  this  statistic  to
          be meaningful,  a particular exposure time must be
          specified.   For example  a 96  hr LC50 is the  con-
          centration  of a particular toxic  substance which,
          after  96  hours  of exposure, will  cause 50 percent
          mortality in a  population of  a particular organism.
          96 hr  LC50  is a fairly common parameter of pollutant
          toxicity.   It is also  frequently  referred to as  the
          TL50  (toxic level 50), or TLm (mean toxic level).

     3.    Threshold measures --  The concept behind  a thres-
          hold measure is that populations  of an organism
          will display essentially zero mortality  (no  matter
          how large the population)  below a particular level
          of exposure.  Such a level is known as a  threshold
          level,  or,  sometimes,  an incipient lethal level.
          Current policy  towards regulating water pollutants
          for the protection of  aquatic and marine  life, in
          which  maximum permissible levels  of pollutant
          concentrations  (standards and criteria) are  set,
          draws  upon  this threshold concept, and indeed
          there  is  much evidence for the existence  of
          thresholds  for  particular organisms and particular
          pollutants.  Sprague,  for example, in  an  article
          on the toxicity of copper and zinc to  young
          Atlantic  salmon16 notes  that  "the relationship
          between concentration  of metal and survival  time
          could  be  fitted by a straight line when logarithms
          were used.   A sharp break in  this relation marked
          the incipient lethal level, where survival becomes
          indefinitely long.  Incipient lethal  levels  were
          48 ug/1 (ppb) of copper  and  600 yg/1 of zinc."
          (see Figure 6-3).  In  terms of the two parameters
          described above, the threshold level  could be
          expressed as the LCO for a particular  time of
          exposure, or else as the concentration at which
          the LTO becomes infinite (the latter was  the
          definition  used by Sprague in the reference  cited
          above).

     Of course,  either of these  measurements could  be
extended to effects other than lethality.   In this  case, the
parameters are expressed as the  (e.g.)  EC50 or ET50, for
effective concentration 50 and effective time 50, respec-
tively.
       J.B. Sprague, "Lethal Concentration of Copper and Zinc
for Young Atlantic Salmon," Journal of the Fisheries Research
Board of Canada 21(1)  (1964): 17-26.
                             -158-

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       0.01'
   CONCENTRATION OF METAL,(mg/1)


0.1              LO
      200
      100
    O
    X
    O
    o
    in
    O
    E-i
    U
      50
      20
    EH 10
                  Copper
                                       Zinc
                                                          10
                         I	i i
                                i i  i I
        20
                50
100 300
1000
5000
                    CONCENTRATION OF METAL, (yg/1)
                                                            10
                                                              t/5
                                                              >H
                                                              <=c
                                                              D
                                                              >H
                                                              EH
                                                              O
                                          O
                                          LD
                                                              O
                                                              EH
    Figure  6-3.   Median mortality-times  of young Atlantic
salmon exposed  to solutions of copper  and zinc.  Vertical
bars indicate 95  per cent confidence limits.   The straight
lines fitted to the points break and run parallel to the
time-axis at the  incipient lethal levels.   The experimental
water had a total hardiness of 20 mg/1 as CaC02 temperature
of 15° C and pH 7.1 to 7.5 except for  two zinc tests in-
dicated by black  squares.  These were  at 17°  and somewhat
different pH values.
                             -159-

-------
     If threshold levels can be shown to exist for marine
organisms (and a wide number of the studies reviewed for
this report suggest that they do for particular pollutants
and organisms),  then they can be used as a basis for setting
"safe levels" for the release of trace metal pollutants into
seawater.  It is therefore important to develop procedures
for estimating threshold levels on the basis of available
data.

     Sprague   notes:

     "Safe" level is used here in an admittedly loose way,
     to mean the concentration of pollutant which does not
     have an adverse sublethal or chronic effect on fish.
     It is not an entirely satisfactory term since it often
     implies more safety than actually exists, but other
     descriptive terms do not seem to have gained any wide
     acceptance.  As used here, a safe level is a statistic,
     whose value is empirically determined as a result of an
     experiment.  Its value is not assigned on the basis of
     judgment.   If a probable safe level is inferred on the
     basis of incomplete information, it should be clearly
     labelled as probable or tentative.  A safe level may be
     specified as referring to one particular life process
     such as reproduction, or to the absence of any and all
     observable effects.  [One way of approximating the safe
     level would be to measure in a bioassay system] the
     median effective concentration  (EC50), i.e., the con-
     centration which just causes the selected response in
     50 percent of the individuals...Following such practice,
     concentrations affecting a negligibly small percentage
     of individuals, such as the EC5 or EC1, could be esti-
     mated with a known degree of accuracy, by conventional
     log probit analysis.1°  This has seldom been done in
       See the data reviewed in J.B.  Sprague, "Measurement of
Pollutant Toxicity to Fish," p. 257.
     18
       A probit distribution is the dose response relation
expected in a population which exhibits normally distributed
toxicity thresholds to a particular substance.  For a par-
ticular level x of a toxic substance in water, the number of
organisms affected will be all those with thresholds less
than or equal to x, which is estimated, using the probit
model, as the integral of the normal distribution for all
concentrations below x.  This model defines a relationship
between level of exposure and percent mortality involving
two undetermined parameters, whose value can be estimated by
fitting experimental LCn data.  Given values of these para-
meters, a dose/response curve is completely defined, so that
estimates can be made of the dosage levels which would cause
insignificant levels of mortality, e.g., the LCI or LC5.

                             -160-

-------
     research on sublethal effects even when it might be
     advantageous; most investigators have attempted to
     estimate (directly)... the safe level.  Sometimes such
     a "no-effect" concentration cannot be measured pre-
     cisely.  The parallel idea in lethal tests, of esti-
     mating the "minimum lethal concentration" has been
     abandoned in favor of the median lethal concentration.

     Sprague here refers to two different methods for
determining safe exposure levels:  direct experimental
determination of levels at which no effects are observed at
statistically significant levels of incidence (a generally
unreliable procedure) ,  and the extrapolation of available
ECn data (using probit or other models)  to estimate ECls or
EC5s.

     More conventionally,  threshold levels are estimated
using numbers called application factors.  Sprague's review
cites the work of Hart, who attempted to develop "an arith-
metic method of extrapolating along the toxicity curve to
the incipient LC50, with the ratios of different LCSOs
(e.g., the 96, 48, and 24 hr LC50s) simulating the slope of
the curve... A basic feature of (their paper)  is that they
estimate the 'presumably harmless concentration1 as essen-
tially 0.3 of the incipient LC50.  Indeed, Hart and col-
leagues recommend exactly that simple calculation when the
incipient LC50 is known."   This factor of 0.3 is known as an
application factor, and its purpose is to estimate safe or
threshold levels when only median or other toxicological
measures are known.  Although application factors can be
grounded in and confirmed by experimental results, or
derived from models using probit or other assumptions, they
are most generally derived from general considerations and
the experience of professional toxicologists.   The estimation
of applications factors for toxic substances for aquatic
organisms has mostly been done for freshwater species, and
the values used have ranged from 0.1 to 0.4 (to prevent
lethality),  or from 0.01 to 0.05 (to prevent chronic, sub-
lethal and cumulative toxicity).  The 1973 EPA Water Quality
Criteria for marine life recommended for most metals an
application factor of 0.01 of the 96 hr LC50 for the most
sensitive resident species, and this is the factor which
should probably be used in evaluating the data presented in
the tables.   This application factor, applied to the median
lethal level, was considered by the EPA to provide a margin
of safety in preventing all significant toxic effects.
                             -161-

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     6.3.5  Adaptation Responses

     It is reasonable to suppose that under conditions of
environmental stress due to high levels of a toxic metal, a
process of natural selection would favor a metal-resistant
subpopulation of a particular species.  Thus, relatively
metal resistant organisms, having a relatively high LC50 or
threshold level for the metal, would be found in chronically
polluted waters, diminishing the toxic response to further
pollution.  This can be a significant factor in evaluating
toxicity data, and in fact, it has been verified experimen-
tally for the copper response of the estuarine polychaete
Nereis.  Bryan and Hummerstone-^ have noted that Nereis
removed from an estuary with extremely high copper levels
due to persistent industrial pollution exhibited a much
higher LT50 at a particular copper concentration than did
Nereis extracted from a relatively clean estuary.


     6.3.6  Synergisms and Antagonisms

     The interactions between two toxic substances can
either be additive  (i.e., the effect of exposing an organism
to a concentration of one metal and another concentration of
a second metal is the sum of the effects noted if the organ-
isms are exposed to the same levels of each metal separately),
synergistic  (i.e., supra-additive), or antagonistic sub-
additive) .  The literature on whether synergisms exist
between toxicants is confusing and often contradictory; at a
minimum, it would seem that the presence of synergisms is
dependent upon the substances and species involved, and upon
the levels of exposure.  The degree of synergism is sometimes
quantified by use of the toxic units concept.  A toxic unit
is defined as the concentration of a metal necessary to
produce a well-defined effect (generally, the LC50 concen-
tration for a particular exposure time is used); all concen-
trations of the meta-1 can then be expressed as some fraction
or multiple of this LC50.  Now suppose an organism is exposed
to 0.5 toxic units of copper and x toxic units of zinc,
where x is variable.  The interaction between the two metals
is additive if 50 percent mortality is observed at the point
when x =  0.5 toxic units  (i.e., the sum of the concentrations
     19
       Bryan and Hummerstone, "Adaptation of the Polychaete
Nereis diversicolor to Estuarine Sediments Containing High
Concentrations of Heavy Metals," Journal of the Marine Bio-
logical Association of the United Kingdom 51  (1971): 845-863.
                              -162-

-------
of Zn and Cu is 1.0 toxic units), synergistic if 50 percent
mortality is observed for x less than 0.5 toxic units, and
antagonistic if 50 percent mortality is observed only when x
becomes greater than 0.5 toxic units.

     Some of the results of recent studies which bear on the
synergistic or additive effects of trace metals on marine
organisms are summarized below:
                               20
     1.   According to Sprague,   "In solutions containing
          both copper and zinc, fish died twice as fast as
          would occur if the two metals were simply additive
          in their lethal action" (see Figure 6-4).
                            21
     2.   Sprague and Ramsay   found an additive relationship
          between the toxicants copper and zinc in the
          vicinity of one toxic unit, but supra-additive
          relationships in the range two to five toxic
          units.  Test organism:  juvenile Atlantic salmon.
                             22
     3.   Barnes and Stanbury   found a synergistic interaction
          between the metals copper and mercury for the
          marine copepod Nitocra; for example 0.026 mg/1 of
          copper produced zero percent mortality; the combi-
          nation, however, produced 9.1 percent mortality
          (complete data are given in Table 6-16).
     20
       Sprague, "Lethal Concentrations of Copper and Zinc for
Young Atlantic Salmon."
     21
       Sprague and Ramsay, "Lethal Levels of Mixed Copper-
Zinc Solutions for Juvenile Salmon."
     22
       C. Barnes and Stanbury, "The Toxic Action of Copper and
Mercury Salts Both Separately and When Mixed on the Harp-
acticid copepod Nitocra," Journal of Experimental Biology
25(3)  (1948): 270-275.
                             -163-

-------
        200
        100
       D

       §  50
1 20
<*>
o
in
         10
                                           Copper
                                           - Zinc
                          Mixtures
                                       \
                                                    10
                                                       w
d
                                                       ff:
                                                       O
O
in
                                                       Eu
                   I
                                   r
          0.1     0-5     1.0      3.0         10.0


             METAL, FRACTION OF INCIPIENT LETHAL LEVEL
    Figure  6-4.  Comparison of median mortality-times  of
young Atlantic  salmon exposed to  solutions of copper,  zinc,
anC. raixtures.   Concentrations are expressed as fractions of
the incipient lethal levels, those for copper and zinc
being added  together for the 2 experiments with mixtures.
                            -164-

-------
                           TABLE 6-16


               EFFECT OF MERCURY AND COPPER ON THE
            MARINE COPEPOD NITOCRA  (PERCENT MORTALITY)
Cu CONC
Mg/1
0
0.026
0.26
2.6
26
0 0.07
0 0
1.3 9.1
11.3 11.9
21.2 --a
42.5
H CONC
0.15 0.31 0.40
1.4 10.0 16.7
14.5 12.7 50.0
20 45.6 43.7
78 82 98
— __ __
Mg/1
0.60 0.70
50 72
61.8 76.4
100 100
100 100
--
1.5
78
87.3
100
100
—
3.0
84
100
100
100
--
4,4
100
100
100
100
--
        a
        — means not available.
                            23
     4.   Eisler and Gardner   found a synergistic interaction
          between zinc, copper and cadmium for the estuarine
          mummichog  (Fundulus heteroclitus).  Sample data:
          60 ppm of zinc alone produced 27 percent mortality
          in 96 hours and 10 ppm of cadmium alone produced
          about 4 percent mortality in 96 hours; the combina-
          tion of the two, however, produced 60 percent
          mortality in the same time period.
                            74
     5.   Corner and Sparrow   found evidence of synergistic
          interaction between copper and mercury  (see Figure 6-5)
     23
       Eisler and Gardner, "Acute Toxicology to an Estuarine
Teleost of Mixtures of Heavy Metals," Journal of Fishery
Biology 5  (1972): 131-142.
     24
       Corner and Sparrow, "The Modes of Action of Toxic
Agents, I.  Observations on the Poisoning of Certain Crus-
taceans by Copper and Mercury," Journal of the Marine Bio-
logical Association of the United Kingdom 35  (1956): 531-548,
                                -165-

-------
              30 ,_


              28
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                  r-JS	:•	">
                             A
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                                 I
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                                              *»

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400
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I 1
600
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20
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                                     CONCENTRATION  (rag metal ion/1.)
               Figure  6-5.  Effects of bipartite  mixtures of equitoxic concentrations
          of copper sodium citrate and mercuric chloride (A), mercuric iodide  (s) , and
          ethylmercuric  (c) on the survival of Artemia larvae  in  seawater  (LT50), curves
          obtained experimentally;	, theoretical curves expected if toxic effects
          of the mixed poisons were exactly additive).   Concentrations of the metal
          ion measured as follows:  Cuas citrate  (upper row,  0...1,000), Hg++  as
          HgCl2 (lower row, 50...0).

-------
                  25
     6.   Ventilla   found evidence for a synergistic effect
          on the growth rate of the marine protozoon Cristigera
          of the trace metals mercury, lead and zinc.  The
          data are given below.
                         TABLE 6-17

          EFFECTS OF MERCURY, LEAD AND ZINC ON THE
                  GROWTH RATE OF CRISTIGERA
                                             REDUCTION IN
     CONCENTRATION                           GROWTH RATE
        (ppm)              SUBSTANCE            (Percent)
0.005
0.3
0.25
HgCl2
Pb(N03)2
ZnS04
12
12
13
     (All three above, combined
      at the same concentrations)                 67
     Much more data are available, but the above references
adequately demonstrate that synergistic interactions between
trace metals can be significant in some systems.
               9 f\
     Livingston   includes an interesting discussion on the
mechanistic rationales for additive, supra-additive, and
antagonistic effects.
     25
       Ventilla and J.S. Gray, "Growth Rates of a Sediment-
Living Marine Protozoan as a Toxicity Indicator for Heavy
Metals," Ambio 2(4) (1973): 118-121.
     9 f\
       American Petroleum Institute, U.S. Environmental
Protection Agency, and Marine Technology Society, "Marine
Bioassays:  Workshop Proceedings"  (Washington, D.C.: Marine
Technology Society, 1974) pp. 245-253.
                              -167-

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     6.3.7  Interactions Between Metals and Other Stressors

     The presence of other environmental stressors, e.g.,
abnormal salt concentrations, abnormal temperatures as a
result of thermal discharges, or abnormally low dissolved
oxygen can increase the toxicity of brine pollutants.
According to Vernberg and Vernberg:^'

     At optimum conditions of salinity and temperature
     (30 ppt, 25° C) fiddler crabs live almost indefinitely
     in seawater containing sublethal concentrations of
     mercury (0.18 ppm).  They can also survive prolonged
     periods of time in low salinity water and high tempera-
     ture (5 ppt, 35° C), but under the latter conditions
     the addition of sublethal concentrations of mercury
     resulted in an LD50 of 26 days for females and 17 days
     for males.

     Although relatively little data are available in this
area, it is an important field for further research.


     6.3.8  Note on Cyanide Toxicity

     Sufficient data on the toxicity of cyanide to marine
organisms was not available to enable a meaningful "safe"
level for this toxicant to be set.  Thus, the approach adopted
in the 1975 Water Quality Criteria was used, in which it was
stated:

     The effects of cyanide on marine life have not been
     investigated adequately to determine separate water
     quality criteria, but based on the physiological
     mechanisms of cyanide, toxicity to marine life
     probably is similar to that of freshwater life.  Since
     marine waters generally are alkaline, the toxicity of
     cyanide should be less than in freshwaters where pH
     fluctuations occur more readily and frequently.  Thus,
     an additional safety factor exists to provide a margin
     of safety and compensation for a lack of specific data
     on which to base the criterion for marine aquatic life.

Therefore, as a tentative safe level the EPA criterion of
0.005 mg/1 is adopted.
     27
       F.J. Vernberg and W. Vernberg, Environmental Physiology
of Marine Animals  (New York:  Springer-Verlag, 1972), p. 331.
                             -160-

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6.4  Effects of Salinity

     The natural salinity of seawater averages about 30 to
35 0/00 (parts per thousand).   In the open sea this salinity
is remarkably constant, although it may decrease by as much
as a factor of ten in estuarine areas following heavy rain-
falls, and increase by a factor of three or more in areas
such as lagoons and tide pools where evaporation is important.
The salinity of oilfield brines is comparatively very high;
Mackin, for example, reports that Lousiiana brines have
salinities as high as 128 and 131 0/00.28  j_t is reasonable
to suppose that exposure of resident organisms to these
abnormally high salinities would represent a severe environ-
mental stress which could either produce direct lethal or
sublethal effects or else decrease the resistance of the
organisms to other environmental stressors such as temperature
and trace metal pollution.  Unfortunately, the overwhelming
proportion of the literature on salinity stress (as reviewed
by Vernberg and Vernberg29 and others) deals with pathological
effects of low salinities on marine or estuarine organisms
(this is because salinity fluctuations downward from 30 0/00
are common in estuaries, where factors such as wind and
temperature gradients can cause wide variations in the
magnitude and spatial extent of seawater dilution due to the
incoming river water.  Low salinities have generally been
considered, therefore, to be of greater environmental
interest than high salinity situations).  A number of papers
have presented data from field studies on the effects of
highly saline oilfield brines on local ecosystems, but these
are of little use in estimating toxic effects of salinity
alone because of the complicating presence of hydrocarbon
and trace metal pollution in the brines.

     The salinity of the brines would represent an extremely
unsuitable environment for the internal operation of most
marine organisms; so if they are to survive in the vicinity
of these high salinities, they must be equipped with special
osmoregulatory (e.g., active transport) systems to regulate
their internal ion balance in the face of a tremendous
         Q. Mackin, A Review of Significant Papers on Effects
of Oil Spills and Oilfield Brine Discharges on Marine Biotic
Communities  (College Station, Texas:  Texas A&M Research
Foundation, Project No. 737, February 1973), pp. 4-8.
     29
       Vernberg and Vernberg, Environmental Physiology of
Marine Animals, pp. 167-175.
                             -169-

-------
salinity difference between their external environment and
internal body fluids.  Organisms which can maintain a
constant internal environment independent of external salin-
ity stress are known as osmoregulators, as opposed to
osmoconformers, whose internal ion composition resembles
that of their external medium.  Another distinction commonly
made is between euryhalinic species, which are capable of
surviving in a wide range of salinities, and stenohalinic
ones, which can only tolerate a rather narrow range of
salinities.  The two sets of terms are not equivalent;
organisms can be partially osmoconforming and yet euryhalinic
Extreme osmotic stress may seriously weaken an organism and
decrease its resistance to other environmental factors; or
it may even saturate the organisms' osmoregulatory capabili-
ties and eventually kill it.

     Some quantitative data on the effect of high saline
stress on organisms are summarized below.

     1.   Davis notes that "Colonies of the polyp Cordylo-
          hora caspia, grown from planulae, developed
          gonophores only in salinities between 5 and
          16.7 ppt, but when normal colonies were amputated
          and allowed to regenerate, gonophores were formed
          at a wide range of salinities though not in fresh
          water nor in salinities higher than 30 ppt."
          Davis also states that the development of the eggs
          of the pupfish Cyprinodon macularius is inhibited
          at both the high and low extremes of salinity  (up
          to about 85 ppt).

     2.   Figures 6-6 and 6-7, respectively, show the effect
          of salinity on the survival of adult fiddler crabs
          and the survival of Sesarma cinereum zoae under
          thermal stress.

     3.   Vernberg and Vernberg note:    "Some animals can
          even survive extremely hypersaline conditions in
          tidal pools cut off from ocean waters.  For
          example, fiddler crabs, Uca rapax, are commonly
          found living on the salt flats of Puerto Rico in
          salinities as high as 90 0/00.  The strong ability
          to hyporegulate is evident in two species of
          crabs, Pacygrapsus crassipes and Hemigrapsus
          oregonesis, which are known to thrive in a hyper-
          saline lagoon  (66 0/00) cut off from the sea.
       Vernberg and Vernberg, Environmental Physiology of
Marine Animals, p. 70.
                             -170-

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-------
                                     U.rapax
                                     U. thayeri
                                     U. pugnax
                                     U. minax
                                     U. pugilator
                   20    35
                    Salinity (%)
     Figure  6-7.  Survival of  larval tropical  and
temperate  zone fiddler crabs exposed to different
salinities at 38° C.  LDso indicates time required
for 50 percent mortality.   (Vernberg and Vernberg,
Environmental Physiology of Marine Animals^ p.  166.)
                         -172-

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          Some species of intertidal zone fish that inhabit
          protective rocky shores show remarkable tolerance
          to high salinities.  Along the Texas coast where
          salinities in tide pools may reach very high
          levels, fish have been found living in salinities
          as high as 142.4 0/00."
     Unfortunately, there do not seem to be enough quantita-
tive data to support the type of analysis which is being
performed for metals and oils.  Salinity related effects
will generally be ignored in this analysis, therefore.  This
may seem rather arbitrary, but that the assumption is not
too severe is suggested by some of the data of Mackin,31
and by our dispersion model ouputs which show relatively
rapid dilution of salinity within very small distances from
offshore drilling rigs in Louisiana.
6.5  Studies of Brine Toxicity and of the Effects of Brine
     Discharges at Offshore Production Sites

     A key deficiency in the use of laboratory bioassay data
in the prediction of on-site tcxicity of oilfield brine com-
ponents is that laboratory experiments are performed, almost
by definition, under a single, highly controlled set of
conditions.  Although bioassay experiments always attempt to
duplicate, to the extent possible, the conditions prevailing
in the natural environment, it is impossible to capture in a
laboratory system the multitude of highly variable physical,
chemical and biological parameters which characterize actual
oilfield sites.  The issue was concisely stated by Mackin:32
"The dream of developing a short-term laboratory study which
would enable us to predict effects on natural communities of
various pollutants is just that:  a dream."  For these
reasons, field studies form an important complement to
laboratory bioassay data.

     Several studies have been performed on the ecology of
oilfield production areas.  Unfortunately, little, if any
information is given in these studies regarding the rate of
       Mackin, Review of Effects of Oil Spills on Marine
Biotic Communities.
     32
       Mackin, Review of Effects of Oil Spills on Marine
Biotic Communities.
                             -173-

-------
brine discharge at the study site so that it is difficult to
evaluate the findings.  The Gulf Universities Research
Consortium  (GURC)  study on the ecology of oilfield areas
is not germane to the objectives of the report since the
production platforms studied were either not dischargers
of brine or discharged brine only intermittently and in
small quantities.   Mackin has suggested a number of general-
izations which can be drawn from field study data.

     1.   The key factor controlling the effects of oilfield
          brines on resident communities seems to be con-
          centration.  Dilution of the brines is extremely
          rapid, and reduction of the brines to apparently
          harmless levels seems to take place due to dilu-
          tion before other environmental processes (e.g.,
          degradation) have a chance to operate to any
          significant degree.  According to Mackin, "The
          dilution in large waterbodies and comparatively
          deep water is almost instantaneous, and dilutions
          of 1,000 parts of seawater to one part of brine
          can be effected in even comparatively shallow
          water in distances of from 8 to 50 feet."

     2.   The area in the vicinity of an oilfield brine
          discharge can be divided into concentric "zones of
          effect," with successively less severe effects
          being observed in zones farther and farther from
          the discharge point.  Mackin identified three
          zones:  an inner zone in which all benthic organ-
          isms, except perhaps bacteria, are destroyed; a
          transition zone in which depression of both
          benthic species numbers andL numbers of individuals
          is observed; and an outer "stimulation zone" in
          which productivity is actually increased over that
          distance from the discharge.  The explanation for
          this stimulatory effect seems to be in the use of
          petroleum hydrocarbons as a nutrient source by
          bacteria, yeasts, fungi, and other phytoplanktonic
          organisms.  The resulting rise in the phytoplankton
          populations stimulates those populations which
          feed on the phytoplankton.  The role of petroleum
          as a toxicant in zones one and two but as a
          nutrient in zone three emphasizes again the impor-
          tance of concentration and dilution in determining
          toxic effects of brine discharges.

     3.   Mobile organisms  (e.g., fish) do not remain in
          zones one and two long enough to be effected, so
          the primary effect is confined to the largely
          sessile benthic organisms.  Of course, indirect
                             -174-

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          ecological effects may result in nonbenthic
          populations as a result of the modification of the
          benthic communities.

     Mackin cites a number of studies in his review to
support this general model of oilfield brine toxicity.  He
discusses the studies of Lunz and others^ on the toxicity of
oilfield brines in bioassay systems to show that beyond a
certain level of dilution no toxic effect is observed (note
that by using the brine in a bioassay system, rather than
its individual components, synergistic and antagonistic
interactions are automatically taken into account).   In one
study of the toxicity of brines to Palaeomonetis pugio, the
most toxic of the brines studied produced a 48 hr LC50 of
about 200,000 ppm to the most sensitive of the organisms
studied.  The least toxic brine had an LC 50 of about
1,000,000 ppm; i.e., a 100 percent brine solution would only
kill 50 percent of the £_._ pugio individuals within 48 hours.
The use of an application factor of .01 together with the
"worst case" LC50 gives an estimated "safe" concentration of
about 2,000 ppm  (corresponding to a dilution of one part of
brine to 500 parts of normal seawater).  In another study
Lunz34 showed that Louisiana brines (salinity 128 ppt) had no
effect on the pumping rates of oysters at bioassay concen-
trations of from 10,000 to 50,000 ppm  (1 to 5 percent).  A
threshold of about 3 percent was observed for any effect on
the ability of oysters to clear a turbid medium. ^
       Mackin, Review of Effects of Oil Spills on Marine
Biotic Communities.
     34
       G.R. Lunz, The Effect of Bleedwater and of Water
Extracts of Crude Oil on the Pumping Rate of Oysters,
 (College Station,Texas:Texas A&M Research Foundation,
Project No. 9, 1950).

       E.J. Lund, "Effect of Bleedwater, Soluble Fraction,
and Crude Oil on the Oyster," Publications of the Institute
of Marine Science 4(2)  (1957): 321-341.
                             -175-

-------
     Data collected by Menzel and Hopkins   seemed to confirm
the existence of "zones of influence."  These investigations
were conducted in the Lake Barre Field (Texaco)  in Louisiana,
and showed heavy oyster mortality within about 25 feet of
the drill platform, a zone of lesser mortality extending out
to 75 feet from the platform, a zone of stunted growth
extending out to about 150 feet from the platform, and no
effect, except possibly some stimulation, beyond 150 feet.
The stimulation effect was described as "weakly significant."
The data for this field is shown in Figure 6-8.   Note that
toxic effects seemed to disapoear beyond about 200 feet from
the platform, so that the effects were rather local.

     A similar study conducted by Mackin in 1971   also
showed zones of effect.  Zone one  (as defined above) ex-
tended out to about 50 feet from the rig; zone two extended
from about 150 to 200 feet; and zone three reached from 400
out to several thousand feet from the rig.  This study
involved an intensive program of biological characterization
of the areas around six oil fields in Texas.  The principal
conclusions were that no effect was observed outside of a
purely local one, and that the local effect was concentrated
primarily on benthic organisms, with the more motile popula-
tions being totally unaffected.  The indices of effect
studies included number of species/station, number of
individuals/sample, taxon diversity, species diversity, and
reproductive capacity.  Among the conclusions of this study
were:

     1.   Exposed organisms exhibited a wide range of
          tolerances to the toxic effects of brines.  The
          least sensitive were the polychaetes  (this is
          consistent with a recent study of the adaptation
       R.W. Menzel, Report on Oyster Studies in Caillou
Island Oil Field, Terrebonne Parish, Lousiana  (Texas:
Texas A&M Research Foundation, Project No.  9,  1950); R.W.
Menzel and S.H. Hopkins, Report on Experiments to Test the
Effect of Oil Well Brine or Bleedwater on Oysters at Lake
Barre Oilfield  (Texas:  Texas A&M Research  Foundation, Project
No. 9, 1951); and R.W. Menzel and S.H. Hopkins, Report on
Oyster Experiments at Bay St. Elaine Oilfield  (Texas:  Texas
A&M Research Foundation, Project No. 9, 1953).

     37J.G. Mackin, A Study of the Effect of Oilfield Brine
Effluents on Biotic Communities in Texas Estuaries  (Texas:
Texas A&M Research Foundation, Project No.  735, November
1971).
                             -176-

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          of the  polychaete Nereis to high copper concentra-
          tions in an English estuary38)r  followed by the
          molluscs,  follosed by the Crustacea,  which seemed
          to be the  Mysicacea,  the Tanaids,  the grass shrimp,
          the amphipods,  and the isopods.

     2.    The picture of  an effect confined to  a local inner
          zone of effect  seems  to be confirmed.  Figure 6-9
          shows typical data from the Trinity Bay field
          stations.   Here,  station 1 was located at about 50
          to 75 feet from the rig; station 2 at 250 to
          300 feet from the rig; station 3 at 500 to 550
          from the rig; station 4 at 1,100 feet from the
          rig; and stations 5 through 12 equally spaced out
          to a final distance of about 2.5 miles.

     3.    "...All bottom  invertebrates are sensitive to
          brine effluent  if the concentration is sufficient
          and none are susceptible provided sufficient
          dilution and chemical and biological  degradation
          occurs.  In the Trinity Bay field there can hardly
          be any  doubt...that there is a healthy, vigorous
          reproductive community in existence over the major
          area of the field."

     4.    "...In  summary, the brine discharge showed an
          effect  on bottom fauna in Trinity Bay field at
          Stations 1 and  2.  The effect ended somewhere
          between Station 2  (300 feet from the  brine dis-
          charge) and Station 3  (500 feet from the brine
          discharge)...and the area affected is approxi-
          mately  0.015 percent of the total bay."

     A somewhat  less cheerful picture is presented by a
number of studies conducted by the Texas Parks  and Wildlife
Department3^ on  oil drilling operations in Chiltipin Creek
in Louisiana. The report produced a variety of evidence to
show that Chiltipin Creek was "nearly devoid of marine life"
     3 8
       Bryan and Hummerstone, "Adaptation of the Polychaete
Nereis diversicolor."

     39
       R.W. Spears, An Evaluation of the Effects of Oil,
Oilfield Brine and Oil Removing Compounds, Environmental
Quality Conference for the Extractive Industries of the
American Institute of Mining, Metallurgical, and Petroleum
Engineers, Inc., June 1971.
                             -178-

-------
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                                                      Mean:   Stations 1-12  13.9
                                   Mean:  Stations  3-12   15.2
                                  5678


                                STATIONS - NOT TO SCALE
                                                                 10
11
12
     Figure  6-9.    Trinity Field,  Trinity Bay - Number of species in relation  to
 the brine discharge  at F]_ platform bottom samples.  Each point is the mean  of
 12 monthly  samples.

-------
  compared with nearby  streams,  unaffected  by oil  drilling
  operations,  which had relatively  rich populations  of  various
  organisms.   Here  relatively  large amounts of brine were
  being produced and discharged  into a  relatively  small
  receiving waterbody,  producing highly toxic environments for
  marine life.   (This contrasts  with the situation observed in
  the areas studied by  Mackin  in which  the  receiving waterbody
  was a large  bay.)   Studies of  the Chiltipin Creek  area
  revealed that the production of two commercially important
  species (the  white shrimp, Penaeus setiferus and the  blue
  crab,  Callinectes sapidus) were drastically reduced in
  Chiltipin Creek compared  to  neighboring tributaries.  The
  effect seemed to  be correlated with periods of low rainfall,
  and chemical  investigation showed high concentrations of oil
  (above those  specified by the  Texas Water Quality  Standards)
  in the Creek.   This provided power evidence for  a  brine-
  related effect on the communities of  the  Creek.

                                     4 0
       A study  conducted by Heffernan   under the  auspices of
  the Chiltipin Creek project  provided  valuable data on the
  toxicity of  brine.  These data are summarized in Table 6-18.
  The bioassay  test period  in  these figures was 48 hours.

       Another  important study of the effects of oilfield
  brines was conducted  by Mackin and Hopkins in 1961 on
  Louisiana oilfields.   The study was an attempt to  trace  the
  effects of brine  discharges  on the ecological communities of
  the study area, and involved consideration of a  variety  of
  historical,  toxicological and  environmental monitoring data.
  Four important conclusions of  the study were as  follows:41

       1.  The history of  the oyster industry shows that
           Louisiana oysters  have  always been subject  to  high
           rates of mortality,  and that periods of  disas-
           trously high mortality  have been frequent as far
           back as the records  go.
     40
       T.L. Heffernan,  J.  Monier,  and S.  Page,  Effects of
Oilfield Brine on Marine Organisms.   An Ecological Evaluation
of the Aransas Bay Area, Job No.  1,    Texas Parks and Wild-
life Department (1972).
     41
       J.G. Mackin and S.H.  Hopkins, "Studies on Oyster
Mortality in Relation to Natural  Environments and to Oil
Fields in Louisiana," Publications of the Institute of
Marine Science 7  (1962): 1-131.
                              -180-

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                        TABLE 6-18


            BIOASSAY DATA ON OILFIELD BRINES
            FROM CHILTIPIN CREEK AREA (TEXAS)
TEST ORGANISM           FACILITY
Brown shrimp            Haas Ditch       24.5 - 26.5

White shrimp            Haas Ditch          28.0

Brown Shrimp            Southwestern     i Q n _ -M c
                           Oil           L  U

White Shrimp            Southwestern        , ., _
                           Oil              1J'b

Blue Crab               Southwestern        9, n
                           Oil              ^x'u
   2.   The study of Louisiana oyster production statis-
        tics and oyster history showed that disastrously
        high mortality of oysters had occurred at times
        both before and after oil production began in the
        oyster-growing area, and that since oil production
        started there had been oyster mortalities in
        places far distant from oil operations as well as
        in and near oilfields.

   3.   Field studies of Texas A&M Research Foundation
        biologists, beginning in 1947, confirmed reports
        that mortality rates were high on many Louisiana
        oyster beds, and that there was a seasonal cycle
                          -181-

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          in mortality correlated with temperature.   Except
          during abnormally warm periods there was little
          mortality in winter,  but oysters began to  die in
          spring and continued  to die steadily all summer
          and into autumn until stopped by cool weather.
          The regular and predictable nature of this mortal-
          ity indicated that it was not abnormal.  The
          general picture was,  rather, that a high rate of
          mortality associated  with summer temperatures was
          normal in much of the Louisiana oyster-growing
          territory.
                         t
     4.    Field studies of Foundation biologists also showed
          that within the region where damage from oil
          operations was claimed (in general, Placquemines,
          Jefferson, Lafourche, and Terrebonee Parishes)
          there were areas where oyster mortality was con-
          sistently low as well as areas of high mortality.
          No correlation was found between rates of  mortal-
          ity of oysters and their proximity to oilfields.
          Indeed, in the Barataria Bay area where most
          damage to oyster production was claimed, the
          highest mortalities were found at the stations
          farthest from centers of oil and bleedwater
          production.  On the other hand, high mortality was
          found to be correlated with high salinity  of the
          water.

     This suggests that wide natural variations in mortality
can frequently swamp any effects due to oilfield brines.
One further important conclusion of the study was that
"crude oil and fractions of crude oil are rapidly oxidized
and destroyed by bacteria which live in Louisiana bay muds."
6.6  Human Health Risks Associated with Oilfield Brines

     Previous sections in this chapter have concentrated on
the risk to fish, plankton, and benthic populations produced
by oilfield brines.  This section will consider the human
health risks created by the concentration of potentially
carcinogenic or otherwise toxic brine components in marine
organisms which may be subsequently consumed by human beings.
Two factors must be taken into account here:  first, the
rate at which these toxic substances are accumulated in
individual organisms  (bioaccumulation) and through the food
chain (biomagnification); and secondly, the potential effects
of these substances on human beings.  Two cases in particular
have attracted much attention in the technical literature:
the problem of biological methylation of mercury in the
                             -182-

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marine environment followed by bioaccumulation of the methyl
mercury thus formed by shellfish destined for human consump-
tion; and the problem of contamination of fish and shellfish
with potential petroleum carcinogens such as benz[a]pyrene.
First, background data on the bioaccumulation of trace
metals and hydrocarbons will be reviewed, and then these two
potential human health problems will be discussed.
     6.6.1  Bioaccumulation of Trace Metals

     Cadmium

     The normal concentration of cadmium in seawater is 0.11
parts per billion  (ppb).   Fleischer^ has reported concentra-
tion factors for a variety of organisms.  Concentration
factors for zooplankton and jellyfish are 13,000 and 11,000
respectively.  Most invertebrates show factors of from 1,000
to 10,000.  Concentration factors in fish are generally less
than 100.  Accumulation is often greater in gills and visceral
organs, as demonstrated by experiments on Chasmycthus gulosus
and Venerupis philippinarum.43


     Chromium

     Chromium is found in seawater at 0.05 ppb.  Many marine
organisms are capable of concentrating chromium by a factor
of several thousand.  Concentration factors on the order of
10,000 have been observed in Crassostrea Virginica (American
oyster), Mya arenaria  (softshell clam), and Mercenaria
     42
       M. Fleischer, A.F. Sarofim, D.W. Fassett et al.,
"Environmental Impact of Cadmium:  A Review by the Panel on
Hazardous Trace Substances," in Environmental Health Per-
spectives, May 1974, pp. 253-323.

     43
       U.S. Environmental Protection Agency, Environmental
Studies Board, Water Quality Criteria 1972, Washington, D.C,
1972.
                             -183-

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                     44         45
mercenaria (quahaug).     Merlini   reports chromium levels
400,000 times those in the ambient environment in the testes
of the sea urchin Tripneustis esculenta.  High concentra-
tions have also been found in the gills and gonads of the
mummichog.^°
     Copper

     The concentration of copper in seawater is 3 ppb.
Raymond^' found copper accumulations in the gut and body wall
of the worm Neresi virens.  Copper uptake is temperature
dependent, the rate roughly doubles with a 10° C increase in
temperature.  Uptake is proportional to animal size, and
decreases with time following a peak after 20 hours of
exposure.  Seasonal changes influence the uptake of copper
by Busycon canaliculatum, the channeled whelk.  Uptake
increases in the early summer with the beginning of the
feeding period, and decreases during the fall and winter
hibernation period.  Copper is accumulated through the
gills, where concentration increases to an equilibrium
concentration after about one hour of exposure, when trans-
port away from the gills equals the rate of intake.  Copper
is transported from the gills to the digestive gland.
Experiments with Nereis diversicolor, another worm, show
copper concentration to be roughly proportional to concen-
tration in the sediments. °  Worms from sediments of high
     44
       B. Pringle, D.E. Hissong, E.L. Katz, and S.T. Mulawka,
 "Trace Metal Accumulation by Estuarine Mollusks," Journal of
 Sanitary Engineering Division  (June 1968): 455-475.
     45
       Margaret Merlini, "Heavy Metal Contamination,"  in
 Impingement of Man on the Oceans, ed. by Donald W. Hood  (New
 York:  Wiley-Intersciences, 1971).

       U.S. Environmental Protection Agency, Water Quality
 Criteria 1972.

     47
       J.E.G. Raymond and J. Shields, "Toxicity of Copper and
 Chromium in the Marine Environment," in Advances in Water
 Pollution Research, Vol. 3, ed. by E.A. Pearson, Proceedings
 of the International Conference, London, September 1962
 (London:  Pergamon Press, 1964) .

     48
       G.W. Bryan, "Adaptation of an Estuarine Polychaete to
 Sediments Containing High Concentrations of Heavy Metals,"
 in F.J. Vernberg and W.B. Vernberg, Pollution and Physiology
 of Marine Organisms  (New York:  Academic Press, 1974) .
                              -184-

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copper content apparently have an increased tolerance to
copper.  The tolerant worms absorb copper more readily, and
are not affected by copper concentrations toxic to unadapted
polycheates.
     Mercury

     Mercury's seawater concentration is 0.03 ppb.  Concen-
tration factors up to 80,000 have been observed in Crassostrea
virginica (American oyster), with maximum accumulation in
the gills.    The highest concentration of mercury in cod
exposed to mercuric nitrate was found in the gills also,
where the concentration factor was 3,760.50
     Nickel

     Concentration of nickel in seawater is reported to be 2
to 5.4 ppb.  Concentration factors in marine organisms range
from 7,000 to 74,000.  Concentration factors for mussels,      ?-.
scallops and oysters are 14,000, 12,000 and 4,000 respectively.


     Lead

     Lead is found in seawater at a concentration of 0.03 ppb.
According to Pringle,52 lead concentrations in the gills,
gonads, and liver of Crassostrea virginica are on the order
of 1,000 times the seawater concentration.  Concentration
factors in the other tissues are somewhat lower.  Whole
organism concentration factors for Crassostrea, Mya arenaria,
and Mercenaria mercenaria are 1,300, 2,300 and 1,700 respectively,
     49
       Frederic C. Kopfler, "The Accumulation of Organic and
Inorganic Mercury Compounds by the Eastern Oyster (Crasso-
strea virginica)," Bulletin of Environmental Contamination and
Toxicology 2 (1974): 275-280.

       U.S. Environmental Protection Agency, Water Quality
Criteria 1972.

       Merlini, "Heavy Metal Contamination."
     52
       Pringle et al., "Trace Metal Accumulation."
                             -185-

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     Zinc

     Seawater concentration of zinc is 10 ppb.  Zinc is
concentrated in the gills and digestive gland of Crassostrea,
and in the gills and kidneys of Cyprinus carpio.53LaminarTa
digitata, a marine plant, accumulates zinc to concentrations
u-p to 1,800 times the ambient concentration.  Experiments
with the polycheate Nereis diversicolor show that concentra-
tion factors in the worms vary by a factor of three with a
factor of 30 variation in sediment concentration.54  This
observation implies that the worms have a substantial degree
of regulatory control over zinc accumulation.  Worms adapted
to high concentrations are about 30 percent less permeable
to zinc than nonadapted worms, and are probably better able
to excrete it.  Therefore, the adapted worms can maintain a
relatively normal zinc concentration and can avoid toxic
effects.

     It is readily apparent from the above discussion that
accumulation is a complicated process, affected by a number
of different parameters.  Present literature is insufficient
to establish a totally clear understanding of the process.
Much more research, and more importantly, standardized
research, will be needed before a definitive understanding
of accumulation can be developed.  Such an understanding
would be useful not only for this study, but also for numer-
ous other analyses of effects of pollutant discharges on
marine ecosystems.
     6.6.2  Hydrocarbon Bioaccumulation

     Many marine organisms have the capacity to take up and
accumulate hydrocarbons from their environments.  This
ability has been demonstrated in mussels, clams, oysters,
crabs, shrimp, sponge, and fish, among other organisms.
Both field and laboratory studies have dealt with the accu-
mulation process.  Although the results of these studies are
varied and often inconsistent, they do serve to demonstrate
that the ability to accumulate hydrocarbons is widespread
among marine organisms.
       U.S. Environmental Protection Agency, Water Quality
Criteria 1972.
     54
       Bryan, "Adaptation of an Estuarine Polychaete."
                              -186-

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     The mechanism and available data on bioaccumulation of
hydrocarbons by marine organisms are summarized in Appendix F
and will not be discussed in any detail here.  For the
purposes of this assessment, our only interest is in the
rate of bioaccumulation of one particular hydrocarbon,
benz[a]pyrene.  Unfortunately, long-term bioaccumulation
data are not available, but one excellent short-term
(24-hour) study is available for the clam Rangia cuneata.
Twenty-four hour exposure of this clam to 0.0305 ppm of
benz[a]pyrene resulted in tissue concentrations of 5.2 and
7.2 ppm benz[a]pyrene.55  Accumulation occurred mainly in the
viscera — digestive system, gonads, and heart.  Thirty days
depuration left 0.07 ppm of contaminants; after 58 days less
than 0.01 ppm remained.


     6.6.3  Hazards of Methylmercury Contamination of Marine
            Organisms

     An important potential human health hazard is created by
the presence of mercury in oilfield brines.  Mercury in the
marine environment can easily find its way into bottom muds
and sediments, where it can be biologically methylated by
anaerobic bacteria  (this process is known to occur in the
bottom muds of lakes, and can presumably occur in the marine
environment as well).  The products of this methylation are
the methylmercury(I) ion, CH Hg+, and dimethylmercury,
(CH3)2Hg, which is spontaneously converted to CH3Hg+ in low
pH environments.56  Although dimethylmercury is fairly volatile,
the methylmercury ion is water soluble and is bioaccumulated
to a significant extent  (bioaccumulation factors on the
order of a few thousand have been reported for a freshwater
fish,  the pike).  The toxicology of methylmercury has been
well studied,  both in animals and in human beings as a
result of events such as occurred in the Japanese city of
Minimata, where significant fractions of the population were
exposed to shellfish contaminated with methylmercury from an
industrial effluent.  The compound is easily absorbed through
the gastrointestinal tract, passes easily through placental
and blood/brain barriers, can cause extensive nervous
damage, and is a powerful mutagen.
       Jerry M. Neff and Jack W. Anderson, "Accumulation
Release, and Distribution of Benzo[a]pyrene-C in the Clam
Rangia cuneata," in Conference on Prevention and Control of
Oil Pollution, U.S. Environmental Protection Agency, American
Petroleum Institute, U.S. Geological Survey, 1975.

       Spears, An Evaluation of the Effects of Oil, Oilfield
Brine and Oil Removing Compounds.

                             -187-

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      A number of legal standards have been set up for maximum
 permissible levels of mercury compounds in fish destined for
 human consumption.  These standards are based on consider-
 ations of available animal and human exposure data,  and are
 considered to represent prudent safety factors which will
 protect exposed human populations from all significant
 neurotoxic, teratogenic, and other effects of methylmercury
 poisoning.  (For a discussion of the rationale for these
 standards, see Skerfving's review of mercury in fish.)57  The
 prevailing limit in the U.S. and Canada, promulgated in
 1970, is 0.5 ppm of mercury in fish.  Assuming a high concen-
 tration factor of about 5,000, this translates into a level
 of no more than 0.1 ppb in seawater.  This, of course,  would
 only apply to sessile organisms continuously exposed to this
 concentration of mercury.


      6.6.4  Human Health Impacts of Benz[a]pyrene

      Among the organic compounds known to be present in
 crude oil is the polynuclear aromatic hydrocarbon benz [a]-
 pyrene, a compound which is known to be strongly carcino-
 genic in animals.  The molecule is hydrophobic, and will
 partition preferentially into lipids of marine organisms,
 where it can be subject to both bioaccumulation and biomag-
 nification effects.  Although no data are available on
 benz[a]pyrene levels in oilfield brines, its presence in
 parent crude oil, together with the fact that oilfield
 brines are known to be enriched in the aromatic fractions of
 crude oil, makes it highly plausible that it is present in
 these brines.  Unlike mercury, enough data do not exist for
 this compound to predict any reasonable safe level for its
 concentration in food.  Therefore, an unacceptable level of
 benz[a]pyrene was defined as one which, after bioaccumulation,
 would not produce a level of BaP in shellfish which would
 exceed the minimum background levels of BaP in other food
 sources.5°  For this purpose a final concentration in food of
 1 ppb was defined as unacceptable.  It should be emphasized
 that this is not to be interpreted as a "safe" level, only
       S. Skerfving, "Mercury in Fish — Some Toxicological
Considerations," Food and Cosmetics Toxicology 10 (1972):
545-556.
     5 8
       For data on levels of BaP in food sources, see National
Academy of Sciences, Committee on Biologic Effects of Atmos-
pheric Pollutants, Particulate Polycyclic Organic Matter,
Chapter 14 (Washington, D.C., 1972), pp. 160-165.
                              -188-

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as an unacceptable level which should not be exceeded.  BaP
is a potent carcinogen, and no information is available to
estimate a threshold level or even to suggest that such a
level exists.
                             -189-

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                        CHAPTER SEVEN
                      IMPACT ASSESSMENT
7.1  Introduction

     In this chapter the data, model outputs, and assessment
methods described earlier in this report will be combined to
estimate the magnitude of brine-related impacts occurring at
the four study sites in Cook Inlet, Hackberry Bay, near
offshore Gulf of Mexico (Grand Isle),  and far offshore Gulf
of Mexico.  The assessment methods used in this chapter were
discussed in detail in Chapter Six, and are presented in
summary in Figure 7-1.

     Briefly, the assessment begins with the definition of a
level for each brine constituent which is safe with respect
to toxic impacts on marine and estuarine organisms.  For two
particular brine constituents, mercury and benz[a]pyrene (BaP),
a further set of safe levels, designed to prevent the bio-
accumulation of these substances to undesirable levels in
shellfish or other organisms which might be used for human
consumption, is defined.  Each of these safe levels implies
a "necessary dilution factor," that is, a brine dilution
required to bring the particular constituent down to its
safe level.  The outputs of the dispersion model, described
in Chapter Five, can then be used to estimate the area in
which any of the constituents is at a concentration greater
than or equal to its safe level.  This area is taken as an
estimate of the area of a zone of impact.

     An alternative definition of a "safe" degree of brine
dilution was also used to take into account possible inter-
actions between the toxicities of two or more brine con-
stituents.  This alternative definition takes into account
the fact that a combination of pollutants each of which is
at or below its individually estimated safe level may itself
be unsafe.  Although inadequate data are available to estimate
quantitatively the interactive toxic effects produced by a
complex mixture of pollutants such as oilfield brine, a
necessary dilution factor can be approximated by use of the
following approach.
                             -191-

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Criteria
LC50 Data
     Sublethal Effects
           Data
                         Data on Human
                         Health Effects
   Estimation of "Safe"
      Concentrations
                                                  Bioaccumulation
                                                    Data (Hg,BaP)
                     Levels in Brines
            Calculation of Necessary
               Dilution Factors
                                Dispersion Model
                                     Outputs
            Determine Dominant
             (Longest Range)
                 Effect
                                          Determine Impacted
                                        Areas(Best,Worst Cases)
      Figure  7-1.  Outline  of  the analysis.
                             -192-

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     Assume that the toxicity of a combination of different
pollutants is the sum of their respective individual toxicities;
i.e., ignore the possibility of antagonistic or synergistic
interactions.  Then, if Cj_ and S^ are respectively the pro-
duced water concentration and safe level of the i.^h pollutant,
the necessary dilution factor for the mixture,  (NDF)   , is
given by the equation^                               °


     £  ci/(NDF)tot   =     1       Z  ^i   =  i
     i=l      s.            
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impacted.  Thus, a particular level of brine impacts in a
highly fertile, productive region which supports large
populations of ecologically and economically important
organisms would probably be more significant than an equiva-
lent level of impacts in an area which is naturally infertile
and nonproductive.  Unfortunately, it was not possible
within the scope of this project to quantitatively assess
the ecological impacts of the different types of ecosystems
which might be affected by brine discharge.

     It should be emphasized that this assessment procedure
only takes direct effects into account, and does not attempt
to analyze subsequent ecological interactions and longer-
range indirect effects resulting from brine toxicity.  For
example, although a particular ensemble of brine constituent
concentrations in an area might cause 25 percent mortality
in a population of embryonic oysters, the reproductive
potential of the oyster population may be large enough to
maintain the population at its pre-impact levels.  Thus,
although a significant direct effect would be produced  (and
would be predicted by this assessment) in the long run the
effect may be relatively insignificant.  Conversely, an
ecological system may be poised in a relatively delicate
equilibrium, so that toxic stresses resulting from brine
discharges may produce long-range effects much greater than
any direct toxic impacts which would be estimated by the
analysis described in this report.

     Another factor ameliorating brine impacts which cannot
be taken into account in this analysis is the selection,
over the course of several generations, for subpopulations
which are relatively insensitive to the effects of particular
brine constituents.  This effect 'has been observed, for
example, in Nereis spp. living in a copper-polluted estuary
(see Section 6.2.5).  Later in this chapter we will comment
on the. agreement between predicted impacts and field data,
and on the extent to which the resiliency  (or, conversely,
the instability) of the ecosystem seems to modify the pre-
dicted level of toxic impacts.

     The assessment methods implemented in this chapter
predict  significantly different impacts on the four study
sites considered  in this report.  This fact illustrates the
importance of such site specific factors as depth and current
velocities in determining the level of brine impacts.
                             -194-

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7.2  Results of the Hackberry Bay Assessment

     The impacts analysis described in the previous chapter
will first be applied in detail to Hackberry Bay to illustrate
the form of the analysis and the methods used.  The methods
are practically identical for the other three study sites,
so for these only the results will be discussed.


     7.2.1  Area/Concentration Relationships

     As described in Chapter Five, the brine dispersion
model was used to generate a set of contours of equal brine
dilution  (isopleths) for each of the sites being studied.  A
typical set of predicted isopleths for the Hackberry Bay
site is shown in Figure 7-2.  A number of computer runs were
made for each site, in order to assess the sensitivity of
the results to assumptions relating to current velocities,
diffusion coefficients, and other model input parameters.
For each run, the areas enclosed by each isopleth were
measured by planimetry, and the data were plotted on a
concentration versus included area graph, which shows, for a
particular concentration value, the area of a site over
which concentration is greater than or equal to that value.
Each site therefore generated a set of these area/ concen-
tration curves, one for each set of numerical assumptions
tested.  The upper envelope of this sheaf of curves defines
a worst (maximum impacted area) case, and the lower envelope
defines a best case.  A base case was also defined using
most probable estimates for the values of each input para-
meter.  The calculated best, worst, and base case curves for
the Hackberry Bay site are repeated in Figure 7-3.

     Since Hackberry Bay is an enclosed area, it is appro-
priate to apply to it the tidal flushing calculation described
in Chapter Four, Section 4.2.  The relationships derived in
that section imply a minimum "background" brine concentration
of about 0.18 percent for Hackberry Bay.  Thus, the area/
concentration curves were only extended down as far as
0.1 percent dilution, and 0.18 percent was defined as the
effective minimum brine concentration over the whole bay.
Areas included by higher concentrations can be estimated
from Figure 7-3.
                             -195-

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  5000
  4000
  3000
  2000
  1000
   500
W
w
  -soo '
 -1000
                           I	I	I	I	I	I	I
t/f  I H7
7///M
                      •400       600
                                                                         X
                                       800
                                                1000      1200
                                                                 1400
 -2000
 -3000
 —«000
 -5000
                                    FEET
       Figure 7-2.
  (Base Case).
                Typical set  of isopleths for  Hackberry Bay site
                                  -196-

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   X3000-
   ;ooc-
CN
 ±>
 «M
 §   -I
     0.01
                    H2,H4,H5
      H6


      H7

BASE CASE HI

      H3
                        HACKBErLRY BAY
                        0.1                   1.0

                          CONCENTRATION  (%)
                                                                10.0
         Figure  7-3.   Plots of area/concentration curves  for
    sensitivity analyses  performed for Hackberry Bay site.
    Base Case assumes  most probable values  of input parameters;
    for other cases, input parameters are  individually varied
    over their range of plausible values.
                              -197-

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     7.2.2  Numerical Data Used in Impacts Analysis

     Table 7-1 summarizes the assumed values of the numerical
parameters (toxic concentrations, etc.) required for this
impact assessment.  In each case the value is stated along
with the source of the data or the rationale for the par-
ticular estimate made.

     Since only incomplete data are available on the chemical
composition of Louisiana brines, concentrations of trace
metals in the brines were generally estimated as the mean of
maximum values which had been observed at sites in California,
Alaska and Texas.

     Toxicological data are generally derived from the
tables and text of Chapter Six.  Since 0.01 application
factors used are meant to be applied to 96 hr LC50 data, a
technique was necessary to extrapolate to the 96 hr values
from the 48 or 24 hr values which were frequently reported
instead.  The data from Eisler" on cadmium toxicity were
used to make this estimate.  Ninety-six hr LC50 data for
cadmium for a number of marine species were plotted against
48 hr LC50 data for the same species, and a ray through the
origin was best-fitted to the eight available data points.
The points gave a reasonably good fit  (correlation coefficient
= 0.86) to the relationship  (96 hr LC50)  = 0.17(48 hr LC50),
which was subsequently used to estimate the 96 hr figures.
A similar procedure was used to obtain the relationship
(96 hr LC50)  = 0.096  (24 hr LC50).  Insufficient data were
available to determine whether this relationsip also held
for toxicants other than cadmium.

     Mercury safe levels in seafood were based upon the
legal standard currently prevailing in the United States and
Canada.  Available toxicological data were totally inadequate
to estimate any sort of a safe level for benz[a]pyrene.
Therefore, an unacceptable level of BaP was defined as one
which, after bioaccumulation, would not produce a level of
BaP in shellfish exceeding the minimum background levels of
      R. Eisler, "Cadmium Poisoning in Fundulus heteroclitus
 (Pisces:  Cyprinodontidae) and Other Marine Organisms,"
Journal of the Fisheries Research Board of Canada 28  (9)
 (1971): 1225-1234.
                             -198-

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                          TABLE 7-1

          VALUES OF IMPORTANT NUMERICAL PARAMETERS
  PARAMETER
VALUE
  RATIONALE
Concentrations of brine
constituents in brines:

     Ag
     As
     Cd
     CN
     Cr
     Cu
     Hg
     Ni
     Pb
     Zn
     Phenol
0.05  ppm
0.37  ppm
0.28  ppm
0.007 ppm
0.12  ppm
0.19  ppm
0.036 ppm
0.39  ppm
0.30  npm
1.25  ppm
3.5   ppm
See Chapter Three and
comments in
Section 7.2.2.
Concentration of oil
hydrocarbons in brines
50 ppm
Table 3-8 ; maximum
post-treatment
levels for "oil and
grease" in brine.
Concentration of BaP in
crude oil
0.4-1.6
  ppm
Data cited in Neff
and Anderson (1975)
Enrichment factor for
aromatics in crude oil
water soluble fraction
   (WSF)
14.29
Anderson et al. (1974) .
This value means that
the ratio (aromatics/
other HC's)  is 14.29
times as great in crude
oil WSF as in the
original crude oil.
Concentration of BaP in
brines
 0.3-1.1      Product of the above
  ppb        three values.  (BaP
             is an aromatic
             hydrocarbon.
                             -199-

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                      TABLE 7-1 (CONT.)
  PARAMETER
VALUE
    RATIONALE
Bioaccumulation factor:

   Hg
   BaP
104-105
236
Laboratory bioaccumu-
lation experiments with
Crassostrea; up to 80
day exposure (Kopler,
1974)

BaP accumulated in clam
Rangia cuneata in 24 hr
period.   (Neff and An-
derson, 1975)
Maximum permissible level     0.5 ppm
of Hg in seafood
           Skerfving  (1972;
EPA Water Quality Criteria:

     Ag
     As
     Cd
     CN
     Cr
     Cu
     Hg
     Ni
     Pb
     Zn
     Phenol
0.001 ppm
0.05  ppm
0.005 ppm
0.005 ppm
0.01  ppm
0.01  ppm
0.0001~ppm
0.1   ppm
0.01  ppm
0.07  ppm
(n.a.)
Taken from 1973 and
1975 EPA Water
Quality Criteria
Documents.
Concentrations below which
no effects were reported on
marine or estuarine organisms
in the literature:

     Oilfield brine
     Crude Oil
     Ag
     As
     Cd
     CN
     Cr
     Cu
     Hg
1%
0.001 ppm
0.0005 ppm
3.0   ppm
0.08  ppm
 (n.a.)
1. 0   ppm
0.002 ppm
0.002 ppm
Tables and text,
Chapter Six.
                            -200-

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                      TABLE 7-1 (CONT.)
  PARAMETER
VALUE
  RATIONALE
     Ni
     Pb
     Zn
     Phenol
0.06 ppm
0.1 ppm
0.006 ppm
0.6 ppm
Minimum reported 96 hr
LCSO's (actual or extra-
polated from 48 and 24
hr values), for adult
organisms:
     Crude oil    a
     Crude oil WSF
     Oilfield brine
     Ay
     As
     Cd
     CN
     Cr
     Cu
     Hg
     Ni
     Pb
     Zn
     Phenol
5 ppm
6%
22%
0.04 ppm
8 ppm
0.2 ppm
(n.a.)
17 ppm
0.2 ppm
(n.a/)
17 ppm
200 ppm
1 ppm
1. 7 ppm
Tables and text,
Chapter Six.  See
Section 7.2.3.
      Extrapolated from data given by Anderson.  The figure
represents the dilution of the complete soluble fraction,
not the concentration of hydrocarbons in the final dilution.
                              -201-

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                REFERENCES FOR TABLE 7-1
Neff,  J. and Anderson, J.  "Accumulation, Release and Distri-
     bution of Benzo[a]pyrene-C14 in the Clam Rangia cuneata,"
     in American Petroleum Institute et al.   1975 Conference
     on Prevention and Control of Oil Pollution - Proceedings.
     American Petroleum Institute.  Washington, B.C., 1975.

Anderson, J., et al.  "Characteristics of Dispersions and
     Water-Soluble Extracts of Crude and Refined Oils and
     Their Toxicity to Estuarine Crustaceans and Fish."
     Marine Biology 27 (1974): 75-88.

Kopfler, F.C.  "The Accumulation of Organic and Inorganic
     Mercury Compounds by the Eastern Oyster (Crassostrea
     virginica)."  Bulletin of Environmental Contamination
     and Toxicology 11 (1974): 275-280.

Skerfving, S.  "Mercury in Fish — Some Toxicological Con-
     siderations."  Food and Cosmetics Toxicology 10  (1972):
     545-556.
                             -202-

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BaP in other food sources.   For this purpose a final con-
centration in food of 1 ppb was defined as unacceptable.  It
should be emphasized that this is not to be interpreted as a
safe level, only as an unacceptable level which should not
be exceeded.  BaP is a potent carcinogen, and no information
is available to estimate a threshold level or even to
suggest that one exists.
     7.2.3  Difficulties Involved in Use of Application
            Factors

     The question arises of whether an application factor of
0.01 applied indiscriminantly to the 96 hr LC50 of the most
sensitive organism studies is an appropriate criterion for
use in estimating safe levels.  The problems which can
result when this approach is applied to the extremely low
LCSOs observed for juvenile and embryonic forms is illus-
trated by the case of silver.,  A 48 hr LC50 of 0.005 ppm has
been reported for silver for Crassostrea embryos.  Using the
relationship between 96 hr and 48 hr LC50's discussed in
Section 7.2.2, this is shown to imply a 96 hr LC50 of
0.000835 ppm, or an application factor threshold of  (0.01)
(0.000835) = 8.35 x 10° ppm.  This is, however, far below
the concentration of silver in natural, unpolluted sea
water, which is 0.3 ppb or 3 x 10~4 ppm.  Clearly, the
application factor approach is not realistic in this case,
since it leaves us with the conclusion that unpolluted sea
water is an unacceptable environment for marine organisms.

     The application of the 0.01 factor has therefore been
restricted in this study to toxicity data for adult  forms.  It
is extremely important to emphasize, however, that the problem
of choosing an application factor to derive "safe" levels
of pollutants from acute toxicity data is by no means a simple
one, nor is there any evidence that it can be solved in a
thoroughly convincing way.  Indeed, it is unreasonable to
expect a simple relation to exist between the relatively
high level of a pollutant capable of inducing mortality in
a short period of time, and the low levels which, under con-
ditions of chronic exposure, may affect one or more of the
multitude of different biological processes or behavior pat-
terns exhibited by various organisms at all stages of their
      For information on levels of BaP in food sources, see
National Academy of Sciences, Committee on Biologic Effects
of Atmospheric Pollutants, Particulate Polyeyelie Organic
Matter, Chapter 14  (Washington, D.C., 1972), pp. 160-165.
                            -203-

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life cycles.   Further discussion of the complexities of the
subject is given in a review paper by Bernhard and Zattera.4


     7.2.4  Numerical Calculations for Hackberry Bay

     The calculations performed for unsafe zone areas for
individual brine constituents and for combined effects in
Hackberry Bay are shown in Table 7-2.  Because of the
significant compositional differences between crude oil and
the crude oil water-soluble fraction, it was decided to use
only the data on the water-soluble fraction for estimating
the toxicity of the hydrocarbon fraction of brines.

     A further advantage of this is that the dispersion of
crude oil WSF around the discharge point can be modeled much
more accurately than can the dispersion of total oil hydro-
carbons.  This is because the predominantly aromatic WSF
hydrocarbons are degraded much more slowly by hydrocarbono-
clastic  (hydrocarbon degrading) microorganisms in the marine
environment than are non-WSF hydrocarbons.  Therefore, their
concentration distributions can be predicted much more
accurately by the brine dispersion model used in this
report, which only takes physical dilution forces into
account.

     The individual effects analysis  (Table 7-2) suggests a
toxicity threshold of about 0.06 percent brine dilution.
The combined effects analysis obtained by summing the NDF's in
Table 7-2  (see Section 7.1) reduces this to about 0.04 per-
cent.  Both estimates may tend to be conservative s'ince some
of the contaminants will probably be subject to effective
concentration reductions greater than those predicted by
the dispersion model as a result of adsorption, sedimenta-
tion, and  (in the case of trace metals) physiological in-
activation by chelation.  On the other hand, the individual
effects analysis, as mentioned above, does not take into
account the effects of emulsified oil hydrocarbons in the
brines.  Moreover, the facts that the limited amount of
available data regarding the detailed composition of oil-
field brines exhibits a wide range in the concentrations of
brine constituents  (see Table  3-2), and that the state of
knowledge of the potential impacts of trace metals and oil
     4
      M. Bernhard and A. Zattera,  "Major Pollutants in the
Marine Environment," in E.A. Pearson, ed., Marine Pollution
and Marine Waste Disposal  (New York:  Pergamon Press, 1975).
                            -204-

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I
NJ
O
Ul
I
                                                        TABLE  7-2


                                         CALCULATIONS  FOR  HACKEERRY  BAY

ESTIMATED "SAFE"
CONTAMINANT CONCENTRATION

Ag
As
Cd
Cr
Cu
Hg
Hg (as a
food
contaminant)
Ni
Pb
Zn
Crude Oil
WSF
BaP (as a
food
contaminant)
Phenol
CN
Total NDF for
Combined Effects
Analysis01
(ppm)
0.0004
0.05
0.002
0.01
0.002
0.0001
c


0.06
0.01
0.01
0.06%

4 x 10~6


0.6
0.005


CONCENTRATION
BRINE
(ppm)
0.05
0.37
0.28
0.12
0.194
0.036
0.036


0.39
0.30
1.25
100%

0.001


3.5
0.007


IN PERCENT DILUTION
NDF3 AT NDF (= 100/NDF)
(ppm)
117
7
141
12
97
356
l,187b


6
30
125
l,600b

250


6
1.4

2,500

0.86
13.64
0.71
8.11
1.03
0.28
0.08


15.5
3.37
0.8
0.06

0.4


17.14
71.4


                        NDF = necessary dilution factor,  i.e.  dilution necessary to reduce each constituent
                  to its safe level.

                       bLargest NDF's.

                       °Safe level is essentially at or below natural level in seawater  ( = 0.03 ppb = 3 x  10~5 ppm)

                        See Section 7.1.  The NDF's for BaP and Hg as food contaminants are  not included
                  in the total NDF.

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hydrocarbons is rapidly expanding, suggest prudence in estima-
ting the potential impacts of brine disposal in marine and
estuarine waters.  Accordingly, a "best guess" of a 0.05 percent
(2,000:1) dilution was made as an estimate of a safe level of
brine dilution.

     Since the "safe" level is below the 0.18 percent back-
ground brine levels predicted by tidal flushing calculations,
essentially the whole of Hackberry Bay is included in a zone
of impact.


     7.2.5  Ecological Considerations

     The Barataria Bay region, in which Hackberry Bay is
located, is a highly productive coastal wetlands area and
one of significant commercial importance.  Therefore, any
brine related impacts produced in that area are likely to be
ecologically and economically significant (see Appendix A).

     The salt waterbodies associated with the coastal salt
marshes of the Barataria Bay region  (Hackberry Bay is one
such waterbody) support high levels of primary production by
diatoms, coccoid blue green algae, green algae, and nanno-
plankton.  This primary production supports a large number
of herbivores, including Acartia tonsa  (the dominant copepod
of the region), menhadden, and mullet.  Detrivores are
numerous in the region including commercially important
species of penaeid shrimp, blue crabs, and oysters.  Important
carnivores include ctinophores  (which feed on zooplankton),
fishing birds, diving ducks, spotted sea trout, sea catfish,
silversides, anchovy, and the bottlenosed dolphin.

     Many commercially important species, although they are
not full-time residents of the Barataria Bay area, spend at
least part of their life cycle there.  The blue crab, which
supports a large fishery, spawns in lower estuarine and Gulf
waters, although the larval stages  (zoae and megalops) are
spent in open Gulf waters.  Near the end of the megalops
stage the blue crabs may enter tidal inlets, and the first
nine months of the juvenile stage are spent in the upper and
lower estuary.  The second year as a juvenile is spent in
the upper estuary where the crab grows to full maturity and
mates.  It is at this time that crabs are usually fished —
usually from ages 12 to 18 months.  The panaeid shrimp
(including the white, pink, and brown shrimp), also com-
mercially important, follow a similar life cycle pattern.
                             -206-

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     Fish species which spawn in the Gulf and use the
Barataria Bay as a nursery ground include the large-scale
menhadden, the Atlantic croaker, the spotted and sand sea
trout, the silver percy, the striped mullet, the spot, and
the bay whiff.

     More detailed information on the ecology of this highly
productive region is given in Appendix A.


     7.2.6  Delineation of Alternative Impact Zones

     The approach adopted in this report was to summarize
impacts at each site by estimating the area of an impact
zone in which some significant level of toxic impacts on
marine hydrocarbons would be felt.  It would be desirable,
as discussed in Chapter Six, to be able to determine the
nature and magnitude of impacts which would occur in each of
a set of concentric regions inside of this impact zone.
Unfortunately, such an analysis is made almost impossible by
the complex sets of interactions which would almost certainly
be observed between the toxic impacts of the dozen or so
contaminants found in brines.  Particular sublethal effects
may be observed as the' result of individual exposure to
several different pollutants, and there is no method avail-
able for estimating the way these pollutants will interact
in a mixture to produce these particular effects.

     Some qualitative feeling for how the type and severity
of effects vary with concentration can be gained from
Table 7-3, in which the effects found for successive levels of
dilution of silver from its initial maximum reported con-
centration in the brine are listed.  Note that the effects
become less severe towards the edge of the unsafe zone, and
that at its borders only embryonic forms are affected.
Unfortunately, it would be impossible to predict how the
types of effects produced by silver in an inner dilution
zone would interact with the effects produced by other
pollutants in the same physical zone.


7.3  Analysis of Impacts at Other Sites;  General Comments

     As was discussed in Chapter Two, this analysis incor-
porates a number of site specific features, including the
resident species, the dispersion characteristics of the
site, and the contaminant concentrations and discharge
rate of the brine.  An examination of the quantitative data
suggests that the most important of these features in determining
the magnitude of impact at a site are the discharge rate
                             -207-

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                                      TABLE  7-3

               TYPES OF  EFFECTS REPORTED IN  THE LITERATURE FOR SILVER AT
            VARIOUS RANGES OF CONCENTRATIONS FOUND INSIDE THE "UNSAFE"  ZONE
     DILUTION
     RANGE
                         CONCENTRATION
                            RANGE
                             EFFECTS  NOTED
i
NJ
O
CO
I
      1-10
10-100
     100-1000
                         0.10-0.01
0.01 ppm-1.0 ppb
                         1.0 ppb-0.10 ppb
Abnormal movement in mud snail
Nassarius induced by 72 hr exposure.
96 hr LC50 for Fundulus; 96 hr
exposure caused severe reduction of
levels of 3 liver enzymes in Fundulus.

Mortality of Crassostrea embryos;
toxicity threshold for adult stickle-
backs.

Induction of developmental abnormalities
in embryos of various sea urchin species,
     DILUTION
                                                      TYPES OF EFFECTS
      1-10


      10-100

      100-1000
                                               Lethality of adult organisms, significant
                                               sublethal effects.

                                               Mortality of embryonic forms.

                                               Teratogenesis,  induction of developmental
                                               abnormalities.

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and dispersion characteristics, the latter being determined
by depth, tidal currents and drift or freshwater current
velocity.  Since information on toxic effects was not avail-
able for all important species at each site, it seemed
reasonable to base all the impacts assessments on the total
group of marine species for which data were available.
Furthermore, because of the wide variability of composition
of produced water at different sites within a geographical
region (a variability which was in most cases larger than
the differences observed between different regions), the
assumption was made that the brine compositions for all
sites could be adequately represented by the concentrations
which were used for Louisiana brines, the derivation of
which was explained earlier.  Therefore, the chief focus in
comparison of the sites was comparison of the dispersion
model outputs.  For all sites, an impacts threshold of
approximately 0.05 percent brine dilution was assumed.
7.4  Analysis of Impacts at Cook Inlet

     7.4.1  Area/Concentration Relationships

     Area/concentration curves for Cook Inlet are shown in
Figure 7-4.  The curves were computed down to 0.05 percent
dilution, the toxicity threshold being assumed in this
analysis.  Because of the enormous tidal flushing volumes,
the calculated background concentration is far below this
level and can be ignored.  Notice that the base case curve
is also a best case over part of its range.

     The estimated area of the impact zone for this site is
between 700,000 ft2 (0.025 mi2) and 50,000,000 ft2  (1.79 mi2)
The base case estimate is 5,000,000 ft2 (0.18 mi2) .


     7.4.2  Ecological Considerations

     Cook Inlet can be divided into three ecologically semi-
distinct parts (see Figure 7-5).  The upper Inlet lies east
of a line extending northward from Point Possession; the
middle Inlet, where most of the current brine discharge
occurs, includes waters from the upper Inlet southwestward
to the latitude of Tuxedni Bay (60° 25' N); and the remaining
portion of Cook Inlet, south of Tuxedni Bay and Clam Gulch,
is commonly called the lower Inlet.  This last region has
the clearest waters, and is the most productive,  supporting
all major species of fish, shellfish, and marine mammals
found in Cook Inlet.  It is this lower Inlet region which is
of most interest to biologists and agencies concerned with
                             -209-

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100,000-,
 10,000 •
1,000.0:
<
<
  100.0:
   10.0
    1.0
    0.1
                                   COOK INLET
                           WORST CASE
             BEST
               CASE
.01
                    11 |	1	1—i i i i i—i—
                    .10            1.0
                      CONCENTRATION  (%)
                                                i i  i 111
                                                   10.0
     Figure 7-4.  Area/concentration curves for Cook  Inlet.
                      -210-

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I
CO
             Figure 7-5.  Map of Cook Inlet.

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wildlife and fisheries management.  Therefore, relatively
little work has been done in the mid Inlet, which is the
area of interest to this analysis, since it contains the
major oil production areas of the Inlet.  What data are
available suggest that the mid Inlet is relatively non-
productive .

     It appears that very few species exist in the silt
laden waters of the western and upper half of the Inlet
(including the mid-Inlet region).  The high tidal amplitude
and the strong tidal currents which scour the bottom make
survival difficult for most benthic organisms.  The great
loads of suspended sediment in these regions limit penetration
of light, confining photosynthesis to a very shallow photic
zone.  Productivity increases as one moves oceanward, to
cleaner, more saline waters.  The lower Inlet waters provide
habitat for a variety of sport and commercially important
fish and shellfish, and numerous other non-fished species.

     In short, the impacts produced by oil platforms in the
mid-Cook Inlet provide us with a case which contrasts strongly
with that of Hackberry Bay.  Not only are the zones of
impact smaller in Cook Inlet  (as a result of site specific
dispersion patterns), but the area impacted seems much less
important, both ecologically and economically.
7.5  Analysis of Impacts at Grand Isle

     7.5.1  Area/Concentration Relationships

     Area/concentration curves for the near offshore site at
Grand Isle are shown in Figure 7-6.  Since this site is in
the open ocean, outside the Gulf of Mexico barrier islands,
the tidal flushing calculations were inappropriate, and no
minimum background level was assumed.  Two different base
cases were used, one assuming a discharge site located
fairly close to the shore of Grand Isle, and one assuming a
site further away from shore.  (These two base cases are
cases N1A and N2A, using the nomenclature of Chapter Five.
The discharge-to-shore distances and other input parameters
assumed for these cases are discussed in detail in that
chapter.)

     The estimated area of the impact zone for this site is ~
between about 900,000 ft2  (0.032 mi2) and about 9,000,000 ft
 (0.32 mi2).
                             -212-

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  1000.0
   100. Ch
 <
 <
    10.0-
     1.0
        0.01
                 N2B VN
                  N1D
                                      GRAND  ISLE
                     WORST CASE
                             BEST CASE
                          N2B

                          N1A (BASE CASE 1)
                          N2A (BASE CASE 2)
                          N1E
                          NIB
                          NIC	
0.1                1.0
    CONCENTRATION (%)
10.0
     Figure 7-6.   Area/concentration  curve for Grand Isle
site in near offshore Gulf of Mexico.
                               -213-

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     7.5.2  Ecological Considerations

     The near offshore Gulf of Mexico is a highly productive
region  (see Appendix A),  which yields extremely high catches
of commercially important fish and shellfish.  The variety
and productivity of this region is suggested by Table 7-4,
which lists some of the significant consumer species found
there.


7.6  Analysis of Impacts at the Far Offshore Gulf of Mexico
     Site

     7.6.1  Area/Concentration Relationships

     Area/concentration curves for the far offshore site  in
the Gulf of Mexico are shown in Figure 7-7.  Since this site
is in the open ocean, tidal flushing calculations are in-
appropriate, and no minimum background level is assumed.

     The estimated area of2the impact zone for this site  is   ~
between about 3,000,000 ft  (0.1 mi2) and about 10,000,000 ft
 (0. 33 iru.2) .
     7.6.2  Ecological Considerations

     The far offshore Gulf of Mexico is a highly productive
region, which yields extremely high catches of commercially
important fish and shellfish, as does the near offshore
Gulf.  The species shown in Table 7-4 can also be found in
the far offshore waters of the Gulf.
7.7  Summary of Impacts Analysis

     The magnitude of impacts observed at each of the study
sites is summarized in Table 7-5.
 7.8  Comments on Agreement of Results with Field Studies

     The extension and, more importantly, the validation of
 this model will require the implementation of field  studies
 specifically concerned with the analysis of brines,  water
 column  samples, and ecological communities in the vicinity
 of production platforms.  Previous  studies in general have
 not generated sufficient data on  the relationship between
 concentrations of metals and hydrocarbons in the water
 column  and in the discharged brine  to confirm the predictions
                            -214-

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                                                 TABLE  7-4
          KEY   CONSUMERS   -  NEAR  AND  FAR  OFFSHORE   GULF  WATERS
                        (ADJACENT  TO  BARATARIA  BAY,   LOUISIANA)
                     INVERTEBRATE
                                                     FISH
COMMERCIAL
SPECIES


(Brown Shrimp)
if Penaeus setiferus
(White Shrimp)
if penaaus durorarun
if ft Anchoa adtchilli
(Bay Ar.chovy)
(Sand Sea Trout)
ft Pearilus burti
                     (PirUc  Shriai?)
                                                    __     _
                                              (Gulf Butterfish)
                 ir •& gallinectes sagicis
                     (Blue  Crab)
                                  ^
                            (Fringed Flounder)
SPORT  SPECIES
                                            •fr Cantropistes gniladelghica
                                              (Rack 5«a Bass;
                                            •fr Trichj-ums  lapturus
                                              (Cutlass Fish)
                                            -^ Leiostonms x_an_thurus
                                              (Spot)
                                                  _  _
                                              (s«a Catfish)
                                          if -fr yj.grogQggn undulatos
                                              (Atlantic CroaJcar)

                                            £ CH 1 Q r g_jtcomb rus chrysu
                                              (Atlantic Bunker)
TROPHICALLY
IMPORTANT
SPECIES
  • jjagmarus gg.
    (Ampnipod)

• if Acartia ton.sa
    (Copepod)

• if Paracalanus st^
    (Copepod)

  if >qphopenaeu8 so^
    (Sea Bob)

  if j^quilla sg.
    (Mantis ShriOTi)
Prionotug rcscua
(Blue Spotted Sea Robin)
ft Stama  sg_.
  iTcm)

ft Ayt^a affiniS
  (L«saer Scaup)

ft Larus atrieillia
  (Laughing Gull)

ft Fregata maoni.ficans
  CFrigata Bird)

ft Larus ph^iladftlphia.
  (Bonaparte' a gull)
ft Tursippa truncatua^
  (Bottlenose Dolphin)
                     .       IS.
                     (P«X«cypod)
                  ir*tr Cibanarius vittatus
                     THermit~Crab)
                     Lolitjuncula brevis
ENDANGERED
SPECIES
                                                          ft Pelecanus qceieJttalia
                                                            (Brown Pelican)
     ~*  D«tritivere
     •ft-  Carniwora

     •  Harbivorv
                                                      -215-

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   WOO.
rg
    B.O-
     001
                                        FAR OFFSHORE

                                           GULF OF MEXICO
                                                       F2,F4
                                     T	1	1	1—I I  I |
                                                to
i—I—r  i r™ i
      100
                            CONCENTRATION (%)
         Figure  7-7.   Area/concentration curves for far  offshore

    Gulf of Mexico site.
                                 -216-

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                          TABLE 7-5

                     SUMMARY OF IMPACTS
  SITE
LOCATION
PROBABLE AREA OF
   IMPACT ZONE
     ECOLOGY
Hackberry
Bay
Onshore
Cook Inlet
Onshore
Grand Isle
Gulf of
Mexico Site
Near
Offshore
Far
Offshore
entire bay (ca.
192,000,000 ft2
or 6.9 mi2)
ca. 5,000,000 ft'
(0.18 mi2)
700,000 -
9,000,000 ft'
                                            .2,
highly productive,
supports blue
crab, panaeid
shrimp, and other
commercially
important spp.

relatively in-
fertile due to
continuous bottom
scouring by tidal
currents and to
high turbidity
highly productive;
supports several
                             (0.025 - 0.32 mi )  commercially
                                               important or
                                               sport species
3,000,.000 -
10,000,000
                            (0.11 - 0.36 mi
                                          .2.
highly productive;
supports several
commercial or
sport species
of this dispersion model used in this report, nor have
they provided detailed information on brine discharge rates
at study sites.  Furthermore, studies of the condition of
ecological communities near production platforms frequently
suffer from an important methodological deficiency in that
they often analyze the condition of the ecosystem by comparison
with reference points distant from the production platform,
and therefore presumably unimpacted.  The existence of
chronic, long-term pollution problems in some areas, however,
may mean that these reference points are themselves strongly
impacted.  For this reason, the actual magnitude of impacts
is probably best determined through comparison with a temporal,
rather than a spatial, reference point.  The Bureau of Land
                             -217-

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Management is currently in the process of organizing such a
"pre-impact" baseline study at the site of future offshore
drilling operations at Georges Bank, Maine, and at other
sites off California, Virginia, and South Carolina.

     Furthermore, field studies on the health of ecosystems
do not provide any data on what may well be the most important
impact of offshore oil operations, which is the bioaccumula-
tion of toxic brine constituents by organisms which are
eventually destined for human consumption.  Potential toxic
impacts of the bioaccumulation of mercury and benz[a]pyrene
by marine organisms have already been discussed, and similar
problems may be expected as a result of the bioaccumulation
of other metal or hydrocarbon brine contaminants.  The data
in Table 7-2 suggest that this class of impact would be
serious down to about three orders of magnitude of brine
dilution.  This is an especially serious problem in areas
such as Hackberry Bay, which are important fishery regions.

     For these reasons it is difficult to confirm the predic-
tions of the model on the basis of field data.  Nevertheless,
the following general comments can be made:

     1.   The literature of brine impacts shows that the
          magnitude of the impact is highly site specific,
          and seems to be correlated most strongly with the
          dilution characteristic of the receiving waterbody.
          Thus, Mackin found little ecological damage in the
          relatively open waterbodies he studied in the Gulf
          of Mexico, while the Chiltipin Creek studies
          demonstrated an extremely strong and significant
          impact in an area with insufficient current and
          tidal flow to rapidly dilute discharged brines
          (see discussion in Chapter Five).  Furthermore,
          Chiltipin Creek impacts were found to be consid-
          erably ameliorated during periods of high rainfall,
          which suggests the importance of dilution effects.

     2.   The tendency for resiliency in established eco-
          systems and the possibility of selection for
          pollution-resistant subpopulations over the course
          of several generations may considerably ameliorate
          the effects predicted in this analysis.  Further-
          more, the oxidation of oil hydrocarbons by marine
          microorganisms may lessen the magnitude of oil-
          related impacts  (although metals would probably be
          scavenged much more slowly than hydrocarbons from
          the water column).  Extensive examination of this
          possibility through the implementation of field
          studies in the Hackberry Bay and Cook Inlet areas
          is indicated.
                             -218-

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     3.    Mackin and Hopkins  reported that oyster mortality
          along the Louisiana coast (including the Barataria
          Bar area) was not correlated with proximity to oil
          fields.  Levels of trace metals in oysters and the
          existence of a number of sublethal effects were
          not examined in this study.   The report also
          demonstrated that there is a significant natural
          variation in oyster mortality, due to current,
          tide, and salinity variations which is much greater
          than the estimated magnitude of brine-related
          mortality, and which was observed before offshore
          operations began in the Louisiana area.  According
          to Mackin and Hopkins:  "Field studies of Texas
          A&M Research Foundation biologists, beginning in
          1947, confirmed reports that mortality rates were
          high on many Louisiana oyster beds and that there
          was a seasonal cycle in mortality correlated with
          temperature.  ... The regular and predictable
          nature of this mortality indicated that it was not
          abnormal."

     4.    Mackin (see Chapter Five) and, more recently,
          Neff, observed a zone of ecological stimulation
          lying outside of the zone of impact which they
          observed in their field studies.  They attribute
          this to the biodegradation of petroleum hydro-
          carbons by communities of marine microorganisms,
          which enable the hydrocarbons to be used as a
          nutrient source by the marine communities.  This
          may be a significant feature of the impact of
          petroleum on marine ecosystems, and deserves
          further attention.  It is suggested that further
          field and laboratory studies be carried out in
          this area.

     In short, the currently available field data are
inadequate for quantitative validation of the model, although
some of the qualitative data are consistent with the analysis
(existence of concentric zones of impact, importance of
site specific dilution rates, etc.).  Ecological field
studies are hampered at many sites by the existence of wide
natural variations in mortality parameters  (both seasonal
and random) which swamp variation due to brine-related
impacts.
      J.G. Mackin and S.H. Hopkins, "Studies on Oysters in
Relation to the Oil Industry," Publications of the Institute
of Marine Science  (7) (1961):  1-131.
                            -219-

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                        CHAPTER EIGHT
                         CONCLUSIONS
     The data and analyses discussed in this report support
the following conclusions:


•    Presence of Toxic Substances in Oilfield Brines

     Produced brines contain a variety of substances known
to have lethal and sublethal toxic effects on marine and
estuarine organisms.  These toxic constituents include oil
hydrocarbons, trace metals (including arsenic, cadmium,
chromium, copper, lead, mercury, nickel, silver, and zinc),
phenol, and cyanide.  Some of these toxicants have been
measured in produced waters at concentrations up to several
orders of magnitude higher than the corresponding EPA water
quality criteria.  In addition to their effect on marine
organisms, many of the brine components (particularly mercury
and the polynuclear aromatic hydrocarbon benz[a]pyrene)
are known to be bioaccumulated in shellfish which may be
used for human consumption and so present a potential human
health threat.


•    Treatment Methods

     Current methods used for separating oil hydrocarbons from
produced water have little if any effect on levels of
dissolved contaminants.  These include the dissolved aromatic
hydrocarbons which are among the most toxic hydrocarbon
components of brines, and the trace metals.


•    "Safe" Levels

     The impact exerted by contaminants present in the
discharged produced water depends on the concentration
levels of the contaminants to which biota in the receiving
waters are exposed.  The concentrations will be a maximum in
the immediate vicinity of the point of discharge, and will
in general decrease with increasing distance from the dis-
charge point.  Toxicological data on the effects of brine
toxicants on marine and estuarine organisms, in conjunction
with data on produced water contaminant concentrations, suggest
 (as discussed in Chapter Seven) that a 0.05 percent level
                             -221-

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of dilution of oilfield brines (i.e., 1 part brine to 2,000
parts receiving water)  is "safe"; i.e., it will produce no
significant level of lethal or sublethal effects on resident
organisms and will prevent the bioaccumulation of brine
constituents to dangerous levels in human food organisms.
Accordingly, a convenient measure of the impact associated
with a given brine discharge is the area around the discharge
point that can be expected to be subjected to produced
waters at concentrations greater than or equal to 0.05 percent.
It should be noted, however, that the 1:2,000 safe level is
based on the maximum produced water contaminant concentrations
which have been measured.  Since data on contaminant levels
in produced waters are sketchy, and since contaminant concen-
trations are highly variable, both between different geographic
regions and different sites in the same region, "safe"
levels at all sites will not necessarily occur at the 1:2,000
dilution level used in this analysis.  It is also extremely
important to bear in mind the fact that the state of knowledge
regarding toxic effects of trace metals and oil hydrocarbons
is expanding rapidly at present.  Hence, the estimate of a
safe level used here should be regarded as provisional only,
subject to revision on the basis of increased knowledge of
toxic effects.
•    Evaluation of Impacts

     The area of the 0.05 percent dilution zone depends on a
number of highly site specific factors.  Such factors include
the rate at which produced water is discharged, the depth of
the receiving water, currents  (tidal, freshwater, drift),
and diffusion coefficients.  Other site specific processes
also affect contaminant dispersion but cannot be readily
quantified.  Processes in this category include adsorption
of contaminants on suspended particles, sedimentation and
transport of sediments, chemical transformation, and biode-
gradation.  Severity of impact depends not only on the
numerical size of the affected area but also on its ecology.
Ecological characteristics are important in that they determine
the value of the area being impacted in terms of the primary
production the area supports, the commercially important
species which live there, and the importance of the region
to particular lifecycle stages of other economically or
ecologically important organisms.  Finally, impacts may also
be evaluated in terms of the size of the impacted area
relative to the size of the receiving waterbody.  The same
area may represent a much severer impact in a relatively
small bay than in a larger, less enclosed waterbody.
                             -222-

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•    Modeling of Brine Dispersion

     The site specific factors of discharge rate, depth of
receiving water, currents, and diffusion coefficients have
been incorporated into a computerized dispersion model which
can be used for estimating the areas of the unsafe  (concen-
tration greater than or equal to 0.05 percent)  zones at each
site.  For each of four specific sites (Hackberry Bay,
Louisiana; Grand Isle, Louisiana; Cook Inlet, Alaska; and
the Ship Shoal oil field in the far offshore Gulf of Mexico),
the computer model was used to give estimates of areas
expected to be subjected to concentration levels down to
0.05 percent.   Several sensitivity analyses were performed
for each site in order to allow for uncertainties in avail-
able data on input parameter values and simplifying assumptions
incorporated in the model.  The results of the computations
for the four sites are summarized in Table 8-1.

                          TABLE 8-1

                     SUMMARY OF IMPACTS
  SITE
LOCATION
PROBABLE AREA OF
   IMPACT ZONE
     ECOLOGY
Hackberry
Bay
Onshore
Cook Inlet
Onshore
Grand Isle
Gulf of
Mexico Site
Near
Offshore
Far
Offshore
entire bay (ca.
192,000,000 ft2
or 6.9 mi2)
ca. 5,000,000 ft'
(0.18 mi2)
700,000 -
9,000,000 ft'
                                           .2,
highly productive,
supports blue
crab, panaeid
shrimp, and other
commercially
important spp.
relatively in-
fertile due to
continuous bottom
scouring by tidal
currents and to
high turbidity
highly productive;
supports several
                            (0.025 - 0.32 mi )  commercially
                                               important or
                                               sport species
3,000,000 -  .
10,000,000 ft'
(0.11 - 0.36 mi")
                                          . 2,
highly productive;
supports several
commercial or
sport species
                            -223-

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•    Onshore Benefits

     No similarity was observed between estimated impacts at
the two onshore study sites.  In Hackberry Bay the impacts
are estimated to be rather severe (see Table 8-1).  Hackberry
Bay is also a productive fishery area.  In the mid Cook
Inlet area tidal mixing results in a rapid dilution of the
discharge away from the discharge point.  The impacted area
is proportionally small compared with the area of the mid
Cook Inlet, and, in addition, is naturally unproductive due
to tidal bottom scouring and high natural turbidity levels.
Therefore, impacts are judged to be relatively small in the
mid Cook Inlet.

     The benefits which would be achieved if the proposed
near offshore BATEA regulations are extended to apply to
onshore discharges are thus highly site specific.  Small,
enclosed, shallow, and biologically productive bays with
large brine discharges will probably stand to benefit con-
siderably.  The benefits to be achieved by prohibiting small
discharges of produced water into larger and deeper coastal
embayments with adequate tidal and freshwater mixing are
likely to be correspondingly small.  A first order estimate
of the magnitude of the benefits to be achieved by a "no
discharge" regulation can be obtained through the use of the
tidal flushing calculations described in Chapter Four,
together with some considerations of the ecology and economic
importance of the region being impacted.
•    Near Offshore Benefits

     In the near offshore Gulf of Mexico waters, the analy-
sis performed for a single site is insufficient to serve as
a complete basis for estimating regional impacts.  In order
to extrapolate from impacts at a single platform to regional
impacts, data on platform locations and discharge rates
throughout the region are needed.

     The benefits to be achieved by prohibiting the dis-
charge of produced waters into near offshore waters will
therefore depend critically on the density of production
platforms and rates of discharge in a particular region.   In
areas where platforms are highly concentrated, aggregate
discharge levels are likely to be large, and impact zones
may overlap.  In such areas significant benefits could
probably be achieved.  In areas with low platform densities
and only small rates of brine discharge the benefits are
likely to be less pronounced.  The analysis performed in
this study should, therefore, be supplemented by the assembly
                            -224-

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of a data base providing information on the location and
discharge rates of production -platforms in near offshore
Gulf of Mexico waters (projected development might also be
incorporated in this supplementary study).   Since the rate
at which water is produced in a given field tends to in-
crease with the age of the field, assessment of the bene-
fits to be achieved by prohibiting the discharge of pro-
duced water should take into account not only the present
rate at which water is produced in a field, but also the
increased rate at which water can be expected to be pro-
duced in the future.
•    Far Offshore Benefits

     In far offshore Gulf of Mexico waters, the major con-
clusion to be drawn from this study is that there would
probably be little reduction in impacts resulting from the
imposition of BATEA regulations over and above those already
achieved by the BPCTCA restrictions.  The more stringent
treatment requirements imposed on far offshore platforms by
the BATEA requirements will do little to remove the dissolved
hydrocarbons and trace metals which are responsible for much
of the toxic impact of oilfield brines.  The impacts resulting
from the produced water discharge of a given field can be
expected to increase with the age of the field, since the
rate of water production generally increases with the age
of the field.
•    Field Data

     It is recommended that programs of field data collec-
tion be initiated to provide further information on the
composition and composition variability of produced waters,
and on dispersion characteristics and ecological features of
brine discharge sites.
                             -225-

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                         APPENDIX A
       ECOLOGICAL CHARACTERIZATION OF PRODUCTION SITES
A. 1  Introduction

     The ecological characterization of Cook Inlet, Alaska
and Barataria Bay, Louisiana, presented in the following
sections, provides an introduction to the key physical,
chemical, and geological features of these areas.  These
sections attempt to present the study areas as ecological
systems, involving dynamic interactions between biota and
environmental variables, and to describe the dynamics of
the principal factors which determine the fates of contami-
nants contained in discharged produced water.

     Physical parameters play an important role in deter-
mining pathways of discharged brine in the environment and
in determining the nature and severity of effects which the
hydrocarbons, trace metals and high salinities have on marine
organisms.  Currents, winds, tides and depth of water are
known to be the key factors influencing effluent dispersion
in the water column, while turbidity, suspended sediments,
and sedimentation rates will influence the residence time of
effluent components in the water column and in the bottom
sediments, through absorption, sedimentation and floccula-
tion.  Bottom sediments of varying mineral composition, and
grain size have different capacities to adsorb, desorb, and
retain effluent components.  In assessment of impacts, fac-
tors such as temperature, salinity, and dissolved oxygen
levels, which often increase or decrease the toxicity of
trace elements to aquatic organisms by changing metabolic
rates or enzyme activity, are of great importance.  These
parameters also influence rates of microbial degradation of
oil.

     In some instances physical data can be used to draw
quantitative assumptions about effluent fates, as in the
case of dispersion models.  Often, however, the state of
scientific knowledge is such that the interactions between
physical parameters and effluent components (e.g., tempera-
ture and trace metals), and the effects of these interactions
on living systems, are only understood qualitatively, and
must be discussed as potential events.  It is felt that des-
cription of these parameters  (and discussion of their inter-
actions in a later section) will provide some insight into
the variable nature of effluent impacts on these systems.
                             -227-

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     Information on the biota of Cook Inlet and Barataria
Bay has been collected to facilitate identification of poten-
tial impacts from brine discharge.  For the species of com-
mercial, sport and trophic importance, a description is given
of their preferred habitat at various stages in the life cycle,
and their place in the food chain.

     The susceptibility of an organism to the toxic effects
of contaminants may vary with an organism's life cycle stages.
Habitat preferences may also vary throughout a life cycle.
For this reason, both factors must be considered together.
This will help to identify the pathways by which oil in the
water column or sediments can make contact with the biota.
Knowledge of feeding mechanisms such as deposit feeding,
filter feeding or membrane diffusion, will assist identifi-
cation of pathways in a similar manner.

     Contaminant-induced effects, which change population
numbers of species in one trophic level, will in turn affect
predator and prey populations on other trophic levels.  Pre-
dicting impacts of this nature requires knowledge of impor-
tant trophic interactions (food webs).

     The characterizations of the study sites have been
organized by ecological units rather than by the "near
offshore," and  "far offshore" distinctions made in the EPA
Development Document.  For Louisiana, the ecological charac-
terization has been divided into two sections, one consisting
of the marshes and the waterbodies of Barataria Bay (which
are actually near offshore waters).  The other section des-
cribes the near offshore and far offshore waters in the Gulf
of Mexico.  The Cook Inlet characterization presents combined
information for near offshore and far offshore water of
Cook Inlet, because little data are available with which to
make a distinction.  The Cook Inlet intertidal region is
treated as a separate ecological unit.
A.2  Cook Inlet Characterization

     A.2.1  Introduction

     Cook Inlet is a large tidal estuary in south central
Alaska, which flows into the Gulf of Alaska just east of the
base of the Alaskan Peninsula.  It is 150 nautical miles
wide at its widest point and Knik and Turnagain Arms at the
                             -228-

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head of the Inlet are 45 and 43 nautical miles long, respec-
tively. 1

     Figure A-l depicts the major bays, points, capes and
islands of Cook Inlet.  For ease of discussion, we have
divided Cook Inlet into three semi-distinct ecological parts.
The Upper Inlet lies east of a line extending northward from
Point Possession.  The waters of the Upper Inlet receive great
loads of suspended glacial sediment from the Susitna River,
Little Susitna River and the rivers emptying into Knik and
Turnagain Arms, and are extremely turbid.

     The Middle Inlet, where brine discharge occurs, includes
waters from the Upper Inlet southwestward to the latitude of
of Tuxedni Bay (60°25" N).  There are four onshore separation
platforms and three offshore facilities discharging brine into
the Inlet:  the Union Oil facility located just south of
Kenai discharges the wastewater into a ravine along which it
flows to Cook Inlet waters.  The Shell Oil facility near
Nikiska and the Marathon plant near West Foreland in Trading
Bay both discharge wastes into the Inlet by pipe.

     Atlantic Richfield Company has a separation facility at
Granite Point which discharges wastes into a trough which
leads into Cook Inlet.  Three offshore platforms owned by
Amoco have separation facilities and dump wastes directly
into Inlet waters.  Figure A-l depicts the location of onshore
and offshore separation facilities.

     The remaining portion of Cook Inlet, south of Texedni
Bay and Clam Gulch, is commonly called the Lower Inlet.  This
region has the clearest waters, and is the most productive,
supporting all major species of fish, shellfish, and marine
mammals found in Cook Inlet.

     Cook Inlet is bordered by a combination of tidal marsh,
mudflats, mountains and lowlands.  Over 100 square miles of
tidal marsh are found in the Susitna Flats, upper Knik Arm,
Chickaloon Flats  (in Turnagain Arms), in Trading Bay and in
Redoubt Bay.  The Aleutian Range and Alaska Mountains lie to
the Northeast and the Chugach and Kenai Mountains lie to the
southeast.  A rim of lowlands separates the mountains from
most of the Inlet though this rim is narrow or absent in the
Lower Inlet, where the mountains meet the sea.  In the Upper
      C.D. Evans, E. Buck, R. Buffler, et al.,  The Cook Inlet
Environment, A Background Study of Available Knowledge
(Anchorage:  University of Alaska, Resources and Science
Center, Alaska Sea Grant Program, August 1972).
                            -229-

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I
to
U)
o
I
                    Figure A-l.   Cook Inlet.

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and Mid Inlet these lowlands are wide, often forming mudflats,
and support fairly high densities of waterfowl.

     Oceanographic and biological information is not readily
available on Cook Inlet waters.  Interest in this type of
data has only developed recently, within the past 10 years,
and the logistics of data collection have presented problems.
The Lower Inlet is the area of most interest to biologists
and agencies concerned with wildlife and fisheries management.
Most Cook Inlet investigations seem to have produced data for
this region in particular.  The Upper Inlet also has been of
interest to planners and managers due to the density of human
population found along Knik and Turnagain Arms.  A number of
studies relating to waste disposal and civil engineering have
generated information about the Upper Inlet.  The major items
of interest in the Mid Inlet are the offshore oil platforms
and the onshore separation facilities, refineries and chemical
plants.  Aside from one major study performed by the University
of Alaska for the Collier Carbon and Chemical Corporation,2
there are very little data available about the Mid Inlet open
ocean or coastal environments.  The characterization presented
here has pieced together published and unpublished information
into a coherent description of the ecology of Cook Inlet.
     A.2.2  Temperature

     Water temperatures in Cook Inlet range from near freezing
(-1.2° C) in February to a high of 15.2° C in August.  The
Inlet is generally well mixed vertically and temperatures are
fairly uniform from top to bottom.  Some thermal stratifica-
tion is observed on the western side of the Mid and Upper
Inlet in the region of freshwater outflow.-^  Figure A-2
depicts surface temperature distribution in May.
     A.2.3  Depth

     The Upper Inlet is a shallow, silt laden basin with
depths less than 20 fathoms.  Turnagain and Knik Arms are
     2
      F.W. Hood, K.W. Natajan, D.H. Rosenberg, and D.D. Wallen,
Summary Report on Collier Carbon and Chemical Corporation
Studies in Cook Inlet, Alaska (College, Alaska:  Institute
of Marine Science, University of Alaska, December 1968) .

      Hood, Natajan, Rosenberg,  and Wallen, Summary Report
on Collier Carbon and Chemical Corporation.
                             -231-

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60° -
     Surface  Temperature
          Distribution
        COOK  INLET
       Figure A-2.  Surface temperature distribution -  Cook  Inlet.
   (P.J. Kinney, J. Groves, and O.K. Button,  Cook Inlet  Environ-
  mental Data, R/V Cruise 065 - May 21-28,  1968 (College, Alaska:
  Institute of Marine Science, University of Alaska,  Report  No.
  R-70-2, 1970), p. 14.)
                              -232-

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the shallowest areas with much of the bottom exposed as tidal
flat during low tide.  There are two channels which extend
southward in the Mid Inlet and past Trading Bay, Redoubt Bay
and Upper Kenai, joining in an area west of Cape Ninilchik.
In the Lower Inlet south of Cape Ninilchik, the channel
deepens to 80 fathoms and widens to extend across the mouth
of the Inlet.  Below the Forelands, the bottom slopes down-
ward, reaching depths over 100 fathoms south of the Inlet
entrance.^

     The Mid Inlet bottom has a fairly gentle slope on the
eastern side, the waters reach a depth of 10 fathoms 2 miles
(near East Foreland) to 12 miles (in Upper Mid Inlet) off-
shore.  On the western side of the Mid Inlet 10 fathom depths
occur from several hundred yards to 5 miles offshore.  Figure
A-3 depicts changes in depth along a transect running from
the Marathon facility at West Foreland across the Inlet to
the Shell Oil plant in Nikiska.  Shallow regions, less than
10 fathoms, are found surrounding Middle Ground Shoal, an
island adjacent to Trading Bay, and Kalgin Island off of
Redoubt Bay.

     Cook Inlet has several deep holes, most of which result
from scouring of the sea floor.  Between East and West Fore-
land in the Mid Inlet the bottom reaches a depth of 75 fathoms
and an 85-fathom hole occurs at the entrance to Kachemak Bay
in the Lower Inlet.  In contrast, Kamishak Bay, on the western
side of the Lower Inlet, is relatively shallow, sloping
toward the Inlet center at a grade of 5 to 10 feet per mile.
     A.2.4  Ice

     Ice begins forming in the Upper Inlet in October and
extends into Lower Cook Inlet as determined by wind and
temperature.  Intertidal areas become coated with ice during
repeated exposures.  Along the tidal flats, ice and sand
accumulate and are stranded with each successive tide,
forming large clumps called stamuki which may reach a
     4
      D.M. Anderson, L.W. Gatto, H.L. McKim, and A. Petrone,
"Sediment Distribution and Coastal Processes in Cook Inlet,
Alaska," in Symposium on Significant Results Obtained from
the Earth Resources Technology Satellite-1, Vol. 1, Section B,
S.C. Freden, E.P. Mercanti, and M.A. Becker (eds.), (Washing-
ton, D.C.:  National Aeronautics and Space Administration,
1973); and Evans, Buck, Buffler, et al., Cook Inlet Environ-
ment, Study of Available Knowledge.
                             -233-

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I
NJ
U)
      W

      O
      A
      -P
      rt)
      En
      K
      W
      Q
 5 -


10 -,


15


20



25


30



35



40


45
         50 -
            0    1
            Y
     West Foreland
     (Marathon oil
        facility)
                       4    5    6     7     8     9     10


                           DISTANCE  FROM  SHORE (Miles)
11
12   13
14
     15
     y
  Nikiska
(Shell oil
 facility)
          Figure  A-3.   Bathymetry profile along a Mid Inlet transect, West  Foreland to
     Nikiska.

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thickness of 40 feet.  Much of the ice found in the Inlet is
floe ice, which increases in thickness up to 1 inch per day.
Ice puts additional stresses on marine organisms in the
winter, particularly those in the intertidal region which
must freeze and thaw with each tidal cycle.
     A.2.5  Tides and Currents

     The tides of Cook Inlet are semi-diurnal with a notable
inequality between successive low waters.  Mean diurnal
range of the tides varies from 13.7 feet at the entrance
to the Inlet to 29.6 feet at Anchorage.  There is a 4.5
hour time lag between high water at the mouth of the Inlet
and high water at Anchorage.  The mean diurnal tidal range
on the east side of the Inlet is greater (19.1 feet in East
Lower Inlet) than it is on the west side (16.6 feet in West
Lower Inlet).   Tidal bores sometimes occur in Turnagain Arm,
reaching heights of 10 feet.6  Table A-l gives the mean
range  (the difference in height between mean high water and
mean low water), the diurnal range  (the difference in height
between mean higher high water and mean lower low water),
and the mean tide level (a plane midway between mean low
water and mean high water measured from the mean lower low
water level) for locations in Cook Inlet.

     Three features strongly influence the tides in Cook
Inlet:  topography, friction, and the Coriolis force.  The
topography of the Inlet may increase tidal amplitude at
certain locations.  In the absence of friction, tidal height
would remain constant between the mouth of the Inlet and
the Forelands, and then would steadily increase.  The ampli-
tude at Anchorage would be twice that at the entrance.
However, as a result of friction, energy is lost.  There is
a net inward transport of energy through the entrance to
replace this loss.  Therefore, the form of the wave is pro-
gressive, with maximum currents occurring less than 3 lunar
hours before local highwater.  The stronger the currents are,
the greater the tidal amplitude on the east side of the
Inlet than on the west.^
      Alaska Department of Fish and Game, Habitat Protection
Section, "Lower Cook Inlet Currents, Tides, Winds, Bathy-
metry and Ice" (map),  Anchorage, Alaska, 1976 (unpublished).

      Evans, Buck, Buffler, et al., Cook Inlet Environment,
Study of Available Knowledge.

      J.C.H. Mungall,  Cook Inlet Tidal Stream Atlas, Institute
of Marine Science, University of Alaska, Fairbanks, Alaska,
1973.

                             -235-

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                        TABLE  A-l
 RANGE  OF TIDES AND  MEAN TIDE LEVEL IN  COOK  INLET


LOCATION
Ushagat Island, Barren Islands
Port Chatham
Port Graham
SELDOVIA, Kachemak Bay
Homer, Kachemak Bay
Cape Ninilchik
Ninilchik
Kenai River entrance
Kenai City Pier
Nikiski
East Foreland
Fire Island
Sunrise, Turnagain Arn~~
ANCHORAGE, Knik Arm
Eklutna, Knik Arm
North Foreland
Drift River Terminal
Texedni Channel
Snug Harbor
lllamna Bay
Nordyke Island, Kamishak Bay


MEAN
11.4
12.0
14.4
15.4
15.7
16.5
16.7
17.7
17.5
17.9
18.0
24.4
30. 3
26.1
b
18.3
15.4
14.0
13.2
13.2
12.9

RANGES (
DIURNAL
13.7
14.3
16.5
17.8
18.1
19.1
19.1
20.7
19.8
20.7
21.0
27.0
33.3
29.0
b
21.0
18.1
16.6
15.7
14.5
15.2

ft)
MEAN TIDE
LEVEL
7.2
7.5
8.6
9.3
9.5
10.1
10.0
11.0
10.4
11.1
11.2
14.2
17. 1
15.3
b
11.3
9.7
8.9
8.3
7.5
8.0
     &A bore frequently  occurs  in Turnagain Arm just after
low water.   Under favorable conditions it is said to reach
a height of 6 feet.

      Because of the  shoal condition of the upper part of
Knik Arm, the channel off Eklutna becomes practically a
nontidal stream during the period when the height of the
tide at Anchorage is  less than  15 feet above mean lower
low water.

     Source:  National Ocean  Survey of  the  National  Oceanic
and Atmospheric Administration, Tide Tables  1976, West Coast
of North and South America, Washington,  D.C.,  1975,  p. 178.
                          -236-

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     The currents of Cook Inlet have been described as being
of moderate velocity.  In the Forelands region, where the
brine discharge points are located, currents are strongest,
reaching a mean maximum velocity of 3.8 knots, with peak
maximum velocities exceeding 6.5 knots at monthly tidal
extremes.   In the Lower Inlet, maximum inward currents
occur 1.5 hours before local high water; in the Upper Inlet
they occur 1.5 to 3 hours before local high water.9  Table A-2
gives the direction of the flood current, the average veloc-
ity of the flood current, the ebb current direction, and the
average velocity of the ebb current, all at strength of
current.  Flood and ebb current directions are the direc-
tions toward which the current flows measured in degrees,
clockwise, from 000° at north.

     Circulation patterns and tidal currents are important
factors in the distribution of nutrients (hence productivity)
in the Inlet, in determining the impact of localized contami-
nants in the water, and in their effects on unconsolidated
bottom sediment.  Depth of water, coastline morphology and
freshwater drainage combine with tidal effects to divide the
Inlet into the three parts which were mentioned earlier.

     The Upper Inlet waters are well mixed laterally, longi-
tudinally and vertically with each tidal cycle.  In summer,
there is a net outward movement of Upper Inlet waters with
each tidal cycle, due to the large inflow of glacial melt-
water from tributary streams.  In winter with the freezing
of these streams, there is no net outflow from the Upper
Inlet and water sloshes back and forth with each tide.10

     The Middle Inlet, where brine discharge sites occur, is
characterized by the net inward movement of saline oceanic
waters up the eastern shore and a net outward movement of
freshwater runoff along the western shore.   There is exten-
sive vertical mixing due to turbulence from swift current
and high Coriolis force; however, lateral separation of
highly saline incoming water and less saline waters is
maintained throughout the Middle Inlet.H
      Evans, Buck, Buffler, et al.,  Cook Inlet Environment,
Study of Available Knowledge.
     9
      Mungall, Cook Inlet Tidal Stream Atlas.

       Evans, Buck, Buffler, et al.,  Cook Inlet Environment,
Study of Available Knowledge.

       Evans, Buck, Buffler, et al.,  Cook Inlet Environment,
Study of Available Knowledge.
                             -237-

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                           TABLE A-2
             MAXIMUM CURRENTS IN COOK  INLET
                                   MAXIMUM CURRENTS
       LOCATION
       FLOOD

DIRECTION  AVERAGE
 (TRUE)     VELOCITY
        EBB

DIRECTION  AVERAGE
 (TRUE)     VELOCITY

Chugach Passage
Iniskin Bay
Anchor Point,
3 miles southwest of
Chinitna Bay
Cape Ninilchik,
1 mile west of
Tuxedni Channel
DEGREES
355
000
000
260
020
330
KNOTS
3.
0.
2.
1.
2.
1.
1
9
4
0
2
1
DEGREES
170
180
195
080
205
160
KNOTS
1
1
1
1
1
1
. 8
.2
.9
.1
.4
.9
Cape Kasilof,
3 miles west of            020
Kenai,
6 miles southwest  of       020
Kenai Packers Cannery
               3.0


               2.4
    205


    195
2.3


2.6
Warf
Nikiski
Nikiski,
0. 8 mile west of
West Foreland, midchannel
Moose Point,
3 miles northwest of
Anchorage,
0.2 mile offshore
Anchorage,
1 mile off of
Knik Arm,
south of Goose Creek
115
000

354
025

065

030

050

015
0.
3.

3.
3.

2.

1.

2.

3.
7
8

8
8

9

5

9

6
285
180

175
205

245

205

220

180
1.
2.

3.
3.

2.

2.

2.

3.
4
6

6
8

6

5

9

9
     Source:  National Ocean  Survey of the National Oceanic and
Atmospheric Administration, Tidal Current Tables 1976, Pacific
Coast of North America and Asia, Washington, D.C., 1975,  p. 223.
                              -238-

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     In the Lower Inlet, the water masses of differing
salinity maintain separation.  On the west side a vertical
stratification occurs with colder saline ocean water under-
lying warmer, less saline inlet waters.  Near Tuxedni Bay,
the rising basin floor creates an upwelling of deeper,
oceanic water -- bringing important nutrients up to the
photic zone.12
     A.2.6  Salinity

     Salinity in Cook Inlet ranges from 32 ppt at the mouth
of the Inlet to 8 ppt at the mouth of the Susitna River in
May.13  Figure A-4 presents surface salinity distribution
in May.

     Salinities in the Mid Inlet region, where brine dis-
charge occurs, range from 30 ppt in February to 21 ppt in
August.  Saltwater enters the Inlet on the eastern side and
freshwater exits on the western side, a combined result of
the Coriolis force and geographic location of the rivers.14

     The waters are well mixed from top to bottom on the
eastern side of the Mid and Upper Inlet.  In the Lower Inlet
stratification is observed with the entering cold saline
ocean water underlying warmer Inlet waters.

     In areas where large quantities of freshwater are con-
tributed,  such as Susitna River, there is a pronounced
halocline and thermocline.  However, freshwater inflow from
the Kenai River enters the Inlet in an area of maximum
currents and creates no salinity stratification.  Waters
     12
       Evans, Buck, Buffler, et al.,  Cook Inlet Environment,
Study of Available Knowledge.

       P.J. Kinney, J. Groves, and D.K. Button, Cook Inlet
Environmental Data, R/V Cruise 065 -  May 21-28, 1968,
(College, Alaska:  Institute of Marine Science, University
of Alaska, 1970).
     14
       Kinney, Groves, and Button, Cook Inlet Environmental
Data.
                             -239-

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60°  -
    Surface Salinity Distribution
         COOK  INLET
           30 nautical miles

           (May  1968)
                              152
150°
         Figure A-4.   Surface salinity distribution - Cook Inlet,
    (P.J.  Kinney,  J.  Groves,  and D.K. Button, Cook Inlet Environ-
    mental Data, R/V Cruise 065 - May 21-28, 1968 (College,
    Alaska:   Institute of Marine Science, University of Alaska,
    Report No.  R-70-2, 1970), p. 13).
                                -240-

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along the western shore have more salinity stratification
due to lesser currents and freshwater input. "Less strati-
fication is observed during flood tides than during ebb
tides.15

     For any estuary a key factor determining the rate at
which pollutants are removed from the estuary is the fresh-
water flow into the estuary.  Table A-3 gives available data
on the sources of freshwater influx for Upper and Mid Cook
Inlet.
     A.2.7  Wind

     Wind speed and direction in Cook Inlet show a notable
seasonal variation.  In January and February, winds are from
the north at 7 to 40 knots.  By April, winds are to the
northwest and have decreased to a maximum of 21 knots.  May,
June, and July are very calm, less than 1 knot.  Summer winds
have a southerly component and pick up speed in August and
September.  In November and December, high velocity (30 knots)
winds blow from the north.  Open waters in Cook Inlet tend
to have higher wind speeds than nearshore waters.16

     Storms of gale force, with 50 to 75 knot winds, are
experienced in the Cook Inlet each winter.  Waves may reach
heights of 15 feet and 6-second periods have been recorded.
Under extreme conditions winds may reach 75 to 100 knots.  '


     A.2.8  Turbidity and Suspended Sediment

     Suspended sediment varies from 0 at the mouth of the
Inlet to 1,540 mg/1 at Anchorage (Figure A-5).  These sedi-
ments, often of glacial origin, are derived primarily from
headwaters of the Matanuska River system.  Suspended sedi-
ments seem to be uniformly distributed with depth in areas
not immediately in the river plume.  Highest values of sus-
pended sediment occur in well-mixed regions of strong tidal
currents — on the east side of the Inlet.  Suspended sedi-
ment is nearly absent at the central and western portions
       Evans, Buck, Buffler, et al.,  Cook Inlet Environment,
Study of Available Knowledge.

       Alaska Department of Fish and Game, "Lower Cook
Inlet Currents, Tides, Winds, Bathymetry and Ice."

       Alaska Department of Fish and Game, "Lower Cook
Inlet Currents, Tides, Winds, Bathymetry and Ice."
                            -241-

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                                                TABLE A-3
                             STREAMFLOW DATA, MID AND  UPPER COOK INLET
I
to

NAMP np STRFAM DRAINAGE AREA n^rnaSrp
NAMc. Ur blrCbAM . . . OXoLHAKuri
(sq. mi.) (ft3/s)
Susitna R.
near Denali
near Cantwell
near Gold Creek
Tributaries of Susitna
Maclaren R.
Tyone R.
Skwenta R. near Skwenta
Talkeetna R.
near Talkeetna
Chulitna R. near Talkeeta
Matanuska R. at Palmer
Knik R.
Ship Crrek near Anchorage
McArthur R.
Chakachatna R. near Tyonek
Beluga R.
Kenai R. At Soldotna
Source: L.L. Selkregg,
19,400
950
4,140
6,160

280
1,400
2,250
2,006
2,570
2,070
1,200
90.5
350
1,120
930
2,010
Alaska Regional
	
2,665
6,824
10,250

1,092
—
6,937
5,299
8,406
4,196
5,800
149
—
4,658
—
5,958
Profiles;
MAXIMUM MINIMUM
DAILY DAILY
DISCHARGE DISCHARGE
(ftVs) (ft3/s)
__
—
55,000
77,700

8,200
—
47,500
63,000
45,000
40,700
—
1,420
—
90,000
—
23,900
South Central Region
	
—
460
950

55
--
600
400
900
360
—
0
--
460
—
1,100
(Anchorage:
         University of Alaska, Arctic Environmental  Information and Data Center,  1974), pp. 87,90

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     Suspended Sediments
    Average Value for Stations in mg/l
         COOK  INLET
60° -
           30 nautical miles

              MAY
          Figure  A-5.   Suspended  sediments - Cook Inlet.   Average
     value for  stations in  mg/l.   (P.J.  Kinney,  J.  Groves, and
     O.K.  Button,  Cook  Inlet  Environmental Data,  R/V Cruise 065 -
     May  21-28, 1968  (College,  Alaska:   Institute of Marine
     Science, University of Alaska,  Report No.  R-70-2,  1970),  p.  23
                                -243-

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of the Inlet mouth.  Organic carbon and silicate concentra-
tions follow the same patterns as do suspended sediment.18


     A. 2 . 9  -Bottom Sediments

     Lower Cook Inlet bottom sediments consist of silty sand
and gravelly sand; Mid Inlet sediments are primarily gravel;
and Upper Inlet sediments contain well-sorted sand (Figure A-6)
Little deposition of sediments takes place in the Upper Inlet
though much of the flocculation may be deposited on the exten-
sive mudflats north of the Forelands.19
     A.2.10  Biology — Cook Inlet Open Waters

     The distribution of plants and animals in the Cook Inlet
waters reflects the complex interactions of tidal mixing of
fresh and salt waters, the large tidal amplitude resulting
in extensive tidal flats, the large loads of suspended glacial
sediments, the scouring action of tidal currents, and the
presence of ice during winter months.

     Little is known about the distribution and abundance of
benthic species in Cook Inlet.  It appears that very few
species exist in the silt laden waters of the western and
upper half of the Inlet.  The high tidal amplitude and strong
tidal currents which scour the bottom make survival difficult
for most benthic organisms.  The great loads of suspended
sediment in these regions limit penetration of light, con-
fining photosynthesis to a very shallow photic zone.  Pro-
ductivity seems to increase as one moves oceanward in the
Inlet to clearer, more saline waters.  The Lower Inlet waters
provide habitat for a variety of sport and commercially im-
portant fish and shellfish, and numerous other non-fished
species.


     A.2.11  Primary Productivity

     Most primary production in the open waters of Cook
Inlet occurs in the form of phytoplankton.  The high silicate
content of incoming sediments and of Inlet waters seems to
favor the growth of diatoms, which appear to be the dominant
     1 o
       Kinney, Groves, and Button, Cook Inlet Environmental
Data.

     19
       Anderson, Gatto, McKim, and Petrone, "Sediment Distri-
bution and Coastal Processes in Cook Inlet"; and Kinney,
Groves, and Button, Cook Inlet Environmental Data.


                             -244-

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60°
         COOK  INLET
        BOTTOM SEDIMENTS
                                       LEGEND:
                                       I) * * J sand
                                           sandy gravel & gravel
                                           gravelly sand with
                                             silt & clay components
       154"
152'
150«
        Figure A-6.   Bottom sediments  -  Cook  Inlet.   (P.J. Kinney,
   J. Groves,  and O.K.  Button,  Cook  Inlet Environmental Data, R/V
   Cruise 065 - May 21-28,  1968  (College, Alaska:  Institute of
   Marine Science, University of Alaska, Report No. R-70-2,
   1970), p.  24.
                               -245-

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phytoplankton.  The presence of silicoflagellates, dino-
flagellates and tintinnids have also been reported.20
It is quite possible that the majority of the phytoplankton
consists of nanno and ultra plankton, which are too small to
accurately collect and identify generically.  Table A-4
presents the major identifiable primary producers in the
open waters of Cook Inlet.

     The rapid exchange of water with the Gulf of Alaska and
strong vertical mixing on the lower east side of the Inlet
support the growth of numerous diatoms and macrophytes.
There are more species of primary producers found in this
region than in the Mid and Upper Inlet, where higher tur-
bidity, brackish water and less nutrient turnover limit
photosynthesis.  Diatom blooms, which occur periodically,
are limited by light intensity and by nitrogen and silica
concentrations in the water.  In the Lower Inlet, macrophtyic
algae  (kelp)  (see Table A-4) found in subtidal and inter-
tidal waters provide food, shelter and living substrate for
epifaunal organisms.  They also serve as nursery grounds for
fish and as wave dampeners and tethers for floating mammals
and birds.21

     Productivity in the Mid Inlet, while greater than that
in Upper Inlet waters, is considerably less than in the
lower portion of Cook Inlet.  Phytoplankton is the only
primary producer and the combination of strong currents,
severe ice conditions in winter and high suspended sediment
loads in summer, limits rates of photosynthesis.  This in
turn affects the number and types of heterotrophic species
which can be supported in the Mid Inlet.
     A.2.12  Consumers

     Zooplankton of Cook Inlet have not been studied in
great detail, but representatives of the phyla Protozoa,
Coelenterata, Ectoprocta, Nematoda, Annelida, Mollusca,
Rotifera, Chordata, and Arthropoda have been found in Inlet
     20
       Evans, Buck, Buffler, et al., Cook Inlet Environment,
Study of Available Knowledge.

     21
       U.S. Fish and Wildlife Service, Office of Ecological
Services, Resources Assessment Lower Cook Inlet  (unpublished),
Anchorage, Alaska.
                            -246-

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                                                                 TABLE  A-4

                                                PRIMARY  PRODUCERS -  COOK  INLET
                           INTERTIDAL
                        (MUDFLAT  AND GRAVEL)
                           NEAR  OFFSHORE WATERS
                                                             FAR OFFSHORE WATERS
 I
K)
                         MACROPHYTIC ALGAE



                       *Ulothrix laetevirens

                       *Enteromorpha intestinalis

                       *Enteromorpha compressa

                       *U)va lactuca
                                                           DIATOMS
                                                                           MACROPHYTIC ALGAE
                 *Melosira  sulcata

                 *Cocconeis scutellum

                 *Biddulphia aurita

                 *Asterionella kariana

                 *Fragilaria sp.
Laminaria sp.

Fucus sp.

Alaria sp.

Nereocystus  sp.
                                                                                                          DIATOMS
*t'flosira  sulcata

*Biddulphia aunta

*Coscinodiscus sp_-

*Coscinodiscus linoatup;

*Coscinodiscus oculus-iridus

*Coscinodiscus stellarif.

*ActinoptYchus sp.

*ftctinoptychus undulatus

*Frgcjilar3 a sp^

'Cocconois sp.

*Coccohois scutolliun

*Dit^luin br irjhtwo] 11 i

*Cyc_lotal_la sp_._

*Astcr]onolla spL

*Astcrionolla k.i
                            NOTE:
'indicates species found in  Mid inlet.

-------
       22
waters.    These species graze on the phytoplankton species
listed in Table A-4.

     The Cook Inlet (primarily the lower portion) provides a
suitable habitat for all the commercially harvestable species
in Alaska and for most of the sport species.23  Table A-5
presents some of the key consumers in Cook Inlet.  The
important shellfish harvested include three species of
crabs, five shrimp species, razor clams and scallops.  The
crab and shrimp species are primarily detritivores, feeding
on newly dead animal material and occasionally on live
amphipods or polychaetes.  The clams and scallops feed by
filtering planktonic material and organic particulate matter
out of the water column.

     The principal fish caught in Cook Inlet are salmon,
steelhead, Dolly Varden, halibut, herring, and smelt.24
Five species of Pacific salmon (Oncorhyncus) are found in
Cook Inlet and associated rivers and lakes.  The pink salmon
are most abundant; sockeye, chum and coho salmon are of
intermediate abundance; and Chinook salmon are least
numerous. 5  Other finfish species caught in deep waters
include butterfish, sole, yellowfin and pollock.

     There are several migratory patterns which can be
observed among fish and shellfish of Cook Inlet.  Many of
the important commercial and sport species are anadromous.
They spend most of their life in Cook Inlet and return to
freshwater coastal streams and rivers to spawn.  In most
anadromous species the adult dies after spawning.  The fry
develop in streams and after hatching may either migrate
directly to the ocean  (as do pink salmon) or may migrate to
a lake entering the ocean later as a juvenile  (as do sockeye
salmon).  Salmon, Dolly Varden, steelhead, grayling and
     22
       Evans, Buck, Buffler, et al., Cook Inlet Environment,
Study of Available Knowledge.

       Alaska Department of Fish and Game, Habitat Protection
Section, "Lower Cook Inlet Fisheries"  (map), Anchorage,
Alaska, 1976  (unpublished).

     24
       U.S. Fish and Wildlife Service, Resources Assessment
Lower Cook Inlet.

       Frank Stefanich, Resources Inventory, South Central
Region;  Fisheries Resources, Resources Planning Team,
Joint Federal-State Land Use Planning Commission, Alaska,
1974.
                            -248-

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                                                    TABLE  A-5
                                     KEY  CONSUMERS  -  COOK  INLET
                                   NEAR  AND  FAR  OFFSHORE  WATERS
                          INVERTEBRATES
                                                           FISH
                                                                                     BIRDS
                                                                                                         MAMMALS
COMMERCIAL * it Paralithodes camtschatica
SPECIES (King Crab)
if if Chionecetes bair?s
(Tanner Crab)
if if Cancer magister
(Dugeness Crab)
• if Patinopectcn caurinus
(Scallops)
if if Pandalus borealis
(Pink Shrimp)
•fr if Pandalus hypsinotus
(Coonstripe Shrimp)
if if Pandalus goniurus
(Humpy Shrimp)
if if Pandalus dispar
•ir Oncorhynchus gorbuscha*
(Pink Salmon)
if Oncorhynchus shawytscha*
(Chinook Salmon)
if Oncorhynchus keta
(Chum Salmon)
if Oncorhynchus kisutch*
(Coho Salmon)
if Oncorhynchus nerka*
(Sockeye Salmon)
if Clupea pallasii*
(Herring)
                      (Sidestripe  Shrimp)
SPORT  SPECIES
                      Pandalus platyceros
                      (Spot Shrimp)
  if Salmo gairdneri*
    (Steelhead)

  if Salvelinus malma*
    (Dolly Varden)

  if HippoqlQSSus stenolipis*
    (Halibut)

  if Thaleichthys pacificus*
    (Smelt)

  if Salmo gairdneri
    (Steelhead trout)

  it Atheresthes s'tomias
    (Flounder)

if it Gadus macrocephalus
    (Cod)
if Enhydra lutria
  (Sea  Otter)

ir Phoca vitulina
  (Harbor Seals)
      if Detritivore

      ^ Carnivore

      •  Herbivore

      NOTE:  An  asterisk {*)  indicates species found  in Mid Inlet.
                                                     -249-

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                                    TABLE  A-5  (CONT.)
             INVERTEBRATES
                                              FISH
                                                                BIRDS
                                                                                         MAMMALS
TROPHICALLY
IMPORTANT
SPECIES
ENDANGERED
SPECIES
Thuriaria sp.* •& Melanitta perpicillata
(Hydrozoan) (Surf Scooter)
it Autolytus sp. (Larvae) £ Larus hyperboreus
(Polychaete) (Glaucous-winged Gull)
• Acartia sp.* ^ Larus sp.
(Copepod) (New Gull)
• Eurytemora sp.* -fr Rissa sp.
(Copepod) (Black Legged Kittiwake)
• Nauplius (Larvae)* -fa sterna paradisaea
(Copepod) (Arctic Turn)
• Pseudocalanus sp.*
(Copepod)
• •*• Balanus sp. (Larvae)*
(Barnacle)
•ft Lamprops sp . *
(Cumacae)
•ft Crago sp. *
(Decapod)
T& Pagurus sp. *
(Decapod)
Sagitta elegans*
(Chaetognath)
•tfr Eumysis sp. *
(Mysid)
• Discorbes sp.*
(Foraminifera)
• Strongylocentrotus droba- ''
chiensis (Sea Urchin)
•fr Thais lamellosa
(Dog Walk)
*-kir Delphinapterus leucas
(Beluga Whales)
* Detritivore
if Carnivore
• Herbivore
NOTE:  An asterisk  (*)  indicates species found in Mid Inlet.
                                            -250-

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smelt are all anadromous fish which are caught at the mouths
of rivers and streams where they congregate before migrating
into freshwater.26

     Other species spend their entire existence in the
saline waters of Cook Inlet, migrating toward shore and into
deeper waters at different stages in their life cycle.
Pandaeid shrimp, king crabs, snow crabs, weathervane scal-
lops and halibut hatch in deep waters, spend several weeks
or months as planktonic larvae, move inshore (to depths less
than 50 fathoms) to take up a semi-benthic existence as
juveniles, and migrate back to deeper waters as adults.  In
an opposite pattern, herring spawn in nearshore subtidal and
intertidal waters, laying their eggs on living plants.  The
larvae mature in shallow waters and as juveniles they group
in small schools and move out to sea.  The dungeness crab
also spends its larval life in shallow waters,  often in
intertidal stands of eel grass, and moves offshore as an
adult.

     Many Cook Inlet species have annual inshore-offshore
migration patterns which may be associated with life history
stages, but are often induced by seasonal changes in water
temperature and ice cover.

     Though many of the species mentioned above are found
predominantly in the Lower Inlet, king, sockeye, coho and
pink salmon, Dolly Varden and steelhead trout all spawn in
rivers and streams of the Mid Inlet.  The Kenai River is an
extremely productive spawning ground for these species.

     A variety of marine mammals inhabit the entire coastal
region of Cook Inlet, but they breed on the islands of the
Lower Inlet.  Sea otters and harbor seals are found on the
west side of the Inlet and in Kachemak Bay.  Sea lions
concentrate on the barrier islands south of Cook Inlet, and
Beluga whales swim up the Inlet as far as the Susitna River.
Killer whales and Dali porpoises are also commonly observed
in the Lower Inlet.27

     A simplified food web for Cook Inlet waters, involving
many of the species discussed here is displayed in Figure A-7
     2 6
       Stefanich, Resources Inventory, South Central Region:
Fisheries Resources.
     27
       M.P. Wennekens, L.B. Flagg, L. Tratsky, et al.,
Kachemak Bay, A Status Report (Anchorage:  Alaska Department
of Fish and Game, Habitat Protection Section, December 1975),
                            -251-

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I
NJ
cn
NJ
I
                                       LITTORAL FEEDING BIRDS*
                                                  BOTTOM
                                                  BENTHIC
                                                                             LIGHT
                                                                                         MAN
                                                                                Depth
                                                                                Meters
                                                                                   -0
                                                   PHYT.OPLAN.KTON
                                                             DETRITUS
     Pocific Holibut
  J   Pocific Cod
^   Alaskan Pollock
^r3   Sockeye Salmon
^J   Chum Salmon
^   Pink Salmon
C^   Dolly Varden
 ^1   Rock Greenling
O'   Pacific Ocean Perch
-x°   Sole and Flounders
ns»   Lolernfish
O»   Larval Rockfish
—   Small Fish, Primarily Pacific Sand Lance
^   Amphipods
•**i   Other Small Crustaceans (Euphausiids, Cumaceans, Copepods)
 ^   Meteropods and Pteropods
 *•   Briltlestars
 iff   Miscellaneous Worms
 4-   Sea Urchin
*-s   Mysids
                     Figure  A-7.   Cook Inlet  food chain.   (L.L. Selkregg, Alaska  Regional
               Profiles;   South  Central  Region  (Anchorage:    University  of  Alaska,  Arctic
               EnvironmentalInformation and Data  Center,  1974),  p.  153.)

-------
     A.2.13  Biology - Cook Inlet Intertidal Region

     Cook Inlet is bordered by a variety of community types.
Tidal marshes, mudflats, and rocky shores dominate the Mid
and Upper Inlet; rocky coastline, fjords and cliffs dominate
the Lower Inlet.  One hundred square miles of tidal marshes
are found in the Susitna Flats, Chickaloon Flats, Trading
Bay and Redoubt Bay in the Upper and West Mid Inlet.  These
areas support high densities of waterfowl.

     The onshore separation facilities at Nikiska and just
below Kenai on the east side of the Mid Inlet, are located
along coasts characterized by upland spruce-hardwood forests.
These forests extend almost directly down to the shoreline,
and are separated from the water by a small drop (50 feet)
and some gravel and rocks.  The diversity of species occu-
pying the intertidal region in these areas is considerably
less than in the Lower Inlet.  A study performed by the
University of Alaska for the Collier Carbon and Chemical
Corporation, in May 1968, reported only five species of green
algae on the Nikiska shoreline.  Most of the faunal organisms
found were relatively sessile, attached to rocks or burrowing
in gravelly sand.  These included hydrozoans, flatworms,
coelenterates, brachiopods, amphipids, isopods, clams, snails,
barnacles, limpets, polychaetes and pycnogonids  (sea spiders).
A total of 46 taxa were reported in this study.28  Table A-6
presents the most important of these.

     The two onshore separation facilities on the West Mid
Inlet are located at Granite Point and near West Foreland
in tidal marsh and swamp communities.  Marsh grasses and
waterfowl are the dominant species.  These areas are also
part of an important bald eagle migration route.29

     The Collier Carbon Study referred to here is one of the
only studies which has sampled organisms from Mid Inlet
intertidal zones.  There are few roads and most observations
of biota seem to have been made by air.  As mentioned in the
introduction to this section, the lack of data makes a com-
plete onshore characterization of the discharge sites (par-
ticularly the western sites)  impossible.
     2 8
       Hood, Natajan, Rosenberg, and Wallen, Summary Report
on Collier Carbon and Chemical Corporation.

     29
       L.L. Selkregg, Alaska Regional Profiles; South Central
Region (Anchorage: University of Alaska, Arctic Environ-
mental Information and Data Center, 1974) .
                            -253-

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                           TABLE  A-6
              KEY  CONSUMERS -  COOK  INLET
             INTERTIDAL  (MUDFLAT  - ROCKY)

COMMERCIAL
SPECIES
SPORT SPECIES



TROPHtCALLY
IMPOPTAHT
SPECIES










ENDANGERED
SPECIES
INVERTEBRATES
•*• Siliqua patula*
(Razor Clam)
it Siliqua patula*
(Razor Clam)


. An^ojsp.™. M,.
(xjr.phipod)
t Gamnarus wilkitzskii*
(Anpnipod)
(Clami"
(Barnacle)
• Idotef;4 entomon*
(Irupod)
• Littonna sp_.«
(Snail)
• Acnna SF-*
(Limpet)
•ft Buccxnium sp. *
(Dog whelk) "
•fr-fr Cancer niagister*
(Crab)
•AEvastorias trochelii
(Soa star)
•fa Thais lamellosa
(Srail)
ir4t Telnmcsaus ch«lragonus
(Horse Crab)
& Pycnopodia sp.
(Sea Star)

BIRDS





•fr Fraterula sp.
(Puffin)
ir Piss,a sp.
(Kittiwake)
•(r Uria sp.
(Muire)
•fr Phalacrocorax sp.
(Cormorant)
tf Lurus) sp.
(dull)







T^Haliaeetus leucoccphal \s_
(Bald Eagle)
MAMMALS

• Alces alcss
( Moose )
• Fangifer tarandusgranti
(Caribou)
if Lutra canadensis
(Otter)













if Detntivoce
•&• Carnivore
• Herbivore

NOTEt  An asterisk (*) indicates species found in Mid Inlet
                              -254-

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A.3  Gulf of Mexico Characterization
     A.3.1  Introduc tion

     The study site in the Gulf of Mexico encompasses the
marshes and nearshore waters of Barataria Bay, Timbalier
Bay, and Terrebonne Bay in Louisiana, and the offshore
waters adjacent to these Bays.  These bays are part of a
larger drainage basin system which divides Louisiana into
distinct hydrologic units.  The study area is depicted in
Figure A-8.

     The Barataria drainage basin encompasses 1,900 square
miles  (1,216,000 acres)  of land and water-^0 ancj is bordered
by the Mississippi River on the east and Bayou Lafourche on
the west.  The drainage basin encompassing Terrebonne and
Timbalier Bays, bordered by Bayou Lafourche on the east and
the Houma Navigation Canal on the west, contains 597,900
acres of land and water.3^

     The two drainage basins are morphologically, physi-
cally, chemically and biologically similar.  Both regions
are composed of a large estuarine waterbody separated from
the Gulf of Mexico waters by a string of barrier islands,
Grand Island, and Grand Terre Islands in Barataria Bay, East
Timbalier Island, Timbalier Island, Wine Island and Dernieres
in Timbalier and Terrebonne Bays.  Both these estuarine
regions are bordered by an intricate system of salt marshes
and bays, extending northward into brackish and freshwater
marshes, lakes and bayous.  These two estuarine systems are
similarly influenced by Gulf currents, by the Mississippi
outflow and by freshwater and tidal inundation.

     The offshore Gulf waters adjacent to Barataria Bay are
also very much like those waters adjacent to Timbalier and
Terrebonne Bays.  They receive similar hydrologic and organic
input from the nearshore and marsh areas, and from the Mis-
sissippi River.  They experience the same meteorologic
conditions and have a similar physical and biological regime.
       Barney Barrett, Water Measurements of Coastal Louisiana
(New Orleans:  Louisiana Wildlife and Fisheries Commission,
Oyster, Water Bottoms and Seafood Division, 1970).

       Barrett, Water Measurements of Coastal Louisiana.
                            -255-

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U1
cr\
I
    ISLES
         Fiqure A-8.   Barataria - Timbalier - Terrebonne Bay  area.

-------
     Both the Barataria and the Timbalier-Terrebonne nearshore-
offshore systems are of interest in this study, but because
the hydrologic,  chemical and geologic features, and resulting
vegetation and associated fauna are alike in these two
systems, only one of these, the Barataria Bay and adjacent
Gulf system, will be discussed in depth in this characteri-
zation.  The first section will describe Barataria Bay, its
marshes and associated waterbodies.  The second section
discusses the near offshore and far offshore waters in the
Gulf of Mexico adjacent to Barataria Basin.
     A.3.2  Barataria Bay

     The areas dealt with in this section of the characteri-
zation are the brackish and salt marshes and their associated
waterbodies.  This includes a number of lakes, Barataria Bay
and Caminada Bay.  Approximately 1,150,000 acres of the
Barataria Basin are wetland and 66,000 acres are water.
Sixty-six percent of the wetlands are freshwater marsh and
swamp  (salinity 0 to 5 ppt), 20 percent are brackish marsh
(salinity 5 to 13 ppt), and 14 percent are salt marsh  (sali-
nity 13 to 30 ppt).32  Figure A-9 displays the distribution
of these wetland communities in Barataria Basin.


     A.3.2.1  Temperature

     Average surface water temperature in Barataria Bay is
approximately 22° C, with monthly averages ranging from a
high in August of 29.5° C to a low in February or March of
13° C.  During a 12-year period (1958-1969) the temperature
extremes, measured by a continuous recorder at Ft. Livingston
(near Barataria Pass), have ranged from 0° C to 36° C.
Warming of Barataria waters begins in February or March and
continues through August; cooling trends begin around Sep-
tember, though this may vary in unusually warm or cool
years.
     32
       L.M. Bahr and J.J. Hebrard, Barataria Basin:  Biolog-
ical Characterization (Louisiana State University, Center
for Wetland Resources, 1976), unpublished.

       Louisiana Wildlife and Fisheries Commission, Cooper-
ative Gulf of Mexico Estuarine Inventory and Study, Phase
II Hydrology, New Orleans, 1971
                            -257-

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                    ;L^m


                          ___                v^S^gBfsjKi



•*  _ * ** T^—i . * * * \- . ?» - *** *,  -"" - ~"1-~ ~_ I:.—.'-_	 <*?  ^^^il^K.        Pv * B»^^ *&*^ r jT^tC*^— —^^l /,' i-^~~^ ~TTS "*J t;*i.". "^i.   r~~1
• '. •   « •» * * , • \ »*  ,».-*.  »	•	 — —	 - 	 -—* ^ *-r % O        t>  T Nrf^' -,. —•^ - ——, \ H U —•* ••• •	 -^"*- —-^J   ^> w—^1
                                                                  eESfc
%cgp::;-> i^^->£
                                   GRAND ISLE
    ,   .A J^f^-f" V'^-^^^^-^c/
  =isS  f -^7>:-±~: • -^..-^^c^C:}^--^?.
                                                       FRESH MARSH
                                                        (0-5 ppt.)
                                                              MARSH
                                                        (6-13
                                                       SALT MARSH
                                                       (H-30 ppt.)
         Figure A-9.  Barataria Bay  narsh types.   tS.H.
    et al., "Environmental Atlas and  Multiuse Management Plan  for
    South Central  Louisiana,"  Hydrologic and Geologic Studies
    of Coastal  Louisiana, Report 18, Vol.  2, plate 8 (Baton
    Rouge:  Louisiana State  University,  Center  for Wetland
    Resources,  1973).
                                 -258-

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     The southern waters of Barataria Bay are warmer in
winter months than northern bay waters; however, in the
spring water temperatures are a few degrees higher in the
north bay.  Top and bottom temperatures rarely differ more
than one degree in Barataria Bay, due to the shallow depths
and mixing action of waves and currents.  In the winter
surface water temperatures are slightly lower than bottom
water temperatures, while the reverse is true in summer.
Figure A-10 depicts a summer isotherm profile across the
middle of the bay.
     A.3.2.2  Depth34

     The Barataria-Caminada Bay water system (which will be
referred to as one unit), occupies 57,709 acres and a volume
of 275,002 acre-ft.  This estuary is extremely shallow, most
of it is less than 4 feet in depth.  The following list
describes the depth patterns of the Barataria-Caminada
system.
DEPTH
(ft)

1
4
7
10
0-
.5
.5
.5
.5
1.5
- 4.5
- 7.5
-10.5
-50
BARATARIA BAY
(acres)
10,771
28,982
2,553
685
560
CAMINADA BAY TOTAL
(acres) (acres)
13,413 24,184
541 29,523
204 2,757
685
560
     34
       Barrett, Water Measurements of Coastal Louisiana
                            -259-

-------
O
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s
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t. Marys l\ i d d I e B a n k Inclspe
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^^ ^^*^* **"»i»_ *~— • ^X^ ^^
^ ^^- " ^^^
^^- "^^
^..x-
x^ •'•
^*"x*fc 	 i-r __, nri— --
~~^ -^ "\ 	 „ 	 	 • 	 ' 	 , . 	 	 . .__ 	 	 '
\ M^^ 30.4
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/
'
.X o
^ -D
s~ ~ $ ~
-r\
o
a>
     J/=3ii'
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Water £ o 11 o r.%

'    - 10 ~
             Figure A-10.  Isothe_rm profile in degrees centriarade  alonq  a  north-south line in
        Barataria Bay on August 8, 1967.  Distance between Grand Terre and  St. Marys  Point
        is 10 miles.  (Louisiana Wildlife and Fisheries Commission, Cooperative Gulf  of  Mexico
        Estuarine Inventory and Study, Louisiana, Phase II Hydrology, 1971, p. 46).

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     A.3.2.3  Tides and Currents

     The normal tide along the Louisiana coast is diurnal
though these are subject to the effects of changing metereo-
logic conditions, such as strong winds or barometric pressure
North winds lower water levels, lengthen the duration of
ebbing tides and reduce the range of flooding tides, while
southerly winds have the reverse effect.

     The average annual tidal range near the mouth of Bara-
taria Bay is 13.3 inches.  Most of the Louisiana coastline
experiences an average tidal range near 1 foot.  Neap tides
range from 3 to 4 inches, while spring tidal ranges average
almost 2 feet.  One of the highest tides recorded was 91.0
inches during hurricane Betsy  (September 9, 1965) and the
lowest was -25.7 inches, recorded during a strong north-
northwest wind (December 21, 1960).  Table A-7 gives the
diurnal range (the difference in height between mean higher
high water and mean lower low water),  and the mean tide
level  (the plane midway between mean low water and mean high
water measured from the mean low water level)  at selected
locations along the Louisiana coast.

     Gulf waters enter Barataria Bay through Barataria Pass,
Pass Abel, Quatre Bayoux Pass and Caminada Pass.  Flooding
waters are normally reflected to the western side, by the
earth's rotation.

     Water circulation in Barataria Bay is primarily tidal.
Tidal currents are strongest at the moon's maximum decli-
nation, with a velocity between 2 and 3 knots.  The velocity
is greatest just below low and high tides, with slack tidal
currents occurring just after low and high water.  The
current in Barataria Pass continues to ebb for a short time
after low water (while the tidal height is rising) and
continues to flood just after high water (while the tide is
falling).  Table A-8 gives the direction of the flood
current, the average velocity of the flood current, the ebb
current direction, and the average velocity of the ebb
       J.G. Gosellink, R.R. Miller, M. Hood, and L.M. Bahr,
^r•' Louisiana Offshore Oil Port:  Environmental Baseline
Study/ Vol. II (Baton Rouge:  Louisiana State University,
Center for Wetland Resources, 1975); and Louisiana Wildlife
and Fisheries Commission, Cooperative Gulf of Mexico
Estuarine Inventory and Study.
                            -261-

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                         TABLE A-7
            RANGE OF TIDES,  AND MEAN TIDE LEVEL
                    ALONG LOUISIANA COAST


LOCATION
Bastian Island
Quatre Bayoux Pass3
Barataria Passa
RANGE

DIURNAL
1.2
1.3
1.2
(ft)
MEAN TIDE
LEVEL
0.6
0.6
0.6
Barataria Bay
  Bayou Island, Grand Isletc
  Independence Island
  Manilla3
Caminada Pass  (bridge)
Timbalier Island,
Timbalier Baya
Pelican Islands,
Timbalier Baya
Wine Island, Terrebonne Bay'
Caillou Bocaa
Raccoon Point, Caillou Baya
Ship Shoal Light3
1.0
0.9
1.0
0.9

1.2

1.2
1.3
1.4
1.7
1.6
0.5
0.4
0.5
0.4

0.6

0.6
0.6
0.7
0.8
0.8
      Tide is chiefly diurnal.
     Source:  National Ocean Survey of the National Oceanic
and Atmospheric Administration, Tide Tables 1976, East Coast
of North and South America, Washington, D.C., 1975, p. 236.
                           -262-

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              TABLE  A-8
MAXIMUM CURRENTS  ALONG LOUISIANA COAST

MAXIMUM CURRENTS

FLOOD
EBB
DIRECTION DIURNAL DIRECTION DIURNAL
LOCATION (TRUE) VELOCITY (TRUE) VELOCITY
DEGREES KNOTS DEGREES
Quatre Bayoux Pass,
Barataria Bay
Pass Abel,
Barataria Bay
Barataria Pass,
Barataria Bay
Barataria Bay,
1.1 miles NE of Manilla
Caminada Pass,
Barataria Bay
Seabrook Bridge,
New Orleans
Cat Island Pass,
Terrebonne Bay
Wine Island Pass
Caillou Boca,
Caillou Bay
Calcasieu Pass
Calcasieu Pass,
35 miles south of
Calcasieu Pass,
67 miles south of
Source : National Ocean
Atmospheric Administration,
290
315
315
355
295
350
015
325
095
020
WEAK
1.
0.
1.
0.
1.
1.
1.
1.
1.
1.
2 105
9 145
5 120
4 160
5 120
2 170
1 195
7 160
3 265
7 205
KNOTS
1. 3
1.6
1.3
0. 5
1.5
0.9
1.5
1.9
0.7
2.3
AND VARIABLE CURRENT
Survey of the National Oceanic and
Tidal Current Tables 1976, Atlantic
Coast of North America, Washington, D.C.,
1975, p. 165.

                  -263-

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current, all at strength of current, for the Barataria-
Caminada Bay passes and other selected locations along the
Louisiana coast.

     The volume and velocity of ebbing waters through the
barrier island passes is usually greater than that of the
flood tide due to freshwater drainage from the north (Table
A-9).  As a result, the western sides of the passes are much
deeper than the eastern sides.  Barataria Pass is 160 to 190
feet deep on the west and 10 to 20 feet deep on the east
side.


     A.3.2.4  Salinity36

     The salinity regime of Barataria Bay changes seasonally
and annually as a function of freshwater flow into the bay,
rainfall, saltwater intrusion via tides and storm surges.

     The bay itself is a broad freshwater-saltwater mixing
zone, characterized by low salinity gradients.  Freshwater,
originating as overflow from the Mississippi River and its
tributaries, and by precipitation surpluses, is stored in
the marsh-swamp environment, and numerous lakes of the upper
estuary, and is gradually released seaward.  Much of the
freshwater drains from the northwest, mainly through Bayou
St. Denis and Grand Bayou, and moves down the west side of
the bay.  Thus, salinities are higher in the east and
northeast sectors of Barataria Bay.

     Saltwater influx is dictated by tidal range, seasonal
wind patterns, shape and size of the estuarine tidal prism,
and size and number of tidal passes between barrier islands.
The salinity of water entering Barataria Bay through passes
which open into the Gulf of Mexico, changes as a function of
Mississippi River discharge and offshore circulation.
       Gosselink, Miller, Hood, and Bahr, Louisiana Offshore
Oil Port; C.L. Ho and B.B. Barrett, Distribution of Nutrients
in Louisiana Coastal Waters Influenced by the Mississippi
River, Technical Bulletin No. 17  (New Orleans:  Louisiana
Wildlife and Fisheries Commission, Oyster, Water Bottom and
Seafood Division, 1975); and Louisiana Wildlife and Fisheries
Commission, Cooperative Gulf of Mexico Inventory and Study.
                            -264-

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            TABLE A-9





FLOOD AND EBB FLOW THROUGH  THE
FOUR MAJOR PASSES
OF BARATARIA AND CAMINADA
BAYS
(Mft3)
PASS
Barataria
Quatre Bayoux
Caminada
Abel
TOTAL
FLOOD FLOW EBB FLOW EBB EXCESS
3,229 3,438
874 1,005
627 653
129 212
4,859 5,308
209
131
26
83
449
Source: Louisiana Wildlife and Fisheries Commission,
Cooperative Gulf of Mexico Estuarine Inventory and Study,
Louisiana, Phase II
Hydrology, 1971, p. 57.

              -265-

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     Surface salinities in Barataria Bay vary from a low of
5 ppt in the upper reaches of the estuary (North of Saturday
Island)  to 25 ppt or more as one nears the Gulf of Mexico.
Figure A-ll depicts average surface isohalines for Barataria
Bay.  During ebbing and rising tides the waters in Barataria
Bay become less saline and more saline, respectively, thus
diurnal variation in salinity is observed.

     Fluctuations in normal salinity patterns are observed
during periods of high river discharge.  Freshwater from the
mouth of the Mississippi follows the Louisiana coastline
from east to west, diluting coastal salinities.  These
waters enter Barataria Bay and may extend northward up to 10
miles, causing a decrease in salinity conditions from
normal levels.  Dilutions also occur as a result of increased
freshwater flow of bayous and rivers directly entering
Barataria Bay.

     Salinity stratification and salt wedges are kept at a
minimum in Barataria Bay by shallow depth, tidal action,
winds and heavy boat traffic.  However, in several areas,
near Independence Island and just north of Middle Bank
Light, there are steep surface salinity gradients.  During
periods of very high river discharge the differences between
top and bottom waters may vary up to 5 ppt.  Figure A-12
displays a salinity profile of Barataria Bay along a transect
from Grand Terre to St. Marys Point.


     A.3.2.5  Winds37

     Strong northerly winds occur in Barataria Bay from fall
to early spring, striking with speeds up to 30 to 40 miles
per hour.  The velocity decreases to 15 to 20 miles per hour
after passage of the front and the winds may persist for
three or four days.  These winds, called Northers, are
accompanied by rainfall when there is a rapid drop in
temperature.  High barometric pressure combined with these
north winds results in extremely low water levels.  The
water piles up along the northern shores of Grand Isle and
Grand Terre as the passes are unable to transport windblown
water out into the Gulf as rapidly as it accumulates.  This
lasts only briefly, then the waters of the bay and Gulf
begin to flow in the same direction, lowering the water
levels of the bay.
       Gosselink, Miller, Hood, Bahr, Louisiana Offshore Oil
Port; and Louisiana Wildlife and Fisheries Commission,
Cooperative Gulf of Mexico Estuarine Inventory and Study.
                            -266-

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                                                              10
                                   ^
     Figure A-ll.  Isohaline map of Barataria Bay.  (Fred Dunham,
Study of Important Estuarine Dependent Fishes, Technical Bulletin
No. 4 (New Orleans:  Louisiana Wildlife and Fisheries Commission,
Oyster,  Water Bottoms and Seafood Division, 1972), p. 7.)
                               -267-

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cr>
CX3
St. Marys Middle Bark Independence G r a
Point /-Water Surface Li







{f*\ / t a *** /**
O / 15 ^ 0
, /' / ' J
1 1 f j i ////////
' ' I 1 '//•'////
/' /,///////
'I I/ l / f ' / ' /
1*1 f • * • /
1 1 ' / / / / 7 / / 7
'/ (./»./ / , //////
ght Jolond. Ter
2526 E7 2829 28 27 26
11 1 J 1 I
/ ''//'/'/ / i j
1 1
/ 1
' /" / I ' '
/ / ' / / /
'//' / / / '
' , / f 1 '
x / / i
' |
' |
' I-
n d
r e





o
a>
Tl
5 -
•y
                                                                                                 •n
                                                                                                 a
                                                                                                 o
           Figure A-12.   Salinity profile of Barataria Bay.  Numbers  are in parts  per  thousand.
       Data  taken on August 8,  1967.   Distance  between Grand Terre and St.  Marys Point is 10
       miles.   (Louisiana Wildlife  and Fisheries Commission, Cooperative Gulf of Mexico
       Estuarine  Inventory and  Study,  Phase  II  Hydrology,  1971, p. 51.)

-------
     Winds also have an important effect on salinity.
Strong southwest to west winds reduce the westward drift of
river water entering the bay, increasing salinities in the
lower estuary and near offshore areas, while east to south
winds bring river water into the area resulting in lowered
salinities in the lower estuary.

     From September to February the prevailing winds are
north to northeast, from April to August they are from
southeast to southwest.  The most infrequently occurring
winds are from the southwest to northwest.

                       00
     A.3.2.6  Turbidity

     Barataria Bay waters are quite turbid due to freshwater
drainage, tidal mixing action and the influence of the
Mississippi River.  The average visibility for a 1968-1969
study was 1.9 feet with extremes ranging from 3.7 to 0.9
feet.  Turbidities were higher in the upper estuary and
decreased towards the Gulf.  Turbidity does not vary con-
sistently with salinity, but seems to fluctuate directly
with total phosphorus concentrations.


                                39
     A.3.2.7  Sediment Chemistry

     Sediments in Barataria Bay are contributed mainly by
the Gulf of Mexico, the Mississippi River, erosion of the
wetlands, and drainage waters from north of the Bay.  Clayey
silt is the dominant sediment type, found along the boundaries
of the bay.  The sediment becomes more silty towards the
marshes, and more sandy towards the Gulf side of the bay.
     3 8
       Gosselink, Miller, Hood, Bahr, Louisiana Offshore Oil
Port; and Louisiana Wildlife and Fisheries Commission, Coopera-
tive Gulf of Mexico Estuarine Inventory and Study.
     39
       C.L. Ho and J. Lane, "Interstitial Water Composition in
Barataria Bay (Louisiana) Sediments," Estuarine and Coastal
Marine Science 1 (1973) :  125-135; Louisiana Wildlife and
Fisheries Commission, Cooperative Gulf of Mexico Estuarine
Inventory and Study; and J.F. Mayer, Jr., Modification of
Solvent Extraction Methods and Determination of Trace Metals
in Selected Aquatic Ecosystems in Louisiana (Master's Thesis,
Louisiana State University, 1975).
                            -269-

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The center of Barataria Bay is primarily sandy silt.
Figure A-13 depicts sediment type distribution in the Bara-
taria region.  The predominant grain size in Barataria Bay
is coarse and percentage of sand content is high relative to
clay content.


     A. 3. 2. 8  Soil Chemistry

     The wetlands of Barataria Bay have a higher clay content
(16 to 30 percent) than do the bay and nearshore sediments,
with clay content decreasing from freshwater, to brackish,
to salt marsh.  Soil salinity increases along this succession
of marshes.  The organic content of soil is higher in the
brackish marsh at 26.7 percent organic carbon and 1.6 percent
organic nitrogen, than it is in fresh or saltwater wetlands.
In the salt marsh soils, organic carbon content ranges from
6 to 9 percent.  A high level of sulfide exists in the
brackish marsh and strongly anaerobic conditions are found
beneath the surface layer of soil.  Heavy metals which
readily absorb to clay minerals are found at higher levels
in the brackish soils  (which have a higher percentage of
clay content) than in the salt marsh soils.  Table A-10
and Figure A-14 present data collected along Bayou Lafourche,
which demonstrates these trends.

     The soils of the salt marsh are gradually being eroded
by marine waters, thus the salt marsh is in a senescent
state.  The boundary between brackish and salt marsh is
gradually migrating inland as the entire coastal zone subsides,


     A.3.2.9  Water Chemistry41

     The nutrient content of Barataria Bay waters varies
spatially and temporally as a function of salinity, rainfall,
river discharge and related nutrients.  Table A-ll presents
1968-1969 nutrient levels for dissolved oxygen, nitrate
(NO3) nitrite  (NC>2), inorganic phosphorus and total phosphorus
     40
       Bahr and Hebrard, Barataria Bay;  Biological Charac-
terization; and Louisiana Wildlife and Fisheries Commission,
Cooperative Gulf of Mexico Estuarine Inventory and Study.
     41
       Ho and Barrett, Distribution of Nutrients in Louisiana
Coastal Waters; and Louisiana Wildlife and Fisheries Commission,
Cooperative Gulf of Mexico Estuarine Inventory and Study.
                            -270-

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                         90 00-
  . \.
     *V2P .""^



                       c; ' IK
                                            0  F
M
                         90 00-
     Figure A-13.  Sediment type distribution  in the Barataria-
Caminada Bay Area.  Base map:   U.S.  Army Corps of Engineers,
scale 1:250,000.   (Louisiana Wildlife and Fisheries  Commis-
sion, Cooperative Gulf of Mexico Estuarine  Inventory and
Study, Phase III Sedimentology, 1971, p.  155.)
                          -271-

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                                         TABLE A-10




                   SEDIMENT CONTENT  - BARATARIA DRAINAGE  BASIN

SAMPLING
STATION
1.
2.
3.
4.
I
^j 5.
to
1 6.
7.


Salt marsh
Salt marsh
Brackish marsh
Brackish marsh

Fresh marsh

Fresh marsh
Fresh marsh
Source: J.F.
of Trace Metals in
SALINITY
(PPt)
19.7
21.8
8.4
6.1

0.62

0.29
0.10
Mayer , Jr
Selected
SEDIMENT
ORGANIC SEDIMENT
CARBON (%) CLAY (%)
7
9
6
26

15

7
7
.5
.0
.5
.6

.0

.5
.1
. , Modification of
Aquatic
Ecosystems
19.7
24.7
30.2
16.8

33.6

24.5
38.1
Fe
(ppm)
494.8
598.9
625.0
562.5

286.4

729.1
833.1
Mn
Cu
(ppm) (ppm)
50.0
27.1
62.5
48.8

30.2

44.8
60.4
Solvent Extraction Methods and
in Louisiana
(Master1
s Thesis,
1.02
2.00
1.21
3.63

5.00

2.35
4.54
Ni
(ppm)
1.64
1.61
1.52
1.50

1.17

1.42
1.79
Pb
(ppm)
0.83
0.67
0.96
0.90

1.31

1.71
1.14
Zn
(ppm)
4.06
3.64
4.48
5.88

3.96

52.03
5.62
Determination
Louisiana
State University, 1975).

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                                                     BARATARI A
                                                     BAY
     Figure A-14.  Sampling stations for sediment  study
(Table 5-10).   (Mayer, Modification of Solvent Extraction
Methods and Determination of Trace Metals in Selected Aquatic
Ecosystems in Louisiana  (Master's Thesis, Louisiana State
University, 1975).
                             -273-

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                          TABLE A-11
NUTRIENT LEVELS — BARATARIA BAY WATER COLUMN  (1968-1969)

YEARLY
AVERAGE
Dissolved O 8.0
(ppm)
Nitrite 0.45
(mg-at/1)
i
^ Nitrate 4.50
*" (mg-at/1)
Inorganic 0.78
Phosphate
(mg-at/1)
Total 2.93
Phosphorus
(mg-at/1)
Source: Louisiana Wildlife
Mexico Estuarine Inventory and
LOW MONTHLY HIGH
MONTHLY
AVERAGE AVERAGE
6.6 (Aug.) 9.5
0.16 (June) 0.87
0.08 (Oct.) 18.90
0.42 (Nov.) 1.31
1.65 (Jan.) 3.91
and Fisheries Commission
Study, Louisiana, Phase I
(March)
(April)
(March)
(Sept.)
(April)
, Cooperative
I Hydrology,
ABSOLUTE
RANGE
6.0-10.5
0.05-1.98
0.00-56.63
0.25-2.06
0.59-6.68
Gulf of
1971.

-------
     Dissolved oxygen levels are directly related to water
temperatures.  In summer months, dissolved oxygen reaches a
low, and increases as temperature sinks and wave action (due
to winds and current) increases.  In general, dissolved
oxygen levels are higher where salinities are lower, in- the
upper and western portions of the Bay.  Average dissolved
oxygen levels in Barataria Bay are close to 8 ppm.

     Nitrate levels are highest in periods of high rainfall
and in regions of low salinity.  This suggests that input of
large volumes of water draining from the north — which
carry with it nutrients and detritus from fresh and brackish
marshes, will increase nitrate levels in Barataria Bay.  The
average nitrate level found in Barataria Bay is 4.5 micro-
moles per liter (ug-at/1).

     Nitrite levels correspond closely to nitrate levels.
Highest nitrite levels occur shortly after high nitrate
values are observed indicating that high nitrite concentra-
tions may result from nitrate reduction.

     Inorganic phosphate, which averages 0.78 ug-at/1, is
highest in the upper reaches of Barataria Bay and like
nitrite and nitrate, may be related to freshwater drainage
from wetlands to the north.  Similarly, total phosphorus is
higher during periods of peak river discharge and corres-
ponding low salinities, and is higher in the upper estuary
than it is near the Gulf of Mexico.  An average value for
total phosphorus is 2.9 ug-at/1 of which approximatley 26
or 27 percent is organic.
                            -275-

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                               42
     A.3.2.10  Wetlands Biology

     The wetlands of the Barataria drainage basin have been
divided into three subunits:   freshwater swamps and marshes,
brackish marshes, and salt marshes.  Each of these subunits
has a characteristic salinity range, vegetative assemblage,
and productivity.  Approximately 66 percent of the Barataria
wetlands is a freshwater environment (0 to 5 ppt); 20 percent
is brackish marsh (6 to 13 ppt)  and 14  percent is salt marsh
(14 to 30 ppt).   Figure A-9 depicts the distribution of wet-
lands near Barataria Bay.  For the purposes of this study,
we will deal only with the brackish and salt marshes, two
systems which have interdependent hydrology, nutrient cycles,
and energy flow.
     A.3.2.11  Brackish Marsh

     The brackish marsh represents an intermediate zone
between the freshwater and marine ends of the Barataria
Drainage Basin.  This area forms a band stretching across
the drainage basin from below the Intracoastal Waterway to
the salt marsh, lakes, and estuaries fringing Barataria Bay.
     42
       Bahr and Hebrard, Barataria Basin;  Biological Charac-
terization; Barrett, Barney, Gillespie, and Cannon, Primary
Factors Which Influence Commercial Shrimp Production in
Coastal Louisiana, Technical Bulletin No. 9 (New Orleans:
Louisiana Wildlife and Fisheries Commission, Oysters, Water
Bottoms and Seafood Division, 1973); J.W. Day, Jr., W.G. Smith,
P.R. Wagner, W.C. Stowe, Community Structure and Carbon
Budget of a Salt Marshand Shallow Bay Estuarine System in
Louisiana  (Baton Rouge:  Louisiana State University, Center
for Wetland Resources, May 1973); Galdry, J. Wilson, and
C.J. White, Investigations of Commercially Important Penaeid
Shrimp in Louisiana Estuaries, Technical Bulletin No. 8
(New Orleans:  Louisiana Wildlife and Fisheries Commission,
Oysters/ Water Bottoms and Seafood Division, March 1973);
Eugene Jaworski, The Blue Crab Fishery, Barataria Estuary,
Louisiana  (Baton Rouge:  Louisiana State University, Center
for Wetland Resources, 1972); Louisiana Wildlife and Fisheries
Commission, Cooperative Gulf of Mexico Estuarine Inventory
and Study; and J. Thomas, P. Wagner, and H. Loesch, "Studies
on the Fishes of Barataria Bay, an Estuarine Community,"
Coastal Studies Bulletin No. 6 (Baton Rouge:  Louisiana State
University, Center for Wetland Resources, 1971).
                            -276-

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At the basin's center the band of brackish marsh is 15 miles
wide, tapering as it approaches the Mississippi River and
Bayou Lafourche on either side.  The major waterbodies of
the brackish marsh are Little Lake, Turtle Bay and Bayou
Perot.

     The dominant plant species in the brackish marsh are
Spartina patens (wire grass) which comprises 45.8 percent of
the marsh vegetation, and Distichlis spicata (salt grass)
which contributes 29 percent.  Spartina alterniflora (oyster
grass, Juneus romerianus (black rush)  and Scirpus olneyi
(three-cornered grass) are also important primary producers.
Table A-12 lists key species of primary producers found in
brackish and salt marsh environments.   Total annual net
primary production in the brackish marsh is estimated at
1 kg/m2, though this is somewhat speculative.43  The brackish
marsh does have the greatest live biomass of any marsh type,
attributed to the dense stands of wire grass and salt grass
which make up 75 percent of the vegetative cover.

     All the marsh trophic systems are detritus-based,
meaning that energy trapped in primary production is utilized
as dead plant material by community heterotrophs.  Herbivores
play a relatively minor role in utilization of primary
productivity.  Insects and marsh snails graze approximately
7 percent of live plant material and muskrats account for
another 2 percent.  The low level of grazing is responsible
for the net buildup of detritus (as peat) which occurs in
the brackish marsh.  The detritus is consumed by a variety
of detrivores including numerous amphipods, nematodes, and
microbes.  These are, in turn, consumed by higher inverte-
brates, oysters, shrimp and crabs, which are preyed on by a
variety of marsh birds and mammals.

     The trophic systems of the waterbodies associated with
the brackish marsh are similarly detritus-based.  Rapid
chemical changes are, characteristic of these areas and
organisms which reside in these estuaries tolerate changes
in salinity and water chemistry through various physiological
mechanisms.  Aquatic macrophytes such as widgeon grass, and
dwarf spikerush, phytoplankton, and shallow water benthic
diatoms, are the primary producers in these waterbodies.
Ducks and other waterfowl graze on some of the macrophytes
but the dominant energy flow pathway is through detri-
tivorous polychaetes, nematodes, amphipids, ostracods, blue
     43
       Bahr and Hebrard, Barataria Basin;  Biological Charac-
terization.
                            -277-

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                                                 TABLE A-12
                                 PRIMARY PRODUCERS - BARATARIA BAY
                      BRACKISH AND  SALT MARSHES  AND ASSOCIATED WATERBODIES
c»
I
                  MACROPHYTES
        EPIPHYTES


FILAMENTOUS        DIATOMS
BENTHIC
PHYTOPLANKTON
Spartina
alterniflora
Juncus
romerianus
Distichlis
spicata
Spartina
patens
Eleocharis
parvula
Scirpus
olneyi
Enteromorpha
Ectocarpus
Cladophora
Polysiphonia
Rhizoc Ionium
Bostrychia
Erythrotrichia
Spirulina
Oscillatoria
Lyngbya
Denticula
Amphiprora
Amphora
Nitzschia
Melosira
Rhopalodia
Diploneis
Cymbella
Cy 1 indrothe ca
Grammatophora
Surirella
Achnanthes
Cocconeis
Pleurosigma
Navicula
Camphylodiscus^
Achnanthes
Amphiprora
Amphora
Anaulua
Caloneis
Cocconeis
Cosmiodiscus
Diploneis
Eunotogramma
Gyros igma
Mastogloia
Melosira
Navicula
Nitzschia
Plagiogramma
Pleurosigma
Rhaphoneis
Stauroneis
Surirella
Trachysphenia
Coelosphaerium
Gomphosphaeria
Merismopedia
Microcystis
Anabaena
Spirulina
Oscillatoria
Actinoptychus
Biddulphia
Chaetoceros
Coscinodiscus
Melosira
Amphiprora
Camphylodiscus
Navicula
Nitzschia
Ankistrodesmus
Gymnodinium
Eugena gracilis
Coccoid greens

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crabs, and other crustaceans.  Acartia tonsa, the dominant
copepod, is both herbivorous and detrivorous.  Estuarine
finfish, such as the spot, flounder, croaker, sea trout,
black drum and red drum feed on these detritivores.   Wading
birds and mammals such as raccoon and otters are often the
top carnivores in the brackish marsh food chains.  Table A-13
lists the key consumers of the brackish marsh, salt marsh,
and associated waterbodies, their importance, and trophic
characteristics.
     A.3.2.12  Salt Marsh

     Salt marshes are normally more subject to modification
by physical processes than other types of wetlands.  The
salt marshes of Barataria Bay (and the whole Louisiana
coast)  are closely associated with the physical regime of
the Gulf of Mexico.  The diurnal and seasonal variations in
water level produced by tidal inundation, storm surges and
freshwater floods, are important to the species which spend
one part, or all of their life cycle in the marshes, and to
the nutrient cycling and waste removal processes so essential
to high marsh productivity.

     A conservative estimate of annual salt marsh production
is 1 kg/m2; however, published estimates have exceeded
3 kg/m2.44  it is generally agreed that salt marshes are the
most productive wetlands and have the lowest species div-
ersity.  Spartina alterniflora (oyster grass) is the domi-
nant producer, comprising 63 percent of the vegetative
cover.   Distichlis spicata (salt grass) and Juneus romerianus
(black rush)  comprise another 25 percent.  Benthic diatoms
and epiphytes on Spartina stems contribute significantly to
primary productivity during winter and early spring, before
Spartina becomes dense.

     Several functional advantages are obtained from a
Spartina-based community.  The extensive root system provides
erosion resistance to the surface sediments, a feature
especially valuable in strong storms or hurricanes.  The
roots also act as a nutrient pump by extracting phosphorus
from aerobic sediments and transporting it to upper portions
of the plant where it can be released to surrounding waters
during tidal inundation.

     First order consumers of the salt marsh (herbivores and
detritivores) include bacteria,  fungi, copepods, amphipods,
     44
       Bahr and Hebrard, Barataria Basin;  Biological Charac-
acterization.
                            -279-

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                                                    TABLE  A-13
                              KEY   CONSUMERS   -  BARATARIA  BAY
       BRACKISH  AND  SALT  MARSHES   AND  ASSOCIATED  WATERBODIES
                     INVERTEBRATES
                                                           FISH
                                                                                       BIRDS
                                                                                                                   MAMMALS
COMMERICAL
AND  SPORT
SPECIES
 Callinecte3  sagidis
 (Blue Crab)


 (Brown Shrir?p)

' Pgrcaeus setifgrus
 (White Shirmp)

' j'^paeus duprarum
 {Pink Shrimp)


 (Oyster)
> -^f -ft Brevoojrtia, patron us
     (Menhadden)

   ft Apcftoa natchjj.li
     (Bay Anchovy)

t ^r iV Micropogon u-idulatus
     {Atlantic Croaker)

   •fr Arius felis
     \Sea Caccish)

   ft LgAOS tomus xanthurus
     (Spot)

     Chlo ros combrus chrysurus
     (Bumper)

   ft Cynpscion arenarius
     (Sand Sea Trout)

   ft Cynoscion nebulosus
     (Spotted Sea  Trout)

 • •& Mugil cephalus
     (Striped Mullet)

   ft Pa r a 1 i c ht h y s  lethos t^igir^a
     (Southern Flounder)

   ft Pggonias cromis
     (Elack Drum)

   •^ Sci^anops ocellata
                                                                                            Procyon lotor
                                                                                            {Racoon)
                                                                                                                 (Otter)
                                                                                                              • Odatra zibethicus
                                                                                                                 (Muskrat)
           Detriti\*ore
                                                   ft Men
                                                                      ^
                                                      (Tidewater Silverside)
THOPRICAuLY
IMPORTANT
SPECIES
• Acartia tonsa
(Copepod)
(Marsh Snail)
• jr Rancea cuncatus
•ff Pelecanus erythrorhyncon
(White Pelican)
it Dichromanassa rufescens
(Reddish Egret)
tV Circus cyaneus
ilrTursioos truncatus
(Bottlenoae Dolpmn)
                     (Clan)
                                                                                   (Marsh
                                                                                   (Gull)
                                                                                 ft Florida  caerulea
                                                                                   ^Little  Blue Hc-on)
ENDA.NGEREO
SPECIES
                                                            •fr Pelqcamis oj^cLc*nr.t^al_ig
                                                               (b roivTi Pf 1 lean)
                                                          -280-

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snails, fiddler crabs, polychaetes, mussels, insects, birds
and mammals.  Grasshoppers and similar insects are the only
true grazers.  Insects are thought to remove about 4 percent
of net primary production.  Microfauna and small macrobenthos
are important consumers in salt marsh sediments, ingesting
approximately half the weight that macrofaunal forms do.
The total biomass of primary consumers is estimated to be 16
g/m2 at the ocean edge of the estuary, 40 g/m2 10 feet
inland, and declining further inland to 5 g/m2.45

     Salt marsh predators include a variety of wading birds,
mammals, insects and spiders.

     The waterbodies associated with salt marshes are the
bays which interface with the Gulf of Mexico, Barataria and
Caminada Bays, and attached lakes.  The salt waterbodies are
about half as productive as the salt marshes themselves, but
the primary production of diatoms, coccoid blue-green
algae, green algae and nannoplankton, may be utilized more
directly than marsh grass.  These waterbodies have the
greatest primary productivity relative to consumption of all
waterbodies in Barataria Basin.

     Major herbivores of these systems include Acartia tonsa
(the dominant copepod), menhaden and mullet.  Detrivores are
quite numerous including commercially important species of
penaeid shrimp, blue crabs, and oysters.  Important carni-
vores include ctinophores  (which feed on zooplankton),
fishing birds, diving ducks, spotted sea trout, sea catfish,
silversides, anchovy and the bottlenosed dolphin (see
Table A-13).

     Many of the faunal species of Barataria Bay mentioned
above have rather complex life-history and migration patterns,
spending different parts of their cycles in different habi-
tats.  There are four basic patterns or categories into
which these species fall:   (1) truly estuarine species,
which spend their entire lives in the bay;  (2) marine
species which spawn in the sea and use the estuary as a
nursery ground;  (3) marine forms which visit the estuary as
adults; and  (4) freshwater fish which occasionally enter the
brackish waters of Barataria Bay.

     Those  species which spend all or almost all of their
life in the brackish and saline waters of Barataria Bay and
associated  lakes include the eastern oyster, the bay anchovy,
     45
       Day, Smith, Wagner, and Stowe, Community Structure
and Carbon Budget, 1973.
                            -281-

-------
the Atlantic needlefish, the tidewater silverside, the
hogchoker and various killifish.  Many benthic species of
nematodes, polychaetes, bivalves, and amphipids also spawn,
hatch, mature and die in estuarine waters.

     Some of the most commercially important species fall
into the second pattern, living in both open Gulf waters and
enclosed bay waters.  The blue crab, which supports a large
fishery, spawns in lower estuarine and Gulf waters.  The
larval stages, zoea (31 to 49 days) and megalops  (6 to
20 days) are spent in open Gulf waters.  Near the end of the
megalops stage the blue crabs may enter tidal inlets, and
the first nine months of the juvenile stage are spent in the
upper and lower estuary.  The second year as a juvenile is
spent in the upper estuary where the crab grows to full
maturity and mates.  It is at this time that crabs are
fished — usually from ages 12 to 18 months.  Those crabs
not caught return to open ocean waters to spawn.46

     The penaeid shrimp, white, pink and brown shrimp,
follow a similar pattern.  They spawn in offshore Gulf
waters at depths of 5 to 17 fathoms.  After hatching the
nauplii lead a planktonic existence for 3 to 5 weeks, then
metamorphose into a postlarval stage and enter the estuary.
Five or six months after hatching the shrimp are mature and
migrate into the open ocean to spawn.47

     Fish species which spawn in the Gulf (usually in
spring) and use the Barataria Bay as nursery grounds include
the large-scale menhadden, Atlantic croaker, spotted and
sand sea trout, silver perch, striped mullet, spot, and bay
whiff.48  Most of these species remain in the estuary until
late summer and return to the open ocean as subadults in the
fall.  However, the sand sea trout and the mullet move
inshore in the fall, spending warmer months in the Gulf.

     Some fish spawn and live primarily in offshore waters
but seasonally visit the estuary in late summer and early
       Jaworski, Blue Crab Fishery.
     47
       Barrett, Barney, Gillespie, and Cannon, Primary
Factors which Influence Commercial Shrimp Production; and
Galdry, Wilson, and White, Investigation of Commercially
Important Penaeid Shrimp.

     48
       Thomas, Wagner, and Loesch, "Studies on Fishes of
Barataria Bay."
                            -282-

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fall.  The jacks, sea catfish, moonfish, and lizard fish
follow sxxch a pattern.

     Occasionally freshwater fish will move downstream and
enter the brackish waters of the Barataria system.  The
spotted gar is one such species.

     Table A-14 lists, by migratory patterns, various
species of fish and invertebrates commonly found in Barataria
Bay.


     A.3.3  Gulf Of Mexico Waters

                         49
     A.3.3.1  Temperature

     Surface and bottom temperatures vary seasonally.  There
is little difference in temperatures of surface and bottom
waters in the fall and early winter.  During the cooler
months, December to April, surface temperatures become lower
than bottom temperatures, and in spring and summer they
become warmer than bottom temperatures.

     Surface temperatures average 26° C, rising to over 30° C
in summer and sinking to 16° C in winter.  Bottom tempera-
tures average 22° C to 23° C, rising just slightly in summer
and sinking to 19° C in winter.  Surface temperature varies
little with distance from shore; however, in summer near
offshore bottom temperatures are one or two degrees higher
than those far offshore, and the trend is reversed in winter.


     A.3.3.2  Depth50

     The near affshore region of the continental shelf
slopes seaward at 15 ft/mi (2.5 m/km).  The average depth
     49
       Barrett, Barney, Gillespie, and Cannon, Primary
Factors which Influence Commercial Shrimp Production; and
Gosselink, Miller, Hood, and Bahr, Louisiana Offshore Oil
Port.

       P. Detking, R. Buck, R. Watson, and C. Merks, "Surface
and Shallow Subsurface Sediments of the Nearshore Continental
Shelf of South Central Louisiana," in Offshore Ecology Study
(Galveston, Texas:  Gulf Universities Research Consortium,
October 1974) .
                             -283-

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                                                                    TABLE  A-14
                                          MIGRATORY PATTERNS OF  BARATARIA  BAY  SPECIES
                   ENTIRE LIFE SPENT
                    IN THE ESTUARY
                                              SPAWN IN  OFFSHORE  //ATERS
                                                 MATURE IN ESTUARY
                                          ENTER ESTUARY  SEASONALLY
                                                AS AN ADULT
                                   FRESHWATER SPECIES
                                  OCCASIONALLY  ENTERING
                                     BRACKISH WATERS
 I
K)
00
Anchoa mllchilli - bay anchovy
Strongylura marina - Atlantic  needlefish
Hen1Jla berylllna - tidewater  silverside
Trinectes rcaculatus - hogchocker
Cyprlnodon varleg.itus - sheepshead
                       minnow
Crassostrea virglnica - eastern oyster
Bi-evoortla patronus - mcnl
-------
 3 miles offshore is approximately 30 feet.   Beyond this
 point,  the grade lessens to a slope of 4 ft/mi to 6 ft/mi
 (0.7 m/km to 1 m/km).


      A. 3. 3. 3  Tides And Currents51

      Tides in this area are dominantly diurnal,  and exert
 their maximum influence on shelf currents in December and
 June when the sun reaches its maximum declination.  The
 minimum influence is felt in March and September when the
 sun is  over the equator.  Any effects of tides on currents
 are superimposed on the net drift of regional currents.

      Movement of the water column offshore Barataria Bay is
 driven  primarily by local and regional winds, passage of
 diurnal tides, and impingement of regional Gulf  of Mexico
 currents onto the continental shelf.  Figure A-15 depicts
 general circulation patterns in the Gulf of Mexico.  The
 site area for this study is located on the northeast corner
 of a counter clockwise circulation current in the northwest
 Gulf of Mexico.  This circulation is modified by those
 factors mentioned above.

      The annual net movement of waters offshore  of Barataria
 Bay is  westerly.  However, net water movement is easterly in
 summer  with surface currents averaging 0.40 knots, onshore
 (towards shore) offshore (away from shore)  mid-depth cur-
 rents averaging 0.26 knots, and onshore bottom currents
 averaging 0.22 knots.   In winter and early spring net water
 movement is westerly,  with surface currents averaging
 0.82 knots.   Mid-depth currents are offshore and bottom
 currents occur onshore and offshore.  In general, current
 speed tends to decrease with depth.  Figure A-16 depicts
 seasonal variations in current movement in the northwestern
 Gulf waters.


      A. 3. 3.4  Salinity52

      In general, salinities on the Louisiana continental
 shelf increase with increasing distance from shore, and with
        Detking,  Buck,  Watson,  and Merks,  "Currents on Nearshore
 Continental Shelf."

      52
        P. Detking,  R.  Buck,  R.  Watson,  and C.  Merks,  "-Hydrog-
raphy on the Nearshore  Continental Shelf of South Central
Louisiana," in Offshore Ecology Investigation (Galveston,
Texas:  Gulf Universities Research Consortium,  May 1974).
                             -285-

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     Figure A-15.   General circuation patterns in the
Gulf of Mexico.  (U.S. Naval Oceanographic Office,
Oceanographic Atlas of the North Atlantic Ocean,
No. 700, Sect. 1,  Tides and Currents.)
                       -286-

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  30-

  Z8-

  26-
           96 
-------
greater depths.  Freshwater discharge from local runoff and
the Mississippi River acts to lower salinity in surface
waters and waters closer to shore.  Mean surface salinities
range from 19 to 21 ppt, while mean bottom salinities vary
from 31 to 33 ppt.  During the second .half of the year
surface salinities are only slightly lower than bottom
salinities and no steep vertical salinity gradients occur.
This lack of stratification is due to thorough mixing of
water by winds and currents in fall and early winter.  In
mid-winter the lessening of freshwater runoff and the bottom
currents are responsible for a rise in bottom salinities to
35 or 36 ppt, the normal salinity of open ocean.  In late
winter, spring, and early summer pronounced vertical salinity
gradients are observed, beginning at depths of 10 feet.  In
spring surface salinities often fall below 15 ppt, a result
of heavy input from local runoff and the flooding Mississippi
River.  During this period there is little exchange between
surface and bottom waters.

     Surface and bottom salinities usually increase in an
offshore direction.  Mean surface salinities in near off-
shore waters do not vary significantly from surface salini-
ties far offshore; they are approximately 19 ppt. However,
mean near offshore bottom salinities average 25.6 ppt, a
value notably lower than far offshore bottom salinities.  At
certain times of the year offshore waters are highly diluted
and salinity increases in a shoreward direction.  This
occurs when the Mississippi River is in a flood stage and
near offshore surface currents flow to the west, or when
strong north winds push brackish waters out of the bays.


     A. 3 . 3 .5  Turbidity53

     Turbidity of offshore Gulf waters is strongly influ-
enced by the magnitude and turbidity of Mississippi River
discharge, by local freshwater discharge, and by current
patterns carrying this flow.  Turbidity is greatest in
shallow waters and areas closest to shore.  Near offshore
stations exhibit visibility ranging from 1.5 to 21 feet
       G.M. Griffin and B.J. Ripy, "Turbidity, Suspended
Sediment Concentrations, Clay Mineralogy of Suspended Sedi-
ments and the Origin of the Turbid Near-Bottom Water Layer,
Louisiana Shelf South of Timbalier Bay," in Offshore Ecology
Investigation  (Galveston, Texas:  Gulf Universities Research
Consortium, May 1974).
                            -288-

-------
with far offshore visibility ranging from 3.5 to 50 feet.
Surface turbidity is highest in May, June, and February, and
lowest in September and March.

     During most of the year a very turbid layer of water is
found near the shelf floor, though it varies seasonally in
thickness and concentration.  The sediments of this turbid
bottom layer have a clay mineral composition identical to
the suspended sediments of the Mississippi River.  During
spring flooding the suspended sediment of the entire water
column bears this same composition.  The turbid bottom layer
is associated with low dissolved oxygen concentrations which
drop further in summer.


                                54
     A.3.3.6  Sediment Chemistry

     Offshore sediments originate from the Mississippi
River, estuarine marshlands and settling silaceous and
calcareous organisms living in Gulf waters.  The sediments
contain high levels of organic materials, associated heavy
metals, and nutrients.

     Nutrient concentrations in sediments seem to be five to
eight times as high as the adjacent water column.  They also
seem to decrease further offshore.  Nitrogen (nitrite plus
nitrate) averages 0.5 to 0.6 ppm and total phosphorus
averages 2.2 to 2.3 ppm.  Hydrocarbon content in sediment
ranges from 3.4 to 19.7 ppm.  Biological Oxygen Demand
ranges from 100 to 740 mg/kg  (40 percent of total OD)  and
decreases with distance offshore.  COD ranges from 14,700 to
21,000 mg/kg and decreases with increased water depth.
Heavy metal values are summarized in Table A-15.  No distinct
trends are observable in metal content relative to depth,
season or distance offshore.


     A.3.3.7  Water Chemistry

     Oxygen, nutrients, and metals are key parameters in
determining the chemical nature of a water body, and the
     54
       Gosselink, Miller, Hood, and Bahr, Louisiana Offshore
Oil Port, Appendix V.

       Gosselink, Miller, Hood, and Bahr, Louisiana Offshore
Oil Port, Appendix V; and Ho and Barrett, Distribution of
Nutrients in Louisiana Coastal Waters.
                            -289-

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                          TABLE  A-15
         GULF  WATERS  -  HYDROCARBON AND METAL CONTENT
                         SEDIMENTS
                           (ppm)
                    WATER
                    (ppb)
 HYDROCARBONS

 HEAVY  METALS
3.4 - 19.7
18 - 64
Cd ND -
Cr ND -
Cu 1.2 -
Fe 1430 -
Pb 5.1 -
Mn 17.5 -
Hg (ppb) 0.0061 -
Ni 2.3 -
Zn 10.1 -
V 28 -
1.5
39.6
8.7
5100
92.8
247
0.0417
57.9
39.9
79
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
0.22 -
0.22 -
ND -
ND -
ND -
ND -

3.1 (surface)
2.8 (bottom)
55.3
29.0
5.7
15.1
18.2
14.2
36.7
26.7
6.8
7.6
1.36
1.14
5.2
22.1
17.0
32.8

     ND = not detectable.

     Source:  J.G. Gosselink, R.R. Miller, M. Hood, and
L.M. Bahr, Jr., Louisiana Offshore Oil Port:  Environmental
Baseline Study, Appendix V (Baton Rouge:  Louisiana State
University, Center for Wetland Resources, 1975).
                            -290-

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type of life it can support.  Often the levels of these
constituents vary spatially with depth or distance from
shore, or temporally with season.

     Surface and bottom concentrations of dissolved oxygen
reflect seasonal trends in temperature, mixing, salinity,
respiration, decomposition and photosynthesis.  High DO
levels are found in conditions of low temperature, high wave
turbulence, low salinity and high photosynthetic rates.

     Surface dissolved oxygen ranges from 6 ppm in summer to
10 ppm in winter.  While cold water and winter storms
increase the probability that surface waters will become
supersaturated with oxygen, uptake by organisms will have
little effect on surface DO levels because oxygen can be
easily replenished at the air/sea interface.

     Bottom dissolved oxygen has greater seasonal variations,
ranging from 1.1 ppm in summer to 7.5 ppm in winter, with an
annual average of 2 ppm in far offshore waters.  Near off-
shore waters have somewhat higher levels with an annual mean
of 3.4 ppm.  A large portion of the bottom waters both near
and far offshore are anoxic (0 to 2 ppm DO) during the
warmer months of the year.  This is thought to be associated
with a turbid bottom layer and high BOD.

     Nitrogen, measured as nitrate plus nitrite, averages
0.14 ppm in offshore waters.  Nitrogen content remains
constant with depths but has higher values in summer months
and in areas further offshore.

     Total phosphorus averages 0.33 ppm with levels slightly
higher in surface waters.  Means of surface, mid-depth and
bottom waters average 0.35, 0.31 and 0.30 ppm, respectively.
Highest surface and mid-depth values are found in winter
months.  Phosphorus levels seem to be a function of salinity
and Mississippi River discharge.

     Mean organic carbon content of near offshore waters is
5 mg/1, while more open Gulf waters average 1.5 to 2.0 mg/1.
High organic content of offshore waters may be contributed
by the Mississippi River plume, detritus exported from the
southern Louisiana salt marshes, and the oil industry.

     Heavy metal concentrations are presented in Table A-15.
All levels are normal for coastal water with the exception
of mercury which is unusually high.
                             -291-

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     A.3.3.8  Gulf Biology56

     The Gulf of Mexico waters adjacent to Barataria Bay
yield extremely high catches of commercially important fish
and shellfish.  This high faunal productivity is attributable
to elevated nutrient levels, resulting from export of
primary production from adjacent wetlands to the Gulf via
waterways draining the coastal system, and from organic
matter carried in the Mississippi plume.  It has also been
suggested that the productiveness of these fisheries par-
tially results from entrapment of offshore marine animals,
which are prevented from eastward migration by the fresh-
water Mississippi discharge and by the extension of the
modern delta  (which narrows the adjacent shelf area).

     Primary production in offshore waters is almost en-
tirely planktonic.  Diatoms, dinoflagellates and nanno and
ultra-plankton are the dominant phytoplankton forms.
Macrophytes are found only on man-made structures such as
oil platforms.  Table A-16 lists major primary producers in
offshore waters.  Planktonic productivity (both phyto- and
zooplankton) is greatest in near offshore waters and de-
creases further offshore along a gradient of decreasing
organic content in the water column.

     Herbivores play a more significant trophic role in
offshore energy transport than they do in the wetlands.
Acartia tonsa and Paracalanus sp. feed on huge amounts of
phytoplankton and particulate detritus, forming a major link
between primary production and higher trophic levels in the
offshore ecosystem.  Despite the high level of grazing,
detritivores still form a key part of the offshore community.
The benthic macrofauna, which are an important food source
for bottom feeding nekton such as flounders, silversides,
spot, and croakers, are dependent on a continual rain of
detritus from the euphotic zone above.  These benthic filter
and deposit feeders include clams, polychaetes, sand dollars,
sea cucumbers, brittle stars, bryozoans, sponges, barnacles
and mussels.  Mud crabs, mud snails and amphipods are motile
forms which scrape detritus from the surface of the ocean
     56
       Fred Dunham, A Study of Important Estuarine Dependent
Fishes, Technical Bulletin No. 4  (New Orleans:  Louisiana
Wildlife and Fisheries Commission, Oyster, Water Bottoms
and Seafood Division, 1972); and Gosselink, Miller, Hood,
and Bahr, Louisiana Offshore Oil Port.
                             -292-

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                     TABLE A-16
         PRIMARY  PRODUCERS -  GULF WATERS
               NEAR AND  FAR OFFSHORE
  DIATOMS
DINOFLAGELLATES
Asterinella
Biddulphia
Coscinodiscus
Cyclotella
Lithodesmium
Navicula
Pleurosigma
Surirella
Stauroneis
Thallasiosira
Fragilaria
Rhizosolenia
  Ceratium
  Exuviaella
  Gonyaulaux
  Gymnodinium
  Peridinium
                         -293-

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floor.  Smaller meiofauna such as nematodes, cilliate proto-
zoa, and microbes are also important detrivores.  Detriti-
vorous finfish include menhaden, mullet, anchovy, croakers,
silversides and threadfins.   These fish feed indiscriminately
on detritus in offshore waters as adults; however, they seem
to be much more selective, searching out specific zooplankton
forms, during the larval and juvenile stages of their life
cycle.

     Many of the offshore predators are the same predators
found in the salt marsh estuaries.  In fact most of these
species are hatched offshore and migrate into the estuary
during their greatest growth periods, to take advantage of
the abundant food supply present.  Offshore predators
include spotted sea trout, red and black drum, red snapper,
flounder, and blue marlin.  Invertebrates such as shrimp,
starfish and boring snails prey on benthic organisms.
Predatory birds feeding offshore include the laughing gull,
ring billed gull, herring gull, frigate birds and brown
pelicans.  The only mammal found in this offshore environ-
ment is the bottlenosed dolphin.  Table A-17 presents the
key consumer species in the ecosystem offshore of Barataria
Bay.  These species were selected for their commercial
importance, abundant numbers, or endangered-species status.
                             -294-

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                                                     TABLE  A-17
                    KEY  CONSUMERS   -  NEAR AND  FAR  OFFSHORE  GULF  WATERS
                              (ADJACENT TO  BARATARIA BAY,  LOUISIANA)
                     INVERTEBRATE
                                                       FISH
                                                                                   BIRD
                                                                                                             MAMMALS
COMMERCIAL
SPECIES
 * Penaeus  aztecus
   (Brown Shrimp)

 ir Penaeus  setiferus
   (White Shrimp)

 * Penaeus  durorarn.il
   (Pink Shrimp)

rif Callinectes sapidis
   (Blue Crab)
if if Anchoa mxtchilli
    (Bay Anchovy)
                                             if Cynoscion arenanus
                                               (Sand Sea Trout)

                                             ir Peprilus burti
                                               (Gulf Butterfish)
                                               Etropus crassostus
                                               (Fringed Flounder)
SPORT  SPECIES
                                             if Centropistes  philadelphica
                                               (Rock Sea Bass)

                                             if Tnchiurus lepturus
                                               (Cutlass Fish]

                                             if Leiostorous xanthurus
                                               (Spot)

                                           if it Arius felis
                                               (Sea Catfish)

                                           ir ir Micropogon undulatos
                                               (Atlantic Croaker)

                                             ifChloroscombrus chrysurus
                                               (Atlantic Bumper)
TROPHICALLY
IMPORTANT
SPECIES
                  • *
   Gamma rus sp.
    (Amphipod)

   Acartxa tonsa
    (Copepod)
                  • ir Paracalanus sp.
                      (Copepod)

                    ir Xiphopenaeus sp.
                      (Sea Bob)

                    ir Sguilla  sp.
                      (Mantis  Shrimp)

                  • •* Mulina SB.
                      (Pelacypod)

                  irir Cibanarius vittatus
                      (Hermit Crab)

                      Loliguncula brevis
                      (Squid)
    Prionotus roseus
    (Blue Spotted Sea Robin)
•ft Sterna sp.
  (Tern)

•{f Aytha affinis
  (Lesser Scaup)

•fr Larus atricillia
  (Laughing Gull)

if Fregata magnif icens
  (Frigate Bird)

if Larus Philadelphia
  (Bonaparte's gull)
if Tursiops truncatus
  (Bottlenose Dolphin)
ENDANGERED
SPECIES
                                                             Pelecanus occientalis
                                                             (Brown Pelicaji)
     * Detritivore

     ir Carnivore

     • Herbivore
                                                         -295-

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                         APPENDIX B
              DESCRIPTION OF DISPERSION MODELS
B. 1  Introduction

     Oilfield brines, once discharged into the receiving
waterbody, are subjected to the processes of dilution,
transport, and diffusion which play a very important role in
determining the distribution of pollutant concentrations.
Since the impact exerted on the marine environment by the
brine discharge depends in large part on the concentration
distributions of the discharged contaminants in the receiv-
ing waters, it is of great importance to understand and
predict the physical dispersion processes which determine
these distribution patterns.  The purpose of this appendix
is to discuss the principles of dispersion modeling and the
models used in this study to estimate the dispersion of the
discharged brine.  The simplest type of calculation, the
tidal prism flushing model, is discussed in Section B.2.
This model is useful for giving the average concentration of
a pollutant in a small bay area but cannot give any infor-
mation regarding concentration contours.  Section B.3
treats the basic ideas and principles involved in modeling
eddy diffusion.  These principles are then applied in
Section B.4 to an analysis of the problem of the dispersion
of a pollutant in a steady uniform current in one direction.
The final section discusses the computerized diffusion model
used in this study to predict concentration contours.  This
model is capable of incorporating three-dimensional diffu-
sion as well as time varying tidal currents which play a key
role in estuarine dispersion.
B.2  Simple Tidal Flushing Calculations for Shallow,
     Enclosed Bays

     Pollutants introduced into an estuary are flushed out
over a period of time by the combined actions of seaward
river flow and mixing at high tides followed by tidal
outflow.  The residence time of estuarine pollutants is
highly dependent on the overall rate at which this  flushing
occurs.  Therefore, one important indicator of the  ability
of an estuary to rid itself of pollutant discharges —
especially if they are conservative — is the flushing time,
or the length of time required for the river flow and tides
to flush an amount of water equal to the low tide volume of
                             -297-

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the estuary.  For very large estuaries or those which have
complicated geometries the flushing time is quite difficult
to compute; however, for small estuaries or rough calcula-
tions, a relatively simple method has been developed to make
reasonable estimates of the length of time, measured in
units of tidal periods, needed to replace the estuary
volume.

     Such calculations are useful for two reasons.  First,
they can be used to gain a rough idea of the length of time
it takes an estuary to rid itself of oilfield brine pollu-
tants dissolved in the water column.  Second, in the case of
continuous discharges, they can be used to determine the
steady state concentrations of those pollutants.  This
second reason is an important one, for the computer model
described in Section B.5, used to determine concentration
profiles around the discharge points, is not capable of
accounting for more than one straight-line boundary of an
estuary.  The rougher, less sophisticated calculations
described below in this section can be used to supplement
the predictions of the computer model in small, enclosed
bays by supplying order-of-magnitude estimates of the
average background levels of discharged pollutants.  These
estimates are not only useful in their own right but can
also serve as checks on the reasonableness of the results
obtained from the computer model.

     The simplest version of the method to be discussed is
based on the fairly crude assumption that the total volume
of water entering the estuary between low and high tides
(incoming river water plus incoming seawater) becomes
thoroughly mixed with the low tide volume before the ebb
tide begins.  On the basis of this assumption, the fraction
of the low tide estuary volume  ("old water") flowing seaward
during the ebb tide can be computed.  In particular, if V is
the low tide volume of the estuary and P is the volume
entering between low  and high tides  (called the tidal
prism), then V + P is the volume of the estuary at high
tide.  Since the tidal prism P is carried away on the next
ebb flow and since the total high tide volume is assumed to
be thoroughly mixed,  the fraction of the volume V of old
water carried away per tidal period is P/(V + P).  The
number T of tidal periods needed to flush out all of the old
water is just the inverse of this fraction:
                            -298-

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This number is a first estimate of the flushing time.

     As ought to be expected, this simple-minded method
generally yields shorter-than-realistic flushing times for
most types of estuaries.2  For most real estuaries, complete
mixing during high tide does not occur, and the ebb tide
does not always carry waters near the head of the estuary
all the way past the mouth and into the open sea.

     Despite this drawback, the approach leads to an equa-
tion relating the low-tide, steady-state concentration of a
given contaminant to the amount of pollutant discharged into
an estuary.  For simplicity we will assume that all of the
discharge occurs between low tide and the following high
tide.  Let the concentration of the contaminant at low tide
(ambient concentration) be CL and its concentration in the
discharge stream be CD in a total volume VD of discharge in
one tidal cycle.  Then the quantity of contaminant present
at low tide is VC^, and the quantity present at high tide is
VCL + VDCD.  From the discussion above, the quantity of
contaminant removed during each ebb tide is
               Q  =
                    V + P
     (VC
VDCD)
Since the concentration is assumed to be at a steady state,
Q_ must equal the amount of contaminant Q+ = V^C^ added per
tidal cycle.  Hence
(VC
                                  = VD
Solving for C-, the steady-state low tide concentration,
gives
                                                      (B-l)
     Hackberry Bay, 29°14', 90°15'  (see Figure B-l) in the
northwest corner of Barataria Bay, Louisiana, provides a
      F.F. Wright, Estuarine Oceanography, Council Education
in the Geological Sciences Publication No. 18  (New York:
McGraw-Hill Inc., 1974), pp. 28-33; and K.R. Dyer, Estuaries;
A Physical Introduction  (London:  John Wiley and Sons, 1973),
pp. 109-114.
     2
      Dyer, Estuaries:  A Physical Introduction, pp. 109-114.
                            -299-

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    HACKSERRY BAY
                                               FRESH MARSH
                                                (0-5 ppt.)
                                               SALT MARSH
                                               (14-30 ppt.)
Figure B-l.   Location of Hackberry  Bay study area.
                         -300-

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good example of the kind of bay for which this approach can
be useful.  It harbors Texaco1s Bay de Chene oilfield, the
site of the largest brine discharge (Vp = 9,747 m3 per tidal
period) in Barataria Bay.  The average tide height in Bara-
taria Bay3 is 0.3 m; if we assume this datum for Hackberry
Bay our estimate of CL is likely to be slightly low, since
the smaller bay probably experiences less extreme tides than
the larger one.  This tide height multiplied by the surface,
area of Hackberry Bay of 1.77 x lO^m2 gives P = 5.33 x 106m ;
if the tide height is 0.1 m, P = 1.78 x 106.  By (B-l),
assuming 0.3 m tides gives

                    CL = 1.8 x 10~3 CD


assuming 0.1 m tides gives


                    CT = 5.5 x 10~3 Cn
                     Li               LJ

Table B-l shows the computed dilution factors for Hackberry
Bay and two other enclosed discharge sites  (the Lake
Washington field operated by Texaco and Exxon and Getty's
Manila Village field in Mud Lake.

     It is important to emphasize that these results have
considerable limitations.  To begin with, the methodology is
based on the assumption that complete mixing occurs during
the flood tide, an approximation which can be used reasonably
only for relatively small, shallow bays like the three
treated above.  Thus no attempt is made to reproduce the
concentration isopleths, in direct contrast to the computer
model.  The implicit assumption that the surface area of a
natural body of water remains constant over a tidal cycle
introduces yet another source of error.  Another underlying
assumption in these calculations is that the concentrations
of pollutants are at a steady state.  While this may be true
over short time intervals or in a time-averaged sense,
seasonal and even weekly variations in the tides and river
inflow may cause significant discrepancies between the
computed concentrations and observed values of background
concentrations.  The method is valid as a means of arriving
at an order of magnitude approximation to the average back-
ground concentrations of contaminants in relatively small,
shallow estuarine bays.
      Barney Barrett, Cooperative Gulf of Mexico Estuarine
Inventory and Study, Louisiana, Phase II Hydrology, and
Phase III Sedimentology (New Orleans:  Louisiana Wildlife
and Fisheries Commission,  1971), p. 55.
                            -301-

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                                              TABLE B-l
                     COMPUTED FLUSHING  TIMES  AND STEADY STATE DILUTION FACTORS

                        FOR OIL FIELD BRINE DISCHARGES IN BARATARIA BAY
NAME OF BAY
HACKBERRY BAY
LAKE WASHINGTON
MUD LAKE
V AREA VD
(M3) (M2) (M3)
l.SOxlO7 1.78xl07 9,747
2. 64x1 O6 5. 78x1 O6 508
1.47xl06 3.22xl06 368
T
(TIDAL PERIODS)
8.30
3.43
5.57
2.52
5.57
2.52
DILUTION TIDAL
FACTOR HEIGHT
5.5xlO"3 .1M
1.8xlO"3 .3M
8.8xlO"4 .1M
2.9xlO"4 .3M
l.lxlO"3 .1M
3.6xlO"4 .3M
I
OJ
O
to
I

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B.3  General Fluid-Dynamic Considerations for Open Bodies
     of Water

     The assumption of uniform mixing employed in the tidal
flushing calculations described in Section B.2 rules out the
possibility of predicting concentrations contours around the
discharge point since averaging pollutant concentrations
over the entire receiving waterbody volume does not give any
information concerning concentration gradients.  For large
bays and estuaries, especially, uniform mixing is not a
reasonable or useful assumption, since the averaging process
will effectively mask the existence of localized areas of
relatively high concentrations.  The impact resulting from
brine discharges depends on the extent to which regions in
the receiving waterbody are subjected to particular levels
of pollutant concentration, and these pollutant concentration
levels vary with distance from the brine discharge sites.
The prediction of pollutant concentration contours requires
a level of modeling more sophisticated than that of the tidal
flushing model.  A very useful approach to the problem of
predicting pollutant concentrations in the receiving water-
body is to apply the physics of fluid dynamics to modeling
the actual diffusion process responsible for the dispersion
of concentrated effluents.  This kind of analysis yields
concentration distributions instead of averages.  Thus,
diffusion modeling generates a more desirable  (i.e., more
informative) type of output than the tidal flushing calcula-
tions, provided the former is applied in a regime where it
is valid.  Large bays are valid regimes because there is room
enough for a variety of current scales — a condition which,
as will be explained, is essential to the estimation of a
natural diffusion rate.

     The problem of interest here is what happens to a
parcel of brine containing pollutants when it is subjected
to a field of currents in an estuary.  Where does it go?
How fast is it diluted?  What area contains concentrations
which are worthy of concern?  To answer these questions, it
is necessary to analyze the actual current fields themselves.
Water currents can be examined at various scales, and the
scale chosen determines to what extent the curvature of the
streamlines, or directions of fluid flow, is significant.
Since logically one chooses the scale of analysis to fit the
size of the pollutant stream, which is constantly expanding,
it is necessary to consider several different ways of viewing
currents.

     If the scale is small compared to the streamline curva-
ture, i.e., if the pollution stream is small compared to the
                             -303-

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distance over which the current remains relatively uniform,
then the current will not disperse the pollutants very much.
Rather, it will tend to carry them more or less intact along
the overall direction of flow.  This situation, illustrated
in Figure B-2, is often described by saying that the charac-
teristic eddy of the current is much larger than the pollu-
tant stream, and the resulting transport is called advection.

     On the other hand, if the characteristic eddy is
smaller than the pollutant stream, the pollutants will be
subject to several different directions of flow over any
small period of time.  The resulting transport pattern,
illustrated in Figure B-3, tends to disperse the pollutant
parcel.  This situation is often described by saying that
turbulent flow causes more pronounced diffusion of the
pollutant stream.   (The reason for the adjectives "more
pronounced" is that diffusion occurs on a molecular scale,
independent of any observable fluid flow.  The component of
diffusion attributable to turbulence is usually called "eddy
diffusion.")

     Modeling this process of diffusion offers a convenient
framework in which to analyze the tendency of pollutant
streams to spread out after they enter the receiving water.
Pollutant streams are characterized by a range of concentra-
tions strewn about a volume of water in some fashion.  For a
given stream, the function c(x,y,z) expressing the concen-
tration at each point  (x,y,z) in the volume defines a
distribution of the pollutant; the degree to which such a
distribution is spread out in any direction (say y) is
measured by the variance,

                           /oo
                            y2d(x,y,z) dy              (B-2)
                          -00

For a diffusing pollutant stream, the distribution is
continually spreading, so that the variance increases with
time.  The rate of this increase indicates the rate of
diffusion, so that a very large part of the task of charac-
terizing a diffusion process is accomplished by defining a
diffusion coefficient E in terms of the time rate of change
in the variance  (spatial spreading) of the pollutant stream:
     4
      Frank D. Masch, "Mixing and Dispersion of Wastes by
Wind and Wave Action," in Advances in Water Pollution Research,
ed. by E.A. Pearson  (New York:  Pergamon Press, 1964), p.  146.
                            -304-

-------
o
Cn
I
                                                                  current streamlines
                         Figure  B-2.   Advection due to uniform,  steady flow.

-------
 I
(jj
o
en
 I
                                                                   current streamlines
                      Figure B-3.  Diffusion due to turbulent  flow.

-------
                    E - £ It (a2)                       (B-3)

Notice that E has the dimensions of area/time.  The reason
for the factor 1/2 is that the variance a2 measures spatial
spreading in both the positive and negative directions
relative to the center of mass of the pollutant stream,
whereas it is customary in discussing diffusion mechanics to
measure dispersion in a given direction in terms of the
positive spreading only.

     The analysis is complicated by the experimental fact
that the spreading rate (d/dt)(a2) of pollutant streams in
natural waters increases as the diffusion process progresses.
In other words, as the scale of the pollutant stream in-
creases because of diffusion, the rate at which further
diffusion occurs also increases, causing more and more rapid
dispersal.  This observation can be explained in terms of
the turbulent effects discussed above.  When a pollutant
stream is small in scale, only currents with comparatively
small characteristic eddies can be considered turbulent with
respect to the stream.  Two representative particles moving
in such an eddy will tend to have very similar trajectories
because of their proximity to each other, so that they will
not be separated quickly at this small scale.  As the scale
increases, the degree to which the motions of two represen-
tative pollutant particles are correlated diminishes,
resulting in a more rapid overall rate of separation.^
Therefore, the eddy diffusion coefficient E is a function of
the scale (i.e., the largest dimension) L of the parcel
formed by the pollutant stream.  Empirical studies have
found that a reasonably accurate expression for the depen-
dence of E on L is given by a power law such as


                         E = aL4/3                      (B-4)

where a is an empirically determined constant.

     Several observations about Equation  (B-4) deserve some
attention.  To begin with, there remains considerable contro-
versy over the accuracy to which eddy diffusion coefficients
can be evaluated.  It is likely that different flow and
depth regimes are best characterized by different diffusion
      Henry Stommel, "Horizontal Diffusion Due to Ocean
Turbulence," Journal of Marine Research 8  (1949): 199-225.
                             -307-

-------
laws.  The 4/3 law in (B-4) fits data for ocean regimes sum-
marized by Pearson^ and has been used in many investigations
of ocean diffusion.

     The second observation is that eddy diffusion, as
defined by (B-4), is nothing more than a sort of statistical
construct devised to alleviate the difficulties encountered
in solving differential equations for complicated velocity
fields.  Analysis at the microscopic scale would involve a
set of equations of motion tracing the path of each minute
parcel of the pollutant as it moved through a current field
which varied both spatially and temporally in a complicated
and irregular way.  Such problems are hopelessly intractable.
The saner approach normally taken for eddy diffusion is to
view the background current field from a macroscopic stand-
point, taking into explicit account only the major features
of speed and direction of the flow.  So that the important
dispersing effect of the irregular details  (turbulence) of
the current fields is not thereby ignored, it is modeled by
lumping all of the eddy-diffusive flow characteristics into
a single factor representing, in a sense, their aggregate
effect on the pollutant stream.  This factor is the non-
molecular diffusive component of the eddy diffusion law
given in  (B-4).  The justification for the form of such a
simplifying assumption must be provided by actual empirical
studies verifying that the hypothetical law accurately
models the measurable behavior of dispersing pollutant
particles in real bodies of water.

     This last point is related tOythe third observation
regarding Equation  (B-4).  Stommel  and others have empha-
sized two approaches to eddy diffusion laws, one "inductive"
(empirical) and the other  "deductive"  (analytical or theore-
tical) .  The inductive approach consists in observing the
scale dependence of the diffusion rate and then calculating
the functional form of this dependence on the basis of field
measurements.  The deductive approach consists in deriving
the functional form from one or more diffusion theories from
physics.  Stommel, for example, demonstrates the derivation
of a 4/3 law from both the Weisaecker-Heisenberg postulates
      N.H. Pearson, An Investigation of the Efficacy of Sub-
marine Outfall Disposal of Sewage and Sludge, No. 14, State
Water Pollution Control Board Publication, Sacramento, Cali-
fornia, 1956.

      Stommel, "Horizontal Diffusion," pp. 199-225.
                             -308-

-------
and the Kolmogoroff postulates.  He cautions, however, that
the empirical approach possesses a more solid foundation in
fact, whereas the theoretical considerations are more useful
in finding an explanation of observed diffusion phenomena in
terms of more fundamental physical laws.  This caveat is
important in light of the fact that several successful
studies of eddy diffusion have deviated from the 4/3 law,
reflecting the view that empirical description, rather than
theoretical explanation, is the overriding concern of
engineering modeling studies.

     The next step in modeling ocean diffusion is to produce
a mathematical expression of the physical relationships
which govern the process.  The basic principle behind dif-
fusion mechanics is that the mass of the pollutant must be
conserved in the absence of decay.  The simplest situation
in which this principle can be applied is also perhaps the
most illustrative:  it concerns the lateral diffusion of
pollutants in a longitudinal current field which is uniform,
i.e., horizontal diffusion perpendicular to the direction of
current flow.  Implicit in this statement of the problem is
the assumption that it is in fact realistic to absorb the
turbulent, non-advective velocity components of the flow
into the eddy diffusion coefficient, leaving explicit only
the hypothesized steady and uniform component.  It should be
noted also that the problem as stated ignores diffusion in
the direction of flow and vertical diffusion through the
water column.

     The conservation of mass for this problem means that
the time rate of change of the pollutant concentration
around every point (x,y) must be accounted for completely by
variations in< the net flux of concentration into or out of
the volume element containing  (x,y).  In mathematical
language,


          oT = ly  (E ff> = ly   [flux in the y direction]

Expanding the total time derivative of the concentration
(left side) using the chain rule gives
          3t   8t 8x   8t 3y   3y    8y

But the problem as stated indicates no explicit dependence
of c on the time  (although there is implicit dependence,
since diffusion depends directly on distance traveled, which
in turn depends on time); also, the axes have been chosen so
that there is no component of the current velocity lying in
                            -309-

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the y direction.  The first of these considerations forces
3c/3t = 0; the second implies 3y/3t =0.  By hypothesis, the
velocity of pollutants in the x direction (i.e., 3x/9t) is
the current speed U.  All of these observations reduce the
equation to


                    0 If - k                    (E-5)

The term on the left in (B-5) represents the advective
transport of the concentration gradient along the x-direction;
the term on the right represents the local spatial variation
of the concentration flux in the lateral (y) direction.
This equation, along with its higher-dimensional analogues,
serves as the basis for the plume model.


B.4  Plume Dispersion in a Steady Uniform Current

     The model to be described in this section is an analy-
tical method for predicting the dispersion of a pollutant
plume in a steady uniform current.  This model is applicable
to situations in which tidal current oscillation can be
neglected compared to a steady current flow in a specified
direction.  The model is thus suitable for simulating  the
dispersion of brine that is discharged into waters in  the
Gulf of Mexico sufficiently far offshore so that tidal
currents are insignificant.  For the Louisiana bay area or
for Cook Inlet, where tidal currents play an important role
in the dispersion of discharge, a model that can incorporate
temporal variation of current is needed.  Such a model will
be discussed in Section B.5.

     The problem analyzed in some detail below is shown in
Figure B-4.  The method used here is essentially that  of
Brooks.   A discharge orifice width  (diameter) b is located
at x=0 in a constant ocean current U in the x-direction.
After the initial concentration CQ of the pollutants has
been established just beyond the point of discharge, the
pollutant stream is swept downstream with the current  speed
U.  As it travels, dispersion in the y-direction occurs, so
that the scale L of the pollutant stream increases with
     Q
      N.H. Brooks,  "Diffusion of Sewage Effluent  in an Ocean-
current," Proceedings of the First International  Conference
on Waste Disposal in the Marine Environment held  at the
University of California, Berkeley, July  22-25, 1959, ed. by
E.A. Pearson  (New York:  Pergamon Press,  1959), pp. 246-267.
                            -310-

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Ocean Current
         Discharge
         Orifice
                                        c(x,y)
                                                    T
                           Initial
                           Concentration
                           co
       Figure B-4.   Lateral  diffusion from discharge  in a steady,
  uniform current field U.

-------
increasing x.  The concentration of pollutant at any point
(x,y)  in the plane will be denoted by c(x,y) and, from the
discussion above, will be governed by (B-5) along with the
appropriate boundary conditions at the point of discharge
(x = 0) :

     1.   If |y| < b/2  then  c(0,y) = CQ   [the initial
                                           concentration]

     2.   If |y| >_ b/2  then  c(0,y) = 0

The following assumptions are necessary to simplify the
analysis:

     1.   There is no variation in the vertical direction.
          This assumption limits the applicability of the
          model to the cases of (1) uniform mixing through-
          out the water column, and  (2)  no vertical mixing
          (as a result, for example, of a pronounced density
          stratification not uncommon in estuaries) in which
          case the analysis can be applied to the dispersion
          of a pollutant in a particular layer of the water
          column.

     2.   Diffusion in the direction of the current  (the
          x-direction) is negligible compared to the current-
          induced advection.

     3.   U is constant in time and uniform, so that the
          diffusive effects of all eddy currents are ac-
          counted for by the diffusion coefficient E.  This
          assumption has the effect of limiting the validity
          of the analysis to a region within which the
          instantaneous spatial variations of current speed
          and direction are small.

     4.   The diffusion coefficient depends spatially only
          on the scale of the pollutant stream, which in
          turn is a function of the distance x over which
          the current  (including turbulence) has had a
          chance to disperse the stream.

The fourth assumption allows an immediate  simplification of
equation  (B-5):  spatially, E is a  function only of x, so


                    E(x) L-| = u ||                    (B-6)
                         9y
                            -312-

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This is very nearly the form of a classical partial differ-
ential equation known as the heat equation, except that E is
a nonconstant function of x.  Since the heat equation has
been solved for a multitude of problems, it is advantageous
to manipulate (B-6) until it can be solved via the simpler
equation.

     To begin with, define EQ to be the value of E(x) when
x = 0, so that

                    E(x) = EQ f(x)
and therefore Equation  (B-6) can be written
                    E
  iJE.
0 , 2
  3y
   U   9c
  f(x)  3x
(B-7)
From here it is a relatively easy matter to "hide" the
x-dependence in the coefficient on the right hand side
behind a change of variables:  define a new "diffusion
distance" £ by
 •L
                          x
f (w)  dw
                                                        (B-8)
Then
By the chain rule,  (B-7) can be written in terms of E, as a
heat equation:
                    ,
                    By
                          U_
                          E,
                                  (B-9)
The solution to this equation has been derived many times;
Carslaw and Jaeger's volume is almost entirely concerned
with it.  The solution which fits boundary conditions  (a)
and (b) is a form of Laplace's solution for an infinite
solid^  (see the supplement to this appendix):
      H.S. Carslaw and J.C. Jaeger, Conduction of Heat in
Solids  (London:  Oxford University Press, 1959), pp. 53-56,
                            -313-

-------
                           b2
                                 - erf
                                                        (B-10)
     At this point it is useful to clear up a question
regarding the scale parameter L.  Since the extent of the
nonzero portion of c is infinite in both the positive and
negative directions for all x > 0, it is pointless to .define
L as the boundary of the nonzero concentration.  Rather, L
will have to be defined in terms of the width parameter
defined for the concentration distribution by Equation  (B-2).
Thus L will establish the boundary defined by the distribu-
tion of a certain percentage of the pollutants clustering
around the line of greatest concentration, y = 0.  For
convenience, L might as well be chosen so that it will equal
b at x = 0.  At this point, Equation  (B-2) reduces to
                  y^» —OO

     a (0) = -~ /   y2c(0,y)dy =
             cnD J~*
                     b/2
                        \
                    -b/2'
                                             C0dy = 12"
                                               u     L
Hence,
                    a(0) =
                           2/3
So the
       expression L = 2/3~ satisfies the stipulation L(0) = b.

     The relationship between L and a can be used to deter-
mine £ as a definite function of x, which is precisely  the
information needed to convert  (B-9) and  (B-10) to a solution
c(x,y).  Recalling the definition of the diffusion coef-
ficient E,  (B-3) yields
                   Id   ,2. _  1 d   /L2
                 -"2dT(a) *  2" 3t  \I2
An appeal to the chain rule converts  the  time  derivative to
the x-derivative :
24
                              if
                                    3* fx
since the speed dx/dt of  the pollutant  stream is  assumed to
be the current speed U.   Differentiating  L^  then  gives
                    „,  .    UL dL
                    E(x) =  12 dlT
                             -314-

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But the function f(x) defining the relationship between  x
and £ is just E(X)/EQ, and from Equation  (B-4)
                    E(x) _ FL(x)l
                         "     -
                                 .4/3
Hence,
                       4/3
                              UL  dL
                             12EQ dx
i.e. ,
dL
dx"
                          12EOVL\1/3
                                                        (B-ll)
This equation is a version of Bernoulli's equation,  and  its
solution  (see the supplement to this appendix)  is:
                            3/2
                   12E
                                           0
                        3b
                    Ub
This solution indicates that the functional  relationship
between £ and x is determined by
                    f(x) =
                              4/3
              = 1 +
2Bx
3b
Now the solution to the diffusion equation given  in  (B-ll)
may be evaluated in terms of x instead of £, using the
relationship  (B-8) to get
                    i - JL.
                    b   26
                                    (B-12)
The final solution, therefore, may be summarized  as  follows:
          c,x,y, .
where
                         Y =
  being given by  (B-12)
                            -315-

-------
     The value of this analysis is threefold.  To begin
with, the results given in (B-9) in combination with  (B-12)
are applicable to far-offshore discharges into an approxi-
mately steady, uniform current regime.  Second, the numeri-
cal values obtained for special problems by using (B-9) and
(B-12) can be used to check the computer program used to
solve the more complicated three-dimensional diffusion
problem encountered for nearshore discharges.  Third,
several qualitative conclusions may be drawn from the
foregoing analysis regarding the nature of the concentration
distribution.  Among these are:

     1.   The diffusion equation for ocean dispersion can
          be solved as a modified form of the classical heat
          equation.  The solution indicates, that after the
          initial concentration at the discharge point has
          been established, pollutants are distributed in
          the lateral direction according to an expression
          involving the error function.  This distribution
          spreads as the pollutants travel downstream.

     2.   The scale of the pollutant stream, measured in
          terms of the variance of its spatial distribution,
          expands slightly faster than the 3/2 power of the
          distance travelled  (see Figure B-5) .

     3.   As a result of the spreading, the concentration at
          the center of the pollutant stream decreases as
          the stream travels, approaching zero asymptotic-
          ally with increasing distance from the discharge
          point  (see Figure B-6) .
B. 5  Plume Dispersion in an Unsteady Uniform Current

     B.5.1  Introduction

     The model to be described in this section is an analyt
ical model for predicting the dispersion of a pollutant
plume in a transient but spatially uniform current.  This
model is applicable to situations in which current variabil
ity is important but in which the assumption of a uniform
current is acceptable, at least for the portion of the
receiving water that is of primary interest.  The model  is
essentially the Transient Plume Model described by Adams et
      ' E. Eric Adams, Keith D. Stolzenback, and Donald  R.F.
Harleman, Near and Far Field Analysis of Buoyant  Surface
Discharges  into Large Bodies of Water, Report No.  205,  Ralph
M. Parsons  Laboratory for Water Resources  and Hydrodynamics,
Department  of Civil Engineering, Massachusetts Institute  of
Technology, August 1975.
                            -316-

-------
I
U)
         •f !_ L
           2 b
                            L=SCALE=2>J3 o
                            E=EDDY  DIFFUSIVITY
                               12E
                 Figure B-5.  Plot of pollutant stream  scale  as  a function of distance
            travelled.

-------
o
 *
X
CJ
  1.0

u 0.8
 §
 H
 EH
 23
 W
 O

 g
 O
 g
 H
 X
 ss
  0.6
    0.4
    0.2
    0.1

   0.08


   0.06












(
V
\










)


\
\
\




3'








\
\


1? 1
Ub








\


?


t







\




4



R
Ea


\









-


\




5



«i
r L i
b}



\
^






/3





V
\

g










^
N
1
     Figure B-6.   Plot of centerline (maximum)
 concentration as a function of distance travelled.
                  -318-

-------
which was developed to predict water temperatures near a
proposed offshore power station.  More recently the model
has been used to analyze the far field temperature distri-
bution associated with power plants sited on Lake Ontario
and Cayuga Lake.H
     B.5.2  The Governing Equation for the Far Field

     The principle of mass  (or heat)  conservation applied to
a differential control volume leads to a governing equation,
the convection-diffusion equation, for the concentration of
the effluent.  In the coordinate system in Figure B-7,
this equation and its boundary conditions may be expressed
as

     3c    3c
     3t   U3x

c(x,y,z,t) is the concentration of the effluent; u, v, and
w(x,y,z,t) are the x, y, and z components of the velocity
field; Ex, Ey, Ez(x,y,z,t) are turbulent "eddy-diffusion"
coefficients; K^ft) is a first order decay coefficient  (via
radioactivity, chemical reaction, etc.); qs and q^ are
transport rates across the surface and the bottom respec-
tively (positive values of qs and qt, imply transport of
effluent out of the liquid volume); and H(x,y,t) is the
water depth.

     Instead of solving for the actual concentration c from
Equation  (B-13), the present model solves for excess concen
tration  (the difference in concentration observed with and
without the effluent discharge) by writing a similar equa-
tion  (with boundary conditions) for the concentration of
       Keith D. Stolzenbach et al., Analytical and Experi-
mental Studies of Discharge Designs for the Cayuga Station
at the Somerset Alternate Site, Report No. 211, Ralph M.
Parsons Laboratory for Water Resources and Hydraulics,
Massachusetts Institute of Technology, May 1976.
                            -319-

-------
effluent in ambient water and subtracting it from Equation
(B-13).   The result is a third equation  (with boundary
conditions) of the same form as Equation  (B-13) for the new
variable

                    Ac = c - c  ,                        (B-14)
                              amb.

     Several simplifications are made to reduce the equation
to a form yielding tractable solutions.

     First the velocity field is considered to be two-
dimensional (w = 0), horizontally uniform, and vertically
sheared  (with arbitrary shear distribution).  Thus

                    u = u(t) + u" (z,t)
                                                        (B-15)
                    v = v(t) + v"(z,t)

where u(t) and v(t) are instantaneous depth averaged veloci-
ties.  Because there is no horizontal variation of velocity,
the assumed velocity field may be ascertained from a time
series of currents measured at one station  (vertical water
column).

     Second, because a solution is to be obtained by super-
position of instantaneous sources, horizontal diffusion is
described by "relative diffusion coefficients."  For hori-
zontally homogeneous, stationary turbulence the magnitude of
these coefficients depends only on depth and the size of the
diffusing patch.  The size is described by the horizontal
standard deviations, ox and ay.  Thus,
                                                        (B-16)
                    Ex = Ex(z'ax)


                    Ey = VZ'V

The vertical diffusion coefficient is assumed to be a
function of z only.

     Finally, the water depth, H, is assumed to be constant.
Using the concept of excess concentration and the above
simplifications, Equation  (B-13) may be rewritten as
                            -320-

-------
[u(t)
                                  [v(t) +v"(z,t)]
                                                  8Ac
                                              3Ac
                       3Ac
                   KsAc,
                                       z =  0
                                                        (B-17)
                              -KbAc,   z = H
     B.5.3  Solution for an Instantaneous Vertical  Line
            Source

     The excess concentration at time T caused  by a verti-
cally distributed line source instantaneously released at
time T is sought.  The first step is to transform to a
coordinate system moving with the mean current  velocity:
       = x
       = y
                        f\
     (t)dt - x
                          0
r
                           v(t)dt -
                                                        (B-18)
Equation  (B-17) is rewritten as
     3Ac   , .,3Ac   _.,3Ac _
       -                 -
                     9Ac
                     3z
                 K Ac,
                  s
                                     z =  0
                            -KbAc,   z = H
                                             (B-19)
     Equation  (B-19) is solved  for  an  instantaneous  release
by the method of moments.  Each term of  the  equation is
multiplied by
                          i i
                         xryr
and integrated over the domain -°°  < xr, yr  <  °°,  to  obtain
equations for the moments c^-; (z, t,T) .  For  instance,  for
                             -321-

-------
i=j=0;i=l,2,3,  j=0;  and j  = 1,2,3, i = 0, the
following seven equations  are derived:
where
                  3c
                    00
                    9t
          3c
            01
                3z\z  3z

                ^  /   3c
           3t

          3c
                 v"c
                        01
           00
            10
4z   9z

   9cn ,
  3t
                 u,,c
                           _
                    00    3z\ z   9z
3c.
                                         3c
              - 2u"c,rt =  2E  cnn
                     10     x 00
                                           20
         9c,
                              z   3z

                                3crt.
           '30
          3t

         3c
           03
                                3c,
                3v"C02 =  6EyC01
                                               (B-20)
                            oo   .,00
                            /"J  /*     •
                              /  Acx^yjdxr
                           — OO *^ —OO
                                               (B-21)
The boundary condition  associated with each equation in
(B-20) is
                                    Z =
                'z   3z
                                                         (B-22)
                           -Kbcijf
     Equations  (B-20)  are  weakly coupled and can be inte-
grated numerically  in  the  order in which they are presented
from t = T to T.  Initial  conditions (for an instantaneous
release at t =  T) are:
                    r>    —
                        ~
                           M_(z) ,    i = j = 0
                                               (B-23)
                           0,
                                 or j  ? 0
                             -322-

-------
where mz(z) is the mass released per  unit  depth  at depth z.
In the computer program, Equations  (B-20)  are  made non-
dimensional and are solved using finite  difference with a
Crank-Nicholson time scheme.

     Familiar statistics describing the  distribution of the
instantaneously released effluent patch  can  be derived from
the moments c.:-;.  For example
                    x" =
                    y" =
'10
:oo
'01
:oo
                                                        (B-24)
                    a  =
                     a  =
                    a  =
'20
:oo
'02
:oo
                          '03

                          ;00
'10
 2
'00

 2
:oo
                                 00

                                3c
        01C02
                                  "00
                2c
            01
                '00
                                    x
                    a  =
C30
coo
3c10°20
2
coo
, 2cio
°l*
                                                        (B-25)
                                                        (B-26)
x" and y" are the xr and yr  coordinates  of the centers of
mass of the patch excess concentration distribution,

                           2    j   2
                         ax  and  Cy

are the variances  (squares of  the standard deviations) of
the patch distribution, and  ax and  ay are skewness coeffi-
cients.  A large number of moments  are necessary to accu-
curately describe a single patch.   However, when a number of
                             -323-

-------
point source solutions are superimposed to form a continuous
solution, it is reasoned that the Oth, 1st, and 2nd moments
for each patch are sufficient to approximate the continuous
plume.  That is, each skewed patch is replaced by a Gaussian
patch with the same Oth, 1st, and 2nd moments.  The peak
concentration of this Gaussian patch is

                          2002
and the approximate excess concentration distribution  at
time T after release at time T is
cinst(xr'yr'z'T'T) =
       (z,T,T)exp
                   [x  - x"(z,T,T)]

                         5
                       2<(z,T,T)
                         x
                                        [y  - y"(z,T,T)]
                                            2(T(z,T,T)
                                             y
                                                        (B-28)
     B . 5 . 4  Solution for a Continuous Release  of  Finite  Size

     The far field plur.ie shown in Figure B-7 can  be  gener-
ated by a set of continuously emitting vertical line sources
of effluent distributed across the cross section  illustrated
in the main diagram below.  Concentrations  can be obtained
by integrating Equation  (B-28) from  T = 0 to T and over  the
width of the source from y' = B/2 to y ' = B/2.  A weighting
factor, my(y'), is used to adjust the strength of the
vertical line sources to match the observed (from a  near
field analysis) lateral distribution of concentration.
              /-TV B/2
c(x,y,z,T)  = /  /    c.   (x ,y ,z,T,T)m  (y')dy'dT
             J0 J -B/2                   Y
                                                        (B-29)
     In practice the above integrations  are  replaced by  a
finite series  (summation) using NI  laterally distributed
instantaneous  sources at each  time  step  and  NT  time  steps
                             -324-

-------
    Virtual  Origin(X ,0)
       H
                                                     X
                                            Discharge Point
                              Prescribed Initial Conditions
                              from Near Field Solution:
                                                    QoD
            1
                                                    DAcc
                                                      i , ,*i

                                                     Ac
                                                           =  1
_ 1
     Figure B-7 .   Far field source conditions.  (E. Eric
Adams, Keith D. StolzenbacJ;,  and Donald R.F. Harleman,
Near and Far Field Analysis of Buoyant Surface Discharges
into Large Bodies of Water,. Report No. 205, Ralph M. Parsons
Laboratory for Water Resources and Hydrodynamics,  Department
of Civil Engineering, Massachusetts Institute of Technology,
August 1975.)
                              -325-

-------
             NT  NI(T,t)
c(x,y,z,T) =            FACTOR cinst(xr'yr'Z'T'T)my
             t=l   n=l

             Qn(x)Acn(T)AT(T,T)

    FACTOR =      NI(T,T)H -                         (B'30)

where QQ is the initial  (discharged) flow rate and Acg  is
the initial concentration or temperature rise  (without
recirculation) .  Also, the initial conditions  for C20 and
CQ2 in Equation (B-23) are altered to represent a partially
developed patch; i.e., one which was "effectively released"
at a previous time and position such that it has migrated  to
the source location and has grown to a finite  size by the
time t = T.  Thus a smooth concentration distribution can  be
achieved near the source.
     B.5.5  Source Conditions

     The characteristics of the  far  field  source of  pollu-
tant are determined as follows with  reference  to Figure  B-7.
First, the source is assumed to  be displaced a distance  xj_
to account for the possible length of  the  steady state
portion of the mixing zone.   (The coordinate system  is
assumed to be chosen such that the discharge is in tne
positive x direction.)  Secondly, the  remaining portion  of
the mixing zone is assumed to have a length RTRANS and to be
oriented in the direction of the prevailing current  direc-
tion.  Next, the initial source  is assumed to  be distributed
evenly over a portion H2 of the  total  depth.   Finally, the
discharge flow is assumed to be  mixed  with the receiving
water in an amount given by the  dilution,  D, which is the
ratio of the mixed flow to the initial flow.

     With the above information  given, the width, B, of  the
source is determined by the following  mass continuity
relationship :

                    DQQ
               B = - V-                                (B
                   HV
where          Qfl =  the  initial  flow
              |v|  =  magnitude  of  the  current speed
                            -326-

-------
     B.5.6  Form of Horizontal Diffusion Coefficients

     Horizontal diffusion of each patch is described by
relative diffusion coefficients, Ex and Ey, that are related
to the size of the patch by:
                      n_
               E  = Aa
                x     x
   X
        a  < a
         x    xc
               E  = Aa x
                X     XC
               E  = Aa
                y
               E  = Aa
  n
   Y
  y

  n
   y
 'yc
        a  > a
         X    XC
  a  < a
   y
  a  > a
   y
                                                        (B-32)
The form of Equations  (B-32) suggests that over a certain
range of length scales  (a < ac) patches undergo "accelerated
diffusion" due to current shear effects, while for large
length scales  (a > ac) diffusion is more accurately  (or
conservatively in the absence of data) described by  constant
diffusion coefficients.  From Equations  (B-3) and (B-32) it
follows that


       2~nx         2'nx
ax(T'T)     =axO(T)     +  (2 - nx)A(T - T)
       2-n
2-n
ay(T,T) y = ay0(T) y -f
a (T T)2 - a2 + 2Aanx
w VL/J./ \J i  a
                                                X    XC
   a  (i,T)2 = a2  + 2Aany
    y          yc      yc
T - T -
               2-n          2-n
              a   y - a n(T)
               yc	yO
                  (2 - Ny)A
                                               a  > a
                                                y
                            -327-

-------
     B.5.7  Shoreline Imaging

     When the discharge is located near a straight shore-
line, two constraints must be imposed.  First, the currents
must be assumed to flow parallel to the shoreline to prevent
advection of the pollutant mass across the boundary.
Secondly, to prevent effective diffusion across the boun-
dary, an image source corresponding to each real source is
assumed to be located on the opposite side of the shoreline.
     B.5.8  Summary of Model Parameters

     The model described in the previous section requires
the specifications of the following parameters:

                    Q_ = initial discharge flow


                   Acn = initial discharge excess concen-
                         tration

                     D = initial dilution

                    x, = initial fixed mixing distance

                    H~ = initial depth of source


                RTRANS = initial variable mixing distance

                     H = total water depth

                XSHORE = distance to shoreline  (if appli-
                         cable)

             u(t),v(t) = horizontal components of velocity
                         as a function of time

              k-,,k ,k,  = internal, surface, and bottom decay
                         coefficients

                    E  = vertical diffusion coefficient
                     z

   A ,A ,n ,n ,a  'avc = parameters describing the hori-
       Y     Y      v    zontal diffusion coefficients
                           -328-

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                  SUPPLEMENTS TO APPENDIX B
           LAPLACE'S SOLUTION TO THE HEAT EQUATION12
     This section examines in detail the solution of the
heat equation  (B-9) given in Appendix B, Section B.4:
                                                        (a-l)
                                                        (
                            -
                    ay2   Eo K

given the boundary conditions

                              if y < b/2

                         0    if y >_ b/2

for a finite line source.  The method of solution employed
here is typical for problems involving spatially continuous
sources in that it considers a continuous source to be a
collection of point sources each contributing to the total
solution.  A refined version of this method is used in the
computer model developed by Adams et al.

     The solution to Equation (a-l) is most easily found by
appealing to the superposition principle:  since the equa-
tion is linear, the solution corresponding to a line source
from y = -b/2 to y = b/2 is just the superposition (i.e.,
the sum or, ,for continous sources, the integral) of the
solutions for the point sources comprising the line.  The
equation describing a point source at (0,y') is just (B-8) ,
with the boundary condition being given by the conservation
of mass principle:  if the initial discharge at (0,y')  is
such that the resulting average concentration on the unit
area surrounding it is CQ , then for any value of C /
                    c  = f c6(C,y)dy                   (a-2)
                         ^—
where eg is the point source concentration.  It is easily
checked that
       G.T. Csanady, Turbulent Diffusion in the Environment
(Dordrecht, Holland:  D. Reidel Publishing Co., 1973),
Chapter 1.
                           -329-

-------
c =
                    exp
                        -(y - y')2
                 A
               = — exp
            4(EQ/UK


           -(y - y')2
                           4EQT
                                           (a-3)
is a solution to  (a-1) for all C > 0;  the  arbitrary con-
stant A can be evaluated by imposing  (a-2) :
               = 2A/TTEQ/U
Therefore,
and the point-source solution  is
           ,y) =
                 2/TTEQT
           exp
-(y - y1)
.   4V
Integrating c§ over all points  constituting the line segment
-b/2 < y < b/2 gives the solution  for  the  line source:
           -b/2
                            exp
                                 -(y  -  y')
                                    4EQT
                               dy'
                            (a-4)
By the definition
        erf(w) = —  /  exp(-z  )dz
                 /if -^ 0

of the error  function,  (a-4) can be  written as

                                      /y - b/2'
                                                        (B-10)
                            -330-

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               SOLUTION TO BERNOULLI'S  EQUATION
     The equation (3-5)


                 dL .
                 dx" ~ l~Ub~llcr '                        (b~1}
is more readily recognized after a  change  of  variables

                  A = L/b,   x  = x/b

and a renaming of constants

                      12EQ
                             (dimensionless)
                       Ub

These simplifications  throw (b-1)  into  the  form  of Ber-
noulli's equation:
                                                       
-------
The initial condition requiring that L = b at x = 0 is
sufficient to determine that the constant C of integration
is equal to unity; therefore,


                  L _  /    2   x\3/2
                  b ~      3
                           -332-

-------
                         APPENDIX C
           FATES OF HYDROCARBONS AND TRACE METALS
                  IN THE MARINE ENVIRONMENT
C.1  Introduction

     A central assumption of the analysis performed in this
report is that the key process leading to the observed con-
centrations of oilfield brine constituents in the vicinity
of a production platform is the dilution of the brine due to
diffusion forces and current patterns.  Thus, it is assumed
that the spatial distributions of brine concentrations
around a platform are adequately represented by the predic-
tive model described in Appendix B, which takes only currents
and diffusion into account.  This is an excellent approxi-
mation, but it is not the complete story.  The components of
oilfield brines are subject to a number of physical, chemical,
and biological processes other than dilution, which can all
affect their physical form, chemical nature, and, therefore,
their toxicity.

     Fundamentally, there are three types of relevant pro-
cesses :

     1.   Degradation processes, such as the microbial or
          photo-degradation of hydrocarbons in the marine
          environment.

     2.   Alteration processes, such as the biological
          methylation of mercury or the oxidation of Cu+
          ions.

     3.   Transfer processes, which move the pollutant from
          one compartment of the marine environment to
          another  (e.g., the transfer of metals from the
          water column to the bottom sediments via precipi-
          tation and sedimentation).

     Generally, data are not yet available which would
enable these effects to be incorporated in any reliable way
in a theoretical or semi-empirical predictive model.  Further-
more, actual data on the rates of these processes in situ
is rare, and only one or two studies have reported actual
metal or hydrocarbon monitoring data in the vicinity of
production platforms.  Therefore, these processes will not
                             -333-

-------
be incorporated into the primary analysis of this report.
Nevertheless, the more important of these processes are
discussed in this appendix to indicate their approximate
rates and the qualitative way in which they might affect
brine toxicity.

     One of the most important of these environmental modifi-
cation processes, and one to which both hydrocarbons and
trace metals are subject, is sedimentation.  The transfer of
a toxic substance from the dissolved to the suspended or
settled fraction of the marine environment drastically
affects its accessibility to resident organisms.  On a_
priori grounds, for example, one might expect precipitation
and sedimentation processes to decrease the toxicity of
metals and hydrocarbons to most swimming fish, but to create
a much more severe toxicity problem for benthic or filter
feeding organisms, and to a large extent these conclusions
are supported by the literature.   (Sedimentation is an ex-
ample of a process which alters toxic impact by affecting
the accessibility of a substance.  Other environmental modi-
fication processes, such as oxidation of trace metals, can
affect toxicity more directly).  Because of the importance
of sedimentation, it will be given primary emphasis in this
appendix.
C.2  Sedimentation

     In general, sedimentation in estuaries occurs as a result
of the aggregation and settling of suspended particulates.
Two major processes have been proposed to explain this
aggregation for general particles:  salt flocculation and
agglomeration by organisms.  Settling is due to a number of
factors including net transport of suspended sediments from
swift river currents to calmer bays (the last is important
in estuaries and is highly dependent on the hydrological
nature of the estuary in question).

     The principle behind salt flocculation is that the
presence of salt ions in water results in an electrolytic
effect which increases the tendency of suspended particles
to adhere to one another.  Flocculation can be regarded as
the result of two separate mechanisms:  .interparticle colli-
sions and cohesion between particles which have been brought
into contact with each other.  Fine-grained suspended sedi-
ments tend to acquire small amounts of electrical charge as
they are buffeted about in the water, and, since similar
particles tend to pick up the same kind of charge, small
repulsive forces develop which inhibit the cohesion phase.
                             -334-

-------
The ions in electrolytic saline water act to neutralize
these small friction-generated charges, increasing the
probability of cohesion.1

     The rate at which flocculation occurs depends on a
number of interacting variables, the most important being:

     1.   Relative distribution of mineral components
          in the sediments.

     2.   Particle size  (the electrochemical forces
          causing floes are too small to have noticable
          effects on clay particles much larger than about
          ly).2

     3.   Salinity.

     4.   Suspended sediment concentration.

     5.   Turbulence and water depth.

Thus salt flocculation is very difficult to analyze in any
quantitative manner.  Although the mechanism has been studied
in detail under controlled laboratory conditions, there is
presently little evidence to support the widely held belief
that increased aggregation due to net particle transport up
the saline gradient is a substantial factor in estuarine
sedimentation.3

     The second major aggregation process, agglomeration by
organisms, is largely the result of filter feeding activity
by oysters, copepods, clams, mussels, scallops, tunicates,
and barnacles.  For example, oysters filter water through
their gills in order to extract food.  The rejected material
is emitted in clumps loosely held together by mucus, and the
      A.T. Ippen, ed.,  "Sedimentation in Estuaries," in
Estuary and Coastline Hydrodynamics  (New York:  McGraw Hill,
1966),  pp. 648-672.
     2
      Ippen, "Sedimentation in Estuaries."

      R.H. Meade, "Transport and Deposition of Sediments in
Estuaries," in Environmental Transport of Coastal Plain Estu-
aries,  Geological Society of American Memoir 133, ed. by
B.W. Nelson (Boulder, Colorado:  Geological Society of
America).
                             -335-

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suspended matter that is eaten is agglomerated into small
fecal pellets.  It is estimated that oysters can deposit
suspended matter at a rate seven or eight times of that
ordinarily caused by gravity.4  in estuaries where filter
feeders are a significant component of the trophic web,
organic agglomeration can be a substantial factor in sedi-
ment deposition.

     The third process by which sedimentation of suspended
particulates may occur is due to the general hydrological
features of estuaries as compared to rivers.  The currents
in a river are often strong enough to support a much greater
suspended sediment load than could be sustained by standing
water.  In estuaries characterized by wide bays and sluggish
currents, the inflowing particulates may encounter less tur-
bulence than that provided by river flow and may sink as a
result.  Naturally, the extent to which this process explains
sedimentation in a given estuary depends on the relative
turbulence of tidal and current flows in the estuary as com-
pared to the turbulence of the incoming, sediment-carrying
flow.  Moreover, the extent to which this process applies to
oilfield brine discharges in the estuary depends on the
location of the discharge points with respect to the incoming
flow, i.e., whether brine is discharged into waters experi-
encing significant river currents, or into waters which are
already relatively calm.
     C.2.1  Sedimentation of Oil-Associated Hydrocarbons

     Most of the existing studies of oil species sedimenta-
tion focus on the fate of oil from accidental spills.  Four
basic processes have been identified in the sedimentation of
materials from oil slicks:^

     1.   Evaporation and dissolution of lighter compounds.

     2.   Uptake of particulate matter  (both organic and
          inorganic) by petroleum.
     4
      Meade, "Transport and Deposition in Sediments in
Estuaries."

      C.B. Gelelein, "Sedimentation Processes Involving
Hydrocarbons in the Marine Environment," in Background Papers
for a Workshop on the Inputs, Fates, and Effects of Petro-
leum in the Marine Environment, compiled by the Ocean Affairs
Board, National Academy of Sciences  (Washington, B.C.:
National Academy of Sciences, 1973), pp. 462-466.
                             -336-

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     3.   Agglutination of dispersed globules followed
          by the uptake of particulates.

     4.   Sorption of dissolved species onto suspended
          particulates.

Of these processes,  (1) is not particularly applicable to
oilfield brines, since they seldom contain large masses of
undissolved, unsuspended, and unevaporated oil species;
(2) is applicable only as it pertains to  (3); (3) may be
applicable to brines containing significant amounts of
emulsified hydrocarbons following the oil-water separator
process; and (4) is likely to be an important mechanism for
hydrocarbon sedimentation from brines.

     The uptake of suspended particulate matter by petroleum
globules is most important nearshore, where high concentra-
tions of suspended sediments frequently result from inflowing
river loads.  The accumulated sediments increase the density
of the hydrocarbon mass, causing fairly rapid deposition
onto the ocean floor.  There may be a biological contribution
to this process:  oil-soaked suspended particles foster some
algal growth, which in turn, attracts small invertebrates.
The invertebrates attach themselves to the particles, again
increasing their density.6

     It is likely that this process is preceded by some
agglutination of dispersed oil particles in the case of
oilfield brine, since the brine itself usually contains very
little oil in any substantially aggregated form.  Because
the surface tension of a volume of water is inversely related
to surface curvature, oil dispersed in water tends to accumu-
late into larger aggregations with boundaries of smaller
curvature, thereby reducing the net potential energy of the
oil-seawater interface.  (This process may be inhibited in
the well by higher temperatures.)  The resulting increase in
volume enhances the uptake of suspended particulates and
hence the rate of deposition.  This rate is also highly
dependent on the quantity of suspended particulates present,
turbulence of the receiving water, and the specific gravity
of the oil particles.  For example, Bunker C oils and Venezuela
and California crudes with specific gravities very close to
carbons."
      Gebelein, "Sedimentation Processes Involving Hydro-
                            -337-

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1.000 do not need to accumulate much particulate matter in
order to acquire the density necessary to sink.^

     Dissolved species of oil enter the sediment phase pri-
marily via absorption or adsorption onto suspended particu-
lates.   The most effective absorbers normally present in
estuarine waters are fine-grained clays of cross-section
less than about 45y.  There is some indication that clays
with high organic content absorb oil species more effectively
than those with less organic matter.  Also, in general,
sorption increases with salinity and decreases with tempera-
ture. 8

     Very little is known about the actual rates of deposi-
tion associated with any of these processes.  Research on
this problem is hampered not only by the lack of systemati-
cally conducted fieldwork but also by the fact that the
quantitative understanding of sedimentation gained in
controlled laboratory experiments cannot be used with any
confidence in applications to field studies in actual estuaries
The mechanisms by which deposited brine organics may become
resuspended also are not understood.  It is thought that
reworking of sediments by tidal activity and by surface and
infaunal organisms may lead to resuspension.9  if this is
the case, then this same reworking may also lead to greater
longevity of oil-associated organics in estuaries.  Biogenic
reworking of sediments may plow some organics down into the
anaerobic subsurface layers of the estuary floor, inhibiting
aerobic degradation.  Despite the current lack of knowledge
concerning its mechanisms, however, sedimentation of oil
species is an important aspect of the long-term fate of oil-
field brine pollution.


     C.2.2  Sedimentation of Metals

     Oilfield brine generally contains appreciable concen-
trations of heavy metal ions.  It is not surprising, there-
fore, that some of these metals find their way into the
      National Academy of Sciences, Petroleum in the Marine
Environment  (Washington, D.C.:  National Academy of Sciences,
1975), pp.50-51.
      g
      National Academy of Sciences, Petroleum in the Marine
Environment.
      9
      National Academy of Sciences, Petroleum in the Marine
Environment.
                             -338-

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sediments of estuaries where brine is discharged.  For
example, Montvalvo and Brady found higher levels of Zn, Cd,
Pd, and Hg in Louisiana bays harboring oilwell activity than
in offshore areas, with levels of Zn, Cd, and Pb substantially
higher near the rigs themselves.10  Of these three metals, no
correlation was found between Cd concentrations and depth;
however, Zn and Pb concentrations were highest in bottom
samples containing more sediment.  These results indicate
that sedimentation should be considered an important fate of
certain heavy metals in discharged oilfield brine.

     Several processes have been proposed to explain the
mechanisms by which metal ions are deposited on the bottom
of estuaries.  Perhaps the most important of these processes
is adsorption onto suspended clay particles which eventually
sink to the estuarine floor.  Rivers carry great quantities
of clays containing oxides of both manganese  (MnOx) and iron
(FeOx).H  These oxides exhibit an affinity for metal cations,
so that trace metal ions introduced into estuarine waters     , „
fed by the rivers tend to be adsorbed onto the clay particles.
This process is influenced by the relative ion concentrations
as measured by pH and salinity, since increases in the
relative concentrations of lighter ions may displace heavier
absorbed cations, and vice versa for increases of heavy
metal concentrations.  However, the wide variation in compo-
sition among different oilfield brines renders the extent to
which brine/seawater pH and salinity differences perturb the
adsorption by clays difficult to quantify.
       J.G. Montavalo and D.V. Brady, Toxic Metal Determi-
nations in Offshore Water Samples, Final Report to Gulf
Universities Research Consortium, Contract No. GU 853-5,
Investigation No. OE-53-HJM, April 30, 1974.

       K.K. Turekian, "Rivers, Tributaries, and Estuaries,"
Chapter 2, in The Impingement of Man on the Oceans, ed. by
Donald Hood (New York:  John Wiley & Sons, 1971).
     12
       J.J. Morgan and R.D. Pomeroy, "Chemical and Geochemical
Processes Which Interact with and Influence the Distribution
of Wastes Introduced into the Marine Environment, and Chemi-
cal and Geochemical Effects on the Receiving Waters," in
Background Papers on Coastal Wastes Management, National
Academy of Engineering, Vol. 1 (Washington, D.C.: NTIS, 1969),
pp. X-l-X-44.
                             -339-

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     Chemical reactions resulting in precipitation are
another possible mode of metal sedimentation from brine/sea-
water mixtures.  It has been suggested that many oil deposits
contain bacteria which reduce sulfate ions in brine to
hydrogen sulfide.13  Over long periods of time, this action
generates a solution which is highly reducing relative to
the comparatively sulfate-rich ocean environment.  When the
two waters are mixed, sulfates in seawater oxidize certain
cations, often resulting in precipitation.  The low concentra-
tions of sulfates in the brines produced from many Louisiana
wells!4 corroborate this hypothesis; however, the precipitates
formed are principally those of Ba, Sr, and Ca.15  Oxidation
by sulfates in seawater does not appear to be a significant
factor in the precipitation of heavy metals from discharged
brine.

     A related process may explain, though, how heavy metals
introduced by discharged waters are precipitated when they
are not themselves present in heavy enough concentrations to
precipitate from aqueous solution.  This process involves
the formation of a solid solution of heavy metals with the
more abundant solids dissolved in seawater.  Discharging
oilfield brine into estuarine waters can be regarded as
mixing two aqueous solutions, each in equilibrium.  If no
solubility changes result from this mixing, as in the case
of mixing two unsaturated aqueous solutions of NaCl, then no
precipitation will occur.  However, it is likely that the
equilibrium configuration for some aqueous solutions containing
ions of both light and heavy metals consists of a solid
solution of heavier metals in some lighter ones,16 in equili-
brium with an aqueous solution.  The solid solution may have
a lower solubility than its separate components, and hence
some precipitation may occur before equilibrium is reached,
even though none of the ions comprising the solid solution
would have precipitated were they to have remained in aqueous
       Telephone conversation with A.G. Collins, March 31,
1976.

     14
       A.G. Collins, Geochemistry of Some Petroleum-Associated
Waters from Louisiana, U.S. Bureau of Mines Report of Inves-
tigations 7326, Washington, D.C., 1970.
       Telephone conversation with A.G. Collins, March 31,
1976.
     16
       Morgan, "Chemical and Geochemical Processes."
                             -340-

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solution.    Examples of such solid solutions are Ca(OH)2 in
Fe(OH)2, PbC>2 in MnC>2 and SrCO3 in CaCo3.  Since the elements
in these complexes generally are not present in stoichiometric
proportions, the precipitates cannot be considered strictly
to have been formed via chemical reactions.  Therefore this
mechanism may explain the sedimentation  (formation of solid
phase) of trace metals for which distinct precipitate phases
in seawater appear thermodymanically unlikely.-^

     Marine organisms also play a role in the long-term
deposition of trace metals.  Organic debris and skeletal
fluorapatite in the deep-sea, or bathypelagic,  zone are
known to accumulate trace quantities of Zn, Sn, Pb, Ti, Cu,
and Ag.19  Brown algae and plankton are also important bio-
accumulators of metals.  Brown algae accumulate tetravalent
and trivalent elements most effectively, then divalent
transition metals, divalent Group IIA metals, and univalent
Group I metals.  Plankton tend to accumulate in order of
decreasing affinity, Fe, Al, Ti, Cr, Si, Ga, Zn, Pb, Cu, Mn,
Co, Ni, Cd.20  Mollusks also concentrate trace metals very
effectively.21

     All of these processes are highly dependent on ambient
conditions of temperature, turbidity, and flow patterns as
well as the chemical composition of the brines in question.
All that can be said given the present state of knowledge is
that, on the basis of sampling studies, measurable amounts
of trace metals discharged from oilfield operations find
their way into estuarine sediments.  The major mechanisms of
this deposition can be identified; however, no reliable
information has been gathered to quantify either their abso-
lute rates or their relative importance.
      . Stumm, Werner, and James J. Morgan, Aquatic Chemistry:
An Introduction Emphasizing Chemical Equilibria in Natural
Waters (New York:  John Wiley & Sons, 1970).
     18
       Morgan, "Chemical and Geochemical Processes."
     19
       Morgan, "Chemical and Geochemical Processes."
     20
       Morgan, "Chemical and Geochemical Processes."
     21
       Energy Resources Co. Inc., A Review of Concentration
Techniques for Trace Chemicals in the Environment, for the
U.S. Environmental Protection Agency, EPA-560/7-75-002,
November 1975, pp. 452-455.
                            -341-

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     C.2.3  Basic Sediment Transport Patterns

     The ultimate distribution of sediments in estuaries
depends on their long-term sediment transport patterns.
These patterns result from the processes by which sediments
are introduced or resuspended into the water column, carried
by currents, winds, and tides, and deposited in more or less
stable configurations on the bottom.  Several general obser-
vations, independent of the specifics of estuarine hydrology,
can be made regarding these processes:22

     1.   Resuspension occurs where mechanical or
          biogenic reworking of sediments is appreciable
          or where shear currents along the bed rise above a
          critical value.  Above this value, increasing bed
          shear generally leads to increased resuspension.

     2.   Deposition occurs where bed shear is below a
          critical value; below this value, decreased bed
          shear generally leads to increased deposition.

     3.   The rate of sediment deposition is limited by
          the rate of sediment formation, e.g., floccu-
          lation, uptake of particulates by oil, etc.

     4.   Deposited sediments may flow to lower lying
          adjacent areas.

     5.   Deposited sediments may be eroded under certain
          flow conditions such as floods or spring tides.

     In addition to these general considerations, the saline
wedge  structure of estuaries has some very important effects
on the patterns of sediment transport and deposition.
Although the net flow of water in estuaries is from upriver
to downriver and then out into the open ocean, the greater
density of  seawater and the periodic longitudinal movement
of saltwater/freshwater interface caused by tides often
gives  rise  to a net bottom flow upstream in the saline
portion of  the wedge.  At the bottom edge of the saline
intrusion this upstream flow is countered by the opposing
river  flow, which tends to be lifted over the wedge as it
moves  downstream.  The saline wedge thus acts as a sort of
dam or weir, since net flow at its base is nearly zero as a
        Ippen,  "Sedimentation  in Estuaries."
                             -342-

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 result of opposing upstream and downstream  flows.  This  region
 of very  small  longitudinal flow is  the nodal point of bed
 shear.

     Because sediment  transport is  most  significant  in the
 bottom layers  of water,  sediments in  the saline portion  of
 an estuary  tend to travel upstream, whereas sediments sus-
 pended in the  river  load tend  to be carried downstream.  At
 the nodal point, some  of the suspended sediments  from both
 the fresh and  saline flows are lifted up from  the bottom zone
 and carried out toward the ocean; the remainder are  deposited
 at the node in shoals.   As can be expected, the intensity
 of this  shoaling depends on the extent of the  saline wedge
 effect -- that is, on  the extent of estuary stratification.

     Highly stratified estuaries, such as the  Southwest  Pass
 of the Mississippi River, are  characterized by low tidal
 ranges and  a large influx of freshwater.  Here, the  shear
 drag of  seaward flowing  freshwater  on the relatively gently
 sloping  halocline pulls  intruding saltwater toward the upper
 layer of the wedge and seaward, drawing  more saltwater land-
 ward along  the bottom  of the wedge.   The weir  effect of  the
 nodal point is therefore enhanced,  and shoaling tends to be
 more pronounced.  The  special  nature  of  highly stratified
 estuaries,  however,  subjects this sediment  transport pattern
 to significant periodic  variations.   For example, the land-
 ward flow of suspended sediments is weakest at low,  falling
 tides, and  seaward flow  dominates at  all depths of the water
 column during  river  flood conditions.23

     In  well-mixed,  vertically homogenous estuaries, on  the
other hand,  the saltwater/freshwater interface is  not so
well defined.   Instead of vertical differentiation (a salt
wedge),  the transition between saline and freshwater in this
type of estuary is more accurately described by a  salinity
gradient upward in the direction of river flow.  Hence,  there
is not localized saltwater boundary, and the weir  effect
characteristic of stratified estuaries is drastically reduced.
Shoaling in such cases will be dispersed, and  such factors
as local topographical peculiarities and the Coriolis force
may play a more dominant if less predictable role  in deter-
mining sediment distribution.

     Of course, sediment transport patterns in any given
estuary may vary according to  the locally prevailing condi-
tions of topography,  major ocean currents, and sediment
     O -3
       Meade, "Transport and Deposition in Sediments in
Estuaries."
                              -343-

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characteristics.  The Coriolis force also has a significant
effect on the movement of suspended sediments, depending on
the shape and width of the estuary.  Despite these effects
which may vary from location to location, the dynamics of
saline intrusion play the largest role in determining trans-
port patterns in many estuaries.  This role can be summarized
as follows.

     1.   Sediments settling on the bottom of an estuary
          tend to be transported upstream.

     2.   Sediments tend to accumulate near the end of
          the saltwater intrusion, forming shoals at the
          nodal point of the bed shear.

     3.   The intensity of this shoaling is greatest
          for stratified estuaries, least pronounced in
          well-mixed estuaries.
C.3  Other Processes Affecting Marine Hydrocarbons

     Oils and oil fractions will undergo a variety of
chemical, physical, and biological alteration processes
after their introduction into the marine environment, and
these can significantly affect the toxic properties of these
oils.  The analysis of these effects is greatly complicated
by the fact that previous studies have dealt almost exclusively
with the crude oil slicks produced as a result of tanker
accidents, a situation which is of little relevance to the
dispersion or degradation of oilfield brines.  Nevertheless,
some generally applicable conclusions do emerge from the
recent literature.

     After their introduction into seawater, crude oil frac-
tions will begin to disperse, in a manner and at a rate
which will depend upon the physical properties of the oil
 (viscosity, density, etc.) and on the magnitude of local
dispersion forces such as current or wind.  As the oil dis-
perses,  some of its more polar components will begin to
dissolve, and the ligher and more volatile hydrocarbons will
volatilize.  Laboratory studies have suggested a strong
molecular weight dependence of the rate at which oil compo-
nents volatilize from seawater.24  The volatilization process
     24
       R.E. Kredier, "Identification of Oil Leads and Spills,"
in Proceedings of the Joint Conference on Prevention and
Control of Oil Spills  (Washington, B.C.:  American Petroleum
Institute, 1971), pp. 119-124.
                             -344-

-------
results in the loss to the atmosphere of the hydrocarbons.
According to a recent National Academy of Science  (NAS)
report:

     These evaporated hydrocarbons enter the atmospheric
     pool of hydrocarbons, and very little is likely to
     return to the oceans as hydrocarbons.  Chemical
     reactions in the atmosphere, such as phtotcatalytic
     oxidations, convert an unknown amount of these
     hydrocarbons into less volatile nonhydrocarbon
     compounds that may re-enter the oceans.  The fate  -5
     and effect of these types of compounds are unknown.

     The sum of these two processes of solubilization and
volatilization is known as weathering, and the end result
is a weathered oil which is denser, more viscous, and
enriched in its content of high molecular weight hydrocarbons
relative to the original unweathered oil.  The quantitative
literature on the weathering rates of oil under different
circumstances has dealt mostly with oil spill weathering,
and so has little relevance to the dilute, emulsified,
highly solubilized hydrocarbons which are contained in
oilfield brines.  Another consideration to keep in mind is
the fact that these brines are generally higher in aromatic
hydrocarbon content than their parent crude oils, due to
the differential solubility of the various oil components in
the brine water  (benzene, for example, has a saturation
solubility of about 1,800 ppm in distilled water, as com-
pared with about 10 ppm for the normal alkane of equivalent
molecular weight (hexane)).  Since much of the toxic activity
of crude oil is concentrated in its aromatic fraction, the
toxicity of the brines is probably higher than would be
predicted from an equivalent dilution of ordinary crude oil.
Although volatilization may remove many of the more toxic
components from the brine, it will also enrich the brine in
a number of others, including the relatively heavy poly-
nuclear aromatics.

     One of the most important processes involved in sca-
venging oil-derived hydrocarbons from the water column is
adsorption onto suspended particulates which are subsequently
deposited in bottom sediments as was discussed in the previous
section.  Hydrocarbons can become entrapped in marine sediments
through a number of processes.  These include ingestion by
zooplankton and the subsequent sedimentation of oil containing
     25
       National Academy of Sciences, Petroleum in the Marine
Environment, pp. 45-46.
                             -345-

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fecal material, adsorption onto suspended mineral particles
which subsequently settle out, and direct adsorption onto
bottom silt and clay.  The chief effect of the adsorption
process is probably to decrease the effect of the hydrocarbons
on organisms other than benthic organisms and filter feeders.
The effect on these two groups will probably be greatly
increased because of the tremendous concentration factor
which is associated with adsorption onto particulates.  In
fact, it has been noted that areas which have significant
concentrations of oil in their sediments usually have "an
impoverished benthic fauna,"26 although the causal relation-
ship has not been clearly demonstrated.

     Although adsorption onto particles seems to facilitate
biological and chemical oxidative degradation of hydro-
carbons, particle-adsorbed hydrocarbons which settle into
sediment seem remarkably stable, probably because of the
anaerobic conditions prevailing within the sediment.  Sedi-
ment-entrapped hydrocarbons also seem to be unusually
resistant to photochemical degradation, except at the very
top of the sediment layer.  According to Blumer and Sass,
"The preservation of hydrocarbons in marine sediments for
geologically long time periods is one of the accepted key
facts in current thought on petroleum formation."27  Experi-
mental studies of oil-contaminated sand columns have suggested
that although 10 percent of the trapped oil oxidized over a
period of several months, the remainder deteriorated at a
much slower rate.28 Solubilization of hydrocarbons from
sediment, and the ingestion of sediment particles by benthic
organisms, provide processes whereby the transfer of hydro-
carbons from water to sediment may be reversed.

     In addition to these essentially physical alterations,
crude oil in seawater is subject to a number of chemical
degradation processes.  Chiefly, these are oxidative pro-
cesses  (auto-oxidative and photo-oxidative) which change the
       U.S. Environmental Protection Agency, Water Quality
Criteria, 1972.

     27
       Blumer and Sass, "Oil Pollution:  Persistence and
Degradation of Spilled Oil," Science 176  (1970): 1120-1122.
     2 g
       Evans and Rice, "Effects of Oil on Marine Ecosystems:
A Review for Administrators and Policy Makers," Fishery
Bulletin 72  (1974): 625.
                             -346-

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relatively reduced aromatic and aliphatic hydrocarbons
species found in crude oil into more oxidized acids, alde-
hydes, and alcohols.  Light acts as an important inducer of
oxidation through the formation of free radical intermediates
and hydroperoxides.   (Photo-chemically induced free radical
intermediates can also polymerize.  The end product of the
polymerization reaction is dense, viscous, relatively polar
"tar.")  Oxidation will be accelerated by physical factors
which tend to disperse or emulsify the oil, and by metallic
catalysts, and many sulfur compounds are strong inhibitors
of oxidation.  A priori chemical arguments support some
general conclusions regarding the relative rates at which
different oil-derived hydrocarbons will oxidize in the
marine environment.29

     Another important class of processes which alter oil in
seawater is biodegradation; indeed, it is probably the chief
pathway by which polluting oils are removed from the marine
environment.  According to Atlas and Bartha:

     Microbial degradation of crude oil appears to be
     the natural process by which the bulk of the polluting
     oil is eliminated and may be the reason that the oceans
     are not entirely covered with oil today.  Under fa-
     vorable conditions microorganisms are quite effective
     in degrading low levels of petroleum.  In areas that
     are well aerated and where the microbial population is
     adapted to oil influx, the rate of oil oxidation at
     20° C to 30° C may range from 0.02 g to 2.0 g of oil
     oxidized/m^/day....  Microorganisms will degrade a
     substantial portion  (40 percent to 80 percent) of crude
     oil, but the degradation is never complete; n-alkanes
     are utilized preferentially and highly branched alkanes,
     cycloalkanes, and aromatics are utilized with difficulty;
     and mixed enrichments are more effective in petroleum
     degradation than mixed cultures.30

     Although much laboratory and field data are now available
on the microbiological degradation of crude oils and oil
components, it remains impossible to make any reliable quan-
titative estimates of the rate at which this process will
remove oil from oilfield brines.  According to the NAS:
     29
       Atlas and Bartha, "Fate and Effects of Polluting Petro-
leum in the Marine Environment," Residue Review  (1973c) : 49-85.

       Atlas and Bartha, "Fate and Effects of Polluting Petro-
leum in the Marine Environment."
                             -347-

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     Neither a single rate nor a mathematical model for
     the rate of petroleum biodegradation in the marine
     environment can be given at present.  On the basis of
     available information, the most that can be stated is
     that some microorganisms capable of oxidizing chemicals
     present in petroleum  (under the right conditions) have
     been found in virtually all parts of the marine envi-
     ronment examined.31

     Nevertheless, a number of factors can be isolated as
being important in controlling the rate of oil degradation.
The composition of the available substrate is critical,
since mircoorganisms are limited in the range of hydro-
carbons they can oxidize.  Pure cultures rarely degrade more
than one hydrocarbon fraction.  Mixed cultures isolated from
the marine environment possess wider degradative capacities,
although preference for intermediate length n-paraffins is
usually observed.  It is uncertain whether this pattern is
a result of the isolation procedure used; certain wild,
mixed cultures developed in media containing cyclic hydro-
carbons, notably napthalenes and polynuclear aromatics, have
been found to degrade such compounds more rapidly than n-
paraffins.32

     Hydrocarbon-oxidizing microorganisms are widely distri-
buted in soil and water.  Relatively few hydrocarbonoclastic
microbes are found in soils or areas of the open ocean
remote from oilfields or oil pollution; they are most
numerous and diverse in places that have been subjected to
chronic oil pollution either from natural seeps or by the
activities of man.  Hydrocarbon-degrading microorganisms are
only rarely found in petroleum as it emerges from oil wells
or in unpolluted ground waters.  One preliminary indication
based on laboratory experimentation is that the abundance
and physiological types of hydrocarbon-oxidizing microbes in
soil and aquatic environments seem to be influenced by the
quantities and kinds of hydrocarbons which have been present
       National Academy of Sciences, Petroleum in the Marine
Environment, pp. 45-46.
     32
       C.E. Zobell, "Microbial Degradation of Oil:  Present
Status, Problems, and Perspectives," in The Microbial Degra-
dation of Oil Pollutants, ed. by D.G. Ahearn and S.P. Meyers
 (Baton Rouge:  Louisiana State University, Center for Wetland
Resources, 1973), p. 5.

       Zobell, "Microbial Degradation of Oil," p. 3.
                             -348-

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     Environmental conditions can significantly affect
microbial hydrocarbon degradation.  Temperature and salinity
changes, wave action, and sunlight can alter the physical
state (emulsification) and ultimately the chemical nature
(oxidation) of the hydrocarbons.  Oil dispersed in aqueous
systems is more suceptible to enzymatic attack; dispersion
is influenced by viscosity, density, chemical composition,
wind speed, current velocity, and temperature.  Some micro-
bial species produce surfactants which tend to emulsity oil
in water.34

     The growth and metabolism of the microorganisms them-
selves are intimately related to environmental parameters.
Free or dissolved oxygen is essential, as is the presence of
accessory growth factors such as nitrogen and phosphorous.
Temperature can exert a profound influence upon growth and
metabolic activity of microbial species.  In general, tem-
perature increases accelerate growth rates, while low
temperatures reduce the rates of biological processes.  The
microbial degradation of oil has been observed at tempera-
tures ranging from the freezing point of seawater (around
-2° C) to about 70° C.  Most species are most active in the
mesothermic range, 20° C to 35° C.

     Deleterious environmental influences upon hydrocarbono-
clastic microbes are microbial predators and toxic substances.
Cytophagic protozoans and other invertebrates can ingest
large numbers of microbes.  Toxic components of oil include
the 'low molecular weight hydrocarbons and the metal ions
frequently associated with petroleum.  It is thought that
low molecular weight hydrocarbons disrupt functional phos-
pholipids of the cell envelope, 35 ancj that heavy metals   .,,
decrease the efficiency of the microbial transport system.

     It is apparent from the above discussion that the number
of factors influencing microbial hydrocarbon degradation is
     34
       Zobell, "Microbial Degradation of Oil," p. 6.

       O.K. Button, "Petroleum — Biological Effects in the
Marine Environment," in Impingement of Man on the Ocean, ed.
by Donald H. Wood  (New York:  Wiley-Interscience, 1971),
Chapter 14.

       P.J. Kinney et al., Quantitative Assessment of Oil
Pollution Problems in Alaska's Cook Inlet  (College, Alaska:
University of Alaska, 1970), p. 9.
                            -349-

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vast.  Consideration of the various parameters must be made
from one location to another as well as within the context
of a given site.  The limited number of reliable and compre-
hensive fluid measurements poses a barrier to large-scale
generalizations; what information that exists for Barataria
Bay and Cook Inlet is discussed briefly below.


Barataria Bay

     According to Meyers and his associates:

     The vast productivity of wetland regions along the
     Louisiana coast, and their proximity to oil-producing
     sites, necessitates a more comprehensive understanding
     of the significance of alterations in the microbial
     community concurrent with oil intrusion and massive
     depositions of petroleum effluents.37

Unfortunately, few studies have been conducted on the effects
of oil pollutants on inshore plant-dominated communities and
their complex microbial ecosystems.  Meyers and his associates
have noted exposure of marsh areas of Barataria Bay to
controlled additions of oil significantly alters the compo-
sition of the yeast community.  Shifts toward an asexual
hydrocarbonoclastic yeast flora have been documented.  The
impact of oil deposition upon major microbial components of
the marshland ecosystem has only recently received attention;
studies on the marine bacteria Benecka have indicated an
ability to readily metabolize a wide range of organic compounds,
including aromatic and aliphatic hydrocarbons.38


Cook Inlet

     Average concentrations of 10  hydrocarbon-utilizing
microorganisms per liter have been reported for Cook Inlet.
According to Kinney and associates, "Biodegradation is more
important than physical flushing in removing hydrocarbon
     37
       S.P. Meyers et al., "The Impacts of Oil on Marshland
Microbial Ecosystems," in The Microbial Degradation of Oil
Pollutants  (Baton Rouge:  Louisiana State University, Center
for Wetland Resources, 1973), p. 221.

     38
       Meyers et al., "The Impact of Oil on Marshland Micro-
bioal Ecosystems," p. 225.
                             -350-

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pollutants from Cook Inlet...the biodegradative capacity of
Cook Inlet is large."39

     The low temperature and high silt content of Alaskan
waters have been examined as potential inhibitors of oil
biodegradation.  It appears that silt does not interfere
significantly with the emulsification properties of hydro-
carbonoclastic microbes.  The extremely cold water lowers
growth rates, so that nutrient concentrations are probably
non-limiting.  Growth rates of isolated microbes grown on
kerosene as a sole carbon source were reduced by a factor
of seven at 50° C, the prevailing summer temperature of
Cook Inlet.40  Psychrophilic (i.e., low-temperature adapted)
oil-oxidizing bacteria from Cook Inlet have been reported
active at 5° C; bacteria from northern Alaska have been
shown to oxidize mineral oil at -1° C.41  In addition to
depression of metabolism', low temperatures interface with
the dispersal of oil by entrapment in ice.

     In both Barataria Bay and Cook Inlet, it is unknown
whether the composition of produced petroleum waters has any
special impact on microbial biodegradation.  Heavy metal ion
concentrations may be inhibitory.  The effect of putative
aromatic enrichment of produced waters cannot be properly
assessed until water composition and aromatic-oxidizing
potentials of hydrocarbonoclastic microbes are determined.
Further characterization of these parameters is critical for
meaningful impact assessment.
C.4  Other Processes Acting on Trace Metals in the Marine
     Environment

     Three processes, in addition to precipitation, adsorp-
tion and sedimentation  (discussed in Section C.2) are im-
portant in altering and modifying the toxicity of heavy
metals in the marine environment.  Their effect on toxicity
is discussed more completely in Chapter Six, so they will
only be briefly mentioned here.  The first is chelation and
     39
       Kinney et al., Quantitative Assessment of Oil Pollution
Problems in Alaska's Cook Inlet, p. 1, 9.

     40
       Kinney et al., Quantitative Assessment of Oil Pollution
Problems in Alaska's Cook Inlet, p. 1, 9.

     41Zobell, "Microbial Degradation of Oil," p. 153.
                             -351-

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other forms of chemical complexation with organic materials
in water.  The second is biological transformation, including,
most notably, the microbiological methylation of mercury;
and the third is oxidation.  This last process is especially
significant since the oxidized forms of many metals (e.g. Cr
(VI)) can be much more toxic than the equivalent reduced
species  (Cr (III)).   As with hydrocarbons, not enough quanti-
tative field or laboratory data is available to enable
reliable predictions of the rates at which these processes
will occur in the marine environment, or the extent to which
they will affect toxicity.
                             -352-

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                         APPENDIX D


           PRODUCTION PLATFORM AND DISCHARGE DATA
     The Bay de Chene oil field located in Hackberry Bay,
Louisiana, adjacent to Barataria Bay, is operated by Texaco.
The Salt Water Disposal Well Report for calendar year 1975
filed with the Louisiana Department of Conservation, Geologi-
cal Oil and Gas Division, Baton Rouge, Louisiana, gives a
figure of 22,374,127 barrels produced salt water (i.e., an
average rate of 61,000 barrels per day).

     Table D-l lists the sources of produced water in Cook
Inlet, Alaska.  The two facilities chosen for analysis in
this study were the Granite Point Production Facility
operated by Atlantic Richfield Company, and the Trading
Bay Production Facility, operated by Marathon Company.

     Block 16 of the Grand Isle Oil Field Area is operated
by Exxon Co.  Produced water data filed with the Houma office
of the Louisiana Department of Conservation gives a 1975
figure of 3,231,300 barrels produced water (i.e., an average
discharge rate of 9,000 barrels per day).

     Block 108 of the Ship Shoal Oil Field Area is operated
by Chevron Company.  Produced water disposal data filed with
the U.S. Geological Survey in Metairie, Louisiana lists two
platforms disposing produced water, S-93 with an average rate
of 9,000 barrels per day, and S-94 with an average rate of
12,000 barrels per day.
                            -353-

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                          TABLE D-l
         SALT WATER DISPOSAL - COOK INLET, ALASKA

OFFSHORE
PLATFORMS3
Bruce
Granite Point
Anna
Granite Point
Dillon
Middle East
Ground Shoal
ONSHORE
FACILITIES
Granite Point
Production
LOCATION
60°59'
151°17'
60°58'
151°18'
60°44'
151°30'
56"
52"
37"
45"
08"
45"
LOCATION
151°25'
14"
DISCHARGE
(bbl/d)
N 493
W
N 41
W
N 5,231
W
DISCHARGE
(bbl/d)
N 5,000
W
OPERATOR
Amoco
Amoco
Amoco
OPERATOR
Atlantic
Richfield
Facility13

Trading Bay
Production
Facility0

Kenai    -,
Gas Field

North of East
Foreland Pro-
duction Facility
 60°49'05" N
151°46'59" W
 60023'53" N
151016'36" W

 60°44'13" N
151"21'05" W
12,500
   262
 3,809
Marathon
Union
Shell
     NOTE:  Footnotes are on the following page.
                           -354-

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                  FOOTNOTES TO TABLE D-l
     aData were obtained from Danfofth G. Bodien, Chief,
Water Permits Section, U.S. Environmental Protection Agency,
Seattle, Washington.  Data are for 1975.

      Atlantic Richfield Company, U.S. Army Corps of Engi-
neers, "Application for Permit to Discharge or Work in
Navigable Waters and Their Tributaries," AK-NPD-NPS-2-00019,
1971.

     °Marathon Oil Company, U.S. Army Corps of Engineers,
"Application for Permit to Discharge or Work in Navigable
Waters and Their Tributaries," AK-NPA-NPA-2-000148, 1971.

      Union Oil Company of California, "National Pollutant
Discharge Elimination System Application for Permit to
Discharge," AD-002455-4, 1974.
     (^
      Shell Oil Company, U.S. Army Corps of Engineers,
"Application for Permit to Discharge or Work in Navigable
Waters and Their Tributaries," AK-NPD-NPA-2-000047, 1971.
                            -355-

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                         APPENDIX E
   CALCULATION OF DISPERSION MODEL INPUT PARAMETER VALUES
E.1  Estimate of Tidal and Freshwater Current Velocities
     for Hackberry Bay, Louisiana

     In the absence of actual current measurements it is
necessary to estimate current magnitudes.  Relatively simple
hydrological calculations will suffice for the purpose of
supplying input parameter values for the dispersion model.
To estimate the tidal velocity, the estuary is assumed to be
represented by a channel as in Figure E-l.  The end at y=0
is assumed to be closed, the width at a distance y=y' along
the channel is given by W(y'), and the area enclosed by the
channel boundaries between y=0 and y=y' is given by K(y').
Thus
              fY'
     K(y') =  /   W(y)dy.
             •^ n
The depth H is a function of both location, y, and of * time,
t, since it varies with the tidal influx and ebb.  It is
further assumed that (1) there is no vertical variation in
the velocity of water in the y-direction, V(y,t), and that
(2) the tidal level rises and falls simultaneously at the
same rate for all points in the estuary channel.  A simple
consideration of the relation of the volume of water in the
estuary in the portion which lies between y=0 and y=y' to
the influx or ebb of water through a vertical cross section
at y=y' then gives the equation:
     K(y')      7    =  -V(y',t)W(y')H(y')
Solving for V gives the equation:

                         9H(y',t)
     v, ,  fc) _   K(y')       9t
       ^y '      " W(y')     H(y',t)
                           -357-

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The depth of water, H(y',t) can be  expressed as a sum of two
components:   (1) a mean depth, Ho(y'), which is time
independent, and (2) a sinusoidally varying component,
(A/2) sin[ (2TT/T) t] , where A is the tidal  range (i.e., the dif-
ference between low tide and high tide)  and T is the tidal period,
Thus
     H(y',t) = HQ(y') + -J-  sin(^- t) ,

     3H(y',t)   = _jr    .  e,2ir_
                  _
      3t           T        — t) ,
and,
     3H(y',t)
        3t
                                   .  ,2TT
      H(y',t)      H(y')+--  sin(r- t)
The maximum value of this ratio  is
      T   H0(y')


so that the maximum current  speed  is  given by:

            • v   K(y')  _TT_     A
      max  (y '   W(y')   T    HQ (y' )


     F-or Hackberry Bay, considering a cross section at the
lower end of the bay:


     K = 4,386  acres  =  19,105 x 104 ft2

     W = 2 miles

     T = 24 hours  (diurnal tides)

so that,
                             -358-

-------
           4-  =  0.658 ft/sec

Thus,
     Vmax =0.658-|-  ft/sec
For A = 1 ft, H  =2.4+0.5=2.9 ft
and,



     V    = 0.658 x —^Q-  =  0.22 ft/sec
      lUclX            £. • _7
For A = 0.25 ft, HQ  = 2.4 + 0.125 =  2.5 ft
and,
     V     = 0.065 ft/sec
      max


Given the value of Vmax the tidal velocity is then given bv
Vmax sin [ (27r/T)t].

     To estimate the freshwater current speed, reference is
made to a tabulation-'- of the flood and ebb flow volumes
through the four major passes to Barataria and Caminada
Bays.  This table is reproduced in Appendix A as Table A-9.
The total ebb excess through the four passes is 449 x 10^  ft
If this is taken to be a measure of the freshwater influx  to
the Barataria and Caminada Bay basin each day, then the
freshwater influx in ft3 per second in 5,197 ft^/sec.  It
may be assumed that this freshwater flow must come from the
north through Hackberry Bay and adjacent bay areas.  Assume
further that the freshwater flow is uniformly distributed
      B. Barrett, Cooperative Gulf of Mexico Estuarine  Inven
tory and Study, Louisiana, Phase II:  Hydrology  (New Orleans;
Louisiana Wildlife and Fisheries Commission, 1971), p.  57.
                             -359-

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through a vertical cross section through Hackberry Bay and
the adjacent bay areas.  The width of this cross section is
approximately 11.8 miles (3 inches on a 1:250,000 scale
map).  Hackberry Bay itself has a width of about 2 miles.
Hence the freshwater flow through Hackberry Bay can be
estimated to be:
          x  5,197 ft3/sec.
Let V0 be the freshwater current speed in ft/sec.  Then the
product of Vo and the area of a vertical cross section
through Hackberry Bay must be equal to freshwater flow
through Hackberry Bay.  Thus, taking the average depth of
Hackberry Bay equal to 2.4 feet,


     V  x  (2 x 5,280 x 2.4)  = ^-Q  x  5,197
      O                        J-J- . o

or,


     V   = 0.035 ft/sec
E.2  Calculation of Tidally Averaged Diffusion Coefficient
     for Cook Inlet

     The procedure used for incorporating the effects of  the
Cook Inlet tidal currents into the alongshore diffusion
coefficient, Ey, is as follows.  First the steady downstream
freshwater flow, Vo, was estimated starting with .the stream
flow data for mid and upper Cook Inlet given in Appendix  A,
Table A-3.  Since stream flow data is available only for
some of the sources feeding into Cook Inlet, an estimate  of
the total freshwater influx was obtained by dividing the  sum
of the known mean daily discharges  (62,234 ft-vsec) bY tne
sum of the corresponding drainage areas  (24,847 square
miles) to give an average ratio of 2.5 ft3/sec freshwater
discharge per square mile of drainage area.  Multiplied by
the total drainage area of 46,927 square miles, this gives
an estimated mean daily freshwater runoff rate of 117,500
ft-Vsec.  The vertical cross section area of mid Cook Inlet
in the vicinity of the oil fields was estimated by  computing
the area enclosed by the depth profile curve given  in
Appendix A, Figure A-3 to be 8,120,000 square feet.  Assuming
that the freshwater flow is equally distributed over this
vertical cross section  (a reasonable assumption in  view of
                             -360-

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the expected vigorous mixing resulting from the rapid tidal
currents),  the ratio of the estimated freshwater discharge
rate to the cross section area gives an estimated downstream
freshwater flow speed of 0.014 ft/sec.

     The analytical solution for the steady-state distri-
bution of a conservative substance discharged into a uniform
estuary at y=0 is:2

                   V
     C(y) = C(0)e ~g^ y
                    y

where y is the distance upstream from the discharge point
and Ey is the diffusion coefficient.  The diffusion coeffi-
cient can be estimated if it is assumed that at a distance
of one tidal excursion, yT, (the distance that a particle
can be moved upstream by the tidal currents during half a
tidal cycle) the concentration will have decreased approxi-
mately to e~^ (=0.37) times its value at the discharge
location.  Then,


     V_o
     E  ^T
      y
and,


     E  = V v
      y    o T


Since the mean upstream tidal velocity is approximately 4
ft/sec in mid Cook Inlet,
     yT = 4 x (6 hrs x 3,600     )   = 86,400 ft.

Using this value for yT and the value of 0.014 ft/sec for V
gives an estimated value for E  of


     E  = 1,250 ft2/sec.
     2.
      Tracor, Inc., "Estuarine Modeling:  An Assessment,"
February 1971, NTIS No. PB-206807.
                            -361-

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This value is not far removed from the value of 4700 ft /sec
obtained for Ey in a study-^ of discharges into an arm of Cook
Inlet, Knik Arm.
E.3  Computation of Diffusion Coefficients for Hackberry Bay,
     Louisiana

     The computation of the values of the diffusion coeffi-
cients, Ex and Ey, for Hackberry Bay, Louisiana, is based on
the theory of diffusion in turbulent shear flows.

     The general form for the diffusion coefficient in a
shear flow is:
     •p = fy H H



where,


     E = diffusion coefficient


     a = dimensionless coefficient


     u* = friction velocity


     H = water depth
The friction velocity, u* is further related to the bottom
shear stress by the relationship:


     To  =  pu*
      R. Sage Murphy, et al., Effect of Waste Discharges into
a Salt Laden Estuary.  A Case Study of Cook Inlet, Alaska,
Publication IWR 26 of the Institute of Water Resources,
University of Alaska, Fairbanks, Alaska, November 1972.
                             -362-

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where,
     T   =  bottom shear stress
      o

     p   =  water density

     The relationship between u*  (or TO) and the mean current
velocity, U, is always an empirical one.  The most general
correlation is the following:


            f  r-,2
     To  =  8 PU


where f is a dimensionless friction factor that is a function
of the roughness of the bottom.  With this formulation one
obtains:
     U
Values of f for natural channels range from 0.01 to 0.1
resulting in a range of u*/U values of from 0.035 to 0.110.

     Another often used correlation is the Mannings formula
which is equivalent to the following equality:
         -  3.8
where n is a coefficient that varies from 0.020 to 0.040 for
natural channels.  Thus for channels from 1 to 10 feet
deep, the resulting u*/U ratio varies from 0.050 to 0.140, a
slightly higher range than indicated by the values of the
friction factor.

     For the purposes of further discussion, the value of
uA/U will be based on a value of n = 0.035 which is commonly
used for natural channels.  Assuming a water depth of 3 feet
yields:
                            -363-

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     -  •  o-1


     The value of the dimensionless coefficient, a, will
depend on the type of mixing being parameterized by the
coefficient, E.  The following table summarizes results
given in a review paper by Fischer:4

     Type of Mixing                Range of a

  Transverse diffusion

     1-D Flows (Channels)           0.1 - 0.7

     2-D Flows (Bays)                 1-2.4

  Longitudinal Diffusion

     1-D Flows (Channels)
                                      5 - 400
     2-D Flows (Bays)

     The above results can now be applied to Hackberry Bay.
The water depth is

     H  =   3 feet

and mean velocity approximately,

     U  =   0.25 ft/sec

Using the values of  a in the above table, and a value of
U/U = 0.1  the following values of E are obtained:
     4
      H. Fischer,  "Longitudinal Dispersion and Turbulent
Mixing  in Open-Channel Flow," Annual Review of Fluid Mechanics
Volume  V, ed. by Van Dyke  (Palo Alto, Calif:  Annual Reviews,
Inc., 1972).
                             -364-

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     Type of Mixing
           Range of E
Base Values Used
In Analysis	
   Transverse Diffusion
     1-D Flow
           0.0075-0.053 ft /sec
                                                     = 0.1
     2-D Flow

   Longitudinal
   Diffusion
           0.075-0.18 ft /sec
          0.375-30 ft /sec
     Ey = 1.0
E.4  Calculation of Initial Dilution for Gulf of Mexico
     Computations

     Produced water is generally more saline and hence more
dense than sea water.  Accordingly, the discharged effluent
tends to sink through the receiving waters and to form a
layer at the bottom of the water column.  In the course of
sinking, sea water becomes mixed with the discharged effluent.
The resulting dilution can be estimated using methods developed
for thermal plume prediction,5 since the dilution of heated
water as it rises through cooler receiving waters is completely
analogous to the sinking plume situation encountered in brine
discharge.

     To estimate the initial dilution, it is first necessary
to calculate the Froude number, F, defined as:
          U
           o
          V
Ap
where,
     U   =  effluent discharge velocity
      M.S. Shirazi and L.R. Davis, Workbook of Thermal Plume
Prediction, Volume 1:  Submerged Discharge, EPA-R2-72-005a
(Corvallis, Oregon:  National Environmental Research Center,
U.S. Environmental Protection Agency, August 1972).
                             -365-

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         =  gravitational acceleration


         =  diameter of discharge pipe


         =  density of receiving water
    Ap   =  difference in density of effluent and receiving
            water

Assuming a discharge pipe diameter of one foot and a rate of
effluent discharge of 1 ft^/sec, Uo = 1.27 ft/sec.  The
density of water as a function of salinity has been tabu-
lated by the U.S. Navy Hydraulics Office, and salinity can   ,
be related to the chloride ion concentration by the relation:
     S(ppt)  = 1.80655 Cl~ (ppt)
Using the value of 61 ppt Cl  in Louisiana produced water
and the value of 19 ppt Cl  in sea water gives
     S      .     =34.3 ppt
      sea water          ^c
     produced water = 110>1 ppt
The above-mentioned density-salinity tabulation then gives
 (using linear extrapolation to obtain the density corres-
ponding to the produced water salinity):


     P      .        1.0228
      sea water


      produced water
      A. Duxbury, The Earth and Its Oceans  (Reading, Mass.:
Addison-Wesley Publishing Co.), p. 116.
                            -366-

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Hence,
     F =  	LilZ	  =  o.95
v.
                   1.0797 - 1.0228
                         1.0228
     For a conservative estimate of dilution, assume that
the effluent is discharged vertically downward.  Then the
chart on p. 81 of the EPA Workbook  (reproduced as Figure E-2)
can be used together with the value of the Froude number,
F = 1, and data on the total water depth to estimate the
initial dilution.  The normalized vertical distance Z/D
plotted on the horizontal axis in Figure E-2 is, in our
notation, the water depth H divided by the diameter of the
discharge pipe, d (more accurately, Z/D is equivalent to
(H - H2)/d where H2 is the thickness of the layer formed by
the effluent at the bottom of the water column;  H2 - H/6).
The vertical axis of Figure E-2 is, in our notation, 1/D,
where D is the initial dilution.  Thus, for example, using a
value of H = 33 feet, and a value of d = 1 foot, the nor-
malized vertical distance is [33-(33/6)]/l = 27.5.  Reading
upwards from 27.5 on the horizontal axis of Figure E-2 until
the F = 1 curve is reached, and then reading across to the
vertical axis gives a value of 1/D = 0.04 or D = 25.
                            -367-

-------
                         1.0
I
CO
CTi
CD
I
                         0.1
                     s
                     ui
                     a.
                     Z
X.
-j
a:
                         0.01
                                 20 27.5  40
                                                                       RNN
                                                                       TEMPERATURE/WIDTH CHART
                                                                       6 • 90"
                          60     80     100

                            VERTICAL DISTANCE Z/0
                                                                 120
140
160
                                                                180
                                                                                            200
                           Figure E-2.  Temperature-width chart for  single jets  discharging
                      into a non-stratified  stagnant  large body of water:  RNN,  9=90°.
                      (U.S. Environmental Protection  Agency, Workbook of Thermal Plume Pre-
                      diction,  Volume 1;  Submerged Discharge, August 1972, p.  81.)

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                         APPENDIX F


                 HYDROCARBON BIOACCUMULATION
     Many marine organisms have the capacity to take up and
accumulate hydrocarbons from their environments.  This has
been demonstrated in mussels, clams, oysters, crabs, shrimp,
sponge and fish, among others.  Both field and laboratory
studies have dealt with the accumulation problem.  Although
the results of these studies are varied and often inconsis-
tent, they do succeed in demonstrating that the ability to
accumulate hydrocarbons is widespread among marine organisms.
In this section the general nature of hydrocarbon uptake,
metabolism, storage and discharge will be discussed, and
summaries of the current understanding of accumulation
capabilities of various organisms will then be presented.

     Uptake of petroleum hydrocarbons from seawater can be
accomplished by four means:

     1.   Ingestion of particles onto which hydrocarbons
          have been adsorbed.  These particles can be either
          biotic (e.g., plankton) or non-biotic  (e.g.,
          sand.

     2.   Adsorption onto exposed body surfaces.

     3.   Active uptake of dissolved or dispersed
          petroleum, as in the gills of bivalves.

     4.   Intake of water into the gut of organisms that
          drink or gulp water.

Entry through the gill membranes of dissolved or dispersed
oil occurs widely in molluscs, crustaceans, and fish.  Many
marine animals ingest contaminated food, sediment particles,
or water.  To date there has been no conclusive demonstration
of food web magnification of petroleum hydrocarbons.

     Once hydrocarbons have been taken up by an organism,
they can be stored and accumulated, metabolized, or dis-
charged.  In general, storage takes place in the hepato-
pancreas of invertebrates, and in the liver of fish.  There
are many other sites of accumulation, however, as will be
discussed below.
                            -369-

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     Marine fish and some marine invertebrates can metabo-
lize both paraffinic and aromatic hydrocarbons.1  Some
copepods can metabolize paraffins, but not aromatics.
Organisms such as phytoplankton, zooplankton, and many
marine invertebrates appear to be unable to metabolize any
hydrocarbons.  Petroleum metabolism occurs in the liver of
fish and in the hepatopancreas of invertebrates.

     Most marine organisms which have accumulated signifi-
cant internal concentrations of petroleum hydrocarbons have
been found able to release much of the contamination upon
transfer to clean, unpolluted water.  Blumer^ reported long
term retention of hydrocarbons by shellfish, but his results
have not been reproduced in subsequent studies.  As will be
shown below, tissue contamination, if not lethal, can gener-
ally be discharged when the source of pollution is removed.

     Clark and Finley  studied accumulation by sea urchins
and crabs exposed to Navy Special Fuel Oil following the
grounding of a Navy vessel on the coast of Washington.
Purple sea urchins accumulated 2.4 ppm dry weight of n-
parrafins; the crabs (Hemigrapsus nudus) contained 1.2 ppm.
These animals were exposed to a continuous low level of
contamination, since oil leaked continuously from the
wrecked ship for a long period of time.
      Richard F. Lee and A.A. Benson, "Fate of Petroleum
in the Sea:  Biological Aspects," in Background Papers for
a Workshop on Inputs, Fates, and Effects of Petroleum in
the Marine Environment  (Washington, D.C.:  National Academy
of Sciences, 1973) .

      M. Blumer, S.  Souza, and J. Sass, "Hydrocarbon Pollu-
tion of Edible Shellfish by an Oil Spill," Marine Biology 5
(1970): 195-202.

      Robert C. Clark, Jr. and John S. Finley, "Long-Term
Chemical and Biological Effects of Persistent Oil Spill
Following the Grounding of the General M.C. Meigs," in
Proceedings of the 1975 Conference on Prevention and Control
of Oil Pollution, American Petroleum Institute, U.S. Environ-
mental Protection Agency, 1975.
                             -370-

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     Hydrocarbon accumulation in shrimp has been studied by
a number of investigators, since shrimp are an important
commercial product, and are consumed directly by humans.
Grass shrimp  (Palaemonetes pugio) exposed to 0.07 ppm naph-
thalenes in an oil-water dispersion accumulated up to 3 ppm  .
wet weight of naphthalenes during a 12-hour exposure period.
Upon transfer to clean water the shrimp discharged the
hydrocarbons readily.  Tissue hydrocarbon levels were normal
after 14 to 38 hours of depuration.  Brown shrimp exposed to
0.3 ppm No. 2 fuel oil for 20 hours accumulated up to 800 ppm
of naphthalenes in the digestive gland.  After one hour
of depuration the abdominal muscle tissue — the part
consumed by humans — had returned to the normal background
hydrocarbon level.  Hydrocarbons were retained in the diges-
tive gland and the gills after 250 hours depuration.  This
is due to the much greater accumulation in the digestive
gland.  The gills, a site of hydrocarbon uptake and release,
can be expected to retain high concentrations for a longer
period of time than other tissues.

     Mussels are often used for contamination experiments
for a number of reasons.  They are widespread and readily
available.  They are a convenient size — small enough to
sample adequately but large enough to dissect for specific
organ analysis.  They are a major energy transfer pathway in
intertidal ecosystems, utilizing plankton and debris as food
sources.  Finally, they have a well known capacity to accumu-
late pollutants.  Clark and Finley5 maintained mussels
(Mytilus edulis) beneath an experimental No. 2 fuel oil
slick for 48 hours, and observed body concentrations of
29 ppm dry weight.  The n-paraffin residual pattern (the n-
paraffin composition of the exposed animal minus the normal
n-paraffin composition) was similar to the fuel composition,
indicating non-selective uptake of hydrocarbons.  Most of
the accumulated paraffins were released when the mussels
were transferred to clean water, although a certain residual
remained.
     4
      Jack W. Anderson, ed., Laboratory Studies on the
Effects of Oil on Marine Organisms;  An Overview, American
Petroleum Institute Publication #4249, 1975.

      R.C. Clark, Jr. and J.S. Finley, "Uptake and Loss of
Petroleum Hydrocarbons by the Mussel, Mytilus edulis, in
Laboratory Experiments," Fishery Bulletin 73  (1975): SOS-
SIS.
                             -371-

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     Lee et al.   examined distribution of hydrocarbons in
different tissues of M. edulis after exposure to heptadecane
and to naphthalene for 24 hours.  Twenty-four hour exposure
to 6.2 ppm heptadecane resulted in the following tissue
concentrations:   (ppt dry weight)   Whole  6.0, Gill - 13.0,
Mantle - 7.8, Adductor muscle - 1.4, and Gut - 20.0.
Results were similar for a four hour exposure to 32 ppm
naphthalene:  (ppt dry weight) Whole - 7.0, Gill - 9.0,
Mantle - 2.0, Adductor muscle - 6.0, and Gut -7.0.  Over
90 percent of the accumulated hydrocarbons were discharged
after transfer to clean water.  No evidence was found for
hydrocarbon metabolism.

     Fossato  transferred mussels (Mytilus galloprovincialis)
from an environment polluted with diesel fuels, gasoline,
and lubricating oils to an unpolluted environment and mon-
itored depuration.  In the first 10 to 15 days the concen-
tration dropped exponentially to about 12 percent of its
initial value.  Thereafter the decrease was extremely slow.
Within the range 7.5° C to 26.0° C the rate of depuration
appeared to be temperature independent.

     Mytilus californianus transferred from clean water to
a polluted area of the San Francisco Bay accumulated 325 ppm
dry weight hydrocarbons in three months.8  Five weeks after
the mussels had been transferred back to the unpolluted
water they had released 90 percent of the hydrocarbons to
the environment.  However, M. edulis that had grown up in
the polluted area experienced only minor losses of contami-
nants during a 10-week period in clean water.  Eggs from
unpolluted organisms of the same species accumulated 332 ppm
dry weight of hydrocarbons during a 10-week exposure to
polluted water.   Seventy-six percent of the contamination
was composed of aromatics.  Results of this study indicate
that mussels transferred from clean to polluted water and
      Richard F. Lee, Richard Sauerheber and A.A. Benson,
"Petroleum Hydrocarbons:  Uptake and Discharge by the Marine
Mussel Mytilus edulis," Science 177  (1972) : 344-346.

      Valentino U. Fossato, "Elimination of Hydrocarbons by
Mussels," Marine Pollution Bulletin 6  (1975): 7-10.
     Q
      Louis H. Disalvo, Harold E. Guard, and Leon Hunter,
"Tissue Hydrocarbon Burden of Mussels as Potential Monitor
of Environmental Hydrocarbon Insult," Environmental Science
and Technology 9  (1975): 247-251.
                             -372-

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back readily discharged accumulated petroleum, whereas
mussels originally taken from the polluted waters retained
much of their hydrocarbon body burden even in clear water.
This may suggest the existence of two types of accumulation:
short-term accumulation in which take-up and release are
rapid, and long-term or chronic accumulation where the
concentration is built up over an extended period of time
and is not readily discharged.

     The American oyster, Crassostrea virginica, has also
been the subject of much study.  J. Anderson^ exposed oysters
to 1 percent oil-water dispersions of four oils for four
days with the following resultant tissue concentrations of
hydrocarbons:  No. 2 fuel oil - 96.7 ppm net weight; Bunker
C oil - 47.4 ppm; South Louisiana crude - 65.8 ppm; and
Kuwait crude - 107.1 ppm.  These results agree with results
of an identical experiment performed by R. Anderson.!^  In
this second study aromatics were found to accumulate to a
greater extent than saturated hydrocarbons.  R. Anderson
also collected contaminated oysters from a polluted area of
Galveston Bay, Texas, and transferred them to clean water to
observe depuration processes.  Within 52 days tissue hydro-
carbon levels were below 0.1 ppm.  This result differs from
the observations described above regarding M. -edulis, which
were not found to depurate readily having grown up in polluted
waters.

     Stegeman and Teal   exposed two groups of oysters
(Crassostrea virginica) to 106 ppb No. 2 Fuel oil for
different lengths of time and observed hydrocarbon uptake.
The original lipid content of one group was, for unknown
reasons, twice that of the other.  Rate of petroleum uptake
was proportional to lipid content.  The rate of increase of
the Accumulated oil/original lipid ratio was the same for
     9
      Anderson, Laboratory Studies of Oil on Marine Organisms.

       Roger D. Anderson, "Petroleum Hydrocarbons and Oyster
Resources of Galveston Bay, Texas," in Conference on Preven-
tion and Control of Oil Pollution, U.S. Environmental Protec-
tion Agency, U.S. Geological Survey, American Petroleum
Institute, 1975.

       J.J. Stegeman and J.M. Teal, "Accumulation, Release,
and Retention of Petroleum Hydrocarbons by the Oyster
Crassostrea virginica," Marine Biology 22 (1973) : 37-44.
                             -373-

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the two groups.  Hydrocarbon concentrations were 334 ppm
after 50 days exposure, and 161 after 35 days exposure for
the high lipid content group.  Uptake was found to increase
to a peak, and then to decrease with increasing time of
exposure.  Aromatics comprised a greater percentage of
accumulated hydrocarbons than of the original oil.  Forty-
one percent of tissue contamination was aromatics versus
only 15 percent of the fuel oil.  This indicates either
selective uptake or selective discharge.  For seawater
hydrocarbon concentrations up to 450 ppb the uptake rate is
proportional to hydrocarbon concentration in the medium.
Thereafter the rate falls.  At 900 ppb, the oysters remain
closed, and uptake is minimal.  Oysters eliminated all but
34 ppm of the accumulated oil upon transfer to clean water.

     Twenty-four hour exposure of the clam Rangia cuneata to
0.0305 ppm benzo[ajpyrene resulted in tissue concentrations
of 5.2 to 7.2 ppm benzo[a]pyrene.^2  Accumulation occurred
mainly in the viscera — digestive system, gonads, and
heart.  Thirty days depuration left 0.07 ppm of contaminant;
after 58 days less than 0.01 ppm remained.

     Anderson   found Rangia cuneata to accumulate 3 ppm
n-paraffins and 158 ppm aromatics during a 24-hour exposure
to a 1,000 ppm dispersion of No. 2 fuel oil in seawater.
The mechanism leading to the disproportionate concentration
of aromatics is unknown.

     In Mya arenaria  (soft shell clam) small micelles of
No. 2 fuel oil appeared to be ingested in the same manner as
food, and were passed directly to the stomach.14  Larger
oil particles were bound by mucus secreted by the gills.
This mucus-oil mixture can later be released or ingested.
     12
      • Jerry M. Neff and Jack W. Anderson, "Accumulation,
Release and Distribution of Benzo[a]pyrene-C in the Clam
Rangia cuneata," in Conference on Prevention and Control
of Oil Pollution, U.S. Environmental Protection Agency,
American Petroleum Institute, U.S. Geological Survey, 1975.

       Anderson, Laboratory Studies of Oil on Marine
Organisms.

     14
       Dennis M. Stainken, "Preliminary Observations on the
Mode of Accumulation of No. 2 Fuel Oil by the Soft Shell Clam,
Mya arenaria," in Conference on Prevention and Control of Oil
Pollution, U.S. Environmental Protection Agency, American
Petroleum Institute, U.S. Geological Survey, 1972.
                             -374-

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Discharge of the accumulated oil in mucus may present a
hazard to bottom dwelling organisms by enhancing petroleum
concentration in the sediment.

     Anderson demonstrated a range of responses of the fish
Fundulus similus to No. 2 fuel oil.  Some fish accumulated
oil to a much greater extent than others.  Accumulation was
found to occur in the gall bladder, heart, liver and brain.
Complete depuration took 366 hours.

     Cod (Gadus morhua) exposed to Kuwait crude accumulated
C15~C33 n-alkanes in the liver.15  C24-C28 n-alkanes were
particularly concentrated, suggesting either selective
accumulation or selective matabolism.  An experiment showing
that hexadecane concentrated in cod liver remains unmetabo-
lized indicated that selective accumulation is probable.
The process of selective accumulation is not known.

     In summary, it is clear that many organisms do have the
ability to take up and accumulate petroleum hydrocarbons
from their environment.  In some cases concentration to
toxic levels can occur.  In many cases, however, marine
organisms appear to be relatively unaffected by internal
hydrocarbon accumulation.  Some organisms can metabolize
oils; most are able to release the contaminants upon trans-
fer to clean water.  There is no evidence for biomagnifi-
cation in the food chain of petroleum concentrations as a
result of accumulation by individual organisms.  It is not
clear that bioaccumulation of hydrocarbons has any partic-
ularly significant negative effects on many organisms.  More
comprehensive, standardized research in this field is needed
before the mechanisms and consequences of oil accumulation
will be understood.
       R. Hardy, P.R. Mackie, and K.J. Whittle, "Discrimi-
nation in the Assimilation of n-alkanes in Fish," Nature
252  (1974): 557-578.
                             -375-

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                              TECHNiCAL REPORT DATA
                        (Plcasr rrnd laanicli(>n* on tin- ret crsc he tor- t f*NO.
           5. REPORT DATr
             (Date of  Issue)  May 1977
           6. PERFORMING ORGANIZATION CODb
7 AUTHOR(S)
 Robert Shore, Joseph Post,  Myron Allen,
 Lisa Levin, Bill Taffel
                                                   8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Energy Resources Company  Inc.
 185 Alewife Brook Parkway
 Cambridge, Mass.  02138
                                                   10. PROGRAM ELEMENT NO.
            11. CONTRACT/GRANT NO.
              68-01-4177
12. SPONSORING AGENCY NAME AND ADDRESS
U.S.  Environmental Protection Agency
Office of Water Planning  and Standards
Waterside Mall
Washington, D.C.	
            13. TYPE OF REPORT ANO PERIOD COVERED
                  Final Report
            14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
 A study was performed  to  evaluate the environmental benefits of the EPA
 BATEA effluent limitations for the disposal of  oilfield brines produced
 in coastal oil and gas extraction.  For each  of four selected locations
 (Hackberry Bay, La.; Cook Inlet, Alaska; Grand  Isle, La.; and Far Offshore
 Gulf of Mexico) data was  gathered regarding the composition of the dis-
 charged brines, rate of discharge, key hydrodynamic variables influencing
 brine dispersion, and  the site ecology.  A computer dispersion model was
 used to calculate the  areas around the point  of discharge that would be
 characterized by a given  dilution level.  An  intensive literature survey
 of the toxic effects of oil hydrocarbons and  trace metals was used togeth-
 er with the dispersion model results to estimate the area of a zone around
 each discharge point outside of which impacts could be expected to be
 negligibly small.  Impacts were found to be highly site-specific in
 nature.
17.
                           KEY WORDS AND DOCUMENT ANALYSIS
               DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS  C. COSATI l-'iuld/Groilp
 Offshore Oil Production,  Oilfield
 Brines, Oil Hydrocarbons,  Trace
 Metals, BPCTC and  BATEA Effluent
 Limitations, Coastal  Waters,  Environ'
 mental Impacts, Dispersion Modeling,
 Toxicity, Water Pollution
13. DISTRIBUTION STATEMENT

     Release Unlimited
19. SECURITY CLASS (Tins Report)

         U
21. NO. OH r>AG£S
   399
                                       20 SECURITY CLASS (Tin

                                                 U
                                                              22. PRICE
EPA Form 22:0-1 (9-73)

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U.S. ENVIRONMENTAL PROTECTION AGENCY (WH-586)
WASHINCTON, D.C. 20460               V        '
          POSTAGE AND FEES PAID
ENVIRONMENTAL PROTECTION AGENCY
                       EPA-335
                                                              SPECIAL FOURTH CLASS
                                                              BULK RATE BOOK

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