903R78100
U.S. ENVIRONMENTAL PROTECTION AGENCY
Region III
Central Regional Laboratory
839 Bestgate Road
Annapolis, Maryland 21401
SPECIAL REPORTS
1978
U.S. EK'v Region III
Icefbn.'j! Center for Environmental
lf-r,0 Arch Street (3PM52)
PJi-l«
-------
Table of Contents
Volume 25
A Water Quality Modelling Study of the Delaware Estuary - January 1978
Leo J. Clark, Robert B. Ambrose, Jr. and Rachel C. Crain - EPA-903/9-78-001
Biochemical Studies of the Potomac Estuary - Summer 1978
Joseph L. Slayton and E. Ramona Trovato - EPA-903/9-78-005
Analysis of Sulfur in Fuel Oils by Energy-Dispersive X-Ray Fluorescence
E. R. Travato, J. W. Barren and J. L. Slayton - EPA-600/9-78-006
Assessment of 1977 Water Quality Conditions in the Upper Potomac Estuary
Leo J. Clark and Stephen E. Roesch - EPA-903/9-78-008
-------
PUBLICATIONS
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION III
ANNAPOLIS FIELD OFFICE*
VOLUME 1
Technical Reports
5 A Technical Assessment of Current Water Quality
Conditions and Factors Affecting Water Quality in
the Upper Potomac Estuary
6 Sanitary Bacteriology of the Upper Potomac Estuary
7 The Potomac Estuary Mathematical Model
9 Nutrients in the Potomac River Basin
11 Optimal Release Sequences for Water Quality Control
in Multiple Reservoir Systems
VOLUME 2
Technical Reports
13 Mine Drainage in the North Branch Potomac River Basin
15 Nutrients in the Upper Potomac River Basin
17 Upper Potomac River Basin Water Quality Assessment
VOLUME 3
Technical Reports
19 Potomac-Piscataway Dye Release and Wastewater .
Assimilation Studies
21 LNEPLT
23 XYPLOT
25 PLOT3D
* Formerly CB-SRBP, U.S. Department of Health, Education,
and Welfare; CFS-FWPCA, and CTSL-FWQA,, Middle Atlantic
Region, U.S. Department of the Interior
-------
VOLUME 3 (continued)
Technical Reports
27 Water Quality and Wastewater Loadings - Upper Potomac
Estuary during 1969
VOLUME 4
Technical Reports
29 Step Backward Regression
31 Relative Contributions of Nutrients to the Potomac
River Basin from Various Sources
33 Mathematical Model Studies of Water Quality in the
Potomac Estuary
35 Water Resource - Water Supply Study of the Potomac
Estuary
VOLUME 5
Technical Reports
37 Nutrient Transport and Dissolved Oxygen Budget
Studies in the Potomac Estuary
39 Preliminary Analyses of the Wastewater and Assimilation
Capacities of the Anacostia Tidal River System
41 Current Water Quality Conditions and Investigations
in the Upper Potomac River Tidal System
43 Physical Data of the Potomac River Tidal System
Including Mathematical Model Segmentation
45 Nutrient Management in the Potomac Estuary
VOLUME 6
Technical Reports
47 Chesapeake Bay Nutrient Input Study
49 Heavy Metals Analyses of Bottom Sediment in the
Potomac River Estuary
-------
VOLUME 6 (continued)
Technical Reports
51 A System of Mathematical Models for Water Quality
Management
52 Numerical Method for Groundwater Hydraulics
53 Upper Potomac Estuary Eutrophication Control
Requirements
54 AUT0-QUAL Modelling System
Supplement AUT0-QUAL Modelling System: Modification for
to 54 Non-Point Source Loadings
VOLUME 7
Technical Reports
55 Water Quality Conditions in the Chesapeake Bay System
56 Nutrient Enrichment and Control Requirements in the
Upper Chesapeake Bay
57 The Potomac River Estuary in the Washington
Metropolitan Area - A History of its Water Quality
Problems and their Solution
VOLUME Si-
Technical Reports
58 Application of AUT0-QUAL Modelling System to the
Patuxent River Basin
59 Distribution of Metals in Baltimore Harbor Sediments
60 Summary and Conclusions - Nutrient Transport and
Accountability in the Lower Susquehanna River Basin
VOLUME '9
Data Reports
Water Quality Survey, James River and Selected
Tributaries - October 1969
Water Quality Survey in the North Branch Potomac River
between Cumberland and Luke, Maryland - August 1967
-------
-------
VOLUME 9. (continued)
Data Reports
Investigation of Water Quality in Chesapeake Bay and
Tributaries at Aberdeen Proving Ground, Department
of the Army, Aberdeen, Maryland - October-December 1967
Biological Survey of the Upper Potomac River and
Selected Tributaries - 1966-1968
Water Quality Survey of the Eastern Shore Chesapeake
Bay, Wicomico River, Pocomoke River, Nanticoke River,
Marshall Creek, Bunting Branch, and Chincoteague Bay -
Summer 1967
Head of Bay Study - Water Quality Survey of Northeast
River, Elk River, C & D Canal, Bohemia River, Sassafras
River and Upper Chesapeake Bay - Summer 1968 - Head ot
Bay Tributaries
Water Quality Survey of the Potomac Estuary - 1967
Water Quality Survey of the Potomac Estuary - 1968
Wastewater Treatment Plant Nutrient Survey - 1966-1967
Cooperative Bacteriological Study - Upper Chesapeake Bay
Dredging Spoil Disposal - Cruise Report No. 11
VOLUME 10
Data Reports
9 Water Quality Survey of the Potomac Estuary - 1965-1966
10 Water Quality Survey of the Annapolis Metro Area - 1967
11 Nutrient Data on Sediment Samples of the Potomac Estuary
1966-1968
12 1969 Head of the Bay Tributaries
13 Water Quality Survey of the Chesapeake Bay in the
Vicinity of Sandy Point - 1968
14 Water Quality Survey of the Chesapeake Bay in the
Vicinity of Sandy Point - 1969
-------
VOLUME 10(continued)
Data Reports
15 Water Quality Survey of the Patuxent River - 1967
16 Water Quality Survey of the Patuxent River - 1968
17 Water Quality Survey of the Patuxent River - 1969
18 Water Quality of the Potomac Estuary Transects,
Intensive and Southeast Water Laboratory Cooperative
Study - 1969
19 Water Quality Survey of the Potomac Estuary Phosphate
Tracer Study - 1969
VOLUME 11
Data Reports
20 Water Quality of the Potomac Estuary Transport Study
1969-1970
21 Water Quality Survey of the Piscataway Creek Watershed
1968-1970
22 Water Quality Survey of the Chesapeake Bay in the
Vicinity of Sandy Point - 1970
23 Water Quality Survey of the Head of the Chesapeake Bay
Maryland Tributaries - 1970-1971
24 Water Quality Survey of the Upper Chesapeake Bay
1969-1971
25 Water Quality of the Potomac Estuary Consolidated
Survey - 1970
26 Water Quality of the Potomac Estuary Dissolved Oxygen
Budget Studies - 1970
27 Potomac Estuary Wastewater Treatment Plants Survey
1970
28 Water Quality Survey of the Potomac Estuary Embayments
and Transects - 1970
29 Water Quality of the Upper Potomac Estuary Enforcemant
Survey - 1970
-------
30
31
32
33
34
Appendix
to 1
Appendix
to 2
3
4
VOLUME IT (continued)
Data Reports
Water Quality of the Potomac Estuary - Gilbert Swamp
and Allen's Fresh and Gunston Cove - 1970
Survey Results of the Chesapeake Bay Input Study -
1969-1970
Upper Chesapeake Bay Water Quality Studies - Bush River,
Spesutie Narrows and Swan Creek, C & D Canal, Chester
River, Severn River, Gunpowder, Middle and Bird Rivers -
1968-1971
Special Water Quality Surveys of the Potomac River Basin
Anacostia Estuary, Wicomico .River, St. Clement and
Breton Bays, Occoquan Bay - 1970-1971
Water Quality Survey of the Patuxent River - 1970
VOLUME 12
Working Documents
Biological Survey of the Susquehanna River and its
Tributaries between Danville, Pennsylvania and
Conowingo, Maryland
Tabulation of Bottom Organisms Observed at Sampling
Stations during the Biological Survey between Danville,
Pennsylvania and Conowingo, Maryland - November 1966
Biological Survey of the Susquehanna River and its
Tributaries between Cooperstown, New York and
Northumberland, Pennsylvnaia - January 1967
Tabulation of Bottom Organisms Observed at Sampling
Stations during the Biological Survey between Cooperstown,
New York and Northumberland, Pennsylvania - November 1966
VOLUME 13
Working Documents
Water Quality and Pollution Control Study, Mine Drainage
Chesapeake Bay-Delaware River Basins - July 1967
Biological Survey of Rock Creek (from Rockville, Maryland
to the Potomac River) October 1966
-------
-------
VOLUME *13 (continued)
Working Documents
5 Summary of Water Quality and Waste Outfalls, Rock Creek
in Montgomery County, Maryland and the District of
Columbia - December 1966
6 Water Pollution Survey - Back River 1965 - February 1967
7 Efficiency Study of the District of Columbia Water
Pollution Control Plant - February 1967
VOLUME 14
Working Documents
8 Water Quality and Pollution Control Study - Susquehanna
River Basin from Northumberland to West Pittson
(Including the Lackawanna River Basin) March 1967
9 Water Quality and Pollution Control Study, Ouniata
River Basin - March 1967
10 Water Quality and Pollution Control Study, Rappahannock
River Basin - March 1967
11 Water Quality and Pollution Control Study, Susquehanna
River Basin from Lake Otsego, New York, to Lake Lackawanna
River Confluence, Pennsylvania - April 1967
VOLUME 15
Working Documents
12 Water Quality and Pollution Control Study, York River
Basin - April 1967
13 Water Quality and Pollution Control Study, West Branch,
Susquehanna River Basin - April 1967
14 Water Quality and Pollution Control Study, James River
Basin - June 1967 ,
15 Water Quality and Pollution Control Study, Patuxent River
Basin - May 1967
-------
VOLUME 16
Working Documents
16 Water Quality and Pollution Control Study, Susquehanna
River Basin from Northumberland, Pennsylvania, to
Havre de Grace, Maryland - July 1967
17 Water Quality and Pollution Control Study, Potomac
River Basin - June 1967
18 Immediate Water Pollution Control Needs, Central Western
Shore of Chesapeake Bay Area (Magothy, Severn, South, and
West River Drainage Areas) July 1967
19 Immediate Water Pollution Control Needs, Northwest
Chesapeake Bay Area (Patapsco to Susquehanna Drainage
Basins in Maryland) August 1967
20 Immediate Water Pollution Control Needs - The Eastern
Shore of Delaware, Maryland and Virginia - September 1967
VOLUME 17 '
Working Documents
21 Biological Surveys of the Upper James River Basin
Covington, Clifton Forge, Big Island, Lynchburg, and
Piney River Areas - January 1968
22 Biological Survey of Antietam Creek and some of its
Tributaries from Waynesboro, Pennsylvania to Antietam,
Maryland - Potomac River Basin - February 1968
23 Biological Survey of the Monocacy River and Tributaries
from Gettysburg, Pennsylvania, to Maryland Rt. 28 Bridge
Potomac River Basin - January 1968
24 Water Quality Survey of Chesapeake Bay in the Vicinity of
Annapolis, Maryland - Summer 1967
25 Mine Drainage Pollution of the North Branch of Potomac
River - Interim Report - August 1968
26 Water Quality Survey in the Shenandoah River of the
Potomac River Basin - June 1967
27 Water Quality Survey in the James and Maury Rivers
Glasgow, Virginia - September 1967
-------
VOLUME 17' (continued)
Working Documents
28 Selected Biological Surveys in the James River Basin,
Gillie Creek in the Richmond Area, Appomattox River
in the Petersburg Area, Bailey Creek from Fort Lee
to Hopewell - April 1968
VOLUME 18
Working Documents
29 Biological Survey of the Upper and Middle Patuxent
River and some of its Tributaries - from Maryland
Route 97 Bridge near Roxbury Mills to the Maryland
Route 4 Bridge near Wayson's Corner, Maryland -
Chesapeake Drainage Basin - June 1968
30 Rock Creek Watershed - A Water Quality Study Report
March 1969
31 The Patuxent River - Water Quality Management -
Technical Evaluation - September 1969
VOLUME 19
Working Documents
Tabulation, Community and Source Facility Water Data
Maryland Portion, Chesapeake Drainage Area - October 1964
Waste Disposal Practices at Federal Installations
Patuxent River Basin - October 1964
Waste Disposal Practices at Federal Installations
Potomac River Basin below Washington, D.C.- November 1964
Waste Disposal Practices at Federal Installations
Chesapeake Bay Area of Maryland Excluding Potomac
and Patuxent River Basins - January 1965
The Potomac Estuary - Statistics and Projections -
February 1968
Patuxent River - Cross Sections and Mass Travel
Velocities - July 1968
-------
VOLUME 19 (continued)
Working Documents
Wastewater Inventory - Potomac River Basin -
December 1968
Wastewater Inventory - Upper Potomac River Basin -
October 1968
VOLUME 20
Technical:Paperso
1 A Digital Technique for Calculating and Plotting
Dissolved Oxygen Deficits
2 A River-Mile Indexing System for Computer Application
in Storing and Retrieving Data (unavailable)
3 Oxygen Relationships in Streams, Methodology to be
Applied when Determining the Capacity of a Stream to
Assimilate Organic Wastes - October 1964
4 Estimating Diffusion Characteristics of Tidal Waters
May 1965
5 Use of Rhodamine B Dye as a Tracer in Streams of the
Susquehanna River Basin - April 1965
6 An In-Situ Benthic Respirometer - December 1965
7 A Study of Tidal Dispersion in the Potomac River
February 1966
8 A Mathematical Model for the Potomac River - what it
has done and what it can do - December 1966
9 A Discussion and Tabulation of Diffusion Coefficients
for Tidal Waters Computed as a Function of Velocity
February 1967
10 Evaluation of Coliform Contribution by Pleasure Boats
July 1966
-------
VOLUME 21
Technical Papers
11 A Steady State Segmented Estuary Model
12 Simulation of Chloride Concentrations in the
Potomac Estuary - March 1968
13 Optimal Release Sequences for Water Quality
Control in Multiple-Reservoir Systems - 1968
VOLUME .22'
Technical Papers
Summary Report - Pollution of Back River - January 1964
Summary of Water Quality - Potomac River Basin in
Maryland - October 1965
The Role of Mathematical Models in the Potomac-River
Basin Water Quality Management Program - December 1967
Use of Mathematical Models as Aids to Decision Making
in Water Quality Control - February 1968
Piscataway Creek Watershed - A Water Quality Study
Report - August 1968
VOLUME 23
Ocean Dumping Surveys
Environmental Survey of an Interim Ocean Dumpsite,
Middle Atlantic Bight - September 1973
Environmental Survey of Two Interim Dumpsites,
Middle Atlantic Bight - January 1974
Environmental Survey of Two Interim Dumpsites
Middle Atlantic Bight - Supplemental Report -
October 1974
Effects of Ocean Disposal Activities on Mid-
continental Shelf Environment off Delaware
and Maryland - January 1975
-------
VOLUME 24
Supplemental Reports
Current Nutrient Assessment - Upper Potomac Estuary - June 1975
Distribution of Metals in Elizabeth River Sediments - June 1976
Effects of Ocean Dumping Activity - Mid-Atlantic Bight - 1976
Interim Report
Statistical Analysis of Dissolved Oxygen Sampling Procedures by
the Annapolis Field Office
Herbicide Analysis of Chesapeake Bay Waters - June 1977
Carbonaceous and Nitrogenous Demand Studies of the Potomac Estuary
Summer 1977
Algal Nutrient Studies of the Potomac Estuary - Summer 1977
VOLUME 25
Special Reports
A Water Quality Modelling Study of the Delaware Estuary - January 1978
Biochemical Studies of the Potomac Estuary - Summer 1978
Analysis of Sulfur in Fuel Oils by Energy-Dispersive X-Ray Fluorescence
January 1978
Assessment of 1977 Water Quality Conditions in the Upper Potomac Estuary
July 1978
VOLUME 26
Special Reports
User's Manual for the Dynamic (Potomac) Estuary Model - January 1979
Lehigh River Intensive - March 1979
Simplified N.O.D. Determination - May 1979
-------
VOLUME 27
Special Reports
A User's Manual for the Dynamic Delaware Estuary Model - April 1980
Assessment of 1978 Water Quality Conditions in the Upper Potomac
Estuary - March 1980
-------
EPA 903/9-78-001
A WATER QUALITY MODELLING STUDY
OF THE
DELAWARE ESTUARY
January 1978
Technical Report No. 62
Annapolis Field Office
Region III
Environmental Protection Agency
-------
EPA 903/9-78-001
Annapolis Field Office
Region III
Environmental Protection Agency
A WATER QUALITY MODELLING STUDY
OF THE
DELAWARE ESTUARY
Technical Report No. 62
January 1978
Leo J. Clark
Robert B. Ambrose, Jr.
Rachel C. Grain
-------
This report has been reviewed by Region III, EPA, and approved
for publication. Approval does not signify that the contents neces-
sarily reflect the views and policies of the Environmental Protection
Agency, nor does the mention of trade names or commercial products
constitute endorsement or recommendation for use.
-------
ABSTRACT
Recent data acquisition, analysis, and mathematical modelling
studies were undertaken to improve the understanding of water quality
interactions, particularly as they impact DO, in the Delaware
Estuary. A version of the Dynamic Estuary Model, after undergoing
considerable modification, was applied in an iterative process of
hypothesis formation and testing. Both model parameters and model
structure were updated and improved through this process until five
intensive data sets gathered in the estuary between 1968 and 1976 were
satisfactorily simulated. The major processes treated in this study
were the advection and dispersion of salinity and dye tracers, nitrif-
ication, carbonaceous oxidation, sediment oxygen demand, reaeration,
algal photosynthesis and respiration, and denitrification. The major
product of this study is a calibrated and verified "real time" hydraulic
and water quality model of the Delaware Estuary between Trenton and
Liston Point. Among the conclusions of general importance are: (1)
algae exert a variable, but generally positive influence on the DO
budget; (2) non-linear reactions (such as denitrification and reduction
of effective sediment oxygen demand) become significant when DO levels
drop below 2 mg/1; and (3) nitrification, which, experiences inhibition
in a zone around Philadelphia, and sediment oxygen demand rival car-
bonaceous oxidation as DO sinks throughout much of the estuary. One
implication of this study is that earlier forecasts of DO improvements
with a simpler, linear model were somewhat optimistic.
i i i
-------
FOREWORD
In all probability, the Delaware Estuary has been the
subject of more modelling studies during the past two decades
than any other estuarine water body in the United States.
While it is hoped that the modelling study documented in this
report will help advance the state-of-the-art, recognition should
also be given to these early pioneering efforts, since they pro-
vided a solid foundation upon which one could build. Without
them, and similar attempts at model application elsewhere, this
report would not have materialized. It is encouraging that
mathematical modelling techniques are gaining increased acceptance
and legitimacy by water quality managers, since they represent a
valuable tool to assist in the decision making process. Used with
intelligence, mathematical models can help frame relevant options
with greater precision and explore the implications of alternate
decisions with greater objectivity than methods available in the
not too distant past. It is toward this end that our efforts are
ultimately directed.
iv
-------
TABLE OF CONTENTS
ABSTRACT
FOREWORD 1v
LIST OF FIGURES vii
LIST OF TABLES
CHAPTER
I INTRODUCTION 1-1
A. Scope of Study 1-1
B. History of the Dynamic Estuary Model 1-4
C. Theory 1-6
1. Network Properties 1-6
2. Hydraulic Model 1-12
3. Quality Model 1-19
II MAJOR MODEL MODIFICATIONS PERFORMED AT AFO II-l
A. Hydraulic Model II-l
B. Quality Model II-l
1. Advection 11-2
2. Dispersion 11-3
3. Seaward Boundary Transfers 11-4
4. Reaction Kinetics II-5
5. Constituent Numbering 11-9
6. Varying Waste Inputs 11-10
7. Output 11-12
III MODEL APPLICATION TO THE DELAWARE ESTUARY III-l
A. Overview III-l
B. Compilation of Data Base 111-2
1. State of Delaware II1-2
2. AFO III-2
3. 1975 and 1976 Co-Op Studies (208 Program) III-3
-------
C. Establishment of Model Network 111-5
D. Calibration of Hydraulic Model 111-8
E. Calibration and Verification of Quality Model III-ll
1. Chloride Simulations III-ll
2. Dye Simulations 111-15
3. Dissolved Oxygen Budget 111-38
a) Introduction 111-38
b) Description of Data I11-39
July 1974 111-41
October 1973 111-48
August 1975 111-54
July - September 1968 II1-66
July 1976 111-86
c) Quality Model Construction III-101
Initial Formulation III-101
Second Formulation III-104
Third Formulation III-104
Fourth Formulation III-105
Fifth Formulation III-105
Sixth Formulation II1-106
d) Comparison of Model Predictions
With Observed Data 111-109
e) Discussion of Reaction Rates 111-131
F. Sensitivity Analysis III-144
IV FUTURE STUDIES AND AREAS OF MODEL REFINEMENT IV-1
ACKNOWLEDGEMENTS
REFERENCES
APPENDIX
-------
LIST OF FIGURES
Number Page
1-1 Fish Tank Analogy for Link-Node Model Network 1-8
1-2 2-D Network with Branching Channels 1-11
III-l Mathematical Modelling Network, Delaware Estuary III-6
III-2 Observed and Predicted Spatial Profiles, May
1970 (11,000 cfs) - Chlorides 111-17
III-3 Observed and Predicted Spatial Profiles,
May 7-22, 1968 (12,300 cfs) - Chlorides 111-18
III-4 Observed and Predicted Spatial Profiles, July 6 -
August 1, 1967 (5,600 cfs) - Chlorides 111-19
III-5 Observed and Predicted Spatial Profiles, Oct. 8 -
Nov. 6, 1969 (4,800 cfs) - Chlorides 111-20
III-6 Observed and Predicted Spatial Profiles, July 10 -
Oct. 20, 1964 (2,450 cfs) - Chlorides 111-21
III-7 Observed and Predicted Spatial Profiles, July 23,
1974 - Dye II1-24
111-8 Observed and Predicted Spatial Profiles, July 24,
1974 - Dye II1-25
111-9 Observed and Predicted Spatial Profiles, July 25,
1974 - Dye II1-26
I11-10 Observed and Predicted Spatial Profiles, July 26,
1974 - Dye II1-27
III-ll Observed and Predicted Spatial Profiles, July 27,
1974 - Dye 111-28
111-12 Observed and Predicted Spatial Profiles, July 29,
1974 - Dye 111-29
111-13 Observed and Predicted Spatial Profiles, July 30,
1974 - Dye II1-30
111-14 Observed and Predicted Spatial Profiles, July 31,
1974 - Dye 111-31
111-15 Observed and Predicted Spatial Profiles, Aug. 1,
1974 - Dye II1-32
vn
-------
Number Page
111-16
111-17
111-18
111-19
111-20
111-21
111-22
111-23
111-24
111-25
111-26
111-27
111-28
111-29
111-30
111-31
111-32
Observed and Predicted Spatial
1974 - Dye
Observed and Predicted Spatial
1974 - Dye
Observed and Predicted Spatial
1974 - Dye
Observed and Predicted Spatial
1974 - Dye
Observed and Predicted Spatial
1974 - Dye
Water
- DO
Water
- NORG
Water
- NH3
Water
Quality
Quality
Quality
Quality
Water Quality
- Chloro. a
Water
- DO
Water
- NORG
Water
- NH3
Water
- N02
Quality
Quality
Quality
Quality
Water Quality
10,100 cfs) -
Water
10,100
Quality
cfs) -
Water Quality
10,100 cfs) -
Data,
Data,
Data,
Data,
Data,
Data,
Data,
Data,
Data,
Data,
DO
Data,
DO
Data,
NORG
July
July
July
July
July
Oct.
Oct.
Oct.
Oct.
Aug.
Aug.
Aug.
22-31,
22-31,
22-31,
22-31,
22-29,
15-17,
15-17,
15-17,
15-17,
6-13,
1-4, 1
6-13,
Profiles
Profiles
Prof i 1 es
Profiles
Profiles
1
1
1
1
1
1
1
1
1
974
974
974
974
974
973
973
973
973
1975
(3
(3
(3
(3
(3
(4
(4
(4
(4
(6,
, Aug. 2,
, Aug. 5,
» Aug. 6,
, Aug. 8,
, Aug. 12,
,900
,910
,910
,910
,910
,020
,020
,020
,020
200-
cfs)
cfs)
cfs)
cfs)
cfs)
cfs)
cfs)
cfs)
cfs)
975 (6,200-
1975
(6,
200-
111-33
111-34
111-35
111-36
111-37
111-43
I I 1-44
111-45
111-46
111-47
111-50
111-51
111-52
111-53
111-57
111-58
111-59
vm
-------
Number
I
I
I
I
I
11-33
11-34
11-35
11-36
11-37
111-38
I
I
I
I
11-39
11-40
11-41
11-42
111-43
111-44
111-45
I
I
I
I
11-46
11-47
11-48
11-49
Water
10,100
Water
10,100
Water
10,100
Water
10,100
Water
10,100
Water
10,100
Quali
cfs)
Quali
cfs)
Quali
cfs)
Qua! i
cfs)
Quali
cfs)
Qua! i
cfs)
Temperature
September 1
Water
(4,800
Water
(4,800
Water
(3,900
Water
(4,800
Water
(4,800
Water
(4,800
Water
(4,800
Water
(4,800
Water
(4,800
Water
(3,900
Qual i
cfs)
Qual i
cfs)
ty
ty
ty
ty
ty
ty
Data,
NH3
Data,
N02 +
Data,
NORG
Data,
NH3
Data,
N02 +
Aug.
Aug.
N03
Aug.
Aug.
Aug.
N03
Data, Aug.
Chloro. a_
, Flow,
968
ty
ty
Quality
cfs) -
Quali
cfs)
Quali
cfs)
Quali
cfs)
Quali
cfs)
Qual i
cfs)
Qual i
cfs)
ty
ty
ty
ty
ty
ty
Quality
cfs) -
Data,
DO
Data,
DO
Data,
DO
Data,
NORG
Data,
NH3
Data,
N02 +
Data,
NORG
Data,
NH3
Data,
N02 +
Data,
NORG
6-13, 1975
6-13, 1975
1-4, 1975
1-4, 1975
1-4, 1975
1-13, 1975
Chlorophyll Data
July
July
Aug.
July
July
July
N03
July
July
July
N03
Aug.
25-Aug. 8,
31 -Aug. 19
22-Sept. 5
25-Aug. 8,
25-Aug. 8,
25-Aug. 8,
31-Aug. 19
31-Aug. 19
31-Aug. 19
22-Sept. 5
(6
(6
(6,
(6,
(6,
(6
,200-
,200-
200-
200-
200-
,200-
, July-
1968
, 1
, 1
968
968
1968
1968
1968
, 1
, 1
, 1
, 1
968
968
968
968
Page
111-60
111-61
111-62
I
I
I
I
I
I
11-63
11-64
11-65
11-69
11-70
11-71
111-72
I
I
I
I
11-73
11-74
11-75
11-76
1 1 1-77-
I
11-78
111-79
ix
-------
Number
111-50
111-51
111-52
111-53
111-54
111-55
111-56
111-57
111-58
111-59
111-60
111-61
111-62
111-63
111-64
111-65
111-66
Water Quality Data, Aug. 22-Sept. 5, 1968
(3,900 cfs) - NH3
Water Quality Data, Aug. 22-Sept. 5, 1968
(3,900 cfs) - N02 + N03
Water Quality Data, July 3-16, 1968
(5,000-15,000 cfs) - Chloro. ^
Water Quality Data, July 25-Aug. 8, 1968
(4,800 cfs) - Chloro. a_
Water Quality Data, July 31 -Aug. 19, 1968
(4,800 cfs) - Chloro. a^
Water Quality Data, Aug. 22-Sept. 9, 1968
(3,900 cfs) - Chloro. a^
Water Quality Data, July 12-16, 1976
(7,500 cfs) - DO
Water Quality Data, July 19-23, 1976
(7,500 cfs) - DO
Water Quality Data, July 12-16, 1976
(7,500 cfs) - NORG
Water Quality Data, July 12-16, 1976
(7,500 cfs) - NH3
Water Quality Data, July 12-16, 1976
(7,500 cfs) - N02 + N03
Water Quality Data, July 19-23, 1976
(7,500 cfs) - NORG
Water Quality Data, July 19-23, 1976
(7,500 cfs) - NH3
Water Quality Data, July 19-23, 1976
(7,500 cfs) - N02 + N03
Water Quality Data, July 12-15, 1976
(7,500 cfs) - Chloro. a_
Water Quality Data, July 19-23, 1976
(7,500 cfs) - Chloro. a_
Water Quality Data, July 12-16, 1976
(7,500 cfs) - Secchi Disc
Page
111-80
111-81
111-82
111-83
111-84
111-85
111-89
111-90
111-91
111-92
111-93
111-94
111-95
111-96
111-97
111-98
111-99
-------
Number Page
111-67 Water Quality Data, July 19-23, 1976
(7,500 cfs) - Secchi Disc III-100
111-68 First Formulation, Initial Structure -
Delaware Estuary Model 111-102
111-69 Final Structure, Delaware Estuary Model III-108
111-70 Observed and Predicted Spatial Profiles,
July 1974 (3,900 cfs) - DO III-112
II1-71 Observed and Predicted Spatial Profiles,
July 1974 (3,900 cfs) - Nitrogen Series III-113
II1-72 Observed and Predicted Spatial Profiles,
Oct. 1973 (3,900 cfs) - DO III-114
II1-73 Observed and Predicted Spatial Profiles,
Oct. 1973 (3,900 cfs) - Nitrogen Series III-115
111-74 Observed and Predicted Spatial Profiles,
Aug. 1975 (7,880 cfs)(HWS) - DO III-116
111-75 Observed and Predicted Spatial Profiles,
Aug. 1975 (7,880 cfs)(LWS) - DO III-117
111-76 Observed and Predicted Spatial Profiles,
Aug. 1975 (7,880 cfs)(HWS) - Nitrogen Series III-118
111-77 Observed and Predicted Spatial Profiles,
Aug. 1975 (7,880 cfs)(LWS) - Nitrogen Series III-119
111-78 Observed and Predicted Spatial Profiles,
July - August 1968 (4,800 cfs)(HWS) - DO III-120
111-79 Observed and Predicted Spatial Profiles,
July - August 1968 (4,800 cfs)(LWS) - DO III-121
111-80 Observed and Predicted Spatial Profiles,
July - August 1968 (4,800 cfs)(HWS) -
Nitrogen Series III-122
111-81 Observed and Predicted Spatial Profiles,
July - August 1968 (4,800 cfs)(LWS) -
Nitrogen Series 111-123
111-82 Observed and Predicted Spatial Profiles,
August - September 1968 (3,900 cfs)(LWS) - DO III-124
-------
Number Page
111-83 Observed and Predicted Spatial Profiles,
August - September 1968 (3,900 cfs)(LWS)
- Nitrogen Series III-125
111-84 Observed and Predicted Spatial Profiles,
July U - Sept. 4, 1968 (3,900-4,800 cfs) - DO III-126
111-85 Observed and Predicted Spatial Profiles,
July 12-16, 1976 (7,900 cfs)(LWS) - DO III-127
111-86 Observed and Predicted Spatial Profiles,
July 19-23, 1976 (7,900 cfs)(HWS) - DO III-128
111-87 Observed and Predicted Spatial Profiles,
July 12-16, 1976 (7,900 cfs)(LWS)-Nitrogen Series III-129
111-88 Observed and Predicted Spatial Profiles,
July 19-23, 1976 (7,900 cfs)(HWS)-Nitrogen Series III-130
111-89 Nitrification Inhibition Pattern Based Upon
Modelling Studies III-136
111-90 Sediment Oxygen Demand Rates 111-141
111-91 Relationship Between Turbidity and Secchi
Disk, July 1974 III-143
111-92 Sensitivity Analysis, Delaware Estuary DO
Model - Temperature (Linear Region) III-147
111-93 Sensitivity Analysis, Delaware Estuary DO
Model - Temperature (Non-Linear Region) III-148
111-94 Sensitivity Analysis, Delaware Estuary DO
Model - Inflow (Linear Region) III-149
II1-95 Sensitivity Analysis, Delaware Estuary DO
Model - Inflow (Non-Linear Region) III-150
111-96 Sensitivity Analysis, Delaware Estuary DO
Model - Reaeration (Linear Region)(Churchill Eq.) III-151
111-97 Sensitivity Analysis, Delaware Estuary DO
Model - Reaeration (Linear Region)(USGS Eq.) III-152
II1-98 Sensitivity Analysis, Delaware Estuary DO
Model - Reaeration (Non-Linear Region)
(Churchill Eq.) III-153
xii
-------
Number Page
111-99 Sensitivity Analysis, Delaware Estuary DO
Model - Reaeration (Non-Linear Region)
(USGS Eq.) III-154
III-100 Sensitivity Analysis, Delaware Estuary DO
Model - CBOD, Oxidation Rate (Linear Region) 111-155
111-101 Sensitivity Analysis, Delaware Estuary DO
Model - CBOD, Oxidation Rate (Non-Linear Region) III-156
III-102 Sensitivity Analysis, Delaware Estuary DO Model
- Nitrification Rates + 100% (Linear Region) 111-157
111-103 Sensitivity Analysis, Delaware Estuary DO Model
- Uninhibited Nitrification Rates (Linear Region) II1-158
III-104 Sensitivity Analysis, Delaware Estuary DO Model
- Nitrification Rates + 100% (Non-Linear Region) III-159
111-105 Sensitivity Analysis, Delaware Estuary DO Model
- Uninhibited Nitrification Rates (Non-Linear
Region) Ill-ISO
III-106 Sensitivity Analysis, Delaware Estuary DO Model
- Intermediate SOD Rate (Linear Region) III-161
III-107 Sensitivity Analysis, Delaware Estuary DO Model
- Background SOD Rate (Linear Region) III-162
III-108 Sensitivity Analysis, Delaware Estuary DO Model
- No SOD Rate (Linear Region) III-163
III-109 Sensitivity Analysis, Delaware Estuary DO Model
- SOD Rate (Non-Linear Region) III-164
III-110 Sensitivity Analysis, Delaware Estuary DO Model
- Denitrification Rates (Non-Linear Region) III-165
Ill-Ill Sensitivity Analysis, Delaware Estuary DO Model
- Photosynthesis Rate (Linear Region) III-166
III-112 Sensitivity Analysis, Delaware Estuary DO Model
- Photosynthesis Rate (Non-Linear Region) III-167
III-113 Sensitivity Analysis, Delaware Estuary DO Model
- Respiration Rates (Linear Region) III-168
xm
-------
Number Page
III-114 Sensitivity Analysis, Delaware Estuary DO Model
- Respiration Rates (Non-Linear Region) III-169
III-115 Sensitivity Analysis, Delaware Estuary DO Model
- Euphotic Depth (Linear Region) III-170
II1-116 Sensitivity Analysis, Delaware Estuary DO Model
- Euphotic Depth (Non-Linear Region) II1-171
III-117 Sensitivity Analysis, Delaware Estuary DO Model
- Algal Densities (Linear Region) III-172
III-118 Sensitivity Analysis, Delaware Estuary DO Model
- Algal Densities (Non-Linear Region) III-173
III-119 Sensitivity Analysis, Delaware Estuary DO Model
- Algal Densities - Bloom Condition II1-174
III-120 Sensitivity Analysis, Delaware Estuary DO Model
- Photosynthesis Rate - Bloom Condition III-175
III-121 Sensitivity Analysis, Delaware Estuary DO Model
- Respiration Rates - Bloom Condition III-176
III-122 Sensitivity Analysis, Delaware Estuary DO Model
- Euphotic Depth - Bloom Condition III-177
xiv
-------
LIST OF TABLES
Number Page
III-l Comparison of USC&GS Tidal Data and Hydraulic
Model Predictions 111-9
III-2 Final Manning Roughness Coefficients, Delaware
Estuary Hydraulic Model 111-10
III-3 Advection Factors and Dispersion Coefficients,
OEM's Initial Chloride Calibration (Flow =
11,000 cfs) 111-12
III-4 Dispersion Coefficient (C4) vs Flow,
Delaware Estuary Model III-16
III-5 Description of Reaction Rates for Delaware
Estuary Water Quality Model 111-131
xv
-------
1-1
I. INTRODUCTION
A. SCOPE OF STUDY
The free-flowing Delaware River water spills over the fall
line at Trenton, New Jersey into its tidally influenced estuary.
Subjected to vigorous ebb and flood tidal currents, this fresh
water slowly makes its way past the large metropolitan center of
Philadelphia-Camden-Chester where thousands of tons of municipal
sewage and industrial wastewater degrade it dramatically. Widening
into a broad, brackish estuary near Wilmington, its pollutants are
being assimilated and diluted even as the estuary receives new
wastewater loads. The water's salinity increases rapidly as the
estuary merges into the Delaware Bay near Listen Point, some 90
miles in distance and 1 to 3 months in time below the fall line at
Trenton.
The water quality problem of particular concern in the
estuary has been low dissolved oxygen (DO) concentrations between
late spring and early fall when temperatures are elevated.
Dissolved oxygen is an important indicator of general water quality.
High DO levels permit the existence of a diversity of life forms and
hence are generally associated with healthy and stable aquatic
environments. Low DO levels, on the other hand, often result from
abnormally high organic pollution levels in a body of water, and can
upset or totally destroy the natural clean water aquatic communities.
The high diversity of these communities is usually reduced, leading
-------
1-2
to a precarious or unstable balance with the changing aquatic
environment. If low DO levels persist or worsen, whole communities
can be replaced by less desirable pollution tolerant families, such
as tubificid or sludge worms. High quality fish having economic
and recreational value, such as bass or perch, are first replaced
by lesser quality fish, such as carp; finally as DO levels plunge
much below 3 mg/1, no species of fish will remain viable. Summer
DO concentrations in the Delaware Estuary often remain below 3 mg/1
between the Ben Franklin Bridge at Philadelphia and the Delaware
Memorial Bridge at Wilmington. Minimum daily DO concentrations
immediately below Philadelphia are frequently less than 1.0 mg/1
during the summer.
The three primary goals guiding this study were (1) to
better understand and define the significant mechanisms affecting the
water quality behavior of the estuary; (2) to provide a more reliable
deterministic tool for accurately predicting the effects of alternative
waste control strategies on the estuary's water quality; and (3) to
establish a sound data and knowledge base which would be a valuable
reference for planning future water quality studies. Major emphasis
was placed on defining those factors which affect dissolved oxygen,
due to its widespread acceptance as a water quality standard by
planning and regulatory agencies in the Delaware Basin.
This report documents the modifications to the Dynamic
Estuary Model performed by the Annapolis Field Office (AFO) and the
subsequent application of the, revised w>del to the Delaware Estuary.
-------
1-3
The final tangible results of this work are the calibrated and verified
hydraulic and water quality models DYNHYD2T and DYNDELA. These mathe-
matical computer models are now available for use in further studies of
the water quality of the estuary, including forecasts of the water
quality response to hypothetical wastewater control strategies. A user's
manual will provide the details necessary for operating the models.
Ongoing tests and studies with these models will be documented in future
technical papers and reports.
-------
1-4
B. HISTORY OF THE DYNAMIC ESTUARY MODEL
The Dynamic Estuary Model (DEM) was originally
developed during the mid 1960's by Water Resources Engineers,
a consultant engineering firm located in Walnut Creek,
California, under contract to the Division of Water Supply and
Pollution Control, U. S. Public Health Service [1]. The
principal individuals associated with the development of this
model were Drs. Gerald Orlob and Robert Shubinski. Estuarine
modelling was still in its infancy at that point in time, and
the DEM was innovative in considering a "real time" computerized
tidal solution of the hydrodynamic behavior of estuaries.
Prior to the development of the DEM, the few estuary models
already in existence relied on a net flow or plug flow analysis
and attempted to reproduce tidal effects through the inclusion
of an artificial dispersion coefficient. Since these models
were non-tidal in nature, the time step for computations was
normally equal to the tidal period (12.5 hrs.) or, for
convenience, one day, and consequently they could not handle short
term pertubations in water quality.
The DEM was initially applied to the Sacramento-San
Joaquin Delta area in California [1]. Other early applications
were to the Suisun, San Pablo and San Francisco Bays [2], [3].
The DEM was first brought to the attention of the Annapolis
Field Office (AFO) by Mr. Kenneth Feigner. Mr. Feigner was the
USPHS project officer during the early developmental and
-------
1-5
application studies in California and was the author of the
basic model documentation report [4]. Staff at AFO (with the
assistance of Mr. Feigner) tested the model rigorously and
performed extensive modifications to the reaction kinetics in
the quality program during its multi-year application to the
Potomac Estuary [5], [6], [7]. The Potomac study was primarily
directed towards refining the model's ability to treat nutrient
cycles (including uptake by phytoplankton) and towards
incorporating algal effects within the DO budget. In addition,
the DEM was also applied to the upper Chesapeake Bay during
1972-73 for the development of allowable nutrient loadings
from the Susquehanna Basin and the Baltimore Metropolitan
Area [8].
-------
1-6
C. THEORY
The DEM consists of two separate but interrelated
components: (1) a hydraulic program, dealing with water motion,
and (2) a quality program, dealing with mass transport and
chemical and biological reactions. The hydraulic program
predicts water movement by solving the equations of momentum and
continuity, while the quality program predicts the movement,
buildup, and decay of water-borne material by solving the
conservation of mass equations. The numerical solution of the
hydraulic and mass equations is accomplished on the same
network, which represents the geometrical configuration of the
estuary. The following sections will discuss in detail the
network and the equations used in the hydraulic and quality
models.
1. NETWORK PROPERTIES
The DEM utilizes a channel-junction (sometimes
called a link-node) network approach, whereby, either through
branching or looping, the pertinent hydraulic and mass balance
equations are applied to uniform segments of the estuary and then
solved in a sequential fashion. The model can accommodate a
range of time and space scales suitable to the dynamic and
physical characteristics of a particular estuary.
Two analogies which are useful in better
understanding the channel-junction network concept and its
application to an estuary are (1) a series of pots connected
-------
1-7
by hoses, and (2) a partitioned irregular fish tank. In the
first case, the pots are analogous to model junctions while
the hoses are analogous to model channels. "Tidal currents"
are created by raising one of the end pots, thereby creating
water movement through the series of pots. The hoses serve
as transport media where physical characteristics governing the
movement of water are defined. The pots serve as receptacles
for the fluid transported where the addition of pollutants and
their dilution, decay, and chemical and/or biological
transformation are defined. The rhythmical raising and lowering
of the pot at one end of the series is analogous to the input
of a tidal wave at the seaward boundary of the model. The
difference in elevation of the water surface is the primary
hydraulic driving force in the pot-hose analogy, the DEM,
and an estuary subject to tidal action such as the Delaware.
The second analogy is that of a long irregular
fish tank, divided internally into sections or "junctions" by
many glass partitions, as illustrated in Figure 1-1. Water is
poured into various junctions (representing fresh water inflow
and wastewater discharge); water is removed from other
junctions (representing river water diversion). The water is
stirred until well mixed. The partitions are then lifted
simultaneously, allowing waves to travel through the tank.
The configuration of the fish tank confines water movement along
pre-determined paths, or "channels". After a short time interval,
-------
Fish tank with partitions,
I 2
6 7 junctions
567
channels
Channels describe the geometry
of the fish tank; junctions
describe the volumes of water
separated by partitions.
Water is poured into some
junctions (representing fresh
water inflow, wastewater inflow,
or flooding tide) and removed
from other junctions (representing
river water withdrawal or ebbing
tide).
*
o
"».
0
*
C
^M
o
c
0
c
9
^^
C
^
3
O
3
'l
o
_
3
The volume of water in each
junction is well mixed.
Partitions are removed; fluid
travels as waves moving through
channels. When partitions are
reinserted, Step 1 begins again.
FISH TANK ANALOGY FOR
LINK-NODE MODEL NETWORK
Figure 1-1
-------
1-9
the partitions are re-inserted, more water is poured into or
drained from the junctions, and the process is repeated.
The channels provide for fluid motion. They
function as transfer units between the junctions. The tidal
wave, river flow and wastewater flow are all propagated from
their initial points by means of the channels. The junctions
function as mass and volume containers. As Figure 1-1 shows,
the fish tank, as a whole, is irregular; each channel, however,
has a rectangular shape depending on the configuration of the
area it represents. The junctions, since they occupy the same
space as half of two neighboring channels, will (usually) be
rectangular except where branching or looping channels are
employed. Since the geometry of the river itself varies
continuously, the more channels in the model, the more closely
the model will approximate the river.
The linear nature of the model implies certain
restrictions, which are easily understood by reference to the
fish tank analogy. The model cannot handle flows normal to the
x-axis. The acceleration caused by a sloping channel or by
wind or Coriolis forces must be negligible. The analogy of the
fish tank is, however, overly restricted in that it does not
conserve momentum from one period of flow to the next, while the
DEM does. The fish tank and the model also differ in that the
fish tank is fully three dimensional, while the model is essentially
one dimensional. The model does take width and depth into
-------
1-10
account by entering them as functions: width as a function of
longitudinal distance along the river (distance along the
x-axis) and depth as a function of distance and time.
Nevertheless, the equations and their results are one dimensional.
For a given channel or junction, the model outputs one set of
results: one flow, one wave height, one DO prediction, one
BOD prediction, etc. A pseudo-two-dimensional effect can be
achieved by branching more than two channels from a single
junction (see Figure 1-2). This is done by subdividing the
river into smaller parts, which yields greater accuracy and
precision in the results, but not true two dimensionality
since the equations used are still in a one dimensional form.
A three dimensional effect might be similarly achieved, though
with considerably more difficulty, since problems arise concerning
interaction between different vertical layers.
The more stratified a body of water is either
vertically or horizontally, the more difficult and complicated
the modelling problem becomes for the DEM. Shallow bodies of
water, such as the California deltas and bays or the Delaware
Estuary, with little vertical stratification and with the
primary flow linearly along the axis of the river, are most
suited to this model.
-------
2-D NETWORK WITH BRANCHING CHANNELS
FIGURE 1-2
-------
1-12
2. HYDRAULIC MODEL
The basic task of the hydraulic model is to solve
the equations describing the propagation of a long wave through
a shallow water system, while conserving both momentum and
volume. The two equations involved are:
£- -u |H. -(k.|u|-u) -g f (1)
and
3H _ 1 3
where :
u = velocity along the x-axis
t = time
x = distance along the x-axis
k = frictional resistance coefficient
(k = gn2/2.208 RV3)
n = Manning's roughness coefficient
R = hydraulic radius
g = gravitational acceleration
H = height of the wave (above arbitrary datum)
b = mean channel width
Q = flow
Equation (1) is associated with the channels and
is the equation of motion expressed in a one dimensional form
where velocity along the x-axis replaces the flow. The first
term on the right hand side represents flow convergence or
-------
1-13
divergence: for a given quantity of water in motion, its
velocity will vary with the cross-sectional area of the channel
through which it flows. Convergence and divergence depend
directly on the water velocity and the change of the cross-
'Nil ^i I I ^ l\,
sectional area along the river, such that -^ = -u ( ^ ) ( 7^-
Since the cross-sectional area is entered in the model in terms
of distance along the x-axis, then A = f(x) and, consequently,
|£- are known. Multiplying |^ by this known |£ gives the ^
shown in equation 1 (7^- = jr x ^-). The second term
represents the frictional resistance: the greater the velocity,
the greater will be the friction. The absolute value sign
ensures that the resistance opposes the direction of flow.
Perhaps the most elusive network input is the Manning roughness
coefficient, n, upon which k depends. Since this parameter is
virtually undefinable, even through empirical methods, it
serves as a "knob" to turn in order to achieve a satisfactory
agreement between the actual and predicted tidal data. The
third term represents gravitational acceleration: the greater
difference in the water surface elevations, the greater will be
the gravitational force exerted. The negative signs on the
right hand side of the equation result from the sign convention
governing flow in the channels. Flow is defined as positive in
the positive x direction, that is, in the direction of the
channels which (in the Delaware model) are numbered up the
river from Artificial Island (channel 9) to Trenton (channel 84).
-------
1-14
Channels 1 through 8 are located in the C&D Canal.
Equation (2), the equation of continuity, is used
to compute the water surface elevations after appropriate flow
transfers are made and is associated with the junction elements
of the network. The height of the wave is inversely proportional
to the width of the channel for a given flow. Likewise, for a
given channel width, the height will vary as a function of
the flow.
Equations (1) and (2) must be converted to
finite difference forms before they can be used in the model.
They therefore become:
Au. Au. AH-j
zt-= -ui 4*7 -Hujl-Uj -a sq- (3)
"Im - "U
At b.Ax.
J J
where i indicates the channel and j the junction in question.
ZQ. is used instead of AQ. since there will
J J
usually be several different flows to be considered (waste
discharges, accretions, transfers, diversions, etc.). At
this point, the equations are now tractable only if there is
no branching in the model. If there is branching, the
velocity gradient ui can no longer be used in the form
Ax.
i+1 Uii0 since there may be several i+1 channels.
-------
1-15
Equation (2) can be used to solve this problem:
M- . 1 .15.
3t " " b 3x
h M - -3 (uA)
D ' 3t ~ 3X
ti V % V
o A 0 A
M = _ k lii y. lA
3X "A 3t " A 3X
In finite difference form:
Au.. b.. AH^ u7- AA^
AxT = - AT At" - AT ZxT
(AH./At and AA./AX. are computed from the predicted water
surface elevations of the junction at both ends of the channel i)
Substituting (5) in Equation (3):
Au. b. AH. u.2 AA. AH.
To solve equations (6) and (4) everything except
Au./At and AH. /At must have assigned values. River geometry is
' J
entered in the model as discretely varying constants. A value
for b. and AX. (or their product, surface area) is entered for
J J
each junction and a value for AX. (length), b. (width), A. (cross
sectional area) or d.. (depth), and k. (roughness) for each
channel. At the beginning of the run, values for channel velocity
and water surface elevations at the junctions must be entered to start
-------
1-16
the solution procedure (initial conditions). All waste
discharges, flow diversions or accretions, tidal height
variations, and tributary flows must also be specified
(boundary conditions). The equations are then solved,
using a modified Runge-Kutta procedure. A step by step
solution of equations (6) and (4) proceeds as follows:
(1) The mean velocity for each channel is
predTcted for the middle of the next time
interval using the values of channel
velocities and cross-sectional areas and
the junction heads at the beginning of the
time interval .
(2) The fljgvsL in each channel at the middle of
next time interval is computed based on the
above velocity and the cross-sectional area
at the beginning of the interval.
(3) The head_at each junction at the middle of
the next time interval is predicted based on
the above predicted flows.
(4) The cross-sectional area of each channel is
adjusted to the middle of the next time
interval based on the above predicted heads.
(5) The mean velocity for each channel is
predicted for the end of the next time
interval using the values of channel
velocities and cross-sectional areas and
junction heads at the middle of the interval.
(6) Steps (2), (3), and (4) are repeated for the
end of the time interval. Computation
proceeds through a specified number of At
time intervals.
The solution will converge, for a given set of boundary
conditions, to a dynamic equilibrium condition wherein the
velocities and flows in each channel and the heads at each
junction repeat themselves at intervals equal to the period
-------
1-17
of the tide imposed at the seaward boundary of the system.
The time required for this convergence will vary from about
1 to 4 tidal periods, depending on the accuracy of the initial
conditions.
When applying the model, the tide and flow
should be relatively steady over the time period being modelled.
The model's predictions are based on the original constant
freshwater flow and tidal characteristics, since it is expensive
to simulate a transient condition having significantly varying
flow or tidal characteristics.
The tidal wave at the seaward boundary is
described by a series of coefficients, A.. These coefficients
J
are obtained from the equation:
Y = Ai + A2 sin (wt) + A3 sin (2ut) + Ai» sin (3tot) + (7)
A5 cos (wt) + A6 cos (2wt) + A7 cos (3wt)
where: u = 12.5 hrs.
The coefficients AI through A7 are actually solved in a special
harmonic analysis program requiring tidal heights as a
function of time as input, which must be run once for every
hydraulic pattern of interest, such as spring tide, neap tide,
or average tide. The tidal data should be referenced to some
convenient datum such as mean sea level (MSL).
The selection of the computational time step
is an important consideration since stability must be
maintained throughout the solution process. Its length is
-------
1-18
dictated by the refinement of the network in accordance with the
stability criterion given below:
X-j 1 (^ ± U.) At
where: x,- = channel length
a- = wave celerity (\rgy)
U.j = tidal velocity
At = time step
As can be seen, the more detailed the model network, the shorter
the time step and vice versa. Normally, a time step on the
order of a few minutes is sufficient for most applications;
however, one must pay special attention to the physical
configuration of an estuary when deciding upon the network
design and the associated time step.
Physical data pertaining to the individual
channel and junction elements must be obtained either from
navigation charts or from actual field measurements. This
data is extremely important for both the hydraulic and quality
components and should be estimated with some degree of accuracy.
The specific parameters that must be defined are as follows:
Channel Elements
1) Length
2) Width
3) Cross-Sectional Area
4) Hydraulic Radius (depth)
5) Frictional Resistance Coefficient
-------
1-19
Junction Elements
1) Surface Area
2) Volume
3) Inflows/Outflows
3. QUALITY MODEL
The task of the quality model is to solve the
equations describing the movement, decay and transformation
of material in a water system by performing a mass balance
(conservation of mass) at each junction element during each
time step of the solution. The quality model utilizes the
identical network employed in the hydraulic model and requires
the hydrodynamic solution, which is extracted and stored onto
magnetic tape, as input. Five constituents, either conservative
or non-conservative, can be handled simultaneously. The com-
putational time step must be a whole multiple of the time step
used in the hydraulic program and evenly divisible into the
tidal period. A time step between 1/2 hour and 2 hours will
suffice for most applications.
The quality component is concerned with
constituents that are introduced to or already contained in
the water in either a dissolved or particulate form, such
as salinity, dissolved oxygen, BOD, algae, and nutrients (i.e.,
nitrogen or phosphorus species). The concentration of
such a constituent at any point along the river will be modified
by the following processes: advection, diffusion, longitudinal
-------
1-20
dispersion, decay, reaeration, exportation and importation.
These processes will be discussed below.
ADVECTION
When a constituent enters the water with a given
concentration c, the tidal wave and river flow will cause it
to be carried up' or down the river at the same velocity at
which the water itself moves (disregarding for the moment the
effects of diffusion). The greater the constituent's
concentration, of course, the more of it will be transported.
Thus, the basic transport equation for advection is:
Ta = u * c (8)
where: T = advective transport of a given mass through a
unit area in a unit time (mass/area/time)
u = velocity
c = the concentration of the constituent with respect
to the water in which it is carried
Applying this equation to a control volume and shrinking it to
infinitesimal size will yield the following one dimensional
concentration equation:
at 3x
Multiplying both sides by A-Sx will yield the following mass
equation:
f =uA || SX (10)
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1-21
which describes the instantaneous advection of mass at cross -
section A. In finite difference form, the equation becomes:
At
i Ai cj
(11)
where j is the junction under consideration and i+1 and i refer
to the upstream and downstream channels, respective!v. This
difference equation describes the net advection of mass into or
out of the control volume (or model junction j) during the
interval At. Even in this form, however, the equation can still
be troublesome to use in the model for reasons discussed below.
NUMERICAL MIXING
At every quality time step, some portion of the
concentration must be advanced one unit: that is, one junction,
forward. Thus, in the drawing below, part of the concentration
in junction 1 will advance to the center of junction 2 in the
first time step; likewise, some of the concentration in junction
2 will advance to the center of junction 3 in time step 2, and
so on.
junction 1
This occurs because the model assumes the complete mixing
within each junction of any mass entering that junction. In
reality, however, the concentration in junction 1 at time step
1 may only advance to the boundary between junctions 1 and 2.
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1-22
In other words, while the model concentrations must move in
unit steps whose distance is dictated by the junction sizes,
the real concentrations are not so constrained. The effect
of this unit motion is called numerical mixing.
Model
Real
te
o
c
o
o
junction 1
junction 2
distance
C(t2)
Certain adjustments must be made in order to insure that the
discrepancy between model and river will not be large and will
not accumulate because of numerical mixing problems.
The greatest difficulty will arise when there is a
high concentration gradient between two junctions. If Ci is
much greater than c2 then the error involved in advancing cx
one unit step ahead to junction 2 will be numerically large.
The solution is to choose a Ci or concentration in the advected
water, which is in between the "actual" values of GI and c2.
The early modelling studies by Feigner [4] showed that, for the
San Francisco Bay System, acceptable values for GI can be
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1-23
achieved by the Quarter Point Method:
c* = (3ci + c2)/4
where c* = the concentration substituted in the model for Cj.
This method also appeared to work satisfactorily in the Potomac,
with the exception of salinity, which exhibited steeper
concentration gradients and necessitated the use of a Third
Point Method:
c* = (2ci + c2)/3
The Upper Chesapeake Bay model, on the other hand, was able to
utilize the actual upstream concentrations for advection
purposes with no apparent problems. With the proper
substitution, the advection equation becomes:
^1 - A1+, «1t, Cl* - A, u. c,* (12)
where GI* represents the upstream concentratton entering the
junction and c2* represents the concentration leaving the
junction. Since the model will actually calculate the
individual accretions and depletions separately, the advection
equation used is:
^§- = A u c* (13)
At
LONGITUDINAL DISPERSION
The velocity of a river varies laterally and
vertically. These variations result in longitudinal dispersion,
by which constituents in the center of the river move forward
faster than those at the side or bottom. Because the model is
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1-24
one-dimensional in form, this phenomenon cannot be directly
accounted for in the model. However, it so happens that the
effects of numerical mixing accidentally produce a somewhat
similar effect, although it is only partially controllable.
Therefore, c* may also be manipulated to help compensate for
the effects of longitudinal dispersion. In addition, the
turbulent (or eddy) diffusion coefficient, discussed in the
next section, can be manipulated to encompass the effects of
longitudinal dispersion.
Side
lateral
Side
vertical
Bottom
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1-25
TURBULENT DIFFUSION
In a calm body of water, molecular diffusion will
slowly operate to bring constituents from regions of high
concentrations to regions of low concentrations. In turbulent
bodies of water, however, this relatively slow process can be
neglected, and only the effects of turbulent diffusion need to
be considered. Turbulent diffusion, the stirring or mixing of
the water by eddy currents due to tidal action or some other
energy field such as density gradients, is essentially a
complex form of advection, which must at present be treated as
a separate process since the velocities and directions of the
eddy currents are not yet predictable. The transport equation
for turbulent diffusion is:
Td - Kd || (14)
where T, is the transport by turbulent diffusion through a unit
area in a unit time, K, is an empirically determined coefficient
which describes the rate of transfer (dimensions Iength2/time)
and 9c/3x is the concentration gradient over the space scale.
Applying this equation to a control volume and shrinking it to
infinitesimal size will yield a partial differential equation
describing the time rate of change of a constituent's
concentration due to turbulent or eddy diffusion:
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1-26
Multiplying this equation by a volumetric term, A6x, yields a
differential equation which relates turbulent diffusion at
cross-section A on a mass flux basis.
Again, converting the mass transfer equation to finite difference
form and expressing distance in terms of a channel element's
length results in:
AM., . AC. , AC.
-sP-** Vl A - Kd «i
where j is the junction under consideration, i+1 and i refer to
the upstream and downstream channels, respectively, and Ac-+1 and
AC.J are the concentration differences along the upstream and down-
stream channels, respectively. This difference equation describes
the net dispersion of mass into or out of the control volume (or
model junction j) during the interval At.
The DEM does not utilize K, directly but rather computes
this rate based upon a simplification of the energy dissipation
relationship and a spatial approximation of the eddy size [4].
The actual equation employed by the model is as follows:
Kd = ck |u |R (18)
where c^ is a dimensionless diffusion coefficient assumed to be
constant, u is mean channel velocity, and R is the hydraulic radius
of the channel .
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1-27
DECAY
Both conservative (such as salinity) and non-conservative
(such as DO or BOD) constituents may be considered in the quality
program. For non-conservative constituents, a further mechanism,
decay, must be considered.
For the first order decay process, the quantity of a
constituent that decays is a function of (1) the amount of the con-
stituent that is present and (2) its decay rate constant, which
at times must be determined empirically. Expressed in differential
form, the first order equation for decay is:
where K equals the rate constant and c the constituent's
concentration. The negative sign indicates that this is a
process of decay and not growth. Unlike the other equations so
far discussed, this one may be easily and usefully integrated:
Ct = C e"K (t " to) (20)
U 0
where C equals concentration at time zero (t ). This expression
is then converted to a difference form for a junction element (j)
and time step At.
ACj,t=Ct-Ct-l = Ct-l (e--l) (21)
and then to a mass equation by multiplying both sides by the
volume:
AM
= V.. Ct_-, (e' - 1) (22)
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1-28
where AMn . equals total mass decayed in junction j during the
v >j
time step At, and C. -, equals initial concentration in junction j
and V. equals junction volume.
J
REAERATION
Dissolved oxygen is involved in a fifth process,
namely, reaeration. This formula, similar to the formula for
decay, is:
{jjf - -KDD (23)
where D = DO deficit (saturation DO minus actual DO) and KD =
reaeration rate (I/time). The mass equation is:
AM ,
-AP^D Dj,t-l VJ W
where AMD . equals mass of oxygen added in time step At to junction
K,J
j by reaeration and D. . , equals initial dissolved oxygen deficit
J >t- 1
in junction j.
IMPORT AND EXPORT
The final method by which the concentration in a junction
may be changed is by import (tributary inflow, waste discharge,
etc.) or export (industrial or municipal use, etc.). The equation
for this is:
AM .
where AM equals total mass of constituent added (or subtracted)
from the junction in time At. Q equals separate inflows (or
)C
outflows) to junction j during time At. For exportation, the
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1-29
concentration c is taken to be that in junction j at time t-1,
Af
while for importation, the concentration of the inflow must be
specified.
SOLUTION OF MASS BALANCE EQUATION
Combining the previous equations which describe the
various processes governing mass transport and distribution
yields the following:
AM. AM . + AM. . + AMn . + AMp . + AMQ . (9f..
1 = a»J K»J D»J K,J e.j (26)
At At
where AM- represents the change in mass occurring in junction j
J
during the time step At for a given constituent.
The solution of this quality equation is a relatively
straight-forward and sequential process involving an explicit,
finite difference technique. The initial and boundary
concentrations as well as waste loading data are entered as input.
The solution then proceeds as follows:
1) The hydraulic extract tape is used to provide
values for velocity and flow (both direction
and quantity) for each channel element in the
network, and water surface elevations at each
junction element for the appropriate time step.
The latter is required to compute junction
volumes, which are necessary for mass determination
(M = V*c).
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1-30
2) All constituent masses are transported via
advection and dispersion.
3) Non-conservative constituent masses are decayed.
The reaeration equation for dissolved oxygen is
applied here.
4) Wastewater loads and other inflows are added.
5) Water diversions are subtracted.
6) Steps 1-5 are repeated for every junction and
channel as necessary.
7) Steps 1-6 are repeated for each quality time
step.
All reaction rates must be entered as constants, but they
are corrected for temperature and time step internally. It should
also be noted that a mathematical discrepancy exists in the quality
program in that certain equations retain their "differential" or
finite difference form while others are of an integrated form.
While this does present certain programming problems, no errors
in the final solution are introduced.
-------
II. MAJOR MODEL MODIFICATIONS PERFORMED BY AFO
A. HYDRAULIC MODEL
The hydraulic model described in the preceding chapter
underwent a single modification before it was applied to the
Delaware Estuary. That modification, the ability to input two
separate and independent tidal waves, was precipitated by the
uncertain effects, particularly in terms of the hydrodynamics, that
the C&D Canal exerts in the lower portion of the Delaware. The
western end of the canal is primarily driven by the Chesapeake tides,
hence the need for two inputs. Two sets of coefficients, one
describing the Delaware wave and the other describing the Chesapeake
wave, must be generated by applying the harmonic regression analysis
to a set of data describing tidal elevation versus time. Tidal
elevations should be referenced to a common datum such as local mean
sea level. Junction 1 accepts the Chesapeake wave and junction 2
the Delaware wave in the present program.
B. QUALITY MODEL
The modifications performed to the quality model by AFO
can be grouped into two categories: (1) those pertaining to the
basic transport mechanisms, i.e., advection and dispersion as well
as seaward boundary transfers which are directly related to trans-
port of mass through the model network and (2) those expanding
the various reaction kinetics by mathematical formulations and
enhancing the flexibility of the model to consider a myriad of com-
binations with a minimum amount of effort directed towards
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II-2
reprogramming and redefining input parameters. The former group
of changes was necessitated by the location of the seaward boundary
in the model and the salinity characteristics that this region of
the estuary exhibits. Unfortunately, it was not feasible to extend
the model network to the ocean thereby eliminating much of the
problem. The second group of changes was done primarily to ease tasks
associated with a potentially complex calibration/verification.
1. ADVECTION
The very steep salinity concentration gradient which
exists in the Delaware Estuary near the model's seaward boundary
greatly accentuated the stability and numerical mixing problems in
the model. There was a tendency for the "stacking up" of mass to
occur in particular junctions during either the ebb or flood phase
of the tide. Obviously, this caused the model to produce erroneous
predictions. One of the things which was done to overcome these
problems was to alter the method by which advective mass transfers
were computed. The C* value, or the concentration of the advected
water (see previous chapter), was not assumed constant;
program changes were made to allow for spatial variation of this
term. Moreover, another option was introduced in the model that
would permit two values of C* to be read in for each channel element;
one would apply to the ebbing phase of the tide and the other,
which may or may not be different, would apply when a flooding tide
occurred. It is difficult if not impossible to explain, in a
physical sense, why C* will or should vary either with time or
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II-3
space. Attempts were made to relate C* to a combination of factors
such as tidal velocity, channel length, concentration gradients
and other physical characteristics, but nothing conclusive ever
evolved from this exercise. One thing is certain: while none of
the advective methods contained in the original model documentation
report [4] worked for the Delaware, the spatially varied and intra-
tidal cycle varied C* computations did produce the first major
breakthrough in minimizing both the stability problems and the
numerical mixing, which had prevented solution accuracy. The
reduction of numerical mixing could be deduced by the fact that
the model was now predicting a much steeper concentration gradient,
similar to observed gradients.
2. DISPERSION
The coefficient used to compute mass transfers
through the turbulent dispersion process, C*, was required to be
a constant in the original model. This did not appear to be real-
istic in the Delaware and consequently a modification was performed
to permit C^ to vary spatially. Unlike the estimation of the ad-
vection concentration, C*, the justification of varying dispersion
rates can be explained in the physical sense. It is a well known
fact that high salinity gradients produce density currents [9],
[10], [11], which constitute a further driving force for dispersion.
Practically all previous modelling studies with the DEM have indicated
this phenomenon in high salinity areas and have required adjustments
to the magnitude of dispersion. Through the use of a spatially
-------
II-4
varying C. term, it was possible to relate dispersion to salinity
and achieve a more realistic representation of an actual process
which is usually quite significant.
3. SEAWARD BOUNDARY TRANSFERS
There was an inherent problem in the original OEM's
handling of the seaward boundary which contributed to the problems
discussed under advection. Although this contribution was restricted
to only a couple of junctions adjacent to the seaward boundary, it
was in these particular junctions where most of the advective
problems were arising. The basic defects in the original DEM were
(1) the boundary concentration over the entire tidal cycle, assuming
that it varied, was virtually unknown but had to be specified, and
(2) these concentrations could not be varied on an inter-tidal
cycle or long-term basis. This created the situation where the user
had to surmise what the final results would be before he started.
Additional flexibility was added to the model's pro-
cedure for transferring mass across the seaward boundary in the
Delaware Estuary (the Chesapeake Bay boundary was excluded since
it was not critical) by eliminating restrictions on concentration
variations. During the ebb portion of the tidal cycle, the con-
centration predicted to be in the seaward junction of the model net-
work was used as the actual concentration of the water advected
across the boundary and out of the system. During a flooding tide,
the concentration of the incoming water was incremented between
the minimum value achieved at the end of the preceding ebb tide
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II-5
and a maximum value, CINMAX, which should theoretically occur at
the very end of flood. Checks were made within the program to
determine when ebb tide ends and when flood tide ends so that
appropriate strategies could be followed. The value assigned to
CINMAX can also be temporally varied in any fashion to reproduce
the actual observed intrusion process occurring during the simu-
lation period.
As can be seen, the method by which seaward boundary
transfers are made is truly dynamic in nature and logical, since
it more accurately represents what is actually taking place in
the prototype. The model's ability to predict salinity distributions
in the Delaware, and especially to achieve the tremendous intra-
tidal cycle fluctuations that normally occur near the seaward
boundary based upon several observations, was greatly enhanced by
this modification to the DEM.
4. REACTION KINETICS
The original version of the DEM could handle five
separate constituents which were either conservative or nonconserv-
ative (first order decay). However, with the exception of BOD-DO,
none of the constituents could be coupled to one another mathe-
matically. This effort was to modify the program so that (1)
constituents could be linked in any conceivable fashion, (2) a
more complete representation of the DO budget including photo-
synthesis and respiration by phytoplankton could be included, and
(3) reactions other than first order could be specified if the
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II-6
data so warranted. Besides addressing the above items to a satis-
factory degree, it was imperative that the model retain as much
of its flexibility as possible and be general enough to treat
most foreseeable situations.
A unique "linear matrix" type of solution was employed
in the model to accommodate the coupling of constituents. Any con-
stituent(s) may be decayed through first order kinetics and the
portion decayed may be transferred to any other desired constituent;
a mass conversion coefficient can be applied so that the units of
mass are compatible. In no case will the conservation of mass
theory be violated. An ideal example of the possible constituent
couplings is nitrification, or the conversion of ammonia nitrogen
to nitrate nitrogen. Nutrient uptake by phytoplankton would be
another example where a mass conversion factor to equate the two
is necessary. In short, any depletion or accretion of material
including any transfer associated with first order reactions may be
considered in the model for any constituent given the proper spec-
ification of input coefficients.
The other major modification to the program involved
the addition of several function operators to the basic mass
balance equation. A brief description of these is given below:
FUNC1 Reaeration (three separate
formulations)
FUNC2 Sediment (or Benthic) Oxygen Demand
FUNC3 Algal photosynthesis as related to model's
predicted chlorophyll concentrations
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II-7
FUNC4
FUNC5
FUNC6
FUNC7
FUNC8
FUNC9
FUNC10
& 11
FUNC12
Algal respiration as related to
model's predicted chlorophyll
concentrations
Algal photosynthesis as related to
user-specified chlorophyll concentrations
Algal respiration as related to user-
specified chlorophyll concentrations
.th
order reaction kinetics where
n f 1
Uptake of ammonia nitrogen by algae
Uptake of phosphorus by algae
Any additional first order reaction -
i.e., settling
Denitrification rate linked to DO.
As can be seen, these function operators provide a
diverse array of reactions, all of which strengthen the model's
capability to treat DO and nutrient budgets. Specifying a non-zero
value for a particular function operator activates that reaction
and requires the input of a rate and other relevant information.
It is important to note that all reaction rates may be varied
spatially by reading in separate values for different groups of
junctions numbered sequentially. This demonstrates an extremely
significant improvement in the model's usefulness, since it is
highly doubtful that rates such as benthic oxygen demand, nitrifi-
cation, and algal death would be constant over an 80 mile stretch
of estuary. Appropriate temperature corrections are also performed
on all rates internally.
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II-8
Three formulations for the reaeration rate have
been employed in the model. The O'Connor-Dobbins Equation, the
Churchill Equation, or the USGS (Langbein) Equation can be used
to compute a reaeration rate for each channel at each quality
time step. If desired, constant reaeration rates can also be
read in directly at the junctions. If an equation is used, the
reaeration rate for a junction having multiple channels is computed
by prorating the individual channel rates according to the magni-
tude of the flow in each channel during the time step. Other
methods for computing reaeration rates can be inserted into the
program without much difficulty.
Another modification to the DEM affecting reaction
kinetics involved adding a variable temperature option. New temper-
atures can be read at desired intervals along with the time period,
in quality cycles, that each temperature is applied. When a new
temperature value is read, all reaction rates (except higher-order
rates) will be corrected for this temperature before utilizing them
in the mass balance equation.* The convenience of this option will
become apparent when longer, inter-seasonal runs are considered.
Final modifications to the reaction linkages and feed-
back (non-linear in some instances) systems in the model were
performed as a result of model testing during the DO calibration and
verification phase. Literature material proved helpful during this
* If a simulation requires the specification of chlorophyll con-
centrations and euphotic depths, these can also be varied by
reading in new values whenever the temperature is changed.
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II-9
endeavor. The most notable of these modifications involved (1) the
inclusion of localized settling of organic material (Org N & BOD)
which is handled by FUNC10 and PUNCH according to first order
kinetics; (2) the feedback of predicted DO concentrations on the
denitrification rate (FUNC12) and the subsequent replenishment of
oxygen through the reduction of the NOg molecule; and (3) the
attenuation of the sediment oxygen demand rate when the DO falls
below the 2.0 mg/1 level. A further discussion of the modifi-
cations specific to the DO model is presented in the next chapter.
5. CONSTITUENT NUMBERING
Several options have been included in the quality
model to permit a considerable degree of flexibility in assigning
actual constituents to the constituent numbers utilized by the
program. The basic purpose of these options was to create the
ability to simultaneously consider in a single model run several
of the same constituents, each having a different reaction rate
or some other distinctive characteristic, without having to repunch
the entire set of junction cards. The junction cards contain
initial and waste load concentrations for each constituent. It
became evident at the outset of the model calibration study that
this ability would substantially reduce the number of runs (and the
cost) required to intelligently appraise the various reaction
rates on an individual basis.
Each of the options added to the model are briefly
described below:
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11-10
Option 1 Constituent numbers 1 through 5
in the model represent the first
water quality parameter.
Option 2 Constituent 1 in the model repre-
sents one parameter; other con-
stituents between 2 and 5 represent
the second parameter.
Option 3 Constituent 1 in the model represents
one parameter, constituent 2 another
parameter. Constituents 3 through 5
represent the third parameter.
Option 4 Constituents 1, 2 and 3 in the model
each represents a different parameter.
The fourth parameter is assigned to
constituents 4 and 5.
Option 5 Similar to option 3 but the parameter
treated as constituent 5 is also
assigned to constituents 3 and 4.
Option 3 sets constituents 4 and 5
equal to constituent 3.
Option 6 Each constituent in the model
represents a different water quality
parameter. Normally used for DO program.
6. VARYING WASTE INPUTS
The model as originally programmed allowed constant
waste loadings only. In its application to the Potomac Estuary,
reprogramming allowed one varying waste source. A proper analysis
of the Delaware Estuary, however, required the ability to consider
multiple varying waste sources for at least three reasons:
(1) There are numerous major waste sources whose
varying loadings could affect stream quality significantly; daily
flow periodicities in sewage treatment plants, for example, could
be important.
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11-11
(2) An understanding of stream quality changes
during spring and fall fish migrations was desired; these periods
are characterized by regular changes in tributary loadings (for
both flow and quality) and in sewage loadings (mainly quality).
(3) An understanding of stream quality response
to such transient loadings as stormwater runoff was desired;
these loadings are characterized by rapid changes in both flow and
quality.
The reprogrammed varying waste load section, then,
had to be flexible enough to allow periodic, long-term transient,
and spike loadings. Furthermore, changes in the quantity of waste
flows had to be independent of changes in quality.
The varying waste input section is divided into two
logically similar subsections which treat varying waste flows and
varying waste concentrations. For each junction with a varying
input, the flow periodicity and number of flow increments per
period are first required. For a sewage flow that changes hourly
over a daily cycle, for example, the periodicity is 24 hours and
the number of flow increments is 24. For a spike load (such as
stormwater) in the middle of a simulation, the periodicity is set
equal to the length of the run, and the number of flow increments
is three (before, during and after). The program then reads the
flow rate and duration for each flow increment. Next, the varying
quality subsection reads in the quality periodicity, number of
quality increments, and quality levels and durations for the
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11-12
junction. All varying waste parameters are stored in arrays and
recalled when necessary throughout the simulation period.
7. OUTPUT
It will be noticed in the following chapter that all
comparisons of model and observed data apply when a slack water
tidal condition occurred. All historical water quality data pre-
sented in this report were collected during a particular slack
tide. Knowing the precise tidal condition during data collection
eases considerably some of the problems associated with model
verification. The original printout options did not lend themselves
to the situation where output is required at numerous consecutive
cycles for different groups of junctions. In essence, this repre-
sents the following of a slack tide up the estuary. Consequently,
a modification was made to the model's printout section.
Under the new system the total number of printout
cycles is specified along with the junction numbers to be printed
out for each cycle and the particular slack tide being represented.
It must be determined, external of the model, when a given slack
water occurs at each junction, which is dependent upon starting
conditions, and then translated to computational cycle numbers
used in the model. In this manner no extraneous printout is
obtained.
The tidal cycle summary printouts tabulated in
Subroutine QUALEX have not been altered.
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11-13
The Annapolis Field Office will prepare and publish a complete
users manual for the basic model described in this report, with
some updated streamlining. The manual, as presently envisioned,
will enumerate the various input data and format requirements,
output options and examples as well as a rudimentary coverage of
the program logic and operation.
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III-l
III. MODEL APPLICATION TO THE DELAWARE ESTUARY
A. OVERVIEW
The application of the Dynamic Estuary Model to the
Delaware Estuary involved the following five major steps:
(1) compilation of the data base, (2) establishment of the model
network, (3) calibration of the hydraulic model, (4) calibration
and verification of the quality model, and (5) definition of the
model's sensitivity to various parameters. Steps (2) through
(5) were accomplished in order, while step (1) required continuous
updating throughout the model application. These five steps are
discussed in sections B through F of this chapter.
Although these general steps are followed in most studies
utilizing the DEM, the scope of each step and its relationship to
the others depends on the overall goals of the study. The basic
structure of the quality model which evolved in Step (4) was
predicated on the three primary goals enunciated in Chapter I:
(1) to better understand and define the significant mechanisms
affecting the water quality behavior of the estuary; (2) to
provide a more reliable deterministic tool for accurately pre-
dicting the effects of alternative waste control strategies on
the estuary's water quality; and (3) to establish a sound data
and knowledge base which would be a valuable reference for
planning future studies. Emphasis was placed on those interactions
affecting dissolved oxygen, due to its widespread acceptance as a
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III-2
water quality standard by planning and regulatory agencies in the
Delaware Basin. Although the DO budget was the ultimate aim, this
study also stressed the crucial importance of first defining the
water movement and the resulting basic transport mechanisms
through careful application of the hydraulic model and the quality
model to salinity and dye tracer data.
B. COMPILATION OF DATA BASE
The single most important data need for this study was
water quality. Three primary sources of water quality sampling
data were utilized during different phases of the modelling study.
1. State of Delaware
Periodic slack water runs up the Delaware
Estuary between Reedy Island and Fieldsboro, N. 0. have been per-
formed by the State of Delaware under contract to the Delaware
River Basin Commission (DRBC) since 1967. Salinity, nitrogen and
DO data collected during some of these surveys, when conditions
approached steady-state, were used for model calibration and
verification.
2. AFO
Starting in late 1972, AFO has been conducting
a considerable amount of sampling in the Delaware Estuary between
Artificial Island and Trenton. Both intensive surveys, comprised of
several slack water longitudinal runs interspersed with transect
sampling or other special studies, and individual runs
up the estuary have been performed several times during the past
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III-3
five years. In terms of mathematical model application, the intensive
data, normally collected within a week's period, is exceptionally
valuable if representative of steady-state conditions. Various fractions
of nitrogen and phosphorus were analyzed during all surveys, along with
DO, BOD5, Chlorophyll a^ and light penetration (Secchi Disk). Occa-
sionally, long term carbonaceous and nitrogenous oxygen demand, heavy
metals, and other parameters of concern were measured in the
laboratory.
In addition to this water quality monitoring, AFO
performed a special dye study in July-August, 1974, for estimating
dispersion, dilution and transport characteristics of the Delaware
Estuary in the vicinity of Philadelphia. Dye was released continually
at a rate of 1.4 Ibs/hr or 25 ppb over a four day period (8 complete
tidal cycles) via the outfall pipe at the City of Philadelphia's
N.E. wastewater treatment plant. Three weeks of monitoring were
conducted in order to track the dye cloud's movement laterally,
vertically, and longitudinally over time.
3. 1975 and 1976 Co-Op Studies (208 Program)
Two very intensive, two week monitoring programs
were initiated by DRBC for the purpose of calibrating and verifying
either a one or two dimensional model. These surveys were conducted
during moderate flow, high-temperature periods in August 1975 and
July 1976. Major participants included AFO, the City of Philadelphia,
and the States of Delaware, Pennsylvania, and New Jersey. Numerous
slack water runs were made from Artificial Island to Trenton, N. J.
-------
III-4
with three boats running abreast as far as Torresdale, Pa. In
addition, a considerable amount of transect sampling was included
in the 1975 survey. Sampling of significant tributary inflows and
waste discharges was conducted during both surveys. Composite
samples were collected at the Trenton water supply intake to establish
input loadings to the estuary from the upper Delaware Basin. Among
the laboratory analyses were BODs, BOD20, DO, NHs, TKN, NCh, NOs,
TPOit, inorg P, chlorophyll a_, fecal coliform, total solids, sus-
pended solids, turbidity, and chlorides.
After water quality, the most important data needs were
municipal and industrial wastewater loads, tidal conditions, and
freshwater inflows. Data pertaining to tides and flows were obtained
from the U.S. Coast and Geodetic Survey and the U.S. Geological
Survey, respectively. A strenuous effort was made to determine waste-
water loadings, particularly from the most significant sources.
Nevertheless, many of the individual water quality data sets lacked
complete information on wastewater flows and pollutant concentrations.
In lieu of wastewater data taken during the water quality surveys,
wastewater loads had to be estimated from NPDES and Corps of Engineers
permit applications, water and waste quality reports, self-monitoring
reports, and special surveys by state and federal agencies. The
August 1975 and July 1976 co-op surveys were the only exceptions,
where some data were obtained at every major wastewater source while
estuary sampling was underway.
-------
III-5
As might be expected, the quality and completeness of
wastewater data varied among waste dischargers and over time. Recent
data from all dischargers tended to be more complete (particularly
the flow rates) due to the self-monitoring requirements of the NPDES
program. An additional report documenting all of the recent waste-
water analyses and trends is planned by AFO for the near future. A
summary of wastewater loadings used for the model simulations of the
five data sets in this report is tabulated in the Appendix.
C. ESTABLISHMENT OF MODEL NETWORK
A network comprised of 76 junctions and 82 channels was
designed for the Delaware Estuary between Trenton, N. J. and Listen
Point, Delaware, a distance of about 80 statute miles. A map con-
taining the network is shown in Figure III-l. The network includes
not only the main stem of the Delaware, but the entire C&D Canal
and the major tidal tributaries as well. Excepting areas where
large islands occur, the configuration of the network can be classi-
fied as one-dimensional. A hydraulic time step of 5 minutes and
a quality time step of 30 minutes are used when running the model
with this network.
Caution was exercised in designing the network grid so that
the actual channels which convey most of the flow in the prototype
are well represented in the model. Channel elements were oriented
to minimize the variations in their widths and depths and to keep
their lengths relatively uniform and compatible with the stability
criteria relationship shown in Chapter I. For the most part, channel
lengths ranged between 1 and 3 miles.
-------
..TRENTON
"\ ,'' )
MATHEMATICAL MODELLING NETWORK
DELAWARE ESTUARY
-------
III-7
Although any geometrical design can be employed for the
junction elements, the one-dimensionality of this network dictated
primarily a rectangular type of grid pattern. In general, a sampling
station corresponded to about every other junction, which is adequate
coverage for most model verification studies. A diagram showing the
relative position of sampling station, model junctions, bridges and
other landmarks, major waste sources, etc., is included in the Appendix.
All of the required physical data for this network were
obtained from the most currently available sets of USC&GS navigation
charts.
-------
III-8
D. CALIBRATION OF HYDRAULIC MODEL
Several simulations were made with the hydraulic model in an
attempt to reproduce the actual tidal wave movement in the Delaware
under an average flow condition. The only variable that was altered during
these runs was the Manning channel roughness coefficient, which
controlled energy losses and thus influenced both the speed of the
wave and the tidal ranges. The waves imposed at the seaward boundaries
of the model were typical for the areas, based upon one year of tidal
records.
The results of the final calibration run, along with actual
prototype data for most USC&GS tidal prediction stations are shown
in Table III-l. Included in this table are both tidal range data
and phasing data which indicate times of high and low water as
referenced to Listen Pt., the seaward boundary of the model on the
Delaware. An examination of the data shown in Table III-l reveals
that the model does indeed simulate fairly accurately the tidal
wave motion in the Delaware Estuary. Actual and predicted tidal
velocities at various locations in the estuary were not included in
the table because of limited data, but some comparisons were made and
they did appear acceptable. The final roughness coefficients are
shown In Table III-2.
-------
Table III-l
III-9
Comparison of USC&GS Tidal Data and Hydraulic Model Predictions
Delaware Estuary
Station
Model
Junction
Ranges
Actual Predicted
(feet)
Phasing*
Actual Predicted
H.W. L.W. H.W. L.W.
(min)
Trenton
Bordentown
Florence
Bristol
Torresdale
Philadelphia,
Brides burg
Philadelphia,
Pier 11
Gloucester
City
Schuylkill River
@ Fairmount Br.
Schuylkill River
@ Point Breeze
Fort Miffl
in
Billingsport
Chester
Oldmans Pt
Christina
New Castle
Reedy Pt.
C&D Canal
@ Biddle
C&D Canal
@ Summit
C&D Canal
Ri ver
Pt.
Br.
75
72
69
68
60
56
51
49
47
54
44
43
36
32
25
23
13
9
6&7
4&5
6
6
6
6
6
6
5
5
5
5
5
5
5
5
5
5
5
5
3
2
.8
.7
.6
.5
.2
.0
.9
.8
.8
.7
.7
.7
.7
.6
.6
.6
.5
.1
.5
.6
6
6
6
6
6
6
5
5
5
5
5
5
5
5
5
5
5
4
3
2
.6
.8
.6
.5
.1
.0
.9
.8
.8
.7
.7
.6
.6
.6
.6
.4
.4
.4
.4
.5
+304
+301
+299
+289
+258
+226
+200
+187
+194
+179
+171
+161
+141
+118
+106
+ 85
+ 55
+ 50
+ 21
- 20
+381
+360
+350
+336
+302
+268
+240
+227
+236
+220
+210
+200
+180
+153
+135
+108
+ 59
+ 60
+ 04
- 53
+280
+275
+265
+260
+235
+205
+190
+180
+180
+170
+160
+150
+130
+100
+ 85
+ 70
+ 40
+ 35
+ 30
-25
+375
+360
+340
+330
+295
+265
+245
+240
+245
+235
+220
+210
+180
+145
+125
+110
+ 50
+ 35
+ 5
-40
@ Chesapeake City
* Referenced to Listen Pt.
-------
111-10
Table III-2
Final Manning Roughness Coefficients
Delaware Estuary Hydraulic Model
Channels
1 -
15 -
18 -
28 -
33 -
37 -
63 -
73 -
14
17
27
32
36
62
72
82
River Mile
87
74
74
64
64
54
28
13
- 74
- 74 (trib)
- 64
- 64 (trib)
- 54
- 28
- 13
- 0
Manning n
0.010
0.015
0.010
0.015
0.016
0.020
0.035
0.040
-------
III-ll
E. CALIBRATION AND VERIFICATION OF QUALITY MODEL
1. Chloride Simulations
The chloride ion is a conservative substance which is ad-
vected and dispersed upstream from the ocean. It is a convenient
measure of salinity and is used interchangeably with that parameter.
Five separate and independent data sets were used to calibrate and
verify the Delaware model for chloride movement. Of special importance
was the confirmation that the transport modifications discussed in
Chapter II could, in fact, handle the steep salinity wedge observed
in the Delaware, and the proper estimation of input coefficients
would permit the model to be predictive rather than descriptive.
Three different flow conditions were considered in order to develop
a relationship between chloride concentrations, which are a function
of freshwater flow, and dispersion coefficients. The fact that
chloride data were not available downstream from Reedy Island created
a problem when specifying conditions at the model's seaward boundary,
which is located 5 miles downstream from Reedy Island. Extrapolations
had to be performed based upon observed local gradients during each
simulation period.
Initially, a data set representing approximately an
average flow condition (11,000 cfs) was selected for model calibration
(all flows here refer to the freshwater flow at Trenton). The time
period was May 14-28, 1970, when flow was extremely steady. Numerous
runs with different assumptions were performed to analyze model
sensitivity and thus to acquire insight on model behavior. The
-------
111-12
following table exhibits the advection factors (C*) and dispersion
coefficients (CiJ used in the final calibration run for 11,000 cfs;
the results of the calibration are shown in Figure III-2.
TABLE 111-3
Advection Factors and Dispersion Coefficients
OEM's Initial Chloride Calibration
(Flow = 11,000 cfs)
River
Channel Mile C* (Flood) C* (Ebb) C_4
1 1.0 0 20
2 1.0 0 30
3 1.0 0 40
4 1.0 0 50
5 1.0 0 60
6 1.0 0 70
7 1.0 0 80
8 1.0 0 90
9 83 .6 0 100
10 80 .33 0 50
11 77 .3 0 10
12 1.0 .33 10
13 .2 0 10
14 .2 0 10
15 .501
16 .501
17 .501
18 .5 0 10
19 .5 0 10
20 74 .5 .1 10
21 .5 0 10
22 .5 0 10
23 .5 0 10
24 72 .5 .25 10
25 69 .67 .33 1
26-82 67-1 .67 .33 1
-------
111-13
»
The agreement between observed and predicted high
water salinity profiles is surprisingly good, considering the
initial difficulties in maintaining both stability and accuracy of
the solution. As can be seen, predicted gradients were extremely
steep except for the network between junctions 13 and 20, a highly
variable and hydraulically complex area near the C&D Canal. The
low water profile, which is not shown in the figure, appeared to be
very reasonable, based upon other data sets; this indicated that
tidal transport and seaward boundary transfers were functioning
properly in the model.
Data collected during a comparable flow period (12,000 cfs)
were used to verify the advective and dispersive inputs shown in the
table above. The results from this verification simulation of the
May 7-22, 1968, chlorides movement are shown in Figure III-3. Again,
a satisfactory agreement was obtained, even though the concentration
gradients were more severe here than in the data set used for
calibration.
The second condition investigated was characteristic
of a typical late summer - early fall Delaware hydrograph when flow
rates average about 5,000 cfs. It was apparent that the greater
salinity intrusion under this lower flow condition would necessitate
a dramatic increase in the dispersion coefficients. The original
advectlon factors were, however, left intact since there was no valid
justification for changing them. The revised dispersion coefficients
yielded by the final calibration run (5,600 cfs - July 6 to August 1,
1967) are presented below for the major channel' elements in the model
-------
111-14
network. The model predictions are shown in Figure III-4 along with
observed data.
Channel River Mile Ct,
9
10
11
20
24
25
26
27
33
34
35 and above
83
80
77
74
72
69
67
64
62
60
58-1
100
100
100
75
50
25
25
25
10
10
1
The next model run was to verify the advection factors
and the dispersion values used in the 5,600 cfs calibration run. The
observed data represented a steady state period between October 8 and
November 6, 1969. The freshwater flow during this period was about
4.800 cfs. The excellent agreement between observed and predicted
data exhibited in Figure III-5 indicated that the model was capable
of accurately forecasting the salinity intrusion process during a
representative low flow situation. It is interesting to note that
the calibration was performed with low slack data whereas the verifi-
cation used high slack data. This demonstrates the versatility of
the model in considering significantly varying situations.
The third verification data set represented an extremely
low flow period which occurred between July and October 1964. In fact,
the 2,400 cfs at that time represented one of the lowest sustained flow
periods on record. The salinity profiles at the beginning and end of
this time period were obtained from a DRBC report [12]. The primary
reason for attempting another verification was to dispel any doubts
-------
111-15
about whether the model was "predictive" or "descriptive." Up until
this point either position could have been argued since the dispersion
coefficients were not defined a priori. In this case, however, an
estimation of the applicable dispersion coefficients for 2,400 cfs was
made based upon the values required for the two higher flow conditions.
This extrapolative approach would thereby subject the model to a true
test of its predictiveness. The flow-dispersion coefficient relationship
used for this verification analysis is presented in Table III-4; it has
been subsequently programmed into the model. The model results based
upon this set of dispersion coefficients are shown in Figure II1-6 along
with observed data. An inspection of these salinity profiles will reveal
the excellent response of the model in predicting prototype behavior
when salinity intrusion rates were at a maximum. It is believed that
this favorable agreement, along with others previously discussed, repre-
sented a good model verification for salinity subject to the limitations
of the data base and the model's seaward boundary location.
2. Dye Simulations
Data collected during and after the July 1974 dye release
at the Philadelphia N.E. wastewater treatment plant (see III.B.2) pro-
vided a valuable opportunity to assess the model's advection and
dispersion inputs in a predominately freshwater region of the estuary.
These transport parameters, of course, could not be adequately validated
through the salinity simulation studies discussed in the above section.
This dye data was considered to be even more valuable because of unique
distinctions associated with this tracer. Dye is quasiconservative and,
unlike salinity, will be advected and dispersed primarily in a down-
stream direction; due to a common point source, dye should closely
-------
111-16
approximate the mixing and transport characteristics of the wastewater
itself.
Table III-4
Dispersion Coefficient (CiJ vs Flow
Delaware Estuary Model
River
Mile
Channel
83
80
77
74
72
69
67
64
62
60
58
55
53
50
48
46
43
40
38
36
33
31
29
27
28
9
10
11
20
24
25
26
27
33
34
35
36
37
39
43
47
48
52
53
55
56
59
61
63
64
Flow (cfs x 1000)
11-12 10-11 9-10 8-9 7-8 6-7 5-6 4-5 3-4 2-3
100
50
10
10
10
1
100 100 100
75 100 100
25 50 75
10 25 50
10 10 25
1 1 10
1
100
100
75
50
25
25
10
1
100
100
100
75
50
25
25
10
1
100
100
100
75
50
25
25
25
10
10
1
100
100
100
75
50
25
25
25
25
10
10
10
1
100
100
100
75
50
25
25
25
25
25
10
10
10
10
1
100
100
100
75
50
25
25
25
25
25
25
25
10
10
10
10
10
10
1
10(
10(
10(
7!
5(
2,
2,
2!
2!
21
2.
2!
2;
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21
1
1
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111-22
Four separate hydrodynamic solutions, each representing a
discrete flow between 3,900 cfs and 8,800 cfs, were required for the
dye simulation. The appropriate sets of dispersion coefficients from
Table III-4 were used, as well as a theoretical first order dye loss
rate computed from a mass balance of field data. This loss rate was
estimated to be 0.02/day. Other than the inclusion of a loss rate,
the original model employed for salinity was left intact, including
all inputs relative to advection. The results of this dye simulation
and the actual dye distributions observed in the Delaware Estuary
during the study period are presented in Figures III-7 through III-
20. Both profiles correspond to either a high or low water slack
condition as indicated. Since the model is based on a real time
system, the predictions closely approximate the particular time
period represented by the different data sets. It should be noted
that appropriate corrections were made to some of the measured
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to reflect significant differences between mid-channel values and
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injection, a sampling run was made to define background concentrations
throughout the study area. These concentrations were normally quite
low (^ 0.1 ppb) but were nevertheless taken into account when analyzing
the dye data for model verification purposes.
-------
111-23
An examination of the observed and predicted dye data
indicated that, in general, the model satisfactorily reproduced the
basic transport of the dye cloud, as evidenced by the close agreement
in spatial position, the bell-shaped characteristics, and the magnitude
and location of the peak concentrations. A few significant discrepancies
did occur with the dye peaks during the early phase of the study when
some of the field data appeared questionable. Mixing problems or
unrepresentative sampling points may have partially accounted for this
problem. Considering the independence of the dye data and the fact that
no manipulations were performed to the model, it is believed that a
successful verification of the advective and dispersive transport
mechanisms was achieved.
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111-38
3. Dissolved Oxygen Budget
a) Introduction
Special emphasis was placed on modelling the dissolved
oxygen budget, due to its widespread acceptance as a water quality
standard. Because of its important role in affecting DO levels in
rivers, and particularly estuaries, considerable attention was directed
towards the major components of the nitrogen cycle. The majority of
the previous models applied to the Delaware Estuary made no attempt
to model specific nitrogen fractions, but rather treated nitrogen solely
in terms of oxygen demand associated with nitrification.
The strategy followed in the model formulation and
calibration studies was essentially one of starting simple, and then
progressing in complexity when the data analysis phase so dictated.
It could be described by the following three step algorithm:
Step 1 Begin with a relatively simple model which
includes the principal reactions affecting
DO; utilize this approach, along with rates
bounded by ranges determined from a literature
search, to "explain" the results of a historical
water quality data set.
Step 2 Test the tentatively calibrated model for other
reactions known or suspected to occur based upon
comparison of observed data trends with simulation
results; include new reactions in a restructured
model to better "explain" the historical data.
-------
111-39
This step of restructuring and recalibrating
the model should be repeated, keeping in mind
the limitations of the available field and
literature data, until adequate confidence
in the model's "prowess" is attained commen-
surate with the goals of the study.
Step 3 Utilize additional independent data sets to
verify that the model is indeed satisfactorily
recreating what is taking place in the proto-
type for a variety of conditions totally
unrelated to the original data set(s) used
for calibration purposes.
b) Description of Data
Five independent sets of water quality data were analyzed
during the course of this modelling study. Their source and basic
content were described in Section B of this chapter. Data sets col-
lected during July 1974 and October 1973 were used extensively for
model construction and calibration, with the exception of algal effects;
algal photosynthesis and respiration were addressed in the August 1975
data set, where their effects became prominent. The fourth and fifth
data sets, covering the periods July - September 1968 and July 1976,
respectively, were used strictly for model verification. The primary
criteria that determined which data sets were selected for model
simulations were (1) the degree to which steady state conditions
prevailed, (2) the intensiveness and completeness of the data, including
wastewater information, and (3) the representation of different
-------
111-40
hydraulic, thermal, chemical or biological conditions to increase
the predictive power of the model.
The first major step in data analysis (and a necessary
prelude to modelling) is a thorough examination of currently available
data in search of common trends and important variations. The fol-
lowing is a summary of the five data sets eventually used in this
study.
-------
111-41
July. 1974
Four high water slack sampling runs were made up the mid-channel
of the Delaware Estuary on July 22, 24, 29 and 31, 1974. During
this period the estuary was warm with a relatively steady flow -
27°C + 0.9°C* and 3906 ±290* cfs at Trenton (disregarding a high
flow of8,740"cfs on July 31). The daily longitudinal profiles for
DO, the nitrogen series, and chlorophyll a_ are plotted in Figures
111-21, 111-22-24, and 111-25, respectively.
The four DO profiles exhibit common significant trends.
There is a steady decline from saturation levels at Trenton to
about 3 mg/1 below Bristol. This "Bristol sag" is followed by a
1 mg/1 recovery in the vicinity of Torresdale. Beginning near
Philadelphia's N.E. STP, DO levels decline rapidly to between 1/2
and 1 mg/1 below the Walt Whitman Bridge. These conditions persist
down to Chester, where a gradual recovery begins. DO concentrations
finally reach 5 mg/1 below Pea Patch Island near Reedy Point.
The nitrogen profiles also show common trends. The decline in
ammonia levels accompanied by similar increases in nitrate strongly
indicates nitrification above and below Philadelphia. The rapid
buildup of ammonia at Philadelphia might result from an inhibition
of nitrification due to the "shock effect" of high organic loading,
low DO, or other unknown toxic pollutants. Finally, a slow decay
* Mean ±S.D.
-------
111-42
of nitrates can be discerned below Wilmington where the masking
effects of nitrification are not present. Organic nitrogen concen-
trations are fairly stable throughout most of the estuary with some
decline occurring in the lower reach.
Chlorophyll a^ levels were somewhat variable but almost ex-
clusively less than 50 yg/1, a value normally associated with a
bloom threshold. Maximum concentrations were measured downstream
of Philadelphia.
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II1-48
October, 1973
Two high water slack sampling runs on October 15 and 17 accompanied
by two transect sampling runs on the 16th and 18th comprised the
October, 1973 data set. This was a relatively steady period, with
temperatures declining from 20°-19°, and flows averaging 4020 cfs at
Trenton. Water quality parameters analyzed were the same as for the
July, 1974 data set. During both transect runs, surface and bottom
samples were taken near the east and west banks in addition to the
mid-channel at ten different stations between Torresdale and Reedy
Point. This transect sampling data, which was intended to show
whether mid-channel surface water samples were representative of the
entire cross-sectional water column, is still undergoing analysts
along with other'data, of a Similar nature. Pertinent findings
will be included in a future document. Mid-channel surface samples
were taken at every station during the two high slack runs. The
resulting longitudinal profiles for DO and the nitrogen series are
plotted in Figures 111-26 through 111-29.
The two DO profiles show a steady decline from saturation levels
at Trenton to around 5 mg/1 just above Philadelphia. No "Bristol
sag" is evident. Near Philadelphia's NE STP, DO levels drop rapidly,
reaching a minimum of 1 - 1.5 mg/1 just below the Walt Whitman Bridge.
A gradual recovery, beginning Immediately, is interrupted by a
secondary sag below Chester. From 2.5 mg/1, oxygen levels improve
quickly below Wilmington.
-------
111-49
The nitrogen profiles exhibit the same trends as the July 1974
data. The most prominent difference is the increase in magnitude
and duration of the ammonia buildup at and below Philadelphia.
These high ammonia levels could be caused by larger waste loadings
or by longer inhibition of the nitrification process due to the
low ambient water temperature. Based on the two data sets described
thus far, it does not appear that low DO levels (i.e., <1.0 mg/1)
directly reduce nitrification rates.
Unfortunately, a complete set of chlorophyll a^ data was not
obtained during this survey, although some measurements were made in
the critical zone between Marcus Hook and Wilmington. Levels were
again in the sub-bloom category (20 - 40 yg/1) with an observable
difference between the two individual sampling runs.
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111-54
August, 1975
Perhaps the most comprehensive data set from the Delaware
Estuary was gathered between July 31 and August 18, 1975 for the
purpose of calibrating a future two-dimensional water quality
model. Under the auspices of DRBC, field crews from AFO, USGS,
the States of Delaware, Pennsylvania and New Jersey, and the City
of Philadelphia sampled 32 water quality stations between Listen
Point and Trenton, as well as the major municipal and Industrial
waste discharges within this reach. Both high and low slack water
surface samples were taken from the east bank, mid-channel and
west bank of the estuary between Listen Point and Torresdale,
and from the mid-channel the rest of the way to Trenton. In
addition, transect samples were taken from the same locations on
alternate days. Several laboratories, including those of AFO,
the State of Delaware, and the City of Philadelphia, contributed to
sample analyses. A detailed evaluation of this voluminous body of
data has not been accomplished at this writing, in part due to the
lengthy process of data quality assurance required in a comprehensive
survey with many participants.
The Delaware River at Trenton experienced declining flows through-
out the survey, averaging 8330 +_ 1080 cfs from July 31 - August 10
and 5870 +_ 290 cfs from August 11 - 18. Water temperatures during the
period averaged about 27°C. The longitudinal DO, nitrogen and
chlorophyll ^profiles are presented in Figures 111-30 through 111-38
and constitute the data collected and analyzed by AFO. This partial
-------
111-55
data set was intended to be used for the Initial verification analysis
of the one dimensional water quality model presented in this report.
The four low water and two high water DO profiles follow the
same trends, but exhibit considerable scatter in some areas of the
estuary, particularly near Philadelphia. The gradual decline from
saturation levels at Trenton to 4 mg/1 at Philadelphia's NE STP shows
no sign of a sag and recovery near Bristol, possibly demonstrating the
effects of a higher than normal summer flow condition. The DO levels
drop off more quickly through Philadelphia, reaching a minimum of about
1.5 mg/1 near the mouth of the Schuylkill River. Recovery is unusually
fast, with DO levels exceeding 5.0 mg/1 above Wilmington and remaining
near that level down to Listen Point. This rapid DO recovery is probably
the result of a large phytoplankton bloom which produced high chlorophyll
^concentrations between Philadelphia and Wilmington.
Although the nitrogen profiles exhibit the same characteristics as in
previous data sets, the spatial trends are less pronounced. The buildup
of ammonia levels at and below Philadelphia does not reach 0.8 mg/1,
and the subsequent decline is gradual. An increase in nitrates below
Philadelphia generally matches the decline in ammonia in terms of
magnitude and position. Both this area and that above Philadelphia
show evidence of nitrification. The organic nitrogen median profile
is characteristically flat, ranging between 0.4 and 0.6 mg/1. Individual
profiles are more variable, but exhibit no discernible trends.
-------
111-56
Particular attention should be paid to the chlorophyll a^
profiles shown 1n Figure m-38, since they differ so greatly
from the levels encountered In either July, 1974 or October,
1973. Maximum chlorophyll a_ concentrations between 100 and 200
yg/1 were measured in the estuary between Philadelphia and Wilmington
during much of the study period. Spatial gradients were rather abrupt
both above and below the centroid of the bloom. Daily profiles, while
showing the same general trends, were extremely variable, possibly
because algal blooms normally occur as discrete patches rather than
as a uniform mixture, thereby increasing sampling uncertainty. The Impact of
this algal bloom on DO concentrations became quite apparent during the
initial attempt to verify the model with this data set. That effort
was unsuccessful because the effects of algae were not considered,
and the speedy DO recovery could not be simulated with existing
mechanisms in the model. A vivid quantification of these algal
effects on the predicted DO distributions is depicted in the sensitivity
analysis section of this chapter.
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111-66
July - September. 1968
In some respects, this data set offered more value than the
others because of its relatively long duration. The fact that
both non-bloom and varying algal bloom conditions were represented
made it particularly appealing from the standpoint of model
verification. Weekly, or in some cases, semi-weekly slack water runs
extending from Reedy Island to Fieldsboro, N. J. were performed by
the State of Delaware from July 3 to September 9. Unfortunately,
the early non-algae phase of the study had very limited value
because of the transient nature of the hydrograph and the difficulty
associated with conducting a meaningful simulation of such a condition.
Figure I11-39 presents the variability of temperature, flow, and
chlorophyll ^concentrations for the entire study period.
The individual DO profiles for the two significant algal bloom
periods, July 26 - August 17 and August 18 - September 6, are shown
In Figures 111-40 through 111-42. For the sake of convenience, low
water slack and high water slack data are presented on separate
graphs. As can be seen, definite similarities exist among these
profiles with regards to minimum DO concentrations and the basic
configuration of the sag. The spatial displacement of the profiles
from one slack to the other can be easily identified. One disturbing
feature of these profiles is the lengthy and relatively constant DO
minimum, a phenomenon that is seldom experienced. It appears that
the sampling procedure prevented the DO concentrations from going
below about 1.0 mg/1, as though the introduction of a residual amount
-------
111-67
of oxygen to the sample, either through pumping or filling the con-
tainer^ was taking place. Data collected by the City of Philadelphia
during the same period showed many DO values approaching or actually
reaching zero. This data will be presented 1n the next section In
conjunction with the model verification study.
Plots of the nitrogen series data for the same time periods are
presented in Figures 111-43 through 111-51 for both high water and
low water conditions. The relatively small amount of scatter among
the individual data points within both periods enhance their value
for model simulation studies. Examination of the nitrogen profiles
reveals that the same basic trends depicted in the other data sets
are further corroborated by this 1968 data. Differences between
one period and the next relate primarily to concentration levels
rather than spatial trends; whether these differences in the in-
organic nitrogen concentrations can be attributed to existing algal
levels is uncertain because of discrepancies in the data itself.
Maximum chlorophyll a_ data for the duration of this 1968 study
are presented 1n Figure 111-39. Individual profiles for each sampling
date within the three separate periods can be seen in Figures 111-52
through 111-55. To summarize, the period from July 3 to July 25 was
of low algal Intensity but very transitory; the following period from
July 26 to August 17 contained maximum algal blooms with chlorophyll
a_ levels ranging between 100 and 150 yg/1; the last period between
August 18 and September 6 exhibited a continued but somewhat lower
bloom condition, with maximum chlorophyll a_ levels ranging between 70 -
-------
111-68
100 yg/1. In all three cases, chlorophyll a_ peaked in the
Philadelphia to Marcus Hook reach.
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111-86
July. 1976
This survey was conducted during a two week period in July, 1976
and was designed for the purpose of verifying a future two-dimensional
model. The product of the Technical Advisory Committee, Delaware
Estuary 208 Planning Program, it was conceptually similar to the
1975 survey and involved the same participants. The major difference
was the exclusion of transect sampling. The same 32 water quality
stations were sampled between Listen Point and Trenton during six slack
water runs. In the reach below Torresdale three boats ran abreast, sampling
along both shorelines as well as the mid-channel. The mid-channel data
collected by AFO personnel will be presented in this report for model
verification purposes. In addition to the estuary monitoring, sampling
was conducted at the major municipal and industrial waste discharges
and the larger tributary Inputs.
The Delaware River flow at Trenton was moderate and steady, averaging about
7,500 cfs. Water temperatures during the period were also steady and
averaged about 25°C. The longitudinal DO profiles observed during
each of the slack water runs are shown in Figures 111^56 and 111-57.
The first figure contains the three low water slack sampling results,
while the second shows similar data for high water slack conditions.
The effects of tidal excursion are quite evident. The actual shapes
of the profiles closely resemble those presented previously for
different time periods. Major DO depressions to 2.0 mg/1 or less
occurred in the vicinity of Philadelphia, followed by a gradual but
steady recovery downstream of Chester. The three low slack runs were
-------
111-87
quite consistent, with maximum DO concentration differences of
about 1.0 mg/1. The variability in the high slack data, however,
was much greater, particularly towards the end of the period.
As with the case of DO, the major nitrogen fractions monitored
during the July, 1976 time period generally showed consistent
patterns with previously described data sets. These data are
presented in Figures 111-58 through 111-63. Organic nitrogen was
least variable, with a buildup from about 0.4 mg/1 to 0.6 mg/1
beginning at Philadelphia. Ammonia nitrogen again experienced a
substantial reduction above and below Philadelphia as a result of
nitrification. Maximum concentrations were about 0.6 mg/1 during
both slack conditions, which is less than some other data sets have
indicated. In one instance (high slack data) this level was unex-
pectedly attained below Trenton. The observed ammonia concentrations
were very consistent within each week of the sampling period. The
spatial variation of nitrate nitrogen, the most abundant form through-
out the estuary, mimicked other data sets in showing an almost
uninterrupted but continual rise between Trenton and Wilmington. Con-
centrations increased from about 0.8 mg/1 to over 2.0 mg/1. The
greatest rate of increase occurred below Philadelphia where nitrification
appeared most prominent, as corroborated by the rapidly declining
ammonia levels. Even allowing for nitrification, however, there
existed a surplus of nitrates near Wilmington, indicating the pos-
sibility of major external sources along this reach of the estuary.
Figures 111-64 and 111-65 present the longitudinal chlorophyll
a_ profiles for the six individual sampling runs. During both weeks
-------
111-88
of the study a sizeable algae bloom was observed in the vicinity of
Torresdale, Pennsylvania and Beverly, New Jersey, as demonstrated
by the high chlorophyll a^ peaks depicted in these figures. As can be
seen, chlorophyll £ levels of 100 yg/1 or more were fairly common in
the bloom area. Examination of the actual algae cells under a micro-
scope indicated that the bloom was comprised of diverse, green,
pollution tolerant species. Other areas of the Delaware exhibited
background algae conditions.
Figures 111-66 and 111-67 present the longitudinal profiles for
Secchi Disk readings, a convenient measure of light penetration. A
significant decline in light penetration occurred below river miles 55
and 45 for LS and HS data sets, respectively; this decline is always
present below Philadelphia, and results from the flocculation of silt
in the freshwater as the salinity wedge is first encountered. A
significant increase in light penetration occurred during the second
(HS) week of this survey at and above Philadelphia. No explanation
for this can be offered at this time.
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-------
III-101
c) Quality Model Construction
A detailed discussion of the quality model's
structure was presented in Chapter II. Many of the reactions
and constituent linkages contained in the model were formulated
prior to the Delaware calibration study with the remainder being
necessitated through this calibration process. To implement our
philosophy of beginning simple, a decision had to be made concerning
which of the model's functional options should be included in the
preliminary analysis. Previous studies of the Delaware Estuary
had shown the necessity of considering, in some fashion, the
oxidation of both carbonaceous and nitrogenous material in the
water column and in the bottom sediments. A description of the
sequential model formulations that were pursued during the course
of this study follows:
Initial Formulation
Figure 111-68 is a schematic diagram outlining
the constituent linkages and reactions employed in the initial
model. Total carbonaceous material oxidized in the water column
was represented by a single parameter, CBOD, coupled to DO in a
linear reaction. The problems inherent in this traditional
formulation, such as the imprecision of the BOD test, the uncertainty
in defining the relationship between 5-day and ultimate first stage
demands, and the uncertainty in projecting decay rates were
recognized, but were considered less troublesome than trying to
model either COD or TOC as an oxygen demand source.
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-------
III-103
The treatment of the nitrogen cycle can be
represented either by the decay of a single parameter, NBOD, or
by a set of multi-stage consecutive reactions. The latter option
was chosen because previous studies had demonstrated the crucial
importance of nitrification on the DO resources of the estuary. The
two oxidized forms of nitrogen, N02 and N03, were combined in the
model because the nitrite fraction is extremely transitory, and
separate laboratory analyses are not normally performed. Both
theory and previous studies show the NH3 -> N02 step to be rate
limiting to the overall nitrification process. All forms of organic
nitrogen were represented by a single parameter. No attempt was
made to distinguish between the dissolved and particulate fractions,
since data of this type were not available. The decomposition of
organic nitrogen (including hydrolysis) to ammonia was treated as
a first order reaction in the model. Although no attempt was made
to model algal growth dynamics in this study, a nitrate loss rate
indicative of algal uptake was included in this initial model
formulation.
The oxidation of carbonaceous and nitrogenous
material in the sediments is a well documented problem in the
Delaware Estuary. Unfortunately, adequate data to permit the
explicit modelling of sediment dynamics do not exist. In fact,
good "in situ" measurements of a gross oxygen demand rate at
various locations in the Delaware were just recently obtained.
Sediment oxygen demand (SOD) is represented in the model as a
zeroth order decay of DO and is input as an areal term.
-------
111-104
Finally, the process of reaeration was represented
by the O'Connor-Dobbins formula; although two other formulas are
available in the model, this was considered more appropriate for
large bodies of water.
Second Formulation
The consecutive reactions comprising the nitrogen
cycle in the original formulation were expanded to include a
feedback loop between nitrate nitrogen and organic nitrogen. This
last reaction, which completes the primary nitrogen cycle circuit,
was intended to represent the biological uptake and conversion of
nitrate to algal cellular material (organic N). The new nitrogen
series feedback model was recalibrated and its importance was
reflected in the altered nitrogen profiles, and decay parameters.
Third Formulation
The second formulation of the nitrogen model
implied that total nitrogen behaved conservatively. To test this
assumption, a mass balance was performed using the model
predictions of total nitrogen for two data sets as compared to
actual field data. A significant loss of nitrogen was found to
occur in the vicinity of major waste sources, especially when DO
concentrations were less than 1 mg/1. Consequently, two sinks for
nitrogen were added to the model structure: (1) settling of
organic nitrogen near major waste inputs, and (2) denitrification
(N03 -> N2 gas) in low DO waters. These additions substantially
improved the predictions of the total nitrogen distribution
-------
III-105
as well as the N02 + N03 distribution.
Fourth Formulation
The third formulation of the nitrogen model was
coupled to the original DO - CBOD model with the addition of a
comparable settling rate for CBOD near major waste outfalls and
the predicted DO profile provided by this formulation was compared
to observed July 1974 data. It was believed that the basic shape
and magnitude of the DO sag, particularly its flatness, could best be
explained by certain non-linear feedback effects which have been
observed by others under low DO conditions [13], [14], [15], [16].
The first change was a modification of the sediment
oxygen demand when predicted DO levels were less than 2.0 mg/1,
such that the effective demand varies as the DO raised to the
0.45 power [15]. The second change was linking denitrification to
DO and CBOD so that the oxygen in nitrite and nitrate was made
available to the active decomposing bacteria [17]. Again, this
newly structured model was capable of simulating more closely the
original data set (July 1974) used for calibration.
Fifth Formulation
It is known that temperature significantly effects
most biological and chemical reaction rates. The next revision
to the model involved the application of temperature correction
factors to permit obtaining the various reaction rates at
temperatures other than the 27°C that existed during the July, 1974
period. This revision required the considerable utilization of
-------
III-106
literature material since no actual field data were available. The
result was a second model calibration using a data set collected
during October 1973 when the temperature was 20°C.
Sixth Formulation
Previous modelling studies of the Delaware Estuary
have assumed no net addition or depletion of DO due to algal
photosynthesis and respiration. The July 1974 and October 1973
data sets containing relatively low, non-bloom chlorophyll a_
values were described reasonable well by the model without
consideration of photosynthesis and respiration. When the model
was tested against the August 1975 data, however, significant
discrepancies between predicted and observed DO were noted in an
area affected by a large algae bloom (chlorophyll a^> 100 yg/1).
Further evidence of algal effects on the DO budget in the Delaware
Estuary has been compiled from the USGS monitor near the Ben
Franklin Bridge. A 24 hour cycle in 1954 exhibited summer DO
values having an amplitude of 0.4 mg/1, with the minimum occurring
near dawn, and the maximum in the mid-afternoon. Unfortunately,
corresponding chlorophyll data were not available.
To investigate the implications of phytoplankton
concentrations on the DO levels in the estuary, reasonable values
for photosynthesis and respiration rates were bracketed in a
literature search, including data AFO generated for the Potomac
Estuary. These rates were then incorporated in the model and
linked to the observed chlorophyll a_, temperature, euphotic depth
-------
III-107
(estimated from Secchi Disk and turbidity observations), and
photoperiod. Calibration of the P and R rates was performed on
the August 1975 data set. These rates were subsequently used to
recalibrate the 1973 and 1974 data sets after being adjusted by
(1) a temperature correction factor found in the literature, and
(2) by observed chlorophyll levels during those surveys. Both
adjustments are computed internally.
It should again be emphasized that this was not
meant to be a predictive model of algal growth dynamics.
Chlorophyll was handled strictly as an external forcing function.
The final model structure is illustrated in Figure 111-69.
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-------
III-109
d) Comparison of Model Predictions with Observed Data
The ultimate test of a model's predictive ability
lies in its relative success in reproducing the basic processes
and mechanisms influencing the prototype. A widely accepted
method of gauging and assessing the confidence one can place in a
model's predictions involves simulating several historical
conditions and comparing model predictions with observed data.
If a favorable comparison results, the model can be considered
either calibrated or verified depending upon the amount and
independence of the observed data and the degree to which model
inputs are "fixed". Normally, a visual inspection combined with
engineering judgement will suffice, although some modellers have
attempted to add more objectivity through the use of statistical
tests.
As discussed previously, three independent sets of
data were used to calibrate the model for the nitrogen cycle and
DO. Complications arising from algal effects necessitated a
greater effort being directed towards the calibration phase,
particularly in terms of DO, than originally planned. A fourth
data set comprised of two separate periods, and a fifth data set
collected in July 1976 were used strictly for the purpose of
model verification. Under this situation, all model inputs were
determined a priori. Figures 111-70 through 111-77 present
observed data and corresponding model predictions for calibration,
whereas Figures 111-78 through 111-88 present similar data for
-------
in-no
verification. Because this model is a real time system, care had
to be taken in selecting output times which nearly coincided with
the particular slack water tide of the observed data.
All of the calibration and verification runs
utilized a simulation period of greater than 16 days in order to
achieve the steady state theoretically represented by the
observed data. It was determined from model runs having longer
durations, made to investigate transient sensitivity response,
that a two-to-three week simulation period was indeed sufficient
to approximate steady state conditions for both the nitrogen and
DO distributions, assuming reasonable initial conditions were
specified.
Each of the figures cited above contain a similar
format for presenting the observed and predicted data. The
observed data are depicted by a bar indicating the range in data.
Predicted data, on the other hand, are shown as a continuous
profile drawn from model output at each junction. Two different
predicted DO profiles are presented for each data set, representing
the occurrence of slack water near the beginning and near the end
of the photoperiod. Since the actual sampling runs normally
started at the lower end of the estuary in early or mid-morning,
the lower profile should be of greater value when interpreting
the data. Inspection of the observed and predicted Org N, 1% ,
N02 + NOs and DO profiles reveals a favorable comparison in every
-------
III-lll
case with respect to the spatial gradients and trends, the
magnitude and position of critical peaks and valleys, and,
perhaps most importantly, the configuration of the DO sag.
Because of the apparent anomaly in the 1968
dissolved oxygen data in Figures II1-78, III-79 and 111-82, a
comparison of the overall range in model predictions with an
extensive body of DO data collected by the Philadelphia Water
Department and USGS during this same period is shown in Figure 111-84.
This highlights the model's ability to accommodate different classes
of data sets (non-slack water and continuous monitor, respectively)
and to predict the dramatic DO variability encountered in the field
due to both the tidal cycle and, when large algal levels persist,
the diurnal cycle.
The final verification exercise, illustrated in
Figures 111-85 through 111-88, was based on the most recent intensive
data set available - July 1976. While the DO profiles show
acceptable agreement, some significant discrepancies in the observed
and predicted NH3 and N03 values are evident. It appears that an
increase in the nitrification rates from earlier data sets would
achieve a better comparison below Philadelphia. This may indicate
either a random or a systematic change from the basic nitrification
inhibition hypothesis developed from older data sets and described
in the next section. The acquisition and analysis of additional
summer data is necessary to more fully assess nitrification
inhibition patterns and trends in the Delaware Estuary.
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III-131
e) Discussion of Reaction Rates
Without a doubt, the most crucial and difficult
aspect of applying and verifying a water quality model is the
proper selection of reaction rates and other coefficients,
particularly those which produce considerable sensitivity to the
model's predictions. In most instances they cannot be defined
in-situ, and attempts to quantitate them through laboratory
experiments leave a lot to be desired since a highly controlled
lab environment can seldom duplicate the complex and dynamic
processes in a real world situation. Moreover, the problem of
reaction rates is obviously compounded when the study area is
influenced by tidal action. Normally, the only recourses
available are to utilize the model itself to "force fit" a given
condition through an iterative process, or to rely on literature
data.
Figure 111-69 illustrates the various interactions
employed by the final version of the Delaware Estuary model and
provides a symbol which designates the rate associated with each
interaction. Table 111-5 describes these rates in further detail
along with the actual values assigned in the model. The reactions
contained in the model represent physical (R2, R7, R8), chemical
(Rl), and biochemical (Rl , R3, R4, R5, R6, R9, RIO, Rll) processes
whose importance have already been recognized and identified.
Most of the temperature correction factors shown in the table were
obtained from the literature. Others were estimated during
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III-134
calibration studies. Some clarification and elaboration of the
data presented in Table III-5 follows.
There are several mechanisms by which organic N
can be converted to ammonia N, including both chemical and
biological, but the principal one assumed in this study was
hydroloysis. Thomann and others have considered it as a first
order reaction [18], Settling of the organic N fraction in a
particulate form (i.e., sewage solids and algal cells) is known
to occur but actual rates are not well documented. Areas of the
estuary where particulate organic N was thought to be exceptionally
high were assumed to be more greatly affected by this deposition
process, hence the rationale for spatially varying the rate R2.
Had better data been available, it would also have been possible
to vary this rate over the tidal cycle to permit the major
deposition to occur at or near slack water tide when settling
velocities are greatest. A similar logic was applied to the
settling of CBOD material, although smaller rates were assumed for
this process. It was believed that the settling of algae would
have a much more dominant role as a sink for organic N then it
would as a sink for CBOD. The rates used for R7, therefore, pertain
primarily to the settling of sewage solids in the vicinity of the
major wastewater discharges.
Nitrification is an extremely difficult reaction to
assess because of the uncertainty surrounding the behavior of the
nitrifying bacteria Nitrosomonous and Nitrobacter as well as the
-------
III-135
lack of quantitative information relative to their existing
populations. It was evident early in this modelling study that
the nitrification reaction did not proceed at the same rate
throughout the estuary. In fact, a zone of inhibition was strongly
suggested by the observed ammonia distributions and by attempts to
reproduce the data with existing waste loads. An hypothesis was
established that attributed the inhibition of nitrification to the
shock effects of heavy organic and industrial pollutant loading
experienced in the Philadelphia area. It was hypothesized that
the areal extent of this inhibition zone was directly related to
temperature and its effects on the repopulation of bacterial
organisms. Figure 111-89 presents the relationship between
temperature and inhibition zone programmed into the model. While
this hypothesis has not been adequately confirmed with actual field
data, which it should, it did seem plausible to Dr. Thomas Tuffey,
a nitrification expert, who performed independent studies in the
Delaware Estuary, and it is somewhat supported by other literature
studies. Subsequent to this work, Bob Tiedemann at Rutgers
University, completed a masters thesis concerning nitrification in
the Delaware Estuary [19]. Nitrifier data taken during 1975 and
1976 basically supported the patterns predicted by this hypothesis.
Unfortunately, this hypothesis, as it presently stands, adds an
element of descriptiveness rather than predictiveness to the model.
It should further be noted that a spatially variable first order
reaction was assumed for nitrification as others have done,
-------
MODELLING STUDIES
IBITION PATTERN BASED UPON
DELAWARE ESTUARY
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III-137
although this is probably an over-simplification to some
extent.
Biological uptake of nitrate nitrogen was
considered as a first order reaction with a constant rate and
was assumed to be mediated by all autotrophic organisms. A
similar method was employed in the Potomac Estuary model with
reasonable success. Recent studies reported in the literature,
however, have underscored the appropriateness of Michaelis-Menton
kinetics to represent both nutrient uptake and algal growth
dynamics. This non-linear reaction, with its rate related to
substrate conditions, should prove valuable for future modelling
endeavors in the Delaware Estuary.
A substantial reach of the estuary experiences
very low DO levels on a fairly consistent basis during the summer.
Although this condition did not appear to inhibit the nitrification
process, it was reasonable to expect areas of denitrification.
Indeed the observed data seemed to support the occurrence of
denitrification since total nitrogen was not behaving
conservatively. Therefore, a non-linear feedback was incorporated
in the model so that denitrification was "turned on" when DO
dropped below 1.0 mg/1 and the rate increased in a two-step
linear fashion to a maximum value (0.28 mg/1) corresponding to a
DO of 0.0 mg/1. The following formulations were employed for this
purpose:
-------
III-138
1.0 > DO > 0.2 :
0.12
Denit. Rate (20°C) = 0.12 + ( Q ^ Q ) . (DO - 0.2)
0.2 > DO > 0.0 :
n ?fi n 19
Denit. Rate (20°C) = 0.28 - ( g g ) (DO)
It was further assumed that the oxygen molecule disassociated
during the denitrification process would contribute to the
bacterial stabilization of the carbonaceous organic material
present in the system.
The deoxygenation rate for carbonaceous BOD was
initially estimated from trial model runs and then compared to
literature values including those derived from earlier Delaware
studies. Two rates were ultimately arrive at - the lower
(0.18/day) applied to the relatively clean portion of the estuary
upstream from Philadelphia and the higher (0.23/day) applied to
the more polluted segments. This approach agreed with the
concept of the reaction and the tendency of organisms to adjust
to a given "food" supply. The actual rates compared favorably
to the literature, although they were substantially lower than
those used by DECS (0.45/day). It should be pointed out, however,
that DECS used a comparatively low SOD rate which might have
compensated somewhat for the high oxygen requirements of the CBOD
reaction. The classical correction factor (1.047) was used to
convert R6 to temperatures other than 20°C.
-------
III-139
The basic uninhibited sediment oxygen demand (SOD)
rates were initially estimated from a combination of data collected
by the DECS Staff and the EPA National Field Investigations
Center (NFIC) Cincinnati, Ohio. This latter effort, performed
during the summer of 1974, was intended to provide in situ
oxygen uptake measurements using a benthic respirometer at about
10 stations between Trenton and the C&D Canal. Because of
equipment problems and serious limitations in the respirometer
(the unit was designed for lake use and not estuaries having
strong tidal currents), however, no such data was obtained.
Instead, samples of the bottom sediment had to be collected and
transported to the NFIC laboratory for uptake analyses. The
results of this study, after adjusting for earlier organic bottom
cover information, were used for the original model calibration
and verification attempts and are depicted in Figure 111-90.
During the summer of 1976, staff at AFO designed
and constructed two benthic respirometers for use in relatively
shallow areas of the Delaware Estuary (i.e., depth <20 feet).
These units were constructed out of sheet metal and have the shape
of a pyramid with a base composed of horizontal and vertical
stabilizing flanges. An internal stirring mechanism and DO probe
were provided to obtain concentration measurements. The
respirometer is positioned (sealed) in the bottom mud manually by
means of a long pole that attaches to a fitting on the apex of the
pyramid. The base area of the respirometer is 4 square feet and
-------
III-140
its volume is 27.6 litres.
Twelve stations were selected between Trenton and
Marcus Hook for in situ benthic oxygen uptake measurements. With
the exception of the upper three, two measurements were obtained
at each station, one along the Pennsylvania shore and the other
along the New Jersey shore at depths ranging from 5-20 feet. The
results of each measurement are shown in Figure 111-90 along with
the actual SOD rates used in the model. All of the data have been
corrected to 20°C. The SOD rates were computed by subtracting
the (small) respiration rate in the water column from the measured
initial slope of the DO concentration vs time relationship inside
the respirometer, where a constant negative slope normally
occurred for the first 30 to 60 minutes of the test. No attempt
wasmade to either define or include the anaerobic process
contributing to a stabilization of the bottom muds, but rather to
isolate the impact of the top few centimeters, where aerobic
conditions would normally exist, on the oxygen resources of the
overlying water. A non-linear feedback was incorporated in the
model to consider the effects of low DO concentrations
(i.e., <2.0 mg/1) on the reduction of the SOD rate [16]. The
expression used for this purpose was essentially from the
literature and is shown in Table 111-5.
Specific studies to define algal photosynthesis
and respiration rates in the Delaware Estuary have not been
performed and considerable reliance had to be placed on the
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III-142
literature again [20], [21L \-22\- Fortunately, AFO had
conducted studies of this nature in the Potomac Estuary and the
rates derived there served as a convenient starting point for
estimating P and R rates for the Delaware. As can be seen in the
table, both rates were a function of the chlorophyll ^concentrations,
which had to be known a priori. The respiration rate was
practically identical to that used in the Potomac, but the
photosynthesis rate underwent some change to reflect the findings
reported in the literature. It should be noted that these rates
were intended to apply to an entire algal community rather than to
specific species.
Respiration was assumed to occur throughout the
day and over the entire water column whereas photosynthesis was
limited to the daylight period (12 hours) and the euphotic depth.
The euphotic depth (1% of ambient radiant energy) was taken to be
3 times the Secchi Disk measurement [23]. A relationship was
established between Secchi Disk and turbidity based upon observed
data collected during some of the water quality surveys. This
relationship, which is presented in Figure 111-91, was used for
certain data sets where turbidity but no light extinction
measurements were available.
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-------
III-144
F. SENSITIVITY ANALYSIS
The importance of an adequate and meaningful sensitivity
analysis to indicate where field and laboratory resources could
best be allocated for improving the reliability and confidence
one might have in a model 's predictions should be underscored.
This is particularly true when either large sums of money or
major water quality management decisions are riding on the outcome
of modelling studies, which is happening with increased frequency.
Model sensitivity has, unfortunately, often been neglected or
just glossed over in studies where the consequences of such action
could have had profound implications.
Since the model described in this report contained
non-linear components, sensitivity results could take on connotations
different from the usual linear analysis. Therefore, care had
to be exercised in the design of a streamlined but useful
sensitivity study. Model runs were performed to determine the
sensitivity of the following rates and other inputs.
1. Physical
a) Temperature (1 change)
b) Inflow (1 change)
c) Reaeration - R8 (3 different formulations)
2. Biological
a) BOD Decay - R6 (1 change)
b) Nitrification - R3 (2 changes)
c) SOD - R9 (2 changes)
-------
III-145
d) Denitrification - R5 (2 changes)
e) Photosynthesis - Rll (1 change)
f) Respiration - RIO (1 change)
g) Euphotic Depth - R12 (1 change)
h) Algal Densities (chlorophyll a_
concentration) (2 changes)
A few comments regarding the sensitivity analysis are in
order. The basic approach taken was to alter the various inputs
used for the original model calibration and verification efforts
to new but reasonable values one at a time. Unfortunately, the
sensitivity runs did not reflect the latest estimates of SOD rates
since they were all made prior to the existence of the new benthic
respirometer discussed in the previous section. This should not,
however, significantly effect the degree of sensitivity indicated
for any of the parameters, including SOD itself. In many
instances only one change of value was assumed which would provide
a meaningful comparison of model results for identifying
sensitivity. In others, two or even three changes were made where
available options, uncertainty, or the suspected implications so
dictated. Each of the above rates was checked for sensitivity under
both linear and non-linear conditions. The July 1974 data set
calibration served to test sensitivity in the non-linear regime;
a hypothetical October incorporating waste loads that would
ensure DO levels greater than 2.0 mg/1, the breakpoint for non-linear
feedbacks, served to test sensitivity in the linear region. Algal
-------
111-146
sensitivity was subjected to additional studies. In addition to
determining sensitivity of algal related rates for a typical level
of algae when linearity and non-linearity existed, special runs
were made to indicate the net effects of the algal levels themselves,
including the large algae bloom that was experienced during August
1975. The total impact of that bloom on predicted DO concentrations
is dramatic, as can be seen in Figure III-119. Additional sensi-
tivity runs related to that high bloom condition, when P and R rates
had a more pronounced effect, were also performed. Finally, some of
the rates associated with the nitrogen cycle were not included in
this sensitivity analysis, due to the lack of sensitivity on the
resultant DO profiles that they exhibited when tested in conjunction
with model calibration studies.
The following figures portray the results of the
sensitivity analysis. The different inputs utilized in the model
for each sensitivity run are shown on the graphs. No attempt was
made to either quantify or compare the degree of sensitivity
associated with every parameter tested but rather to allow the
readers to draw their own conclusions.
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IV-1
IV. FUTURE STUDIES AND AREAS OF MODEL REFINEMENT
Four distinct areas where future studies should be directed
in the Delaware Estuary are enumerated below. If these studies
are implemented and prove to be successful, it is believed that
the predictive capability via mathematical modelling should be
greatly enhanced in many respects.
1) The refinement of certain biological rates is
perhaps the most important area to study. Of particular
importance is the nitrification rate and the hypothesis currently
adopted that governs the inhibition characteristics of this
reaction. The revelation experienced with the 1976 data set in
terms of an apparent reduction in nitrification inhibition
exemplifies the need for this study. Other rates in the model
which should undergo further refinement because of their particular
importance are those for photosynthesis, respiration, and SOD.
2) The development and application of a model capable
of addressing phytoplankton production and its relationship to
nutrient cycles and the DO budget is strongly suggested by data
simulation and sensitivity studies in the present study.
3) The refinement of the model's advection and
dispersion components to more accurately represent these
processes as they occur in a real system and to minimize numerical
problems associated with the solution techniques would be
desirable.
-------
IV-2
4) The development and utilization of a two
dimensional network with this model would be useful to better
assess the water quality impact of storm water and other shock
loads as well as to improve the predictive resolution in the
lateral plane where such gradients are known or suspected.
-------
ACKNOWLEDGEMENTS
A study such as this requires the cooperation of many individuals
and institutions. Data needs in particular are too intensive to be
handled by one field office, or even one agency. The Delaware River
Basin Commission (DRBC), with the assistance of the State of Delaware's
Department of Natural Resources and Environmental Control, has
compiled a very detailed water quality data base which dates to 1967.
The City of Philadelphia maintains a less comprehensive but quite
useful estuary monitoring program dating from 1949. The United
States Geological Survey (USGS) is not only responsible for the vital
discharge data from tributaries, but also several continuous water
quality monitors in the estuary. The necessary physical data describing
the estuary came from the U.S. Coast and Geodetic Survey.
A special body of data was generated by the "208" program under
the supervision of the Delaware Valley Regional Planning Commission.
Two comprehensive and intensive water quality and wastewater data
sets required the cooperation of all members of the Technical Ad-
visory Committee to the 208 programthe Delaware Department of Natural
Resources and Environmental Control, the Pennsylvania Department of
Environmental Resources, the New Jersey Department of Environmental
Resources, the City of Philadelphia Water Department, USGS, and
DRBC, along with the Annapolis Field Office.
In addition to these government agencies, we would like to
specially acknowledge the numerous industries and municipalities
-------
along the estuary who provided valuable data characterizing their
wastewater discharges both through the NPDES self-monitoring
program and their own separate monitoring programs.
Finally, many individuals gave us valuable advice, technical
assistance and independent perspectives. Deserving special mention
are those persons representing the various agencies comprising the
Technical Advisory Committee, including Dr. Robert Shubinski and
Dick Schmaltz with Water Resources Engineers. Dr. Ken Young of GKY
Associates also provided helpful advice. Dr. Thomas Tuffey, formerly
at Rutgers University, and Bob Tiedemann, a former graduate student
at Rutgers, gave us valuable outside perspective on the process of
nitrification in the Delaware Estuary.
-------
REFERENCES
1. Water Resources Engineers, Inc., "A Water Quality Model of the
Sacramento-San Joaquin Delta," Report to the U.S. Public Health
Service, Region IX, June 1965.
2. Water Resources Engineers, Inc., "A Hydraulic Water Quality
Model of Suisun and San Pablo Bays," Report to the Federal Water
Pollution Control Administration, Southwest Region, March 1966.
3. Federal Water Pollution Control Administration, "San Joaquin
Master Drain - Effects on Water Quality of San Francisco Bay
and Delta," January 1967.
4. Feigner, K. and Howard S. Harris, "Documentation Report," FWQA,
"Dynamic Estuary Model," FWQA, U. S. Department of the Interior,
July 1970.
5. Clark, L, J. and Kenneth D. Feigner, "Mathematical Model Studies
of Water Quality in the Potomac Estuary," Annapolis Field Office
Technical Report, 33, Region III, Environmental Protection Agency,
March 1972.
6. Jaworskig, N. A., Leo J. Clark, and Kenneth D. Feigner, "A Water
Resource - Water Supply Study of the Potomac Estuary," Annapolis
Field Office Technical Report 35, Region III, Environmental
Protection Agency, April 1971.
7. Clark, L. J. and Norbert A. Jaworski, "Nutrient Transport and
Dissolved Oxygen Budget Studies in the Potomac Estuary,"
Annapolis Field Office Technical Report 37, Region III, Environmental
Protection Agency, October 1972.
8. Clark, L. J., Daniel K. Donnelly and Orterio Villa, Jr., "Summary
and Conclusions from the forthcoming Technical Report 56, Nutrient
Enrichment and Control Requirements in the Upper Chesapeake Bay,"
Annapolis Field Office, Region III, Environmental Protection Agency,
August 1973.
9. Dailey, J. E. and Donald R. F. Harleman, "Numerical Model for the
Prediction of Transient Water Quality in Estuary Networks,"
Report No. 158, Department of Civil Engineering, Massachusetts
Institute of Technology, October 1972.
10. Harleman, D. R. F., "One Dimensional Mathematical Models in State-
of-the-Art of Estuary Models" by Tracor, Inc. (under contract to
FWQA), 1971.
-------
11. Thatcher, M. L. and D. R. F. Harleman, "A Mathematical Model for
the Prediction of Unsteady Salinity Intrusion in Estuaries,"
Technical Report No. 144, Ralph M. Parsons Laboratory, Department
of Civil Engineering, Massachusetts Institute of Technology,
February 1972.
12. Delaware River Basin Commission, "Final Progress Report - Delaware
Estuary and Bay Water Quality Sampling and Mathematical Modeling
Project," Trenton, New Jersey, May 1970.
13. Department of Scientific and Industrial Research, "Effects of
Polluting Discharges on the Thames Estuary," Water Pollution
Research Technical Paper No. 11, Her Majesty's Stationery Office,
London, 1964.
14. Thomann, R. V., D. J. O'Connor, and D. M. DiToro, "Effect of
Nitrification on the DO of Streams and Estuaries." Notes for
Manhattan College Summer Institute, 1975.
15. Thomann, R. V., "Systems Analysis and Water Quality Management."
Copyright 1972 by Environmental Science Services, Division of ERA.
16. McDonnell, A. J. and S. D. Hall, "Effect of Environmental Factors on
Benthal Oxygen Uptake," Journal of the Water Pollution Control
Federation, Vol. 41, No. 8, Part 2, August 1969.
17. Thomann, R. V., D. J. O'Connor, and D. M. DiToro, "Modelling of
the Nitrogen and Algal Cycles in Estuaries."(Presented at the
Fifth International Water Pollution Research Conference, San
Francisco, California, July 1970.)
18. O'Connor, D. J., R. V. Thomann and D. M. DiToro, "Dynamic Water
Quality Forecasting and Management." Prepared for Office of
Research and Development, U. S. Environmental Protection Agency, 1973.
19. Tiedemann, R. B., "A Study of Nitrification in the Delaware River
Estuary," The Graduate School of Rutgers University, New Brunswick,
N. J., June 1977.
20. Williams, R. B. and M. B. Murdoch, "Phytoplankton Production and
Chlorophyll Concentration in the Beaufort Channel, North Carolina,"
Limnology and Oceanography, Vol. 11, No. 1, January 1966.
21. Flemer, D. A., and J. Olmon, "Daylight Incubator Estimates of
Primary Production in the Mouth of the Patuxent River, Maryland,"
Chesapeake Science, Vol. 12, No. 2, June 1971.
-------
22. DiToro, D. M., "Algae and Dissolved Oxygen," Notes for Manhattan
College Summer Institute, 1975.
23. Holmes, R. W., "The Secchi Disk in Turbid Coastal Waters,"
Limnology and Oceanography, Vol. 15, No. 5, September 1970.
-------
APPENDIX
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60 POQUESNG TRIB
NODE TOTAL
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61 ULING3RO MUN
61 RANCCCAS TRtB
NODe TOTAL
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o o o
a o o
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o o o
ro ro
0 0 C3
o o a
o o
O PJ (\J
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64 BRLINGTN MUN
64 TFNNFCO INO
..NODE TOTAL
ir> tn
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71 USSTRMTP IND
71 USSRODML IND
NODF TOTAL
st t .4-
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72 B&ROPNTN MUN
NODE TOTAL 1
co r- sr>
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a oo r^
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o o «-
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77 HAMILTON MUN
73 CROSUICK TPIB
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NODE TOTAL 1
a in o
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76 HORRISVL MUN
76 ASSNPINK TRI3
NODF TOTAL
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29 CHRISTNA TRIB
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ro ro
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r- r-
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-123.68
30 BRANDYMN TRI8
NODE TOTAL
»- in S»
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31 PENSGROV MUN
31 OPEOGMOR INO
NODE TOTAL
t- ft- 00 ' in
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O O O T-
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33 OLDMANS TRIB
33 ALLDCHEM IND
33 PHOENIX IND
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00
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o o o o o o
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ro ro ro
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39 UCARBIDE IND 1
1
1
1
KOBE TOTAL 1
OO UN. »- Ntf K> T- '
a o ,- o o CM
5 -3 g ° S S
in o o ^ o r>.
S ro R ro S *
o o o o o «-
£ § S f-: S ~
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IA -3 ^ ^ 0 IS
O O 0 0 O «-
OO OO OO OO OO
oo oo oo oo oo
r-.- IA«- IN-.- IA<- lAr-
OIA OlA OlA OlA CIA
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oo oo ao ao oo
r-o roo oo rao r^o
Kir- ryr- (Mr- *t- rOr-
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rvjo r*o oo mo r-o
r- rO r-
oo oo oo oo oo
Or- 'Or- Or- OO r- in r-
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r- rvj (\j r i r<-
ill i
g 3 S S is1
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0
0
»
1
NODE TOTAL
43 GLOSTiCO MUN
10
o
o
o
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o
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ON
(M
O
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0
o o
0 0
o IA
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0
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0
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T- O P- O
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o a P- o
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ro I
1
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43 M08ILCP1 IND
43 SHELL IND
t-
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p-
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if> in
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PJ O
r- -o
tn o«
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p-
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44 GULFOIL2 IND
44 GULFOIL1 IND
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47 SCHUYLKL
NODE TOTAL
o> in m ro o
o o o o -
O in o M 00
o a a o o
«4 t- t »- N-
O O O O O
o o o o ' o !
10 -O .» » oo
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ro r^ K> * r^
o o a o «-
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N-O OO OD OO
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00 O M M
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1 t 1 1
CD
H- Z Z Z
a 3 => 3
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CD 31 31 < t- -
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h- -J ^: a.
t» -J O LU UJ
f* uj CK t- a
co eo co ac o
z .
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00 00 00 00
4 <» -J -*
o co ro *NJ do o» o-
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o ro o o o o & '
r- 00 to fO if\ *4 -^
cj ao o o o r- oo
o^ ^o -^ o ^o -^f «-
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ro ^ ro a
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o ro oo oj ro
00 O^ O O «- Od (XI
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t ^>
1
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KIT- ror- ro^- ror- ro^ ro^-
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r. r- rvj,- ^ y. 00^. fv f sfl r-
rxj r- 1^ INJ o» pg
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ro o i*- o oa aa oo too
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tA O ft* O N- N «*
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1 1
CJ
IA
w
1
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3
50 GLOSTRCY r
..NODE TOTAL
o o
tf\ *\
0 0
o- a
00 00
^- t
o o
0 0
T- T-
O 0
0 0
0 0
o o
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T- ^
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1 1
o
o
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z
51 AHSTAR 1
NODF TOTAL
K> i ro
^ ! *;
^ r-
O O
O O
O O
O O
0 I O
o o
0 O
o o
0 0
o o
in o
N. r-
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r- *
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O O
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0
0 O
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sO ^O
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X, CO
f\j nj
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0
go
1
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52 NATSUGAR
. NODE TOTAL
s
o
a
a.
ui
a.
o
o
-------
.3
0" !O V*
(A O [O "
i- a i-
O PJ K>
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r- oj oj
ro ru m
O O i O 4
o- o o
a o i*-
o a o
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r- a CM
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o o o
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t~ OJ T-
m o LA
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o o o
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T- r-* r-
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PJ
a o o
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T- ro r-
o 'o oo
o in IA
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i i
o
O
KI
I
54 CAMOEN N MUN
. NODF TOTAL
to vn a* o*
M o a ">
«o o N. »-
CM ^ K> K>
t>- r- oo 1*1
o i- to
^ *
o a
T- o a T-
T- O O T- i
0 <
o a o o
.J O O »
IA \f\ O
OJ O O PO
m o o KI
o o oo a o
o o o o o o
rvi »- ro i- ro *-
O ut O tn O I/*
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r* «-
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NO O O O O
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O O 0 O
o* o o o o a
00 «- O r- O «-
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00 t- O r- t- r-
M -1 00 N
0- O !n -*
ftj (M If* «-
O* 1 1 O
CO "1
O 0 0
O O *G
'«
O* r- ro "
fk> 1 1
1
55 PHILA NF MUN
55 GEORGPAC IND
55 PENSAUKN MUN
.NODE TOTAL
<\l 1 IM
o 1 o
o o
O" o*
r- T-
0 O
o o
o i a
0 0
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C»J PO
0 O
0 0
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Kl »-
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tn ^~
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r~ ^~
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Kl T-
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1 1
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t
58 PALMYRA MUN
.NODE TOTAL
oj in h-
« O **
OJ O CJ
m oo T-
0 O O
N. o oo
rvj M
o o o
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OO O N-
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T- O O 0
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o o o o
Csl O 00 O
T- T- «~ t
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f\J r- Kl «-
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O Os O
o ru rw '
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1 1
0 0
0 0-
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CO «-
IA I
1
61 RANCOCAS TRIB
61 ULING3RO MUN
NODE TOTAL
ro ro
o o
o o
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in in
o o
PO Kl
o a
o o ,
0 Os
O 0
N- f*.
O 0
O 0
o o
0 O
Kl *-
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0 0
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CM «-
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r- r-
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in o
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0 0
ru (\j
i i
0
K)
t
64 TFNNECO IND
NODE TOTAL
a* o o *
«" O T-
o in o m
o >* r^ ^
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O O Q O
in O r- o
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ooo
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1 1
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Kl O
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65 NESHAMNY TRIB
65 FALLSTUP MUN
NODE TOTAL
ru o a o
o a a a
ro o r- «-
(\i «- rj flo
O O O T-
m ro a
o o o o
a o o o
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73 CROSWICK TFI9 1
73 HAHILTON MUN
NODE TOTAL
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o o
0 0
4 -4
r- £ .
0- 0V
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1
75 TRENTON MUN
.NODE TOTAL
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l>- IM O
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00 C
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1
61 RANCOCAS TRIE
61 WLINGBRO MUN
HODE TOTAL
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0 O
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r- r~
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rvj (NJ
1 1
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I
64 TENNECO IND
1
."NODE TOTAL
' .. A . . -.
jO O* ' UN
Kl O f*»
-4 O -4
o ro <\J
00 1^- O
fM O fO
co ^* rv
CM fM in
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O* r- -* *-
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rg *rf ro ^
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N- 0 *- 0
fM r- r- r-
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CT O O
CO T I O-
1 t
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1
65 NESHAHNY TRIB
65 FALLSTUP MUN
.-NODE TOTAL
N K ho »o
f\j o o ro
o o a o
ro *- <> >»
ru CM r\j r*.
o a o o
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ro oj in
O PJ O M ^O
0 O O 0
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< M «-
t 1 1
66 OTR&ASNK TRIB
66 BRSTLTUP MUN
66 ROHMSHAS IND
NODE TOTAL
Jl
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ro M o o - o oo o>
IM K 4 -O O
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72 BOROENTN MUN
.AOOE TOTAL
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73 CROSHICK TRIB
73 HAMILTON MUN
rlMODE TOTAL
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14 SALEMCTY MUN
NODE TOTAL
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21 GETTYOIL I NO
NODE TOTAL
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0 0
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30 BRANDYUN TRIB 1
1
1
1
NODE TOTAL 1
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31 PENSGROV MUN
31 OPEOGHOR IND
KODE TOTAL
4 r- oo I oo
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39 UCARBJDE IND
NOOE TOTAL
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O O O O O M
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O m ** r- o PO
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48 HTEPHRAN HUN
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65 NESHAHNY TRIB
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69 LUR8UCKS HUN
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76 ASSNPINK TRIB
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-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-903/9-78-001
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
"A Water Quality Modelling Study of the
Delaware Estuary"
5. REPORT DATE
January 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Leo J. Clark, Robert
Rachel C. Grain
8. PERFORMING ORGANIZATION REPORT NO.
B. Ambrose, Jr., and
Technical Report 62
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Annapolis Field Office, Region III
U.S. Environmental Protection Agency
Annapolis Science Center
Annapolis, Maryland 21401
10. PROGRAM ELEMENT NO.
2BA644
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
same
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SP
In~hous£i tine..
ONSOiRIINIGi AGEN CY CO DE
EPA/903/00
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Recent data acquisition, analysis, and mathematical modelling studies were under-
taken to improve the understanding of water quality interactions, particularly as they
impact DO, in the Delaware Estuary. A version of the Dynamic Estuary Model, after
jndergoing considerable modification, was applied in an iterative process of hypothesis
formation and testing. Both model parameters and model structure were updated and
improved through this process until five intensive data sets gathered in the estuary
Between 1968 and 1976 were satisfactorily simulated. The major processes treated in
:his study were the advection and dispersion of salinity and dye tracers, nitrification,
:arbonaceous oxidation, sediment oxygen demand, reaeration, algal photosynthesis and
"espiration, and denitrification. The major product of this study is a calibrated and
/erified "real time" hydraulic and water quality model of the Delaware Estuary between
"renton and Listen Point. Among the conclusions of general importance are: (1) algae
2xert a variable, but generally positive influence on the DO budget; (2) non-linear
-eactions (such as denitrification and reduction of effective sediment oxygen demand)
Decome significant when DO levels drop below 2 mg/1; and (3) nitrification, which ex-
Deriences inhibition in a zone around Philadelphia, and sediment oxygen demand rival
:arbonaceous oxidation as DO sinks throughout much of the estuary. One implication of
:his study is that earlier forecasts of DO improvements with a simpler, linear model
vere somewhat optimistic.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Sedimentation oxygen demand
Nitrification Dissolved oxygen
Photosynthesis Salt water
Respiration intrusion
Biochemical oxygen demand
Estuaries
Mathematical models
-------
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(a) DESCRIPTORS - Select from the Thesaurus of Engineering and Scientific Terms the proper authorized terms that identify the major
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EPA Form 2220-1 (9-73) (Reverse)
-------
?A 902/9-79-005
BIOCHEMICAL STUDIES
OF THE
POTOMAC ESTUARYSUMMER 1978
-------
-------
EPA 903/9-79-005
BIOCHEMICAL STUDIES
OF THE
POTOMAC ESTUARYSUMMER 1978
May 1979
Joseph Lee Slayton
E. Ramona Trovato
Annapolis Field Office
Region III
U.S. Environmental Protection Agency
-------
Table of Contents
Page
Tabulation of Figures ii
Tabulation of Tables iii
I. Introduction . . . : 1
II. Conclusions 4
III. Procedures 6
IV. C30D and NOD Kinetics in The Potomac Estuary 8
V. Oxygen Demand of Algal Respiration and Algal Decay 19
VI. Phytoplankton Elemental Analysis/Methods of TKN 25
Digestion of Algal Samples
VII. Potomac Long-Term BOD Survey Data 28
References 35
-------
Figures
Page
No.
1. Study Area 3
2. General BOD Curve: Y = L0(l-10'kt) 8
3-4. River Samples-Oxygen Depletion Curves 10-11
5. Plot of NOD2Q vs (TKN x 4-57) 15
6. STP Effluent Samples-Oxygen Depletion Curves 17
7-9. Oxygen Depletion Curves of Algal Respiration and Decay ... 20-22
-------
Tables
Page
1. Station Locations 2
2. Thomas Graphical Determinations of k-|g, L0, and r for River CBOD's . 12
3. Thomas Graphical Determinations of k-jg, L0, and r for River NOD's . . 13
4. Thomas Graphical Determinations of kio» L0, and r for STP CBOD's . . 16
5. First Order Correlation Coefficients for STP NOD's 18
6. Phytoplankton Oxygen Depletion 23
7. BOD5 Requirements for Algal Decay and Respiration 24
8. Phytoplankton Elemental Analysis 26
9. Results from Three TKN Digestion Methods 27
-------
-------
I. Introduction
During the summer of 1978 an intensive survey of the middle
reach of the Potomac River was undertaken by the A.P.O. (Table 1 ,
Figure 1). As part of this work biochemical assays were performed to:
(1) determine the carbonaceous and nitrogenous oxygen demand
rate constants for river and STP effluent samples;
(2) establish the relative contributions to the BODg of algal
respiration and the oxygen utilized in algal decay; and
(3) characterize the elemental composition of the phytoplankton
present and establish the relative digestion efficiencies
of several methods of algal TKN determinations.
The mention of trade names or commercial products in this report
is for illustration purposes and does not constitute endorsement or
recommendation by the U.S. Environmental Protection Agency.
-------
Table 1. Station Locations
Station Number
Station Name
RMI
Buoy Reference
P-8
P-4
1
1-A
2
3
4
5
5-A
6
7
8
8-A
9
10
10-B
n
12
13
14
15
15-A
16
Station Number
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
Chain Bridge
Windy Run
Key Bridge
Memorial Bridge
14th Street Bridge
Hains Point
Bellevue
Vloodrow Wilson Bridge
Rosier Bluff
Broad Creek
Ft. Washington
Dogue Creek
Gunston' Cove
Chapman Point
Indian Head
Deep Point
Possum Point
Sandy Point
Smith Point
Maryland Point
Nanjemoy Creek
Mathias Point
Rt. 301 Bridge
Treatment Plant Name
Piscataway STP
Arlington STP
Blue Plains STP East &
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
0.0
1.9
3.4
4.9
5.9
7.6 C "1"
10.0 FLR-231 Bell
12.1
13.6 C "87"
15.2 N "86"
18.4 FL "77"
22.3 FL "67"
24.3 R "64"
26.9 FL "59"
30.6 N "54"
34.0
38.0 R "44"
42.5 N "40"
45.8 N "30"
52.4 G "21"
58.6 N "10"
62.8 C "3"
67.4
West
-------
Figure 1. Study Area
Potomac Estuary
-------
II. Conclusions
(1) The carbonaceous oxygen demand of the Potomac River samples
followed first order kinetics with an average deoxygenation
constant ke = 0.12 day "^ and standard deviation = 0.03 day"1
= 0.051 day"1)-
(2) The growth kinetics of river nitrification were more erratic
but in general were first order with an average ke = 0.10 day"'
and standard deviation of 0.06.
(3) The CBODs on the average was 58% of the BOD5 for river samples
and" therefore estimates of CBOD5 from BODs values are prone to
error unless a nitrification inhibitor is employed.
(4) The CBOD of the Potomac STP effluent samples followed first .
order kinetics with an average ke =0.16 day"' and standard
deviation of 0.05.
(5) The NOD for the STP effluent samples had a significant lag
time resulting in poor correlation coefficients for first
order fit. This lag time was probably an artifact of the
APHA dilution method, since nitrification in the receiving
waters was immediate.
(5) The NOD2o observed for river samples did not significantly
differ from the product of 4.57 and the TKM concentration
(4.57 x TKN).
-------
(7) In concentrated algal samples the average algal contribution
to the 8005 was 0.027 mg BODs/yg chlorophyll a_. The predominant
species present was the filamentous blue green algae Pseudanabaena,
(8) Phytoplankton decay represented 70% of the algal BODs and algal
respiration accounted for the remaining 30% of the five day
oxygen depletion.
(9) The average composition of the phytoplankton present in the
study area was (mg/yg):
Org C/Chlor a_ = .021 ; P04/Chlor a. = .002; TKN/Chlor a_ = .005
(10) Relative to manual digestion the Technicon continuous digestor
and Technicon block digestor recovered respectively an average
of 58% and 83% of the algal TKN.
-------
III. Procedures
Biochemical Oxygen Demand: The BOD test is outlined in Standard
Methods APHA, 14th edition1. All dissolved oxygen measurements
were made with a YSI BOD probe #5720 and a YSI model 57 meter.
The BOD of river water was determined on unaltered samples. STP
effluent samples were altered by: the addition of 1 ml of stale
settled sewage (seed); sufficient sodium sulfite (Na2$03) to
dechlorinate the samples; and dilution with APHA dilution water.
Nitrification: Formula 2533 nitrification inhibitor (Hach Chemical
Co.) was dispensed directly into the BOD bottles. Two bottles
were filled with each sampleone received the inhibitor and
represented CBOD and the uninhibited bottle expressed total BOD.
The NOD was determined by difference2.
Algal BOD Measurements; The algae in 4 to 10 liters of sample were
concentrated by continuous centrifugation (Sharpies Continuous
Centrifuge Model T-l at 12,000 rpm and 1.5-2 liters/min). The
pellet was resuspended in 500 ml of collected supernatant. The
resultant suspension was diluted in a 300 ml BOD bottle as follows:
a. 50 ml suspension + 250 ml supernatant
b. 50 ml suspension (freeze dried) + 250 ml supernatant
c. 50 ml deionized water + 250 ml supernatant
a1. 50 ml suspension + 249ml supernatant + 1 ml seed/bottle
b1. 50 ml suspension (freeze dried) + 249ml supernatant +
1 ml seed/bottle
cl. 50 ml deionized water + 249ml supernatant + 1 ml seed/bottle
The sample composite on September 6 consisted of approximately
2 gallons each from stations: 8; 8A; 9; 10; and 10B.
The composite of September 14 consisted of about 1/2 gallon each
from stations: 8; 8A; 9; and 10. Twenty ml volumes were used
instead of the 50 ml volumes indicated above for this composite.
Freeze Drying: Samples were freeze-dried in a Virtis model 10-100
Unitrap freeze-drier. The suspension was spread as a thin sheet
and slowly frozen to avoid foaming and to shorten drying time.
Samples required 4 to 6 hours to reach the manufacturer's specified
end point.
The freeze-dried samples were washed into BOD bottles with
supernatant from centrifugation.
Elemental Analysis;
1. Sample Preparation: Samples were stored on ice and returned to
the laboratory where 4 to 8 liters were immediately concentrated
using a Sharpies T-l Continuous Centrifuge at 12,000 rpm and
1.5-2.0 liters/min. Microscopic examination revealed no
-------
apparent morphological damage to the predominant phytoplankton
species present. The pellet was resuspended in 250 ml of
clear supernatant, which had been collected during centrifugation,
Aliquots of the suspension and the supernatant were chemically
analyzed. The supernatant values were used for blank corrections,
2. Chlorophyll a: The photosynthetic pigment from 5-20 ml of
algal suspension was retained on a 0.45y Millipore filter and
extracted into 90% acetone with grinding. The extracted
solution was centrifuged and measured spectrophotometrically3.
3. Total Organic Carbon (TOC): 10 ml of algal suspension was
diluted to 100 ml in a volumetric flask using deionized water.
A blank was run using 10 ml of supernatant river water
diluted to 100 ml in deionized water. The samples and
calibration standards were then acidified by the addition of
1 ml of 6% phosphoric acid to 25 ml and purged free of
inorganic carbon with oxygen. The total organic carbon
was then determined on a Beckman 915 TOC analyzer1*.
4. Total Phosphate: 5 ml of sample and blank were diluted to
25 ml with deionized water. The sample and blank were
placed in aluminum foil covered pyrex test tubes to which
ammonium persulfate and sulfuric acid were added and auto-
el aved at 15 psi for 30 minutes. The digests were then
analyzed for total phosphate by the Techm'con automated
ascorbic acid reduction method^.
5. Algal Nitrogen: 5 ml of sample and blank were diluted to
25 ml with deionized water. The prepared solutions were
then analyzed for TKN by the following methods:
A. He!ix_: Samples and blanks were digested by a Technicon
Continuous Digester (Helix) and analyzed by the
automated colorimetric phenol ate method1*.
B. Manual : Samples and blanks were manually digested
with 10 ml aliquots placed in reflux tubes and 8.0 ml
of H2S04/K2S04 digestion solution added. The tubes
were placed over flame until boiling and reflux
stopped. The contents of the tubes were washed
into a graduated cylinder with deionized water and
brought to 50 ml. The resultant digests were analyzed
using a Technicon Continuous Digestor (Helix) and
the Technicon automated colorimetric phenol ate method1*.
C. Block: Samples and blanks were analyzed by a Technicon
Block Digestor BD-40 and analyzed by the sal icy!ate/
nitroprusside method5.
The blank carried throughout these methods was used to correct
for non-algal nitrogen.
-------
IV. CBOD and NOD Kinetics in the Potomac Estuary
Biochemical oxygen demand (BOD) is a bioassay in which the
oxygen utilization of a complex and changing population of micro-
organisms is measured as they respire in a changing mixture of
nutrients. That portion of the BOD due to the respiration of organic
matter by heterotrophic organisms is termed the carbonaceous oxygen
demand and that portion resulting from autotrophic nitrification
is termed nitrogenous oxygen demand. Nitrification is the conversion
of ammonium to nitrate by biological respiration. These BOD
components were delineated using an inhibitor to nitrification. The
inhibitor, formula 2533 of the Hach Chemical Company, has been shown
2£;7
to effectively stop the growth of Nitrosomonas . The product consists
of 2-chloro-6 (trichloromethyl) pyridine, known as nitrapyrin, plated
onto an inorganic salt. The salt serves as a carrier because it is
soluble in water. The organic component is not biodegradable* even
after 30 days of BOD incubation, and therefore does not contribute
to the measured carbonaceous oxygen demand2.
The shape of the oxygen depletion curves (Figures 2,3, and 4)
were such that the slope of the curves decreased with increased time
of incubation.
Figure 2: General BOD Curve
Curve Equation: y = L0(l-10"kt)
t = elapsed time of incubation in the dark at 20°C
y = BOD; mg/1 oxygen consumed after time t
o ! / LO = ultimate BOD; the oxygen used in the total
degradation of the substrate
k = deoxygenation constant; a constant which
reflects the rate at which a substance is
oxidized--a function of temperature, biota
and the nature of the substrate.
Time
o
-------
The rate of reaction associated with oxidation-respiration (Ay/At)
was initially rapid corresponding to an initial relatively large
substrate concentration. This rate decreased with time as the
oxidizable substrate was depleted. Other nutrients are provided
in excess and do not effect the rate of oxygen consumption in the
standard BOD test. The quantity and nature of the organic material
in the sample will limit oxygen consumption and determine the rate
of depletion. This type of reaction, in which the rate is proportional
to the amount of the reactant remaining at any time is referred to
as a "first order" reaction. In general, the first order reaction
pattern was observed for both the carbonaceous oxygen demand and the
nitrogenous oxygen demand BOD components of Potomac River samples.
Long-term BOD incubation data were used to give the best available
estimate of k-jQ and L0 using the Thomas Graphical Determination8'9'10 in
1 /^
which a plot of (t/y) ' vs. t yielded a linear relation where
k-|Q = 2.61 x (slope/intercept) and Lo = (2.3 x (intercept)3 x Iqo)
The correlation coefficient of the linearized data was taken as a
measure of goodness of fit to first order reaction kinetics.
The CBOD results for river samples were compiled in Table 2.
The average (n=23) k-]o value for river CBOD's was 0.051 day" or
ke = 0.12 day~1 with an average correlation coefficient = 0.98 and
standard deviation = 0.03 (base e). The value of ke obtained in a 1977
Potomac study8 was 0.14 day"1 , with n = 43 and a standard
deviation of 0.02. The ratio of CBODs to BODs was found to be 0.58 in
the 1978 study.
The NOD of the river samples (Table 3) followed first order kinetics
with a correlation coefficient of 0.86 (n=22) and an average ke of 0.10
day""'. The standard deviation of ke was 0.06.
-------
Figure 3; River Samples-Oxygen Depletion Curves
01
a.
cu
o
c
o>
en
>-,
x
0
7.0-
6.0-
5.0-1
4.0-
3.0-
2.0-
1.0-
Woodrow Wilson Bridge Station 5
Sept. 11, 1978
= .054
8 10 12
Time (Days)
Ft. Washington Station 7
Sept. 11, 1978
8 10 12
Time (Days)
14 16
18
Tota'
BOD
NOt
CBOE
Tot
BO
CBO
-------
Figure 4 : River Samples-Oxygen Depletion Curves
en
7 -
6 -
5 -
5 4
0)
c
»
X
o
1 -
Indian Head Station 10
August 23, 1978
Total
BOD
CBOn
MOD
1 1
2 4
i
6
i
8
1
10
!
12
l
14
i
16
1.
18
1
20
Time (Days)
8 -
§ 6
cu
!"
X
c
4 -
Ft. Washington Station 7
September 25, 1978
Total
BOD
CBOD
8 10 12
Time (Days)
16 1R
-------
Table 2; Thomas Graphical Determinations of
L, and r for River CBOD's
Date
Aug.
- Sta
14
5
7
8A
10
n
14
16
r
.931
.951
.966
.958
.991
.984
.985
(day'1)
.045
.059
.038
.057
.067
.062
.089
(mg/1 )
2.5
2.0
5.3
4.8
5.5
4.2
2.1
Calc.*
CBODs
(mg/1 )
1.0
1.0
1.9
2.3
2.9
2.2
1.4
Calc.
CBOD2Q
(mg/1)
2.2
1.9
4.4
4.4
5.2
4.0
2.1
CBOD5/BOD5
.50
.42
.50
.70
.74
.73
...
Calc.
BOD5
(mg/1)
2.0
2.4
3.8
3.3
3.Q
3.0
...
Aug. 28
Sept. 11
Sept. 25
5
7
8A
10
n
14
16
5
7
8A
10
n
14
16
5
7
8A
10
n
H
16
5
7
8A
10
n
14
16
.931
.951
.966
.958
.991
.984
.985
.993
.996
.992
.994
1.000
.990
.996
.994
.990
.987
.989
.940
.981
.997
.999
.99i6
(.931)
(.231)
(-.231)
(.126)
(.557)
.045
.059
.038
.057
.067
.062
.089
.046
.040
.039
.033
.029
.027
.056
.059
.054
.044
.044
.041
.054
.069
.079
.049
(.020)
Lag
4.5
5.7
6.5
5.2
6.7
3.4
5.8
5.0
5.9
7.9
6.7
5.1
3.5
5.5
5.4
7.2
(15.7)
r: (correlation coefficient)
n = 23
Average = .98
Std. deviation = .02 (base 10)
k10'-
n = 23
Average = ... c
Std. deviation = .015 day' (base 10)
CBOD5/POD5:
n = 19
Average = .58
Std. deviation = .15
.051 day'1 or ke = .12 day'1
1.8
2.1
2.4
1.7
1.9
0.9
2.8
2.5
2.7
3.1
2.7
1.9
1.6
3.0
3.2
3.1
(3.2)
3.9
4.7
5.4
4.1
5.0
2.4
5.4
4.7
5.4
6.8
5.9
4.3
3.2
5.3
5.3
6.5
(9.5)
.43
.43
.71
.51
.60
.38
.93
.39
.61
.70
.69
.49
.41
4.2
4.9
3.4
2.8
3.2
2.4
3.0
6.4
4.4
4.4
3.9
3.6
7.9
* calc. = Calculated value based u
Thomas Graphical determi:
-------
Table 3: Thomas Graphical Oetermi net ions of k
-|0
0,
and r for River MOD's
Date
Aug.
- Sta
14
5
7
8A
10
n
14
16
r
.957
.780
.939
.600
.949
.802
-.441
hOi
(day )
.077
.032
.037
.019
.037
.024
Lag
L0
(mg/1 )
1.7
4.7
5.5
5.3
3.0
3.6
Calc.*
NODS
(mg/1 )
1.0
1.4
1.9
1.0
1.0
.8
Calc.
N0n20
(mg/1 )
1.7
3.6
4.5
3.0
2.4
2.4
Potential**
NOD
(mg/1 )
2.5
2.9
2.8
1.9
2.3
1.3
( .9)
Aug. 28
5
7
8A
10
11
14
16
.600
.995
.978
.996
.989
.876
.877
.017
.067
.039
.037
.048
.049
.030
13.8
5.2
2.9
3.1
3.1
1.9
0.8
2.4
2.8
1.0
1.1-
1.3
1.5
0.2
7.4
5.0
2.4
2.5
2.7
1.6
0.5
Sept. 11
Sept. 25
5
7
8A
10
11
14
16
.974
.216
.276
.658
.727
.735
.995
.104
Lag
Lag
.022
.023
Lag
.088
r: (correlation coefficient)
n = 22
Average = .85
Std. deviation = .14 (base 10)
6.7
4.0
5.2
1.1
4.7
.9
1.2
0.7
6.7
2.5
3.4
1.1
7.2
5.1
2.5
2.4
2.3
1.5
1.4
5
7
8A
10
n
14
16
.877
.994
.628
.755
.937
-.619
-.381
.049
.098
.028
.023
.039
Lag
Lag
9.1
2.6
4.8
5.0
4.7
3.9
1.7
1.3
1.2
1.7
8.1
2.5
3. A
3.3
3.9
7.0
2.9
2.9
3.1
2.3
(1.4)
(1.4)
8.3
(5.0)
(4.3)
3.4
3.7
(3.5)
3.3
* calc. = calculated
** Potential NOD = 4.57 x TKN
n = 22
Average = .045 day" or ke
Std. deviation = .026 day'1
"''
.104
(base 10)
-------
The NOD results agreed with previous Potomac demand studies8 in which
the average NOD ke was 0.14 day""' with a standard deviation of 0.05.
The larger standard deviation observed for the NOD reflects
both the more fragile nature of nitrification11 and the method by
which it was determineduninhibited depletion minus inhibited depletion.
The NOD20 was found not to be significantly different from the
potential NOD expressed as 4.57 x TKN (Figure 5). The critical value
of the paired t-test at a 95% confidence level was 2.08 and the
calculated value was 0.37. The 4.57 constant is the stoichiometric
conversion factor for the milligrams of oxygen consumed by the oxidation
of ammonia to nitrate.
The CBOD kinetics observed for the sewage treatment plant effluents
were first order with an average ke of 0.16 day"^ (n = 36 and standard
deviation of 0.05). The average correlation coefficient was 0.98f
(Table 4, Figure 6).
The NOD kinetics observed for the sewage treatment plants were
characterized by a lag period (Figure 6) which resulted in poor
correlation to first order reaction kinetics (Table 5). This lag
time was probably an artifact of the APHA dilution method, since
nitrification in the receiving waters was immediate. Because the
Potomac waste treatment effluents are characterized by high ammonia
levels8, the initial lack of nitrification is probably the result of
an insignificant number of nitrifying bacteria in the samples and/or
in the seed innoculum. The long term BOD oxygen depletion data is
included in Section VII.
-------
Figure 5: NOD20 (Inhibitor) vs NOD (TKN x 4.57) River Water Samples
v = 19778
= 1978
1978
NOD9n vs (TKN) X 4.57
^n = 22
Correlation coefficient * .872
Least Squares: Slope = .886;
y-intercept = .455
Paired t test
Degrees of freedom = 21
t found = .374
t critical (a = .050;
a/2 = .025) = 2.080
10 11
NOD20 (Inhibitor)
(mg/1)
-------
Table 4: Thomas Graphical Determinations of k-jQ, L0, and r for STP CBOD's
Date - Sta
Aug. 14
S-l
S-2
S-3 E
S-3 W
S-4
S-5
S-6
S-7
S-8
Aug.
28
S-l
S-2
S-3 E
S-3 W
S-4
S-5
S-6
S-7
S-8
Sept. 11
S-l
S-2
S-3 E
S-3 W
S-4
S-5
S-6
S-7
S-8
Sept. 25
S-l
S-2
S-3 E
S-3 W
S-4
S-5
S-6
S-7
S-8
Name
Piscataway
Arlington
Blue Plains
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains East
Blue Plains West
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains East
Blue Plains West
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
East
West
ik
r
1.000
.997
.999
.997
.999
.995
1.000
.993
1.000
kio
(day-1)
.060
.032
.081
.054
.080
.053
.050
.064
.024
Lo
(mg/1)
12.8
17.3
109.4
21.1
45.9
18.3
29.3
24.7
31.4
Calc.*
CBOD5
(mg/1)
6.4
5.3
66.3
9.7
27.7
8.3
12.9
12.9
7.44
Calc.
CBOD20
(mg/1 )
12.0
13.2
106.7
19.3
44.8
16.7
26.4
23.4
20.8
East
West
ik
1.000
.997
.999
1.000
.998
.993
1.000
1.000
.998
.067
.092
.067
.067
.071
.069
.053
.060
.032
11.7
9.90
41.8
32.0
47.7
12.9
22.9
24.4
26.6
6.3
6.5
22. *
17.2
26. R
7.1
10.4
12.2
8.20
11.2
9.8
39.8
30.6
45.9
12.4
20.8
22.9
20.5
.975
.969
.982
.994
.987
.994
.988
.977
.950
.079
.094
.077
.082
.087
.078
.077
.060
.049
15.9
11.0
30.1
26.4
33.8
20.4
22.5
23.9
23.0
9.5
7.3
17.7
16.1
21.4
12.0
13.2
11.9
9.9
15.5
10.9
29.2
25.8
33.2
19.8
21.8
22.4
20.5
.885
.933
.00
.999
.991
.987
.954
.992
.964
.059
.062
.090
.071
.113
.115
.071
.095
.103
18.4
17.1
42.0
68.5
41.6
15.3
32.5
22.4
15.8
9.1
8.8
27.1
38.2
30.3
11.2
18.1
15.0
11.6
17.2
16.2
41.4
65.9
41.4
15.2
31.2
22.2
16.6
36
Average = .071 day""1 or ke = .16 day'"1
Std deviation = .021 day-T (base 10)
* calc. = calculated value based upon
Thomas Graphical determination
r: (correlation coefficient for
first-order kinetics)
n = 36
Average = .986
Std Deviation = .024
1 C
-------
Figure 6: STP Effluent Samples - Oxygen Depletion Curves
c
o
c.
CD
C
OJ
en
>,
x
O
50 -
40
30
20
10 -
Piscataway STP Station 1
August 14, 1978
r = .894
Total
BOD
N NOD
8 10 12 14
Time (Days)
CSOD
16 18 20 22
en
C
o
OJ
n.
a;
cu
X
o
90
80
70
50
50
40
30
20
10
0
Westgate STP Station 5
September 11, 1978
Total
BOD
NOD
CBOD
10 12 14
16
18
20
22
-------
Table 5: First Order Correlation Coefficients for STP NOD's
Sta.
3-1
3-2
3-3
3-3
S-4
S-5
S-6
S-7
S-8
Name
Piscataway
Arlington
Blue Plains East
Blue Plains West
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Aug 14
r*
-.744
.060
-.574
-.335
-.597
-.591
-.538
.957
-.722
Aug 28
r
-.863
-.995
-.886
-.892
-.905
-.902
-.582
-.993
-.982
Sept 11
r
-.629
.351
-.642
.972
-.994
-.778
-.594
-.778
-.709
Sept 25
r
-.210
.987
-.816
-.833
-.872
-.619
-.816
-.829
-.619
r - correlation coefficient
-------
V. Oxygen Demand of Algal Respiration and Algal Decay
Potomac BODs samples containing algae historically8'12 expressed
significantly high oxygen demand. The oxygen demand of such samples
was the result of: algal respiration; the decay of phytoplankton; and
the carbonaceous and nitrogenous demand of other non-algal sample
constituents. To resolve the BOD fractions of the sample, it was
assumed that algae represented the only significant particulate
contribution to the BOD of the sample. The non-algal BOD of the
sample was assumed to be associated with the soluble organic and
ammontum/nitrite fractions of the sample. The non-algal or background BOD was
measured in the supernatant which had been obtained from the
centrifugation of the algae containing samples. It was further assumed
that the BOD of freeze-dried algae corrected for seed addition and
the BOD of the dilution water (river water supernatant) represented
the biochemical oxygen demand of algal decay. Freeze-drying has been
shown to effectively kill phytoplankton without significantly altering
their physical structure13 thus providing a method of separating algal
respiration and algal decay measurements in a BOD analysis.
The results of these experiments are presented in Figures 7,8,and 9
and Tables 6 and 7. Algal decay was found to be the major contribution
to algal 6005 with an average mg algal BQDg per yg chlorophyll a_ of
0.019. Algal respiration represented about 30% of the algal BOD^
contribution with an average of £.008 mg algal BOD5 per yg chlorophyll a_.
The predominent species present in the Potomac during this study was the
-------
Figure 7: Oxygen Depletion Curves of Algal Respiration and Decay
September 14, 1978
7 -i
6 -
5 -
I 4
+j
QJ
"a.
0> -5
o 3
c
OJ
Ol
>> ?
x £
o
1 -
River water supernatant used as dilution water
Free;
Driec
O Algal suspension
X Algal suspension,
freeze-dried
* River water
supernatant
blk
= .066 day"1 L0 = 2.0
i i i
5 n 14
Time of Incubation (days)
7 -
5 -
4
^j
O)
"D.
& 3
c
o>
CT>
i H
Q
River water supernatant used as dilution water
1 ml seed/300 ml BOD bottle
Free2
Driec
'1
.966 k10 = .049 day"1 L0 = 2.3
5 11 14
Time of Incubation (days)
-------
Oxygen Depletion (rog/1}
ro
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Ji
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I _
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<
ro
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s
P
rt
TO
i-S
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TO
b^
~
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P
rt
P
3
rt
o-
t i
7?
>
H^
OQ
P
t '
in
C
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'D
C
3
in
(-
O
3
rti
4
TO
TO
N
TO
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O.
H
TO
Cu
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OQ
P
^
in
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T3
TO
3
in
H-
O
3
CO
o
x
*<
o
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n>
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rt-
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n> o
T3 C
3 ro
cr i"
ro
-s o
-h
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oo
ro
to
CL
CD
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rt-
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CL
ro
o
01
-------
Oxygen Depletion (nrrg/1)
n>
rl
3
D
-5
O
-------
Table 6: Phytoplankton Oxygen Depletion
Date/Sample
Days of Incubation
Sept. 6, 1978
Algal Suspension
Algal Suspension
Freeze-Dried
River Water
Supernatant Blk
Seeded Al gal
Suspension
Seeded Algal
Suspension
Freeze-Dried
Seeded" River Water
Sept. 14, 1978
Algal Suspension
Algal Suspension
Freeze-Dried
River Water
Supernatant Blk
Seeded Algal
Suspension
Seeded Algal
Suspension
Freeze-Dried
Seeded River Water
5
9.8
6.4
3.0
10.0
9.3
2.8
5
2.4
2.2
1.4
2.6
2.0
1.1
8
12.0
8.5
3.4
12.6
10.8
3.3
11
5.0
3.8
1.2
5.0
3.5
1.4
12
13.8
9.8
3.6
14.4
12.0
3.6
14
5.1
3.6
1.7
5.3
3.2
1.8
19
16.6
11.4
9.3
17.2
14.3
4.4
25
6.7
5.0
1.9
7.0
4.8
2.1
33
19.1
13.1
5.1
19.8
16.1
5.2
0-5
-------
Table 7: BODs Requirements for Algal Decay and Respiration
Decay
'/ \ \
/ BODs - Background]x Dilution]*
((freeze- BODs / factor /
dried /
chloro a
5-Day
Algal Decay
mg 0? depletion
Date
Sept. 6
Sept. 14
Sept. 6
Sept. 14
algal
suspension)
mg/1
6.4
2.2
9.3
2.0
mg/1
3.0
1.4
2.8
1.1
6.0
15.0
6.0
15.0
yg/l
1386
810
1386
810
average
Respiration
Date
Sept. 6
Sept. 14
Sept. 6
Sept. 14
/
\ BOD5 ~
1 algal
V V suspension
\
mg/1
9.8
2.4
10.0
2.6
BODs \X
(freeze-
dried /
algal
suspension)
mg/1
6.4
2.2
9.3
2.0
\
Dilution)*
factor j
6.0
15.0
6.0
15.0
chloro a.
yg/l
1386
810
1386
810
average
yg cm or a_
.0147
.0148
.0281
.0167
.019
5-Day
Algal Respira
8
mg Oj depletion
yg cm or a_
.0147
.0037
.0030
.0111
.008
-------
filamentous blue-green algae Psuedanabaena. Figures 7,8,and9 also
revealed that seeding of the samples with 1 ml per bottle of stale
settled sewage1 had little effect upon the amount and rate of oxygen
depletion. This suggested that the supernatant contained sufficient
microorganisms for algal decay.
VI. Phytoplankton Elemental Analysis and Methods of TKN Digestion
of Algal Samples
The algae bloom of Psuedanabaena occurred in mid to late September
with a chlorophyll a_ peak of 159 yg/1 on September 27. The elemental
composition of the phytoplankton is compiled in Table 8. The average
elemental ratios to chlorophyll a_were: .021 mg C/vg chlorophyll a_;
.0054 mg N/yg chlorophyll a_; and .0020 mg P04/yg chlorophyll a_. It
should be emphasized that the results are based on the overall
phytoplankton standing corp. The nitrogen values reported for elemental
analysis were obtained by the automated colorimetric phenol ate procedure
employing the continuous (helix) digestor with preliminary manual
digestion. Neither the Technicon block digestor nor the Technicon continuous
digestor alone provided satisfactory digestion of algal TKN. The data
from side-by-side algal digestions are compiled in Table 9. The
average recovery relative to preliminary manual digestion for the
Technicon continuous digestor and block digestor were 58% and 83%
respectively. This suggested that 42% of algal nitrogen was refractory
to the Technicon continuous digestor. This agreed with a 50% TKN recovery
estimate suggested in a previous study.14
-------
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-------
Table 9: Results From Three TKN Digestion Methods
Date
Sept.
Sept.
Sept.
Sept.
Station
7 5-A
8-A
9
10
10-B
11 8-A
9
10-B
11
n 8
8-A
9
10
26 8-A
9
10
10-B
11
average
std. deviation
Manual
mg/1
TKN
14.52
15.14
15.14
14.89
15.89
15.89
15.89
14.52
15.14
29.27
28.28
23.32
29.05
21.73
25.17
34.66
31.95
26.74
Block
mg/1
TKN
11.10
14.50
13.03
14.47
14.09
13.63
14.06
13.09
14.36
19.49
20.00
_ _ _
___
16.58
17.74
20.63
19.46
30.88
28.02
24.00
26.30
20.60
20.32
Helix
mg/1
TKN
9.15
9.52
9.27
9.52
9.27
9.21
8.81
8.24
8.06
12.92
12.61
11.83
11.83
13.65
16.86
22.36
22.84
18.53
Helix
Manual
.63
.63
.61
.6*
.58
.58
.55
.57
.53
.44
.45
.51
.41
.63
.67
.65
.71
.69
.58
.09
Block
Manual
.76
.96
.86
.97
.89
.86
.88
.90
.95
.67
.71
.76
.82
.82
.77
.89
.81
.75
.82
.77
.76
.83
.08
Helix
Block
.82
.66
.71
.66
.66
.68
.63
.63
.56
.65
.63
*
__
.82
.77
.82
.87
.72
.80
.95
.87
.90
.91
-------
VII. Potomac River Long-Term BOD Survey Data - Summer 1978
Date 8/14/78
Station
5
Days of Incubation
10 15
8-A
10
n
14
16
Date 8/28/78
Station
5
8-A
T*
C*
N*
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
T
C
2.4
1.3
1.1
2.7
1.3
1.4
4.3
2.3
2.0
3.9
2.9
1.0
4.6
3.5
1.1
3.5
2.6
0.9
1.8
1.6
0.2
T
C
N
*T-BOD (mg/1)
*C-CBOD (mg/1 )
*N-NOD (mg/1)
3.0
1.4
1.6
4.4
1.3
3.1
6.3
2.8
3.5
5.3
3.1
2.2
5.8
4.0
1.8
4.7
2.9
1.8
2.0
1.6
0.4
3.4
2.1
1.3
4.9
1.7
3.2
8.0
3.9
4.1
6.8
4.0
2.8
7.0
4.7
2.3
5.6
3.7
1.9
2.4
2.0
0.4
Days of Incubation
7 13
4.3 9.3
2.4 3.2
1.9 6.1
6.2 8.0
2.7 3.8
3.5 4.2
4.4 6.4
3.1 4.3
1.3 2.1
21
3.8
2.2
1.6
5.3
1.9
3.4
8.7
4.4
4.3
7.2
4.4
2.8
7.3
5.0
2.3
6.2
3.8
2.4
2.9
1.8
1.1
20
10.8
3.9
6.9
9.4
4.7
4.7
7.7
5.4
2.3
-------
VII. Potomac River Long-Term BOD Survey Data * Summer 1978 (con't)
Date 8/28/78 (con't)
Station
TO
14
16
Date 9/11/78
Station
5
8-A
10
11
14
16
T
C
N
T
C
N
T
C
N
T
C
N
Days of Incubation
7 13 20
3.6 5.2 6.6
2.2 3.2 4.1
1.4 2.0 2.5
4.2 6.1 7.6
2.5 3.9 4.9
1.7 2.2 2.7
1.4 2.7 3.9
1.2 1.8 2.4
0.2 0.9 1.5
3.8 4.9 5.8
3.5 4.5 5.2
0.3 0.4 0.6
Days of Incubation
6 10 14
21
T
C
N
T
C
N
T
c
N
T
C
N
T
C
N
T
C
N
T
C
N
3.7
1.7
2.0
3.3
1.9
1.4
2.1
2.1
2.5
1.9
0.6
___
1.2
1.2
0
2.2
2.1
0.1
8.9
2.9
6.0
4.9
3.1
1.8
4.8
3.6
1.2
4.4
2.9
1.5
3.9
2.0
1.9
2.0
1.7
0.3
3.5
3.5
0
9.8
3.5
6.3
6.0
3.9
2.1
7.7
4.6
3.1
6.6
4.2
2.4
6.3
3.2
3.1
2.8
2.3
0.5
4.3
4.2
0.1
n.o
4.0
7.0
6.7
4.5
2.2
9.1
6.2
2.9
7.8
5.0
2.8
7.1
4.1
3.0
3.8
2.7
1.1
5.0
4.6
0.4
12.2
4.6
7.6
7.6
5.4
2.2
9.9
6.7
3.2
8.9
5.9
3.0
8.0
4.0
4.0
4.5
3.2
1.3
5.8
5.0
0.8
-------
VII. Potomac River Long-Term BOD Survey Data - Summer 1978 (con't)
Date 9/25/78
Station
5
8-A
10
n
14
16
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
Days of Incubation
3 7 14
6.1 8.5 11.0
2.3 3.8 4.8
3.8 4.7 6.2
2.7 6.2 8.4
2.1 3.8 5.7
0.6 2.4 2.7
2.5 7.1 10.5
2.1 4.1 7.6
0.4 3.0 2.9
2.5 7.6 11.0
2.0 6.2 9.1
0.5 1.4 1.9
2.3 5.7 11.2
1.5 3.8 8.6
0.7 1.9 2.6
0.8 2.0 4.5
0.7 1.1 2.9
0.1 0..9 1.6
1.1 1.6 2.7
0.6 0.7 1.7
0.5 0.9 1.0
Date 8/14/78
Station
S-l
T
C
N
20.1
7.2
12.9
Days of Incubation
10 15
38.7
9.6
29.1
41.6
10.8
30.8
21
43.5
11.4
32.1
S-2
S-3 (E)
T
C
N
T
C
N
21.0
6.0
15.0
81.0
75.0
6.0
22.8
9.0
13.8
157,
88,
41,
n,
29,
69.0
174
96.0
78.0
55,
13,
42,
181,
96,
85.5
-------
VII. Potomac SIP Long-Term BOD Survey Data - Summer 1978 (con't)
Date 8/14/78 (con't)
Station
S-3 (W)
S-4
S-5
S-6
S-7
S-8
Date 8/28/78
Station
S-l
S-2
S-3 (E)
S-3 (W)
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
r
N
T
C
N
T
C
N
T
C
N
Days of Incubation
6 10 15 21
21.6 60.0 73.8 77.4
10.8 15.0 18.0 18.3
10.8 45.0 55.8 59.1
36.0 72.0 87.0 92.3
31.5 36.8 40.5 40.3
4.5 35.2 46.5 52.0
14.1 41.7 59.4 72,
9.6 12.8 14.4 16.
4.5 28.9 45.0
18.6 39.9 51.3
14.7 20.0 23.6
3.9 19.9 27.7
30.6 44.4 43.5
15.2 18.0 20.7
15.4 26.4 22.8
10.2 38.7 56.4
8.7 13.1 17.4
1.5 25.6 39.0
Days of Incubation
7 13 20
9.6 43.7 71.7
7.8 9.8 10.5
1.8 33.9 61.2
12.3 22.8 46.8
7.8 8.4 8.6
4.5 14.4 38.2
28.5 79.5 148.5
27.0 36.0 36.8
1.5 43.5 111.7
24.0 67.5 117.8
21.0 27.0 28.5
3.0 40.5 89.3
6
5
56.1
55.8
25.8
30.0
46.8
22.5
24.3
75.5
21.2
54.3
-------
VII. Potomac STP Long-Term BOD Survey Data - Summer 1978 (con't)
Date 8/28/78 (con't)
Station
S-4
S-5
S-6
S-7
S-8
Date 9/11/78
Station
S-l
S-2
S-3 (E)
S-3 CM)
S-4
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
Days of Incubation
7 13 20
42.0 87.0 132.0
33.0 39.8 42.8
9.0 47.2 89.2
9.5 22.8 47.7
8.9 10.4 11.7
0.6 12.4 3F.O
19.4 42.0 47.9
13.1 17.7 20.1
6.3 24.3 27.8
25.2 41.4 53.6
15.0 20.1 21.6
10.2 21.3 . 36.0
11.7 22.4 52.4
10.8 16.1 20.4
0.9 6.3 32.0
Days of Incubation
6 10 14
21
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
11.4
7.8
3.6
28.8
6.0
22.8
13.5
13.5
0
13.5
12.0
1.5
1.8
16.5
1.5
39.0
10.2
28.8
50.4
8.4
42.0
20.3
20.3
0
22.5
18.0
4.5
27.0
24.0
3.0
52.8
11.4
41.4
68.4
8.4
60.0
34.5
22.5
12.0
49.5
21.0
28.5
46.5
27.0
19.5
62.4
13.2
49.2
70.8
8.4
62.4
69.0
24.0
45.0
78.0
22.0
56.0
76.5
27.0
49.5
63.0
15.0
48.0
87.0
10.4
76.6
79.5
28.5
51.0
90.0
24.0
66.0
99.0
31.0
68.0
-------
VII. Potomac STP Long-Term BOD Survey Data - Summer 1978 (con't)
Date 9/11/78
Station
S-5
S-6
S-7
S-8
Date 9/25/78
Station
S-l
S-2
s-3
S-3 (W)
S-4
S-5
Days of Incubation
6 10 14
21
T
C
N
T
C
N
T
C
N
T
C
N
9.0
9.0
0
9.9
9.9
0
9.6
9.0
0.6
7.8
7.8
0
14.4
13.2
1.2
15.0
15.0
0
14.4
13.2
1.2
12.0
10.2
1.8
44.4
16.2
28.2
32.4
17.4
15.0
31.8
16.2
15.6
42.6
14.4
28.2
76.2
16.8
59.4
51.6
18.0
33.6
55.8
18.6
37.2
69.0
16.8
52.2
91.2
18.6
72.6
55.2
21.0
34.2
64.2
22.8
41.4
79.8
21.6
58.2
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
7.8
5.4
2.4
22.8
5.4
17.4
31,
19,
12.0
63.
27.
36,
Days of Incubation
7 14
40.2 49.2
13.8 14.4
26.4 34.8
60.0 91.8
12.6 13.8
47.4 78.0
69.0 108
31.5 37,
37.5 70,
123.0 163,
45.0 60
78.0 103.5
,5
,5
,5
.0
30.0
24.0
6.0
9.0
9.0
0
52
31
21
,5
,5
.0
m,
37
73,
15.6
11.4
4.2
59.4
13.8
45.6
-------
VII. Potomac STP Long-Term BOD Survey Data - Summer 1978 (con't)
Date 9/25/78 (con't) Days of Incubation
3 7 14
Station
S-7
S-8
T
C
N
T
C
N
11.4
11.4
0
14.4
9.6
4.8
21.0
16.2
4.8
60.0
11.4
48.6
42.0
20.4
21.6
94.8
15.6
79.2
-------
References
1. "Standard Methods for The Examination of Water and Wastewater,"
14th ed., APHA, 1975.
2. Slayton, J.L. and Trovato, E.R., "Simplified N.O.D. Determination,"
34th Annual Purdue Industrial Waste Conference, Purdue University 1979,
3. Strickland, J.D.H. and Parsons, T.R., "A Manual of Sea Water
Analysis," Bulletin 125, Fisheries Research Board of Canada,
Ottowa, 1960, p. 185.
4. Environmental Protection Agency, Methods for Chemical Analysis
of Water and Wastes. 1974.
5. Gales, M.E., "Evaluation of The Technicon Block Digestor System
for Total Kjeldahl Nitrogen and Total Phosphorus," EPA-600/4-78-015,
Feb. 1978, Environmental Monitoring Series, E.P.A. Cincinnati,
Ohio.
6. Young, J.C., "Chemical Methods for Nitrification Control,"
24th Industrial Waste Conference, Part II Purdue University,
pp. 1090-1102, 1967.
7. Young, J.C., "Chemical Methods for Nitrification Control,"
J.W.P.C.F., 45, 4, pp. 637-646 (April 1973).
8. Slayton, J.L. and Trovato, E.R., "Carbonaceous and Nitrogenous
Demand Studies of The Potomac Estuary, AFO Region III, Environmental
Protection Agency, 1977.
9. Thomas, H.A., "Graphical Determination of B.O.D. Curve Constants,"
Water and Sewage Works, p. 123-124, (March 1950).
10. Moore, W.E. and Thomas, H.A., "Simplified Methods for Analysis of
B.O.D. Data," Sewage and Industrial Works, 22, p. 1343-1355, 1950.
11. Finstein, M.S., et al , "Distribution of Autotrophic Nitrifying
Bacteria in a Polluted Stream," The State Univ., New Brunswick,
N.J., Water Resources Res. Inst. W7406834, Feb. 1974.
12. Clark, L.J. and Roesch, S.E., "Assessment of 1977 Water Quality
Conditions In The Upper Potomac Estuary, E.P.A. 903/9-78-008,
July 1978.
13. Fitzgerald, G.P., "The Effect of Algae on B.O.D. Measurements,"
J.W.P.C.F., Dec. 1964, pp. 1524-1542.
14. Slayton, J.L. and Trovato, E.R., "Algal Nutrient Studies of the
Potomac Estuary", AFO Region III, Environmental Protection
Agency, 1977.
-------
-------
TECHNICAL REPORT DATA
I'li'zst: read Insir.ictio'i1; on llic re.crs? before complain,;)
flTFc ORT NO. \2'
v EPA=9Q3/q-jq=flQ5_ 1
T'TTYri: AND SUBTITLE
Biochemical Studies in The
Potomac Estuary
^^^ 0. L. SI ay ton and
E. R. Trovato
^yT^T^FOHMING ORGANIZATION NAM= AND ADDRESS 1
Annapolis Field Office, Region III
U.S. Environmental Protection Agency
Annapolis Science Center
Annapolis, Maryland 21401
12 SPONSORING AGENCY NAME AND ADDRESS
3 RECIPItN PS ACCESSION NO.
j. REPOHT DATE:
Summer 1978
6. PERFORMING ORGANIZATION CODS
3. PERFORMING ORGANIZATION REPORT
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
13. TYPE OP REPORT AND PERIOD COVE
14. SPONSORING AGENCY COD5
Same
EPA/903/00
15. SUPPLEMENTARY NOTES
. ABSTRACT
The carbonaceous and nitrogenous oxygen demand of Potomac River and STP effluent
samples was determined during the summer of 1978. The oxygen depletion kinetics
were studied during long term incubation using an inhibitor to nitrification. The
average deoxygenation constants (ke) for the river sample CBOD and NOD were 0.12
day" and 0.10 day" , respectively. The CBOD of the Potomac STP effluent samples
followed first order kinetics with an average ke - .16 day" . The NOD for the STF
effluent samples had a significant lag time resulting in poor correlation
coefficients for first order fit. The average algal contribution to the 8005 was
0.027 mg/ug chlorophyll a^ with 70% due to decay an'd 30% due to respiration. The
average elemental composition of the phytoplankton present in the study area'was
determined to be (mg/yg chlorophyll a_): .021 TOC, .002 P04 and .005 TKN. : ;
Forty-two percent of algal nitrogen was found to be refractory to the Technicon
Continuous Digester. ",
17. " KEY WORDS AND DOCUMENT ANALYSIS
s. DESCRIPTORS
Biochemical Oxygen Demand
Nitrification
Algal Respiration and Decay
Algal Elemental Composition
:;;. DISTRIBUTION STATEMENT
b.lDENTIFIERS/OPEN ENDED TERMS
Deoxygenation Kinetics
Lag Time
Oxygen Depletion Curve
TKN Digestion
19. SECURITY CLASS ('I Iris KeportJ
20. SECURITY CLASS { I'ldf p.iyc)
c. coSATi Field/G
?1. NO. Of- PAGES
35
22. f'RICt.
t:orr,i 2220-] (9-73)
-------
EPA 903/9-78-006
ANALYSIS OF SULFUR IN FUEL OILS BY
ENERGY-DISPERSIVE X-RAY FLUORESCENCE
January 1978
Technical Paper No. 15
Annapolis Field Office
Region III
Environmental Protection Agency
-------
Annapolis Field Office
Region III
Environmental Protection Agency
ANALYSIS OF SULFUR IN FUEL OILS BY
ENERGY-DISPERSIVE X-RAY FLUORESCENCE
E. R. Trovato
J. W. Barron
J. L. Slayton
-------
DISCLAIMER
The mention of trade names or commercial products in this report
is for illustration purposes and does not constitute endorsement or
recommendation by the U.S. Environmental Protection Agency.
-------
INTRODUCTION
Sulfur oxides have long been recognized as significant air
pollutants. With increased usage of sulfur containing fuels, an
increase in atmospheric sulfur dioxide content will become an
ever more important problem. Legislation has been passed governing
the allowable levels of sulfur in fuels in an attempt to control
this source of air pollution.
Energy-dispersive x-ray fluorescence (EDXRF) can provide a
rapid, non-destructive method of analysis of sulfur in fuel oils.
Because the EDXRF system is automated and minimal sample preparation
procedures are involved, a reduction in the time and cost of
analysis is possible.
-------
EXPERIMENTAL
Materials
Sulfur standards of: 2.14, 1.05, 0.268, and 0.211 weight
percent sulfur in fuel oil were obtained from the National
Bureau of Standards. In addition, sulfur standards prepared
by commercial sources were obtained with concentrations in
weight percent sulfur of: 2.02, 1.06, and 0.49. Actual
samples analyzed by wavelength-dispersive x-ray fluorescence
with the following weight percent sulfur concentrations were
also analyzed: 2.95, 2.10, 2.05, 2.00, 1.61, and 0.33.
Zinc, barium, and lead standards were prepared from Conostan
Metallic-Organic standards.
Equipment
A Finnigan 900 Series energy dispersive x-ray fluorescence
spectrometer and data system were used for all EDXRF analyses.
Procedure
The determination of sulfur in fuel oils follows the procedure
outlined-in ASTM D2622-671: Standard Method of Test for Sulfur
in Petroleum Products (X-Ray Spectrographic Method) with
minor changes in the procedure to accommodate the energy
dispersive equipment. A brief outline of the procedure follows:
a. Place the sample in an open cell sample cup over which
0.25-mil Mylar film has been stretched and attached
with a snap-on ring. Attach microporous film to the
open-end of the sample cup to prohibit the oil
from escaping.
-------
b. Place the samples in the x-ray beam, apply vacuum,
and allow the atmosphere in the x-ray chamber to
come to equilibrium. Instrument operating conditions
are found in Table III.
c. Determine the intensity of the SK& peak at 2.307 Kev
and make background measurements adjacent to the peak.
d. If the sample contains interfering elements in
concentrations greater than those listed in ASTM
D2622-67, dilute the sample by weight with white oil.
Calibration
a. Determine the net SIQv intensity for all standards
and samples.
b. Determine the weight percent sulfur by ratio against
the 2.14 weight percent sulfur standard reference
material using net intensities or by comparison to a
calibration curve of sulfur net intensity vs. concentration.
c. Measure a sensitivity standard at frequent intervals
and determine the net counting rate for each sample.
-------
RESULTS AND DISCUSSION
Commercially obtained standards, NBS standards, and previously
analyzed field samples were analyzed by energy dispersive x-ray
fluorescence. The accuracy results shown in Table I and precision
results shown in Table II, indicate the high degree of precision and
accuracy obtainable by this method of analysis. The average recovery
was 97^ (Table I) and a plot (Figure I) of found weight percent sul-
fur vs. known weight percent sulfur gives a correlation coefficient
of 0.999. A paried-t test applied to the data indicates that there
is no difference between the found and known values at a 95^5 confi-
dence level. An average standard deviation of 0.02 weight percent
sulfur was found over the O.l6 to 2.00 weight percent sulfur range.
A plot of the standard calibration curve (Figure II) is linear with
a correlation coefficient of 0.9997, further facilitating analysis by
this method.
The minimum detectable amount2, defined as 3x(intensity of the
background)1''2, is 0.11 weight percent sulfur; this is below the
majority of legislated limits of sulfur concentration in fuel oil in
the United States^.
The analysis of fuel oil samples by energy-dispersive x-ray
fluorescence is accurate and precise, requires minimal sample
preparation, and is non-destructive. It also simultaneously deter-
mines sulfur and its interfering elements, phosphorus, zinc, barium,
calcium, and chlorine. These factors combine to produce an overall
increase in the efficiency of analysis of sulfur in fuel oils.
-------
TABLE I
Comparison of Sulfur Results Found by Classical and EDXRF Methods
Date of
Analysis
10-28-75
8-12-76
2-11-77
2-14-77
4-27-77
Origin
Field Sample
Field Sample
Field Sample
Secondary Std.
Field Sample
Field Sample
Secondary Std.
Field Sample
Field Sample
Field Sample
Field Sample
Secondary Std.
NBS
Secondary Std.
NBS
NBS
NBS
NBS
Secondary Std.
NBS
NBS
NBS
Secondary Std.
NBS
Classical
wt. % S
2.95
2.10
2.05
2.02
2.00
1.61
1.06
2.94
2.10
2.00
1.61
1.06
1.05
0.49
0.268
0.211
1.05
0.211
1.06
1.05
1.05
0.268
0.24
0.211
correlation coefficient = .999
EDXRF
wt. % S
2.98
2.07
2.05
1.94
2.04
1.68
0.99
3.04
2.13
2.04
1.67
1.01
1.04
0.48
0.264
0.206
1.02
0.155
1.00
1.06
1.03
0.231
0.22
0.192
mean
s
* R*
101.0
98.6
100.0
96.0
102.0
104.3
93.4
103.4
101.4
102.0
103.7
95.3
99.0
98.0
98.5
97.6
97.1
73.4
94.3
101.0
98.1
86.2
91.7
91.0
= 97. %
= 6.7%
t-statistic = .540
degrees of freedom = 23
*R = Recovered
-------
Figure I: Plot of Found Weight Percent Sulfur vs Known Weight Percent Sulfur
3 D
>>
Found
wt. % S
2.0
r = .9990
m = 1.028
b = -0.04027
2Jl
Known wt. % S
-------
TABLE II
Results of Duplicate Analyses of Field Samples
Duplicate I
wt. % S
.16
.16
.16
.16
.16
Duplicate II
wt. % S
.17
.17
.19
.21
.17
s = .02% S
difference
Toi
.01
.03
.05
.01
0.3-1.0%
.72
.96
.99
.93
.59
.44
.72
.98
.98
.91
.58
.44
s = .01% S
0
.02
.01
.02
.01
0
> 1.0%
1.99
03
04
05
74
09
.96
1.63
,92
.01
.00
.04
.74
.08
.94
.63
.07
.02
.04
.01
0
.01
.02
0
s = .02% S
s = (I(d2) /2k)-*
where: s = standard deviation
d = difference between duplicates
k = number of samples
-------
TABLE III
Instrument Operating Conditions
Date
of Voltage Amperage Time Colliroator
Analysis Kv ma sec Path Filter diameter mm
10-28-75 10 4 500 vacuum none 1
8-12-76 10 1 500 vacuum none 6
2-11-77 10 0.8 500 vacuum none 6
2-14-77 10 0.8 1000 vacuum none 6
4-27-77 10 0.8 1000 vacuum none 6
-------
-igure II: Plot of SKa Net Intensity vs Weight Percent Sulfur
300
r = .9997
m = 144.99
b = -5.246
200:
1 0 0 h
Weight % Sulfur
-------
REFERENCES
1. ASTM D2622-67, ASTM Standards on Petroleum Products and Lubricants,
ASTM Committee D-2, September 1967
2. Bertin, Eugene P., Principles and^ Practice of X-Ray Spectrometric
Analysis, Plenum Press, Me\v York, 1975
3. Martin, Werner and Stern, Arthur C., The World's Air Quality
Management Standards, Volume II: The Air Quality
Management Standards of the United States, U.S.
Environmental Protection Agency, Office of Research
and Development, Wash., D.C., 1974, pg. 113-124
4. U.S. Environmental Protection Agency, Office of Water Programs
Operations, National Training and Operational Technology
Center, Participant's Handbook for the Drinking Water^
Chemical Laboratory Certification Course, pg. E9-20
ACKNOWLEDGEMENTS
We would like to thank: Dr. Jungers, EPA, RTP; Mr. Al Curry,
Aerospace Fuels Lab; Mr. Mac Dill, AFB, Tampa, Fla.; and Mr. Al Kewing,
Mobil Oil, Paulsboro, N.J. for providing analyzed samples and
commercial standards utilized.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
EPORTNO 2.
IPA 903/9-78-006
ITLE AND SUBTITLE
.nalysis of Sulfur in Fuel Oils by Energy Dispersive
X-ray Fluorescence
UTHOR(S)
:. R. Trovato, J. W. Barren, J. L. Slayton
ERFORMING ORGANIZATION NAME AND ADDRESS
.nnapolis Field Office, Region III
.3. Environmental Protection Agency
.nnapolis Science Center
unnapolis, Maryland 21/401
SPONSORING AGENCY NAME AND ADDRESS
lame
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
January 1978
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
Technical Paper 15
10. PROGRAM CLEMENT NO.
8BD144
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
In House; Final
14. SPONSORING AGENCY CODE
EPA/903/00
SUPPLEMENTARY NOTES
ABSTRACT
Energy dispersive x-ray fluorescence was used to analyze for sulfur in oil in
sommercially prepared standards, NBS standards and laboratory samples. The
,echnique of energy dispersive x-ray fluorescence for sulfur was found to be
iccurate, precise, and required minimal sample preparation. In addition it
ras non-destructive, and enabled the simultaneous determination of sulfur and
ts interfering elements: phosphorus; zinc; barium; calcium; and chlorine.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
I -ray Fluorescence Sulfur Analysis
>ulfnr ;>termi nation Fuel Oil
. DISTRIBUTION STATEMENT
i'"loe;i^ 1 o in: lie
b.lDENTIFIERS/OPEN ENDED TERMS
Energy -dispersive X-ray
Fluorescence Sulfur
Analysis
19. SECURITY CLASS (This Report)
UNCLASSIFIED
20. SECURITY CLASS (This page)
UNCLASSIFIED
c. COSATI Field/Group
21. NO. OF PAGES
in
22. PRICE
A Form 2220-1 19-73)
-------
,MSI RUCTIONS
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EPA 903/9-78-008
ASSESSMENT OF 1977
WATER QUALITY CONDITIONS
IN THE UPPER POTOMAC ESTUARY
July 1978
Leo 0. Clark
and
Stephen E. Roesch
-------
-------
EPA 903/9-78-008
TABLE OF CONTENTS
Chapter Page
List of Figures ii
List of Tables iii
I. INTRODUCTION 1
II. DESCRIPTION OF MONITORING PROGRAM 5
III. FINDINGS AND CONCLUSIONS 13
A. General 13
B. Dissolved Oxygen 15
C. Algae 37
D. Nutrients 46
E, BOD 48
F. Estuary loadings 49
G. Herbicides 52
IV. FUTURE STUDY NEEDS 55
V- APPENDIX 56
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LIST OF FIGURES
Number Page
1 Secchi Disk vs. Chlorophyll a_ 14
2 DO Profile - September 8, 1977 16
3 Potomac Estuary DO Data: Rosier Bluff 23
Swan Creek (Drogue Study)
August 16, 1977
4 Potomac Estuary DO Data: Rosier Bluff 24
Piscataway Creek (Drogue Study)
August 30, 1977
5 Diurnal Transect Data: Potomac Estuary 26
at Hains Point - August 8-9, 1977
6 Diurnal DO Data - Hains Point 27
7 Diurnal Transect Data: Potomac Estuary 29
at Woodrow Wilson Bridge
August 9-10, 1977
8 Diurnal DO Data - Woodrow Wilson Bridge 30
9 Diurnal Transect Data: Potomac Estuary 32
at Fort Washington - August 10-11, 1977
10 Diurnal DO Data - Fort Washington 33
11 Chlorophyll a_, BOD, and DO Time Plots 39
12 Nitrogen - Chlorophyll Relationship 43
13 Phosphorus - Chlorophyll Relationship 44
A-l DO Isopleth: Potomac Estuary - 1977 56
A-2 Chlorophyll a^ Isopleth: Potomac Estuary 57
1977
A-3 NH3 Isopleth: Potomac Estuary - 1977 58
A-4 N02 + N03 Isopleth: Potomac Estuary - 1977 59
A-5 TP04 Isopleth: Potomac Estuary - 1977 60
A-6 Pi Isopleth: Potomac Estuary - 1977 61
A-7 BOD5 Isopleth: Potomac Estuary - 1977 62
ii
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-------
LIST OF TABLES
Number Page
1 1977 Potomac Estuary Sampling Stations 6
2 Potomac Slack Water Runs 7
3 1977 Potomac Productivity Study 18
4 Analysis of Diurnal DO Variability - 20
August 16, 1977
5 Oxygen Production - Respiration Balance 21
6 Comparison of Surface and Bottom DO - 28
Mains Point
7 Comparison of Surface and Bottom DO - 31
Woodrow Wilson Bridge
8 Comparison of Surface and Bottom DO - 34
Ft. Washington
9 Analysis of Diurnal DO Data 36
10 Relationship between Organic N&P and 41
Chlorophyll a_
11 Relationship between Inorganic N&P and 42
Chlorophyll a_
12 Summary of Sewage Treatment Plant 50
Effluent Data
A-l Summary of 1977 Potomac Estuary Data 63
m
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Chapter 1
INTRODUCTION
The water quality problems of the Potomac in the Wash-
ington area have been recognized since the days of President
Lincoln. Most of the difficulties at that time manifested them-
selves as sewage related odors which were abundant on warm summer
evenings. It was not until the 1930's that treatment facilities
were constructed to alleviate the obvious odor problems and less
obvious potential health hazards. Since that time, there has been
a continual race between expanding population and construction of
treatment works in order to adequately treat the increased waste-
loads. Needless to say, treatment facilities still lag behind
current and anticipated needs in the Washington Metropolitan Area.
A major objective of the Water Quality Act and its
amendments is to "maintain the physical, chemical and biological
integrity of the Nation's waters". In the 1950's and 60's, changes
in growth of aquatic plants in the Potomac were documented. These
biological perturbations were indicative of more basic changes
taking place in the physical and chemical environment supporting
these aquatic plants. Such biological changes serve as barometers
pointing to ecological imbalance within the supporting environ-
ment, in this case the Potomac Estuary.
Extensive field studies in the Potomac Estuary were
conducted by EPA from 1966 to 1970. These studies pointed out
the two major water quality problems existing during that period.
1
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These were an oxygen deficit brought about by discharge of organic
wastes and excessive eutrophication brought about by overenrich-
ment of the estuary with nutrients, particularly nitrogen and
phosphorus. These studies resulted in the publication of Technical
Report 35, which documented the scientific efforts carried out up
to that time by EPA's Annapolis Field Office (AFO).
Now, nearly a decade later, these problems are receiving
increased attention from regional planners, as attempts to find
a solution have grown more complex. The water quality problems
of the Potomac Estuary must be considered along with other local
environmental issues, such as: water supply needs incorporating
a low flow policy, pressure to rerate treatment capacity at Blue
Plains, land treatment alternatives, and other legitimate concerns
that must somehow be orchestrated into an overall regional
management plan, which is at the same time rational, cost-effective,
and meets the needs of the public.
It is within this framework of competing uses of the
Potomac and conflicting needs of the public that EPA designed a
two-year water quality study to update the available data base
and provide current information on the status of the Potomac
Estuary. Our studies will not answer the many questions raised
by the various constituencies served by the Potomac, but they will
provide factual documentation on the river's health and an indica-
tion of the water quality trends evolving. Such information is
basic to the decision maker in formulating the available options
from which a workable decision can be made. It is this foundation
-------
of scientific reality that we are attempting to investigate and
document.
This report is intended to present the information
gained from the first half of the current two-year study effort.
The field phase was performed during the summer of 1977 and the
findings and conclusions herein evolved during the data interpreta-
tion and analysis phase that followed. Tabulations of the raw
data along with numerous graphs depicting this data are contained
throughout the text and in the Appendix. The ongoing usage of this
data within the context of mathematical modeling and for updating
portions of Technical Report 35 will be documented at a later time.
The specific objectives associated with this intensive
study of the Potomac Estuary's water quality are as follows:
Principal Objective
Provide the first phase of an updated technical data
base that will be necessary to address the denitrification deferral
issue at Blue Plains.
Secondary Objectives
1. Provide data for updating the verification and
improving the predictive reliability of AFO's
existing mathematical model of the Potomac
Estuary.
2. Determine the response of the Potomac Estuary
to the upgraded treatment currently in existence
at Blue Plains.
3. Provide a basis for establishing water quality
trends with particular emphasis on a comparison
3
-------
with data collected during the critical period
of 1965 - 1970.
4. Define current point source nutrient and oxygen
demanding loads entering the Potomac Estuary
along with those being contributed from the
Upper Basin.
5. Monitor the impact of a storm event in the WMA
on the widespread quality characteristics (as
opposed to high frequency monitoring for local-
ized effects) of the Estuary.
6. Determine the magnitude of selected herbicides
entering the Estuary from upstream and signifi-
cant point sources, and their extent in the
Estuary itself.
-------
Chapter II
DESCRIPTION OF MONITORING PROGRAM
This intensive monitoring program, conducted during
the period of July 18 to September 8, was comprised of three
distinct but interrelated phases: (Each of these phases will be
discussed below.)
A. Ambient Water Quality Monitoring
During six different weeks of the study period, two
boat runs, each following a slack water tide condition, were made
from the Route 301 Bridge (river mile 67.4) to Chain Bridge (river
mile 0.0). The stations sampled enroute, along with their river
miles and station number, are presented in Table 1. Because of
time constraints, these stations were sampled only within the
main channel and near the surface (i.e. no transect type data was
obtained). Shown in Table 2 are the approximate starting and
ending times for each run, and the significant rainfall events
that occurred during the study period. As can be seen, about an
equal number of low water and high water slack conditions were
sampled.
The following is a list of parameters that were analyzed
in conjunction with the ambient monitoring. All of these parameters
were measured routinely at every sampling location (with the
exception of herbicides, which were done only twice), as well as
ultimate (20 day) BOD and phytoplankton counts, which were done
on a selective basis.
5
-------
-------
TABLE 1
1977 POTOMAC ESTUARY SAMPLING STATIONS
Station
Number
P-8
P-4
1
1-A
2
3
4
5
5 -A
6
7
8
8-A
9
10
10-B
11
12
13
14
15
15-A
16
Name
Chain Bridge
Above Windy Run (opposite Georgetown
Reservoir
Key Bridge
Memorial Bridge
14th Street Bridge
Mains Point
Bellevue
Woodrow Wilson Bridge
Rosier Bluff
Opposite Broad Creek
Fort Washington (Piscataway)
Dogue Creek - Marshall Hall
Opposite Gunston Cove
Chapman Point - Hallowing Point
Indian Head
Deep Point - Freestone Point
Possum Point
Sandy Point
Smith Point
Maryland Point
Opposite Nanjemoy Creek
Mathias Point
Route 301 Bridge
RMI*
0
1.90
3.35
4.85
5.90
7.60
10.00
12.10
13.60
15.20
18.35
22.30
24.30
26.90
30.60
34.00
38.00
42.50
45.80
52.40
58.55
62.80
67.40
*Miles below Chain Bridge
-------
TABLE 2
POTOMAC SLACK WATER RUNS
JULY - SEPTEMBER, 1977
Date
7/17
7/18
7/20
7/21
7/25
7/27
8/01
8/03
8/05
8/14
8/22
8/24
8/29
8/30
8/31
9/06
9/08
Tide
LWS
LWS
HWS
LWS
LWS
HWS
HWS
HWS
*
HWS
HWS
LWS
Start
Time
1125
1245
1100
0855
1145
0830
1035
1130
1055
0910
1245
0930
End
Time
1700
1710
1505
1410
1610
1301
1540
1535
1512
1313
1700
1335
Remarks
Rain - .24"
Rain - .59"
Rain - .30"
Rain - 1.08"
Rain - .33"
Rain - 1.20"
Rain - 1.23". Fish kill
between Broad Creek and
Piscataway Creek
Rain - .40"
Fish kill between Broad
Creek and Piscataway
Creek
*Missed LWS
-------
Nitrogen Series
TKN
NH,
NOg + N03
Phosphorus Series
Total PCL (filtered and unfiltered)
Inorganic PO. (filtered and unfiltered)
Carbon Series
Total C
Total Organic C
Biological
Chlorophyll a_
Phytoplankton Counts & Identification
Physical
Temperature
Turbidity
Secchi Disc
Other Chemicals
PH
BOD5
BOD°ultimate
DO
Salinity
Selected Herbicides
Atrazine
Simazine
B. STP Effluent Monitoring
A 24 hour composite effluent sample was obtained from
each of the major wastewater treatment plants (collected by plant
operators) in the WMA during the same days that the slack water
boat runs were being performed. These samples were preserved on
ice and returned to the AFO laboratory for analyses. The
8
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parameters that were analyzed included the nitrogen, phosphorus, and
carbon series (as contained in the aforementioned parameter list)
along with BOD5 and BODult on a once-per-week basis. In addition,
herbicide analyses were completed on one occasion. The following
is a list of the facilities that were sampled during this study:
Arlington Fairfax Co. - Pohick Creek
Alexandria Fairfax Co. - Dogue Creek
Blue Plains Fairfax Co. - Hunting Creek
Piscataway Fairfax Co. - Westgate Creek
At the time these STP samples were collected, AFO
personnel obtained a representative flow measurement in order that
mass loading rates could be computed.
C. Special Studies
Several special studies were incorporated in this monitor-
ing program to address the eutrophication state of the Potomac and
its relationship to the prevailing DO values that were being
measured. Much of the design and methodology employed in these
special studies was for the purpose of better defining various
model inputs, as required by its representation of the DO budget.
Practically all of these studies were performed before, in the
Potomac, with a high degree of success.
1. Algal Elemental Composition Analysis
Concentrated samples of the algal cells were collected
at different times, and at different locations in order to determine
the relative quantities of carbon, nitrogen, and phosphorus actually
contained within the cellular material. This information would
-------
have value in ascertaining the nutritional requirements of the algae,
and in interpreting whether or not a nutrient limited situation existed.
2. Bioassay Experiments
Dr. George Fitzgerald, University of Wisconsin, developed
several algal bioassay procedures for demonstrating whether the
environment has supplied limited or surplus quantities of nutrients.
These tests rely on in-situ algae but can be performed in a labora-
tory by measuring surplus phosphorus uptake, the enzyme alkaline
phosphatase, and the ammonia absorption potential under dark condi-
tions. The alga] elemental composition analysis and Dr. Fitzgerald's
bioassay experiments are very complementary in assessing the impact
of nutrients on algal growth.
a. Light and Dark Bottle Studies
Both clear and opaque bottles were submerged at two
different depths (in and below the euphotic zone) and at several
different locations within the algal bloom for a period of 4-6
hours. The differences in the oxygen content of the bottles
can be used to estimate the effects of algal photosynthesis and
respiration. If one knows the ambient chlorophyll concentrations,
these P and R rates can be expressed very conveniently on a per ug
chlorophyll basis.
4. Benthic Oxygen Demand Studies
AFO had previously designed and utilized a benthic
respirometer that could be applied in estuarine environments, so long
as the water depths did not exceed 15-20 feet. This respirometer
was "planted" at several locations in the Potomac Estuary for
10
-------
at least one hour, and periodic DO readings within the
chamber were obtained. The magnitude of the DO variations as a
function of time constitutes an indication of the benthic oxygen
demand rate. One inherent assumption of this procedure is that
the benthic rate proceeds much quicker than the rate of bacterial
respiration within the water column.
5. Long Term BOD/Nitrification Rate Study
Since the characteristics of the treated wastewater
being discharged to the Potomac Estuary have changed significantly
during the past few years (particularly in the case of Blue Plains),
it was believed that previous estimates of both the carbonaceous
and nitrogenous oxidation rates may no longer be valid; therefore,
long term (i.e. 20 days) incubated bottle tests in the laboratory
were performed on a weekly basis using river samples, STP effluent
samples, and samples of the water entering the estuary at Chain
Bridge. An adequate number of DO measurements were obtained from
both inhibited and noninhibited samples to distinguish the individual
reaction rates and ultimate BOD values.
6. Diurnal Transect Sampling
Three stations were selected for cross-sectional (transect)
sampling at hourly intervals, for a total period of 24 hours. Data
of this nature is invaluable for assessing the impact of algae on
DO concentrations throughout the water column. However, since
this diurnal sampling was conducted at a fixed point, the tidal
effects had to be accounted for.
7. Drogue Studies
In order to obtain additional data related to a senri-
11
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diurnal DO cycle, but without having to consider the troublesome
tidal effects, two special studies were performed wherein a
floating drogue identifying a parcel of water was followed. Hourly
surface sampling was conducted while following the drogue with
samples being analyzed for DO and Chlorophyll.
It should be noted that separate reports, documenting
the special laboratory studies relating to algae and oxidation
rates, have been prepared and published by AFO.*
*Algal Nutrient Studies in the Potomac Estuary, Joseph Lee Slayton
& E. R. Trovato
Carbonaceous and Nitrogenous Demand Studies in the Potomac Estuary,
Joseph Lee Slayton & E. R. Trovato
12
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Chapter III
FINDINGS AND CONCLUSIONS
A. General
1. The 1977 Potomac Estuary Intensive Survey was conducted
during an extremely critical period (July 18 - September 8), as
evidenced by ambient flows and temperatures. River flows after
water supply withdrawals averaged about 1500 cfs, with the range
extending from 940 to 3600 cfs. Water temperatures averaged about
27.6°C. The maximum water temperatures (30-31°C) were as high as
any ever documented in the Estuary.
2. The water clarity of the Potomac Estuary was quite
low, as usual, particularly in the middle reach, which supports
the major algal blooms. Typical Secchi Disk readings were about
20-24 inches. Minimum values (during large algal blooms) ranged
between 7-12 inches, whereas the maximum readings in the extreme
upper reach (above Mains Point) ranged between 30-35 inches. (See
Figure 1.) Turbidity levels followed a similar pattern with respect
to water clarity.
3. An effort was made to identify rapid temporal changes
in the water quality of the Estuary based on the data collected
during slack water runs, and to relate changes to the occurrence
of storm events. No consistent pattern between these significant
changes (of which there were several for DO, BOD, and TP04) and
preceeding climatological conditions could be discerned. Even
Secchi Disk and turbidity readings could not be closely associated
13
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Figure 1
SECCHI DISK VS. CHLOROPHYLL a
POTOMAC ESTUARY - PISCATAWAY CR. TO POSSUM PT.
(1977 DATA)
38 -
36
34
32
30
28
26
24
22
20
18
16
14
12
10
8
6
4
2
J I
0 20 40 60
80 100 120 140 160 180 200 220 240 260 280
Chlorophyll J.-Jig/1
14
-------
with particular storm events. This is not intended to imply that
storm water and/or combined sewer overflows do not adversely affect
the Estuary, but that these effects may be masked by the various
"in-stream" reactions and transport processes taking place, or
possibly, that the sampling did not occur at the most opportune
time.
4. Numerous regression/correlation analyses were per-
formed using data (see Table A-l) for each of the major para-
meters monitored during this study. Those which yielded statistically
significant results are shown below:
Y (dependent) X (independent) r
.73
.58
.62
.66
.76
.68
.58
.54
.55
.51
1. Minimum DO concentrations measured during the twelve
slack water runs varied between 2-3 mg/1. (See Figure A-l.) These
low DO levels normally occurred in the immediate vicinity of the Blue
Plains STP. The most critical DO profile was observed on September 8.
(See Figure 2) ,_
a) BOD5
b) Chloro
c) Chloro
d) Chloro
e) Pi
f) NH3
g) N02 + N03
h) Secchi Disk
i) BOD5
j) Secchi Disk
B. Dissolved
TKN
BOD5
TP04
PH
TP04
TKN
TKN
Chloro
TP04
Turbidity
Oxygen
-------
Figure 2
DO PROFILE
POTOMAC ESTUARY
SEPT. 8, 1977
Temp = 27°C
Flow = 1100 cfs
8
10
20 30 40
Miles Below Chain Br.
16
50
60
70
-------
2. Based upon a statistical analysis of intensive type
data collected in the Potomac Estuary during 1965, 1968, 1969,
and 1970, as well as the 1977 data, it can be concluded that DO
concentrations in the critical reach downstream of Blue Plains
have, in fact, improved with time. While difficult to quantitate
because of data anomalies and limitations, it appears that on the
average, DO levels have increased by about 1.0-2.0 mg/1. All of
this data was collected at surface stations having similar algal
bloom intensities, and was taken during low flow and high tempera-
ture conditions, making the data as comparable as possible.
3. A series of light and dark bottle DO analyses were
performed at depths of 1 foot and 6 feet between Broad Creek and
Indian Head. (See Table 3.) The purpose of this special study
was to estimate representative rates of algal photosynthesis and
respiration. Although a considerable amount of variability occurred,
the data was averaged and the following rates resulted:
P - 0.0140 mg 02/ug Chloro/hr
R - 0.0015*mg 02/ug Chloro/hr
*It was estimated that about 25% of this total respira-
tion rate was attributable to bacterial respiration, producing a
net algal respiration rate of 0.0011 mg 02/ug Chloro/hr.
These rates, it should be noted, compared quite well
with the original values presented in Technical Report 35 and used
in the Dynamic Estuary Model (P = 0.012 and R = 0.0008 mg 02/ug
Chloro/hr) along with a euphotic depth of 2.0 feet.
17
-------
Table 3
ee ,- i
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O^5 O QS
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O O O O
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00
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0.35
0.36
in vo o cn ro
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i OOOO OOO
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to
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r CSJ
n ro
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r-in co ro in «» o co o CM co cot)-to en 4-csj *.
- o
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CO
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8
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C -M-r
O
-------
4. The oxygen production rate observed on August 16
between 0600 hours and 1200 hours was +0.0020 mg 02/ug Chloro/hr.
(See item 7) The results of a light/dark bottle study performed
during this time period within the same reach of the Potomac
Estuary was used for comoarison purposes. Assuming a water depth
of 15 feet and a euphotic zone of 2.0 feet, the P and R rates (0.014
and 0.0015 mg 02/ug Chloro/hr) translate to a net oxygen production
rate of +0.0004 mg Og/ug Chloro/hr. Assuming a water depth of
25 feet and a euphotic zone of 6.0 feet, the same P and R rates
translate to a net oxygen production rate of +0.0019 mg 02/ug
Chloro hr, which compares very favorably with the observed produc-
tion rate. (See Table 4)
5. An oxygen balance was developed utilizing the average
P and R rates obtained from the light and dark bottle studies. If
a euphotic zone of 2.0 feet is assumed, a zero net production of
oxygen is expected to occur when the water depth is about 13 feet.
Greater water depths will produce a net depletion of oxygen, whereas,
lesser water depths will produce a net addition of oxygen. The
actual quantities of oxygen added or consumed will, however, be
a function of the chlorophyll level. If a euphotic zone of 4.0
feet is assumed, and if it is further assumed that the same P rate
applies, there will be a net production of oxygen even when the
water depths are 25 feet. (See Table 5)
6. Seven measurements of the sediment oxygen demand
rate were made using a specially designed benthic respirometer.
The results are presented below:
19
-------
Table 4
ANALYSIS OF DIURNAL DO VARIABILITY
POTOMAC ESTUARY - AUGUST 16. 1977
(BROAD CREEK AREA)
Observed Increase in DO:
Time = 0600 - 1200 + .0020 ^/^ Ch1°r°/hr
Time - 1200 - 1700 + .0075 2/ Chl°r°/hr
Estimated Increase in DO Based on P&R Data:
Productivity Results (8/16/77)
P = 0.014 mg 02/yg chloro/hr
R = 0.0015 mg 02/ chloro/hr
Assumptions_fl_ (used in Model)
Water Depth « 15 ft
Euphotic Zone = 2 ft
.014 * yf - .0015 = +.0004 mg °2/Mg ch1oro/hr
Assumptions #2
Water Depth = 25 ft
Euphotic Zone = 6 ft
.014 * - .0015 = .0019 mg °2/yg chloro
/hr
20
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TABLE 5
OXYGEN PRODUCTION-RESPIRATION BALANCE
POTOMAC ESTUARY
P =
Depth
(ft.)
5
10
15
20
25
5
10
15
20
25
5
10
15
20
25
CHLORO A
0.014 MG 0?/U9 CHLORO/HR.
Increase in 02 Over
Water Column Due to
Photosynthesis for
12 Hours/Day
Euphotic Zone
6.72
3.36
2.24
1.68
1.34
Euphotic Zone
10.08
5.04
3.36
2.52
2.02
Euphotic Zone
13.44
6.72
4.48
3.36
2.68
= 100 yg/1
R = 0.0011 MG
Decrease in 02 Over
Water Column Due to
Respiration for
24 Hours /Day
= 2.0'
2.64
2.64
2.64
2.64
2.64
= 3.0'
2.64
2.64
2.64
2.64
2.64
= 4.0'
2.64
2.64
2.64
2.64
2.64
02/yq CHLORO/HR.
Net
(ing/ 1 /day)
4.08
0.72
-0.40
-0.96
-1.30
7.44
2.40
0.72
-0.12
-0.62
10.80
4.08
1.84
0.72
0.04
21
-------
Station
Key Bridge -
VA Shore
Hains Point
Bellevue -
VA Side
% mile below Wood-
row Wilson Bridge
MD Side
Rosier Bluff -
MD Shore
Fort Washington -
Mid River
Dogue Creek -
MD Side
Rate
(gr/m2/day)
3.5
2.1
3.6
3.1
Remarks
1.4
1.5
5.3
Unrepresentative - main channel
of river (almost entire width)
contained a hard bottom.
Representative.
Soft, muddy bottom - probably
representative.
Soft bottom but unrepresentative
- bottom was hard along MD side
of shipping channel from Woodrow
Wilson Bridge to near Goose
Island.
Hard bottom with clay and
gravel - representative.
Soft bottom - representative.
Soft bottom - representative.
7. Two attempts were made to track and monitor a discrete
parcel of water in the Upper Potomac Estuary between Rosier Bluff
and Piscataway Creek over a semi-diurnal period extending from
0600 hours to about 1700 hours. A floating drogue was used for
this purpose. During both occasions (August 16 and 30), tidal
conditions, weather conditions, flows, and water temperatures were
very similar.
On August 16, the DO concentration (surface) was 1.5
mg/1 at 0600 hours and increased to about 5.5 mg/1 by 1700 hours.
(See Figure 3.) The ambient chlorophyll concentration was 80
ug/1. Computed net rates of oxygen production were 0.0020 mg Op/
ug Chloro/hr between 0600 and 1200 hours and 0.0075 mg 02/ug Chloro/
hr between 1200 and 1700 hours.
22
-------
Figure 3
f
§
SMI
a
LU
< =>
t °
< O
a oc
O * K
0 * £
> Ut i-
ac UJ .
< oc CD
3 O *-
ts
o
s
o
&*.
SAAH
i
I
I
Hi
o
§
1
O
f
S
§
Ul
si
m
oc
UJ
CO
O
oc
o
O
»
x:
Q
L/SIAI
23
-------
Figure 4
SMI
00
8
(A
Ul
3
O
<
5
o
o
c
=
CO
IS
o *
2
w
o
a.
OC
UJ
55
o
oc
8 3
i-S
*0
in
I
o
o
01
a.
~fc
O
M
SMH
01
00
c a
° E
<0
L/BIAI
24
-------
On August 30, the DO concentration (surface) varied
from 3.0 mg/1 at 0600 hours, to 11 mg/1 at 1700 hours. (See
Figure 4.) This variation translated to a net oxygen production
rate of 0.0049 mg 02/ug Chloro/hr. The ambient chlorophyll con-
centration was 135 ug/1, and the weather was again mostly sunny
and hot.
8. Diurnal (24 hour) transect sampling was performed at
three stations during the week of August 8. These stations were
Mains Point, Woodrow Wilson Bridge, and Fort Washington. The
comments relating to the observed data at each station, followed
by a general conclusions statement, based upon a detailed interpre-
tation of this data, are given below:
a) Hains Point data (surface and transect mean) showed
a classical diurnal DO pattern. (See Figures 5 and 6 and Table 6.)
The total variability of the surface data was about 4.5 mg/1 (2.5
- 7.0 mg/1), whereas the transect mean data experienced a total
variability of about 3 mg/1 (3.5 - 6.5 mg/1). Variations at the
bottom were about the same as the surface, but not in phase. The
mean bottom DO was 3.9 mg/1. The average chlorophyll level was
65 ug/1.
b) Neither the mean transect data, nor the bottom
data collected at the Woodrow Wilson Bridge demonstrated a classical
diurnal DO pattern, although both showed substantial variability
(2-7 mg/1 and 1 - 4 mg/1, respectively). (See Figures 7 and 8
and Table 7.) The surface data, on the other hand, did demonstrate
such a pattern, with DO concentrations varying from about 8 mg/1
25
-------
Figure 5
DIURNAL TRANSECT DATA
POTOMAC ESTUARY @ HAINS PT.
AUGUST 8-9, 1977
Transect
Range
. Transect
Mean
A Mid Channel, Surface
ADO * 3Mg/1
T Chloro a
TPO>i
Ebb
Ebb
12 I 234 567 89 10 II 13 I 2 3 4 5 6 7 8 9 10 11 12
8/8 Hours 8/9
26
-------
Figure 6
t
in
o
C
o
OQ
CD
in
n
CM
CT)
oo
oo
r-
CD
- oa
27
-------
Table 6
COMPARISON OF SURFACE AND BOTTOM DO
Date Time
8/08 1200
1300
1400
1500
1600
1700
1800
1900
2100
2200
2300
2400
8/09 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
POTOMAC ESTUARY - 1977
HAINS POINT
Surface
Chloro DO
(yg/l) Tide (mg/1)
60 | 3.6
§ 3'7
80 I 5.1
1 1
u_
60
>
85
4.0
7.2
7.1
7.3
S 6.4
70 £ 6.4
50
45
3.8
6.5
5.1
4.5
80 "g 4.1
o
C 4.0
65
80
2.9
2.7
2.7
3.8
75 ^ 4.3
f~i
^ 3.9
45
'
1 4.3
* 4.5
ADO* 4.5
Avg. 4.7
Bottom
DO Depth
(mg/1 ) (feet)
2.5 30
4.8
2.0
1.9
1.5
1.9
2.8
4.6
6.5
6.0
6.8
5.6
5.1
4.0
3.4
3.0
3.0
2.9
3.6
3.8
3.8
4.9
4.6 >'
4.5
3.9
28
-------
Figure 7
DIURNAL TRANSECT DATA
POTOMAC ESTUARY (o^WOODROW WILSON BR.
AUGUST 9-10, 1977
DO
Transect
_[ Range
0 Transect
Mean
A Mid Channel, Surface
ADO = 5 Mg/1
I2 I 2 3 4 5 6 7 8 9 10 II I2 I 2 3 4 5 6 7 8 9 10 II 12
I
-------
Figure 8
DIURNAL DO DATA
WOODROW WILSON BR.
Tidal & Diurnal Effects
in Harmony
Opposing Tidal &
Diurnal Effects
Surface
8
Smooth Approximation
Bottom
Daylight
Darkness
Daylight
11 12 13 14 15 16 17 18 19 20 21 22 23 24 1 2 34 5 6 78 9 10 11 12
Flood I Ebb I Flood I Ebb
30
-------
Table 7
COMPARISON OF SURFACE AND BOTTOM DO
Date Time
8/09 1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
8/10 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
POTOMAC ESTUARY - 1977
WOODROW WILSON BRIDGE
Surface
Chloro DO
(ug/1) Tide (mg/1)
60 t 4.7
1 5.5
80 1 6.9
^ 7.7
75
>
130
90
.c
.c
LL.
80
70
>
i
9.2
f 5.8
K 6.8
8.3
6.7
6.0
5.5
4.9
5.0
t
3.8
95 o 3.0
o
[I 1.7
100
90
/
80
-C
j£
U
45
>
2.0
2.4
2.4
2.5
1.8
] 2.8
0.8
3.7
ADO* 6.0
Avg. 4.5
31
Bottom
DO Depth
(mg/1 ) (feet)
1.9 15
1.3
1.7
3.4
1.1
3.8
3.0
2.2
3.0
6.5
2.1
1.1
2.3
2.0
2.5
2.4
2.7
4.0
3.3
2.8
2.2
1.5
1.0
1.0 ^
2.5
2.5
-------
Figure 9
DIURNAL TRANSECT DATA
POTOMAC ESTUARY (a) FORT WASHINGTON
AUGUST 10-11, 1977
13.0 12'4 12.7
10
8
40.-
20
1.2
1.0
.8
.6
S
T
O
R
M
Transect
J_ Range
9 Transect
Mean
A Mid Channel, Surface
ADO = 4 Mg/1
Chioro a
TPO,,
Flood
Ebb
Flood
Ebb
I 2 3 4 5 6 7 a 9 10 II 12 I 2 3 4 5 6 7 8 9 10 II 12
8/10 Hours 8/11
32
-------
Figure 10
DIURNAL DO DATA
FORT WASHINGTON
Tidal & Diurnal Effects
in Harmony
Opposing Tidal &
Diurnal Effects
Surface
Smooth Approximation
o
a
Bottom
Daylight
Darkness
Daylight
11 12 13 14 15 16 17 18 19 20 21 22 23 24 1 2 3 4 5 6 7 8 9 10 11 12
Flood | Ebb | Flood | Ebb
33
-------
TABLE 8
COMPARISON OF SURFACE AND BOTTOM DO
Date Time
8/10 1200
1300
1400
1500
1600
1700
1800
1900
2200
2300
2400
8/11 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
POTOMAC ESTUARY - 1977
FORT WASHINGTON
Surface
Chloro DO
(wg/l) Tide (mg/1)
60 6.3
>
45
5.6
7.6
-a
§ 8.0
60 C 7.6
70
/
60
7.1
r 8.5
8.8
5.2
-Q c r
.a 0.5
1 1 i
55
>
/
45
5.0
( 5.5
5.5
-o 6.6
o
60 ° 3.5
1 1
50
-
45
6.1
5.8
7.1
4.9
5.3
-Q
40 £ 4.5
[ 3.8
Bottom
DO Depth
(mg/1) (feet)
2.4 45
3.2
3.2
3.1
4.1
5.8
3.8
4.2 1
2.9 30
3.5 45
3.6
3.8
3.9
3.3
4.2
4.8
5.2
5.0
4.5
4.1
3.8
4.3
8/30
0600
BROAD CREEK
120
ADO-
Avg.
34
3.1
4.0
6.0
4.0
2.0
4.0
20
-------
in late afternoon to about 2 mg/1 just before dawn. The mean sur-
face DO was 4.5 mg/1, and the mean bottom DO was 2.5 mg/1. The
average chlorophyll level was 80 ug/1.
c) In the case of Fort Washington, a classical
diurnal DO pattern could not be discerned in the transect mean
surface, or bottom data. (See Figures 9 and 10 and Table 8.)
The former exhibited a total variability ranging between 4-8 mg/1,
and the latter a range from 2.5-5 mg/1. The variability pattern
of both the surface and bottom data were quite similar. The mean
surface DO was 6.0 mg/1, and the mean bottom DO was 4.0 mg/1. The
average chlorophyll level was 55 ug/1.
It is important to recognize that two separate phenomena
are the major factors influencing the DO concentrations described
above: tidal action, and the algal photosynthesis/respiration cycle;
moreover, these processes, at certain times, will work in harmony
(i.e. be complementary), while at other times, they will be opposing.
An attempt was made to at least discern, if not quantitate, their
individual effects. (See Table 9.) Examination of longitudinal
DO gradients at the surface during slack water runs, and a comparison
of the observed DO variability at both surface and bottom waters (in
light of what was considered to be typical tidal variations), leads
to the conclusion that at the first two stations (1) algae produce
a large diurnal cycle in surface waters which exceeds the local
tidally influenced DO variations, and (2) this diurnal cycle is
undetectable in bottom waters where the tidal influence alone
accounts for practically all of the variability. It can be inferred
35
-------
TABLE 9
ANALYSIS OF DIURNAL DO DATA
POTOMAC ESTUARY
Station
Mains Point
Transect Mean
Surface
Bottom
Woodrow Wilson Bridge
Surface
Bottom
Fort Washington
Surface
Bottom
Rosier Bluff -
Swan Creek
Surface
Rosier Bluff -
Piscataway Creek
Surface
Summary
Chloro
(ug/1)
65
65
65
80
80
55
55
80
ADO
(mg/1)
3.0
4.5
4.5
6.0
2.5
4.0
2.0
Remarks
4.0
Algal influenced,
Algal influenced.
Tidal influenced,
Algal influenced.
Tidal influenced.
Algal influenced,
Random variation.
Algal influenced.
135 8.0 Algal influenced.
60-135 4-8
36
-------
that the vertical mixing time is of sufficient length to either
dampen out the diurnal cycle entirely, or to transmit it out of
phase with the surface at a decreased magnitude. At the third
station, it appears that tidal action constitutes the dominating
force, with respect to diurnal DO fluctuations.
C. Algae
1. Chlorophyll levels were highly variable, both over
time and space. Maximum concentrations of about 300 ug/1 were
recorded during one week in August between Gunston Cove and Indian
Head. Average values in the critical reach (between Dogue Creek
and Deep Point), were about 150 ug/1, and minimum values were less
than 100 ug/1. (See Figure A-2.)
2. Algal mats, floating on the surface of the Potomac
Estuary, were never observed during the course of this study, as
they were during the late 1960's; however, the greenish tint was
present in the high bloom areas extending from about the Woodrow
Wilson Bridge to Sandy Point. The indigenous forms of freshwater
algae this past summer appeared to be almost microscopic in size,
and well dispersed in the water column.
3. A bloom of marine algae, which imparted a "mahogany
tide" condition, was observed during the first week of the study
in the higher saline waters near the Route 301 Bridge. Chlorophyll
levels within the bloom peaked at about 400 ug/1.
4. Phytoplankton counts and species identification were
performed. During the early phase of the survey, when chlorophyll
levels were about 100 ug/1 or less, there appeared to be some
37
-------
diversity in algal populations, as both green and blue-green
varieties were observed; however, as the study progressed, and
chlorophyll levels attained their peak values, the blue-green algae
Oscillatoria became the dominant form, almost to the complete exclu-
sion of the other forms observed earlier. This behavior could
possibly be explained by the fact that Oscillatoria grow in long
strings, making it difficult for zooplankton to feed on them.
Assuming that other forms of algae are depleted due to continual
grazing by zooplankton, Oscillatoria would no longer have to compete
for the available nutrients. This would permit them to proliferate
greatly. Actual cell counts at this time were in the range of
70,000 to 90,000 per ml. Anacystis cyanea, the dominant form of
algae inhabiting the Potomac Estuary during the 1960's, was not
present to any noticeable degree.
5. An interesting situation, which warranted special atten-
tion, occurred between August 24, and September 8, when algal levels
declined drastically (as evidenced by a chlorophyll reduction of 200
ug/1). During this time period, data collected from Dogue Creek
to Deep Point showed that BOD5 concentrations increased 5-6 mg/1,
while DO concentrations decreased about 5 mg/1 (10 to 5 mg/1),
allowing for the fact that Blue Plains was exerting a greater than
usual influence upon DO on September 8,
(See Figure 11.) The effects of massive algal death and decomposition
on the DO budget may be quite significant, as indicated by this
data.
38
-------
Figure 11
8
cB
0
o
03
I
O
a
a
o
CO
10
9
8
7
6
5
4
3
2
1
0
10
9
8
7
6
5
4
3
2
1
CHLORO a, BOD, & DO TIME PLOTS
POTOMAC ESTUARY - 1977
Dogue Creek Hallowing Point
V
\
A Chloro 3 200 pig/11 \
A B0D 5 6 Mg/1 | \
A 00 s*5Mq/1 1 *
Indian Head Deep Point
pO...
V/^
.' \?s
A Chloro = 200/zg/1 |
A B0D = 5 Mg/1 f
s»5Mg/1 |
1 I i 1 1 t
300
200
100
5
o
loi
I
-------
6. Two separate and independent methods were used to esti-
mate a relationship among nitrogen and phosphorus utilization (in-
organic forms), algal content of carbon nitrogen and phosphorus
(organic forms), and chlorophyll a_. One method was based on an
analysis of the field data which emphasized spatial differences in
nutrient levels, while the other was based on an actual composition
analysis of the algal cells in the laboratory. The conclusions drawn
were as follows:
a) The mean ratio between organic nitrogen and chloro-
phyll indicated by the field data was 0.0028 mg N/ug Chloro, with a
standard deviation of 0.0008 mg N/ug Chloro. This ratio becomes
0.0056 mg N/ug Chloro if a 50% nitrogen recovery rate is assumed
for the analytical procedure followed in the laboratory. The mean
ratio between organic phosphorus and chlorophyll, also obtained from
field data, was 0.0019 mg PO./ug Chloro, with a standard deviation
of 0.0004 mg PO^/ug Chloro. (See Table 10 and Figures 12 and 13.)
b) Compositing selected inorganic nitrogen and phosphorus
field data as a function of chlorophyll, yielded typical ratios of
0.01 mg N/ug Chloro, and 0.0011 mg PQJug Chloro, respectively.
(See Table 11 and Figures 12 and 13.)
c) Ten different laboratory analyses of the algal cells
for elemental composition provided a range of data as shown below:
OrgC: Chloro - 0.012 - 0.037
OrgN: Chloro - 0.003 - 0.013
- 0.007
Org P: Chloro - 0.001 - 0.003
(average = 0.002
40
-------
RELATIONSHIP BETWEEN
Date
7/18
7/20
7/25
7/27
8/03
8/22
8'24
8/29
8/31
9/06
3/08
Station
7
8
10
8A
9
10
10B
11
6
7
5A
6
7
8
8A
9
10
10B
6
7
8
8A
9
10
10B
11
12
5A
6
7
8
8A
9
10
108
11
12
13
6
7
8
8A
9
10
10B
11
8A
9
10
10B
11
12
13
14
10
10B
11
*Assume 50% "ecovery
ORGANIC
N & P AND
CHLORO A
POTOMAC ESTUARY
Chloro
(mg/1)
147
132
104
110
123
118
129
120
112
104
124
104
130
169
172
276
306
264
284
198
139
147
261
306
303
312
228
168
118
122
129
152
180
190
261
300
294
200
158
111
111
134
176
188
172
195
171
148
104
146
180
130
180
186
146
254
188
100
130
120
A 1
Org *
N
(mg/1 )
0.83
0.44
0.32
0.25
0.30
0.28
0.35
0.23
0.29
0.33
0.24
0.28
0.41
0.56
0.79
1.10
0.89
0.87
0.54
0.27
0.66
0.70
0.99
1.09
1.05
0.81
0.57
0.52
0.46
0.61
0.74
0.85
0.90
0.77
0.55
0.28
0.24
0.33
0.23
0.40
0.40
0.56
0.40
0.62
0.43
0.38
0.45
0.23
0.37
0.30
0.25
Org
P04
("3/1 ?
.18
.16
.23
.25
.28
.22
.25
.29
.21
.27
.29
.30
.29
.29
.30
.42
.46
.44
.42
.35
.30
.32
.39
.41
.50
.43
.35
.30
.19
.25
.23
.31
.30
.41
.49
.44
.50
--
.25
.21
.24
.32
.37
.37
.42
.40
.33
--
.19
.22
.30
.20
.34
.33
.28
.30
--
.21
.28
.24
Max
Mm
Mean
Std Dev
Ma N*
Mg Chloi
.0056
.0033
.0029
.0020
.0025
.0022
.0029
.0021
.0028
.0027
.0023
.0022
.0024
.0033
.0029
.0036
.0034
.0031
.0027
.0019
.0045
.0027
.0032
.0036
.0034
.0036
.0034
.0044
.0030
.0034
.0039
.0033
.0030
.0026
.0028
.0018
.0022
.0030
.0017
.0023
.0021
.0033
.0021
.0036
.0029
.0026
.0025
.0018
.0021
.0016
.0010
.0056
.0010
.0028
.0008
.0012
.0012
.0022
.0023
.0023
.0019
.0019
.0024
.0019
.0026
.0023
.0029
.0022
.0017
.0017
.0015
.0015
.0017
.0015
.0018
.0022
.0022
.0015
.0013
.0017
.0014
.0015
.0018
.0016
.0020
.0018
.0020
.0017
.0022
.0019
.0015
.0017
.0016
.0019
.0022
.0024
.0020
.0020
.0024
.0021
.0019
.0018
.0015
.0017
.0015
.0019
.0018
.0019
.0012
.0021
.0022
.0020
.0029
.0012
.0019
.0004
-------
TABLE 11
RELATIONSHIP BETWEEN
INORGANIC N & P AND CHLORO
Date
7/20
7/27
8/01
8/03
8/22
8/24
8/29
8/31
9/06
Reach
(Stations)
6-11
5- 9
7-11
5- 8
5-8A
8A-11
5- 7
7-10B
6- 8
4- 6
5-1 OB
5-10B
4- 7
5A-10B
5A- 8
5-10B
3- 7
5-11
POTOMAC ESTUARY
Chloro
(mg/1)
90
90
120
50
50
70
50
100
100
90
180
200
80
150
60
100
60
100
A
AN
(mg/D
.9
1.0
.8
.8
.5
1.0
1.0
1.8
1.9
1.6
1.7
1.7
AP
(mg/D
.10
.04
.06
.06
.05
.06
.05
.08
42
-------
-------
Figure 13
PHOSPHORUS CHLOROPHYLL RELATIONSHIP
POTOMAC ESTUARY - 1977
Field Data
OrgP
x Lab Data
O Field Data - Inorg P
0 TR#35
100
Chloro a_-
44
-------
For the sake of comparison, the average values of
these ratios, which were contained in Technical Report 35 and were
based on laboratory findings, are given as follows:
0.045
0.010
mg Chloro
mg N
mg Chloro
n 003 mg P0d
u>UUi:i ug ChToro
d) The variability encountered in the 1977 phosphorus-
chlorophyll ratio data, depending upon whether the organic or
inorganic fraction is used, may be attributable to either analytical
inaccuracies or, possibly, some form of recycling process.
7. Algal bioassays that were developed by Dr. George
Fitzgerald, University of Wisconsin, were run on Potomac Estuary
samples. Phosphorus related bioassays (i.e. luxury PO^ uptake
and alkaline phosphatase) indicated that this nutrient was not rate
limiting algal growth, but rather, that a surplus might have existed,
The data obtained from the nitrogen related bioassay (i.e. ammonium
uptake rates in the dark) was somewhat inconclusive, but did indi-
cate that inorganic nitrogen was approaching a limiting situation
during the latter phase of the study.
8. A laboratory experiment (acetylene reduction) was
performed near the end of the survey to determine if the blue-green
algae in the Potomac were fixing atmospheric nitrogen (this was a
definite possibility, since inorganic nitrogen concentrations in the
water column were almost non-existent); the results of the test,
however, were negative.
45
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D. Nutrients
1. Maximum NhU concentrations generally varied from about
1.0 to 1.5 mg/1, and invariably occurred in the immediate vicinity
of Blue Plains. (See Figure A-3.) The dramatic decrease in NH3
to virtually undetectable levels, accompanied by a comparable increase
in N02 + N03 over a ten mile stretch of river, indicated that
nitrification was proceeding at a rapid rate because of the high
ambient temperatures.
2. The NOo + NCL nitrogen form peaked in the area of
maximum nitrification (below Blue Plains) at a level between 1.5 -
2.0 mg/1. (See Figure A-4.) Farther downstream, the concentrations
diminished greatly because of algal uptake or other biological
utilization.
3. As expected, significant quantities of both soluble and
particulate forms of organic nitrogen were present in the Upper
Potomac Estuary throughout the study period.
4. Several forms of phosphorus were measured, with the
most notable ones being total phosphorus, and filtered inorganic
(reactive) phosphorus. With the exception of the September 8 run,
TPO^ concentrations were relatively constant in the estuary down-
stream of Blue Plains varying between 0.5 and 0.8 mg/1. (The
latter figure was obtained when a maximum algal bloom was present.)
(See Figure A-5.) The filtered Pi was more variable (0.1 - 0.3 mg/1)
on a spatial basis, but did not behave as expected. Instead of
diminishing to reflect its utilization by phytoplankton, concentra-
tions generally increased in a downstream direction regardless of
46
-------
ambient algal bloom conditions. (See Figure A-6.) Data collected
by the USGS during a similar time period confirmed this distribution
of reactive phosphorus in the Upper Potomac Estuary.
5. Maximum phosphorus concentrations, occurring in the
Upper Potomac Estuary near Blue Plains, showed a substantial decrease
(>50%) in 1977 over previous years, when levels ranging between
1.5 to 3.0 mg/1 were experienced. Inorganic nitrogen, on the other
hand, did not exhibit a well defined trend in either direction
within this same reach.
6. Concentrations of total inorganic carbon generally
varied from about 20-30 mg/1, with no particular spatial or temporal
pattern evident. Even when maximum algal levels were encountered,
inorganic carbon levels persisted above 20 mg/1, leading one to
believe that this nutrient is extremely abundant in the Potomac
Estuary and does not have growth rate limiting consequences.
7. An analysis of the spatial distribution of nutrients
and chlorophyll (i.e. phytoplankton densities) in the Potomac
Estuary, indicates that the inorganic nitrogen may be limiting algal
growth in the area of maximum production (downstream of Hallowing
Point), since concentrations of both NH3 amd N03 become non-detectable
as bloom conditions progress. It is suspected that light may be
the limiting factor in the upper zone (i.e. upstream of Piscataway
Creek), where considerably lower chlorophyll levels are normally
found.
8. There is no indication, based on the observed water
quality monitoring data, that phosphorus is a rate limiting nutrient
47
-------
at the present time. The fact that inorganic (soluble) phosphorus
concentrations actually experienced an increase in areas of algal
bloom production indicates that recycling/regeneration or possible
recruitment from the benthos may be important reactions which should
be further investigated.
E. BOD
1. Maximum BOD5 concentrations in the vicinity of Blue
Plains ranged from about 8-12 mg/1. A BQD5 of 10 mg/1 was also
measured in the area of a peak algae bloom on August 29. (See
Figure A-7.)
2. Long term (e.g. 20 days) inhibited and non-inhibited
BOD analyses were performed on many of the river samples in order to
approximate the first order decay or oxidation rates for both the
carbonaceous and nitrogenous components. The mean rates provided
by this study are as follows:
CBOD - 0.14/day (base e - 20°C) (Std. Dev. = 0.023)
NBOD - 0.14/day (base e - 20°C) (Std. Dev. = 0.053)
3. The CBOD rates were also estimated for the major load
inputs to the estuary. The average value for the wastewater
effluents was 0.17/day (base e - 20°C), and that for the Chain
Bridge station was 0.13/day (base e - 20°C). The standard devia-
tions were 0.046 and 0.026, respectively.
4. A sizeable percentage of the BOD5 measurement for the
wastewater effluents was attributable to the nitrification reaction.
Consequently, the ratios of CBODult/BOD5> and CBODult/CBOD5 were
significantly different. The results of this special long term
48
-------
rate study indicated these ratios to be 1.30 and 1.75, respec-
tively.
F. Estuary Loadings
1. Blue Plains is by far the largest single point source
discharger of oxygen demanding material and nutrients in the Potomac
Estuary. (See Table 12) During the study period, it contributed
an average flow of 276 mgd, and the following average loadings:
% of Total Point Source
Parameter Average Loading Wastewater Load
BOD5 58,000 Ibs/day* 78*
TKN 36,500 Ibs/day 75
NH3 32,500 Ibs/day 76
N02 + N03 250 Ibs/day 14
TP04 12,200 Ibs/day 55
2. For comparison, the average pollutant loadings from
Blue Plains in 1970, based on an average flow of 252 mgd, were
estimated to be as follows:
% of Total Point Source
Parameter Average Loading Wastewater Load
BOD5 104,000 Ibs/day 75
TKN 46,200 Ibs/day 85
N02 + N03 2,000 Ibs/day 55
TP04 52,000 Ibs/day 75
3. The non-tidal portion of the Potomac River continues
to be a significant contributor of BOD and certain nutrients to
the estuary. This is demonstrated by the relatively high average
*0n September 8, 1977, a mechanical breakdown occurred at the Blue
Plains treatment plant, causing a BODc loading of 344,000 Ibs/day.
If this loading were included in the analysis, the average BODc load
would be 82,000 Ibs/day,which constitutes 85% of the total point
source BODr load generated by the Washington Metropolitan Area.
-------
TABLE 12
SUMMARY OF SEWAGE TREATMENT PLANT EFFLUENT DATA
Flow
(mgd)
TC
(mg/D
TOC
(mg/0
TP
(mg/1)
Pi
(nig/I]
TKN
(mg/1;
NO, + NO,
NH-j
(mg/1!
BODr
(ma/1)
BOD
(mg/T)
Turbidity
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
Max.
Mean
Min.
'lax.
Mean
Min.
Max.
Mean
Min.
Max.
1977 POTOMAC INTENSIVE
^
ID
3
a
0
21
11.91
7.50
16.00
43.97
29.15
87.03
12.66
6.72
28.37
2.98
1.96
5.00
2.36
1.72
4.07
6.00
4.01
12.90
4.73
1.74
6.77
4.53
2.33
12.90
6.57
0
17.40
c
o
+J
en
c
£
-------
concentrations of these pollutants measured at the Chain Bridge
station during the study period, as shown in the table below:
Parameter
BOD5
DO
TKN
Org.-N
NH
N0
TP0
Average
Concentration
(mg/1)
2.58
7 41
/ " I
.49
.46
.03
.03
.25
.04
02
* \JL.
32.28
5.43
42.88*
Standard
Deviation
(mg/1 )
.77
4fi
. *TU
.10
.10
.03
.04
.04
.05
0?
« Uc.
2.60
3.30
23.20*
Average
Loading
(Ibs/day)
2,358
444
415
29
25
230
40
28,533
4,693
41
Inorg. PO.
Filt. Inorg. P04
TC
TOC
Chlorophyll a^
4. Storm sewer and combined sewer contributions from the
WMA were estimated (order .of magnitude type) based upon the best
available information. These loads, along with the two other major
loads to the Potomac Estuary (point source and upper basin inputs),
were translated to a total poundage for the study period and are
summarized and compared in the following table:
51
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Flow q
Volume (ft3)
BODr (Ibs)
Total N (Ibs)
Total P04 (Ibs)
Point Source
2.4 x 109
3.7 x 106
0.8 x 106
1.1 x 106
Upper Basin
6.5 x 109
1.0 x 106
0.1 x 106
0.1 x 106
Urban
2.2 x 109
2.0 x 106
0.3 x 106
0.5 x 106
5. On September 8, the last day of the survey, Blue
Plains was discharging a very poor quality effluent, as evidenced
by a BOD5 concentration of 132 mg/1 (344,160 Ibs/day, loading).
This BODc has since been refuted by Blue Plains personnel, but USGS
field staff sampling the Potomac has corroborated the fact that on
this date, the effluent from Blue Plains was very poor. Its impact
on the receiving water quality was considerable. The BOD concentra-
tions in the estuary near Blue Plains exceeded 11.0 mg/1 on September 8,
the highest value recorded during the survey. More importantly, the
DO concentrations on this date ranged between 1.8 and 4.0 mg/1 over
a 20 mile stretch of estuary from Bellevue to Indian Head. Other
water quality parameters, such as nutrients, were also elevated
during the September 8 run.
G. Herbicides
1. Special analyses for the herbicides atrazine and simazine
were performed on samples collected at approximately every other
station in the Potomac Estuary on July 18, and August 22. These
are widely used herbicides on corn crops, which have been identified
in other areas of the Chesapeake Bay.
52
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a) On July 18, a day following a rainfall event of 0.25
inches, maximum concentrations of both atrazine and simazine occurred
between the Woodrow Wilson Bridge and Dogue Creek. The levels
varied from .84 - 1.15 ug/1 and .49 - .78 ug/1, respectively. The
incoming concentrations at Chain Bridge were .46 ug/1 and .34 ug/1,
respectively.
b) On August 22, following an extended dry period,
atrazine and simazine concentrations were considerably lower in the
estuary: 0.4 - 0.5 ug/1, and 0.3 - 0.4 ug/1, respectively. Again,
maximum levels were recorded in the upper portion of the estuary near
and below Washington. Concentrations at Chain Bridge did not change
radically with atrazine being 0.38 ug/1 and simazine, 0.33 ug/1.
c) Atrazine and simazine were also monitored in the
effluents of the major sewage treatment plants and at Chain Bridge
on July 11. The results are shown in the table below:
Atrazine Simazine
Location (ug/1) (ug/1)
Piscataway STP .75 .38
Arlington STP 1.21 .54
Blue Plains STP 1.72 .55
Alexandria STP 1.08 .52
Westgate STP .26 .28
Hunting Creek STP .70 .10
Dogue Creek STP 1.06 .19
Pohick Creek STP 1.39 .52
Chain Bridge .92 .49
53
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The comparatively high values recorded at Chain
Bridge may have been due to a 0.43 inch rainfall which occurred on
July 9. The reason for the even higher values at most of the sewage
treatment plants has not been adequately determined.
54
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-------
CHAPTER IV
FUTURE STUDY NEEDS
In addition to a continued ambient monitoring program in
the Potomac, forthcoming intensive studies to be conducted by AFO
will include the following elements to rectify present data gaps:
a) Expanded drogue studies to include 24
hour sampling at both surface and bottom.
b) Improved delineation of the BOD load
to include not only the carbonacenous
and nitrogenous components,but the
algal components as well.
c) Use of a photometer/transmissometer to
better define the euphotic zone in the
Upper Potomac Estuary.
d) Further SOD studies to extend the area
of coverage and to obtain a better
resolution of the data.
Another future study need concerns an improved definition
of the phosphorus budget and the role of suspended sediment as a
contributor of and a transport media for different forms of
phosphorus. Other reactions which should be considered and inves-
tigated in more detail as part of the phosphorus budget include
recycling and remineralization, both within the water column as
well as at the water sediment interface. This study, however, is
presently beyond the capabilities of AFO.
55
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-------
APPENDIX
-------
-------
Figure A-l
DO ISOPLETH (Mg/1)
POTOMAC ESTUARY - 1977
_o
"3
m
I
S
55
50
45
40
35
30
25
20
15
10
16 18 202224262830 1 3 5 7 9 11 13151719212325272931 2468
July August Sept.
56
10
-------
Figure A-2
CHLOROPHYLL_a_ ISOPLETH (pg/1)
POTOMAC ESTUARY - 1977
100
16 18 202224262830 1 3 5 7 9 11 13151719212325272931 2 4 6 8 10
August Sept.
57
-------
Figure A-3
NH3ISOPLETH
POTOMAC ESTUARY - 1977
00
.£
£
u
&
I
55
50
45
40
35
30
25
20
15
10 '
5 -
i i i i
i i i i
0
16182022242628301 357 9111315171921232527293124 6 8 10
July August Sept.
58
-------
Figure A-4
N02 + N03ISOPLETH(Mg/1)
POTOMAC ESTUARY - 1977
I
i
' ' i. . ' ' 'IIII
16182022242628301 357 9111315171921232527293124 6 8 10
July August Sept.
59
-------
Figure A-5
TP»ISOPLETH(Mg/1)
POTOMAC ESTUARY - 1977
w
e
ca
Ji
55 r
20
15 -
16182022242628301 357 9111315171921232527293124 6 8 10
July August Sept.
60
-------
Figure A-6
FILTERED Pi »ISOPLETH (Mg/1)
POTOMAC ESTUARY - 1977
55
60
45
40
35
m 30
~S
m
i
25
20
10
i j i i i i i i i i i i i i i i i i i i i i i i i i I
16182022242628301 357 9111315171921232527293124 6 8 10
.AsP04 -»"'V August
61
-------
Figure A-7
BOO ISOPLETH (Mg/1)
POTOMAC ESTUARY - 1977
CO
e
1
u
3
i
5
4 V. _.
16182022242628301 357 9111315171921232527293124 6 8 10
July August Sept.
62
-------
TABLE A-l
Summary pf 1977 Potomac Estuary Data
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