U.S. ENVIRONMENTAL PROTECTION AGENCY 903R77100
Region III
Central Regional Laboratory
839 Bestgate Road
Annapolis, Maryland 21401
SUPPLEMENTAL REPORTS
1975 - 1977
ia,FM»W» -dtfit-
Volume 24
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Table of Contents
Volume 24
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 - July 1977
Statistical Analysis of Dissolved Oxygen Sampling
Procedures by the Annapolis Field Office - July 1976
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
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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
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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
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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 8 .
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
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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
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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 Enforcement
Survey - 1970
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30
31
32
33
34
Appendix
to 1
Appendix
to 2
3
4
VOLUME 11 (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 durirrg 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
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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, Juniata
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
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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
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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
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VOLUME 19 (continued)
Working Documents
Wastewater Inventory - Potomac River Basin -
December 1968
Wastewater Inventory - Upper Potomac River Basin -
October 1968
VOLUME 20
Technical ; Papers:,
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
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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
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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
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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
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CURRENT NUTRIENT ASSESSMENT
UPPER POTOMAC ESTUARY*
Current Assessment Paper No. 1
June 1975
Thomas H. Pheiffer
Annapolis Field Office
Region III
U. S. Environmental Protection Agency
* Presented at the Interstate Commission on the Potomac
River Basin Symposium, "The Biological Resources of
the Potomac Estuary," June 4, 1975, Alexandria, Virginia
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ABSTRACT
In order to assess the current nutrient impact on the upper
Potomac Estuary, 1973-74 data from major wastewater sources were com-
pared to previous data to note possible trends. A comparison of
recent water quality data with 1969-70 data at three control sampling
stations shows reductions of inorganic phosphate in the upper estuary,
particularly at the historical bloom area for blue-green algae. The
absence of massive algal blooms since 1972 is noted, together with
a discussion of the framework necessary to develop the predictive
capability to quantitatively identify the cause-effect relationships
in the estuary.
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Types of Nutrients
Plant growth requires nutrients. Plant physiologists classify
nutrients into two categories. Macro-nutrients are those chemical
elements required by plants in large amounts. The macro-nutrients are
carbon, hydrogen, oxygen, phosphorus, potassium, nitrogen, sulphur,
calcium, iron, and magnesium. Micro-nutrients include molybdenum,
boron, manganese, zinc, and sometimes, even iodine and chlorine.
They are just as essential to plant growth as the macro-nutrients, but,
as their name implies, they are required by plants in minute quantities,
Their abundance in nature relative to plant needs is evidenced by the
lack of case histories on micro-nutrients as rate limiting growth
factors.
Of the various nutrients, carbon, nitrogen, and phosphorus have
received more attention in the field of water pollution biology.
These three elements have life cycles in which they undergo changes
in chemical composition as they interact with various components of
their immediate environment. Concerning the life cycles, only the
phosphorus is not open to the atmosphere for replenishment purposes.
In the case of carbon, a constant diffusion rate from the atmosphere
into the water column exists at normal pH and temperature ranges. In
fact, the oceanic carbonate system is, in most cases, in equilibrium
with the atmospheric Ct^. Changes in the partial pressure of C02 in
the atmosphere or changes in the aquatic carbonate cycle can effect
changes in the rate of C02 dissolution into water bodies.
As with carbon, there exist natural source factors which influence
the abundance of nitrogen in the aquatic environment. The atmosphere
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is composed of approximately 80 percent nitrogen, which is roughly the
equivalent of 148,000 tons of nitrogen in the atmosphere for every acre
of land area [i]. Literature values show nitrogen from rain water and
o
airborne particulate matter contribute 480 Ibs/mi per year [2]. In
addition, atmospheric nitrogen being so inert in the free state allows
certain groups of soil bacteria and blue-green algae to fix nitrogen.
The literature pretty much establishes the fact that certain groups
of blue-green algae can fix nitrogen directly from the atmosphere.
The literature, however, is split on the ability of Microcystis sp. and
Anacystis sp. (blue-green algae) to fix nitrogen [2,3]. These are the
pollution tolerant phytoplankton identified as being prevalent during
massive blooms in the freshwater portion of the Potomac Estuary. The
basic point to be made, is that it is imperative to establish as soon
as possible the nitrogen fixation abilities of Microcystis sp. and
Anacystis sp. in the freshwater estuarine environment of the Potomac.
Phosphorus enters the aquatic environment from the erosion of soils
and from man induced inputs such as human and industrial wastes.
Because of the nature of its sources, it makes sense that phosphorus
can be controlled to the extent that it could be made the rate limiting
nutrient to curb and hopefully reverse an accelerated eutrophic
condition.
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Impact of Nutrients
Let us turn our attention to the impact of nutrients. We can
probably say, in general, that nutrients are present in sufficient
concentration in most water bodies to provide for the needs of aquatic
organisms. In the presence of light, photosynthesis occurs and plant
biomass is created. In a healthy environment the plant biomass is
grazed on by zooplankton, which is followed by an ordered series of
events to complete the food chain.
When there exists an overabundance of nutrients in a system,
massive algal blooms of an undesirable nature can occur. This con-
dition first presented itself in August-September 1959, when blooms of
the nuisance blue-green algae Anacystis sp. were reported in the
Anacostia and Potomac Rivers near Washington. Chlorophyll a_ at Indian
Head and Smith Point for 1965-66 and 1969-70, as shown in Figures 1
and 2, indicate that algae had not only increased in density but became
more persistent over the annual cycle. The figures also show a decrease
in chlorophyll ^concentrations during the 1973-74 sampling cruises.
The exact nature of this decrease has yet to be determined.
When algae is not consumed by higher trophic forms, which is the
apparent case with the blue-greens in the Potomac Estuary, the effects
of massive blooms can be quite devastating. Jaworski, et al. [4],
estimated that the combined ultimate oxygen demand of nitrogen and
carbon resulting from the death of algal cells during intense summer
bloom conditions in the estuary is approximately 490,000 Ibs/day, if
exerted. For comparison purposes, this load would be greater than the
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MAINS POINT
MILES KU3W CHAIN BRIDGE = 760
CHLOROPHYLL a
POTOMAC ESTUARY
UPPER REACH
AUG SEP
FIGURE - I
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SMITH PONT
MUS KLOW CHAM
CHLOROPHYLL a
POTOMAC ESTUARY
MDOU ml LOWER REACH
MJQ. tff. OCT. NOV. OCC
JUNL JLL. AUG.
301 BRIDGE
MLCS KLOW CHAM
MJ& XT. OCT. MCV.
PtCY P«NT
MLES IEUOW CHAH
WOGE > W.20
. 1 JW
*-)-> W)D
MM JUN.
FIGURE -2
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total oxygen demand by all wastewater discharges into the upper estuary.
Other undesirable effects of accelerated eutrophication include decreases
in the dissolved oxygen budget caused by algal respiration, creation of
nuisance and aesthetically objectionable conditions, and possible toxic
effects on other aquatic organisms.
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Major Sources of Nutrients
The major sources of nutrients to the upper Potomac Estuary can
be categorized as follows: wastewater treatment plants within the
Washington Metropolitan Area, contributions from the upper freshwater
basin, and stormwater runoff from the highly urbanized area of
Washington, D.C.
Figures 3 and 4 present wastewater nutrient enrichment trends
and ecological effects on the upper Potomac Estuary. The loadings
represent the major wastewater treatment plant sources within the
Washington Metropolitan Area. With respect to Figure 3, Jaworski,
e_t al_. [4], hypothesized that the nuisance plant conditions did not
develop linearly with an increase in nutrients. Instead, the increase
in nutrients appeared to favor the growth and thus the domination by
a given species. As nutrients increased further, the species in turn
was rapidly replaced by another dominant form. For example, water
chestnut was replaced by water milfoil which in turn was replaced by
blue-green algae.
Figure 4 is a presentation of the current wastewater treatment
plant loadings to the upper estuary. The loadings show a gradual
decrease in total phosphorus (as P) from 24,000 Ibs/day at the end of
1969 to 16,310 Ibs/day as an average for 1974. BOD5 loadings have
shown a downward trend from a high of 154,000 Ibs/day in 1971 to the
current rate of 119,870 Ibs/day (1974). Total nitrogen loadings were
also lower in 1972 and 1973, but showed a slight increase during 1974,
the average being 59,710 Ibs/day.
7
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Since 1972 there has been a noticeable absence of dense blue-green
algal blooms of any duration in the upper estuary. In the historical
bloom area near Indian Head (30.6 miles below Chain Bridge), chloro-
phyll a_ levels were observed in range of 25-70 yg/1 and 40-78 yg/1
during the 1973 and 1974 summer seasons, respectively. (See Figure 1.)
In contrast, during the 1969 and 1970 summer months, chlorophyll a^
approached and on two observed occasions, in July and August 1970,
exceeded 200 yg/1.
It is premature to hypothesize that the absence of massive blooms
is a direct result of reduced wastewater loadings in the Washington
Metropolitan Area. If there are no massive blooms this summer and
in subsequent years, and if wastewater loadings continue to decline,
a more definitive cause-effect relationship would be established between
nutrient concentrations and algal populations. Also, the relative
merit of Hurricane Agnes as a cleansing mechanism must be viewed as a
transient phenomenon. After all, Hurricane Camille provided a flushing
of the estuary in August 1969 which did not appear to significantly
reduce the algal populations. The essence of this brief discussion is,
at this time, we do not know all the causitive agent or agents that
trigger massive blue-green algal blooms in the Potomac Estuary. This
point will be developed later in this paper.
The relative contribution of nutrients to the Potomac Estuary
from its upper basin has been documented by the Annapolis Field Office,
EPA, in Technical Report Nos. 15 and 35 [4,5]. In summary, this
previous work established that during a selected low-flow of 1200 cubic feet
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per second (cfs), at which the loadings will be equaled or exceeded
95 percent of the time, the total phosphorus contribution from the
upper basin is 3.7 percent of the total phosphorus load to the estuary.
In contrast, the load from the wastewater treatment plants in the
Washington Metropolitan Area constitutes 96 percent of the total phos-
phorus load. The disparity in loadings is similar for total nitrogen.
With regard to the upper basin nutrient contributions, Technical
Report 35 [4] concluded that a 50 percent reduction in the phosphorus
load from the upper Potomac River, together with the recommended
phosphorus reductions in the Washington Metropolitan Area, is required
if the recommended phosphorus criteria are to be achieved in the upper
estuary. In order to realize the 50 percent reduction, it was con-
cluded that the wastewater contribution from point sources of 6,100
Ibs/day must be reduced to 700 Ibs/day. Should this recommendation be
implemented, point sources of phosphorus would have to be reduced by
90 percent.
During August 1973, and again on three separate occasions during
the summer of 1974, the Annapolis Field Office carried out intensive
surveys in the upstream reach from Chain Bridge to just above the
confluence of the Monocacy River with the Potomac, a distance of ap-
proximately 38 miles. The purpose of these studies was to assess
current water quality conditions. The revealing finding of the surveys
was the significant biological activity taking place in the reach.
Chlorophyll a^ had not been measured previous to the surveys. During
August 6-9, 1973, chlorophyll a^ levels of 150 yg/1 were observed
between river miles 17 and 26, or the area from Seneca Creek upstream
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to the mouth of Goose Creek. From June 18-20, 1974, chlorophyll averaged
about 60 yg/1 in the same reach, while during the period July 16-18, 1974,
the levels averaged about 40yg/l. On September 3, 1974, a chlorophyll
concentration of 310 yg/1 was observed about one mile above Seneca Creek.
During this observation dramatic decreases in nitrate nitrogen and
inorganic phosphorus were noted suggesting that these compounds were
being utilized by the algae.
A review of earlier chlorophyll a_ data (1966-70) indicates that
upstream algal activity was not occurring to the extent recently ob-
served. For example, just below the fall line at Key Bridge, chlorophyll .a_
levels in 80-90 yg/1 range were recorded in July-August 1973, with a
historically high value of 171 pg/1 observed on September 5, 1974. The
previous levels in this vicinity were around 30 yg/1. This indicates a
carry over or upstream contribution of chlorophyll a^ or algal biomass to
the upper estuary. But, this condition does not persist down the estuary.
The impact of the freshwater algae on estuarine biological communities
has not been evaluated. Extensive analyses of all available upstream
water quality data will be carried out by the Annapolis Field Office in
order to establish any significant changes in upstream loadings as well
as the species identification and significance of the recently observed
algal blooms.
With respect to the impact of nutrients from stormwater runoff
on water quality of the estuary, a few general conclusions can be drawn
at this time. The significance of stormwater nutrients on the eutro-
phication process will depend on the magnitude, intensity, and duration
of the storm event, the time of occurrence of the storm, and whether
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or not the nutrients reach the critical growth zone in a readily
available form. To date, the actual impact of stormwater on water quality
in the estuary has not been evaluated. As part of its NPDES permit for
Blue Plains, the D. C. Department of Environmental Services is required
to monitor stormwater loadings.
Based on earlier work of Roy Weston Associates and Philip Graham,
Council of Governments, on water quality aspects of stormwater, the
Annapolis Field Office has, based on rainfall records of 1973-74, cal-
culated the relative pollutant loadings from combined and separate
storm sewers within the Washington, D.C., Beltway for different
rainfalls, including the frequency of the rainfalls. These estimates,
with appropriate updating to reflect forthcoming monitoring data, will
be useful in future modelling efforts where the ability to predict
diurnal fluctuations on a real time basis will be developed.
13
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-------
Water Quality Data Trends
Data presented earlier in this paper showed marked reductions in
wastewater loadings from the major sources in the Washington Metro-
politan Area. In order to evaluate the effects of the reduced loadings,
a comparison is made of the 1973-74 and 1969-70 nutrient data from
three representative sampling stations in the upper estuary.
The Mains Point sampling station is located 7.6 miles below Chain
Bridge, the fall line. Hains Point can be considered the control point,
i.e., the area located above the influence of the Blue Plains Waste-
water Treatment Plant. The inorganic phosphorus (as PC>4) concentrations
(Figure 5) show a general decrease over those of 1969-70, while nitrate
nitrogen concentrations (Figure 6) between the periods of 1969-70 and
1973-74 appear to have remained unchanged. Ammonia nitrogen (Figure 7)
did not exhibit the high peaks shown in 1969, yet the recent data show
no dramatic decline over 1970 concentrations.
The Woodrow Wilson Bridge sampling station is expected to show the
effects of the major wastewater discharges. A comparison of the ammonia
and nitrate nitrogen data show no significant changes for the periods of
comparison. The inorganic phosphorus appears to have dramatically
declined. On close examination, however, the high peak in May-July 1969
could be due to the low flow conditions (3000 cfs) and the buildup of
phosphorus from the discharges. During August 1969 Hurricane Camille
and higher flows (8000 cfs) flushed the estuary, as can be seen by the
sharp drop in phosphorus concentrations. Likewise, the high peak of
3.4 mg/1 inorganic phosphorus (as PO/^) in September 1970 is associated
14
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-------
INORGANIC PHOSPHATE CQNCENTRW1CN
POTOMAC ESTUARY
4 see-wo
1973-1974
HAMS
MLES KL.OW CHAIN BMOGC « 7.10
I9«9«I -9TO
WOOOROW WILSON BRIDGE
MLES eCLOW CHAM BROGC 12.10
^TT j
«» I «
(NOAN HEAD
MU5 BELOW CHWN BADGE « 30i60
1973-1974
APK. MAT JLM.
AUO S£* OCt NOW DCC.
TO. ' IMA.
SMITH POINT
MLCS aCLOW CHAIN BRKX3C - 44.AO
1973-1974
ft*. MM AM
JUK ' JUL MM. SOt OCT.
Dec. I j**c ra.
* WTO
. I j*
»*-*-*
Q*-
«i-
301 BRIDGE
MILES BELOW CHAM BWOGC = 67.4O
JAM. PU.
«r- j .MM. nm.
0.7-
CA-
OS-
i ^^
I OJ-
A
JUP*. JUC
FIGURE - 5
-------
-------
1-0 -
at-
O*-
OJ-
az-
0.1 -
NITRATE and NITRITE NITROGEN a$ N
POTOMAC ESTUARY
MAINS POINT
ML£S BELOW "CHAM BRIDGE « 7.60
JUN, JUL AUG SEP OCT NOV DEC JAN. FEB.
APR MM JUN JUL AUG SEP
WOODROW WILSON BRIDGE
MLES '
JAN. Ftl
JUN. JUL. AUG. SEP OCT MOV DEC
. --
fsn-
03-
O2-
0.1 -
FEB, MAR APR MAY JUN.
' AUG. ' SEP
INDIAN HEAD
MLES BELOW CHAIN BRIDGE « 30.60
IJ-
L2 -
(U-
05-
0>-
03-
02-
0.1 -
JMC TO. MAft Am. MW JUN. JUL
SMTTH POINT
MLES BELOW CHAIN BRIDGE » 46.BO
FO. ' MAN.
MAV JUN JUL AUG
JAR FEB MAM
MAY JUN
SEP OC
NOV DCC
JUN. JUL AUG SCP
£a«-
+ -JW-
Sf "^
os-
tt2-
ai-
301 BRIDGE
MILES BELOW CHAIN BROGE > 67.40
as-
cf a*-
+ y OJ-
!p" OJ-
01-
JAN FEB. MAM APH MAY
PINEY POINT
MILES BELOW CHAIN BRIDGE = W.2O
APR MAV
JUL AUG.
-------
-------
n-
" a?-
0.6-
05-
a«-
OJ-
02-
0.1-
AMMONIA NITROGEN as N
POTOMAC ESTUARY
HAINS POINT
MLES BELOW CHAIN BRIDGE * 7.60
MJG SEP
if"
as-
a*~
az-
JAM FEB MM APR MAY JUN JUL AOG SEP OCI NOV DEC. JAN FEB.
APfl MAY JUN
WOODROW WILSON BRIDGE
MLES BELOW CHAIN BRIDGE = 12.10
O-fr-
aa-
aT-
exe-
<"-
104-
Q3-
02-
FtB. MAfi.
INDIAN HEAD
MLES BELOW CHAIN 8RIOGE = 30.60
SEP. OCT
AUG. SEP.
FEB. MAA.
JUN JUL. AUG. SEP
FIGURE - 7
-------
-------
with the low flow condition (1600 cfs). It was during this period of
low flow and high temperatures that algal mats encroached into the
Tidal Basin.
The Indian Head sampling station, 30.6 miles below the fall line,
is located in the historical bloom area of the blue-green algae. The
nitrate and ammonia nitrogen have remained fairly constant as was
noted at the two upstream stations. The 1973-74 inorganic phosphorus
(as PO^) concentrations were consistently lower at Indian Head when
compared to the 1969-70 concentrations. While 1969 was a low-flow year,
the freshwater inflows for 1970 (10,500 cfs) and 1974 (11,500 cfs) were
similar. This would infer that the differences in comparative phos-
phorus levels for 1970 and 1974 were not greatly effected by freshwater
flows.
The literature states that an average N/P ratio, by atoms, is
about 15 or 20 to 1. In general, if the ratio is less than 10:1 the
system can be considered nitrogen deficient. If it is greater than
25:1 the system may be phosphorus deficient. At the Indian Head sampling
station the N/P ratios for inorganic nitrogen versus inorganic phos-
phorus on a yearly average basis for the comparative study periods are
as follows: 14.0:1, 1969; 16.9:1, 1970; 32.3:1, 1973; and 31.4:1, 1974.
In the same order the ratios for the summer seasons (May-September)
were: 21.4:1, 15.9:1, 31.3:1, and 28.0:1. (It should be noted that the
data sets for 1973 and 1974 summer seasons were limited to 6 and 7,
respectively.)
It is quite evident that in this particular area of the estuary
the system has switched from nitrogen deficient to nitrogen abundant.
18
-------
-------
It should be stated that atomic ratios cannot be taken as an absolute,
but they can serve as a useful tool to evaluate the respective relative
shifts in the abundance of nutrients.
It is most important to point out that while intense algal popu-
lations were not observed in the last couple of years in the upper
estuary, there were sufficient concentrations of nutrients to support
algal growth. According to the literature, 10 yg/1 (.01 mg/1) of
inorganic phosphorus can stimulate an algal bloom [6]. During the critical
summer months of 1973 and 1974, at Indian Head, concentrations of in-
organic phosphate were measured at .35 and .27 mg/1, respectively. Why
there were no major blooms is not fully understood.
19
-------
-------
Water Quality Predictions
Finally, because of current economic considerations, the role of
nitrogen in the eutrophication process of the Potomac Estuary has to
be defined. The Dynamic Estuary Model of the Potomac Estuary has been
modified by the Annapolis Field Office so that the yield of algae is
determined either by phosphorus or nitrogen; the nutrient that produces
the least growth in any given time or place is the controlling factor.
Model runs have been made using the nitrogen and phosphorus limi-
tations set forth in the Blue Plains NPDES permit, as well as nutrient
limitations recommended for the other major discharges to the estuary,
and freshwater inflows to the estuary of 9000, 3000, and 1000 cfs.
Preliminary results show that chlorophyll production is fairly
uniform with both N and P control and P control only, at the higher
flow (9000 cfs). At the 1000 and 3000 cfs flows the reduction of chloro-
phyll with N and P control is in the range of 10-20 yg/1. It could be
expected that at high flow conditions an ample supply of nutrients from
sources other than treatment plants would be available for algal growth.
In order to answer the phenomena of why blooms occur and why
blooms do not occur, the Annapolis Field Office has begun to lay out
the framework of a new model that represents the state-of-the-art
in the area of eutrophication dynamics. The model should have the
predictive capability to assess the function of light, temperature, and
nutrients as rate limiting factors in the eutrophication process in
the Potomac Estuary.
20
-------
-------
Coupled with the modelling effort, an extensive monitoring effort
is being planned. The purposes of the monitoring program are:
1. To provide data for model calibration and verification.
2. To perform specialized field and lab studies (e.g., algal
bioassays) to assist in identifying limiting nutrients
and algal growth characteristics.
3. To assess both the seasonal and long term water quality
trends in the estuary.
The combined information from the modelling and monitoring
programs should provide the information necessary to quantitatively
identify the cause-effect relationships in the estuary.
21
-------
-------
REFERENCES
1. Millar, C. E., L. M. Turk, and H. D. Foth. 1962. Fundamentals of
Soil Science (3rd Ed.). John Wiley and Sons, New York.
2. "Scientific Fundamentals of the Eutrophication of Lakes and
Flowing Waters, With Particular Reference to Nitrogen and Phosphorus
as Factors in Eutrophication," Environment Directorate, Organi-
sation for Economic Co-Operation and Development, Paris, 1971.
3. Fog, G. E., W. D. P. Stewart, P. Fay, and A. E. Walsby. 1973.
The Blue-Green Algae. Academic Press, Incorporated, New York.
4. Jaworski, N. A., L. 0. Clark, and K. D. Feigner. "A Water Resource-
Water Supply Study of the Potomac Estuary," CTSL, MAR, WQO, U.S.
Environmental Protection Agency, Technical Report No. 35, April 1971.
5. Jaworski, N. A. "Nutrients in the Upper Potomac River Basin,"
CTSL, MAR, FWPCA, U. S. Department of the Interior, Technical
Report No. 15, August 1969.
6. Allen, H. E. and J. R. Kramer. 1972. Nutrients in Natural
Waters. John Wiley and Sons, New York.
22
-------
-------
EPA 903/9-76-023
DISTRIBUTION OF METALS IN
ELIZABETH RIVER SEDIMENTS
June lc>76
Technical Report No. 61
Arinapolis Field Office
Region III
Environmental protection Agency
-------
This report has been reviewed by EPA and approved for
publication. Approval does not signify that the contents
necessarily 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.
-------
EPA 903/9-76-023
Annapolis Field Office
Region III
Environmental Protection Agency
DISTRIBUTION OF METALS IN ELIZABETH RIVER SEDIMENTS
Technical Report
Patricia G. Johnson
Orterio Villa, Jr.
Annapolis Field Office Staff
Maryann Bonning Sigrid R. Kayser
Tangie Brown Donald W. Lear, Jr.
Leo Clark James W. Marks
Gerald W. Crutchley Margaret S. Mason
Daniel K. Donnelly Evelyn P. McPherson
Gerald R. Donovan, Jr. Margaret B. Munro
Margaret E. Fanning Maria L. O'Malley
Bettina B. Fletcher Thomas H. Pheiffer
Norman E. Fritsche Susan K. Smith
Victor Guide Earl C. Staton
George Houghton William M. Thomas, Jr.
Ronald Jones Robert L. Vallandingham
-------
TABLE OF CONTENTS
Page
I. Introduction 1-1
II. Summary and Conclusions II-l
III. Geographical Description III-l
IV. Experimental IV-1
V. Results and Discussion V-l
VI. Appendix I - Data Tables and Figures VI-1
VII. Appendix II - Frequency Distribution Histograms ... VII-1
VIII. Appendix III - Description of Sediment Samples .... VTII-1
IX. Appendix IV - Toxicity of Metals to Marine Life ... IX-1
-------
FIGURES
Page
1. Vicinity Map III-2
2. Sewage Treatment Plant Location Map III-6
3. Industrial Discharges 111-10
k. Sampling Stations III-5
5. Distribution of Cadmium V-3
6. Distribution of Copper V-4
7. Distribution of Chromium V-5
8. Distribution of Mercury V-6
9. Distribution of Lead V-7
10. Distribution of Zinc V-8
11. Distribution of Iron V-9
12. Distribution of Aluminum V-10
13. Frequency Distribution - Cadmium VII-1
14. Frequency Distribution - Copper VII-1
15 Frequency Distribution - Chromium VII-2
16. Frequency Distribution - Mercury VII-2
17. Frequency Distribution - Lead VII-3
18. Frequency Distribution - Zinc VII-3
19 Frequency Distribution - Iron Vll-k
20. Frequency Distribution - Aluminum VII-4
21. Water Content Correlation - Entire Area V-15
22. Water Content Correlation - Eastern Branch V-15
23 Water Content Correlation - Southern Branch V-15
2k. Water Content Correlation - Main Branch V-15
25. Bottom Sediment Classification V-19
26. Organi c Sediment Index V-21
27. Sampling Locations at or near STP Locations V-24
-------
TABLES
Page
1. Municipal Wastewater Loadings - 1971 III-7
2. Industrial Discharges (including Mass Emission Rates)...111-8
3. Operating Parameters IV-3
4. Distribution by Geographical Area V-2
5. Cadmium Concentrations at Sampling Locations VI-1
6. Copper Concentrations at Sampling Locations VI-2
7. Chromium Concentrations at Sampling Locations VT-3
8. Mercury Concentrations at Sampling Locations VI-4
9. Lead Concentrations at Sampling Locations VI-5
10. Zinc Concentrations at Sampling Locations VI-6
11. Iron Concentrations at Sampling Locations VI-7
12. Aluminum Concentrations at Sampling Locations VI-8
13. Skewness Values V-12
14. Water Content - % at Sampling Locations VI-9
15. Concentration Ratios between Elizabeth River Sediments
and Chesapeake Bay Sediments V-17
16. COD Concentrations at Sampling Locations VI-10
17. Metals in Elizabeth River and Baltimore Harbor
Sediments V-26
18. Metals in Elizabeth River and Chesapeake Bay Sediments . V-28
19. Metals in Elizabeth River, Delaware River, Potomac
and James River Sediments V-29
20. Metals in the Earth's Crust V-31
21. Toxicity of Metals to Marine Life DC-1
22. Trace Metals - Uses and Hazards K-2
23. % Organic Carbon at Sampling Locations VI-11
24. % Organic Nitrogen (TKN) at Sampling Locations VI-12
25. Organic Sediment Index at Sampling Locations VI-13
26. Elizabeth River Bottom Sediment Classification V-20
27. Organic Sediment Index as a Description of Elizabeth
River Bottom Deposits V-23
28. Total Volatile Solids Concentrations at Sampling
Locations VI-14
29. Oil and Grease Concentrations at Sampling Locations .... VI-15
-------
ABSTRACT
In order to develop a current inventory of metals contamination
of the Elizabeth River, sediment samples were collected at ninety-six
(96) stations in February of 197^ and analyzed for Cd, Cu, Cr, Hg,
Fb, Zn, Al and Fe using atomic absorption spectrophotometry.
Concentration levels were compared with levels found in another highly
industrialized harbor complex, other estuarine systems and in
Chesapeake Bay sediments geographically removed from the study area.
Distribution patterns of various metals are outlined for reference
to various Inputs. Possible mechanisms for transport and distribution
are discussed.
-------
1-1
INTRODUCTION
The Elizabeth River is a tributary of the James River located
in Virginia. The river is largely estuarine in nature and as such is
a physical and chemical mixing zone. A major physical characteristic
of any estuary is that its volume and comparatively sluggish tidal
cycles slows the inflow of fresh water. As a result of this
decreased velocity the load of suspended matter introduced into the
system settles to the bottom, rendering the sediment a reservoir for
a diverse and heterogeneous accumulation of material, much of
which may have potential toxic properties (l). This natural condition
tends to create a "sink" for many metallic compounds due to their
reactions with particulate matter. Heavy industrial loadings
increase the potential toxicity of the bottom sediments to aquatic
life.
The Elizabeth River is an example of an excessively utilized
waterway in regard to waste assimilation. Due to its relatively
shallow nature, the low dispersion and transport characteristics
mentioned above, accompanied by low freshwater flow rates, and its
intensified industrial, commercial and domestic development, the
Elizabeth River's ability to assimilate the diverse wast;e input
from these sources is severely limited. These inputs from other
than natural sources take many forms. Discharges from primary
treatment plants contribute to the widespread water quality problems
associated with this area. The overflow of pumping stations
-------
1-2
has contributed to the high coliform levels in the receiving waters.
Progressive stream fertilization by domestic and industrial waste
inputs, primarily from nitrogen and phosphorus, has contributed
to recurring eutrophication problems. Industrial and commercial
inputs from varied chemical and domestic processes add further
to the burden of the river. Fish kills, frequent reports of oil
spills, and other accidents associated with shipping lanes further
characterize the pollution problems in the Elizabeth River (2).
Richardson (1971), in a study of the benthic community of the
Elizabeth River, found the dominant organisms to be those types
that are pollution tolerant, with wide geographic range, and
which rarely dominant other communities except under stress
conditions. "Non-selective deposit feeders were found in low
numbers because of the lack of oxygen and high concentration of
hydrogen sulfide found in the deposits below 1 cm. Suspension
feeders and selective deposit feeders were favored because of the
good supply of well aerated detrital material in the sediment
surface and trapped in abundant oyster shells." (46) A similar
study by Boesch (47) reported the same result - the Elizabeth River
is characterized by the presence of pollution tolerant species.
Although it is not the intent of this effort to deal with
toxicological effects in any detail, it should be noted that the
State of Virginia has found some areas of the bottom toxic to
fish (1), the Virginia Institute of Marine Science has reported high
xevej.a ol PD (i>?U ppm), Hg (3 ppm), Zn (1200 ppm), and Cu (300 ppm)
-------
1-3
in bottom sediments (2), and the Bureau of Shellfish Sanitation
has designated the Elizabeth River a "condemned area" for the direct
marketing of shellfish (16). The oysters must be placed in a
cleansing area for a fifteen (15) day period prior to sale. Zn
(» 2000 ppm), Cu (25-100), and Cd (1.0 - 2.0 ppm) values have
been found in Elizabeth River oysters (36). Although it is not
necessarily unusual to find such elevated levels (levels of
20,000 ppm have been found near outfalls disposing zinc (50)),
inputs manifested in the biota to such a degree may be of public
health significance. Certainly the ability of the oyster to
concentrate metals is well documented (50, 51). What remains
unclear is the mechanisms of transfer from the sediment or water
phase to the biological phase, and since little information exists
on the bioavaliability of these elements, it is difficult to
correlate a given, measured concentration of a metal with a specific
toxic level. Considerations such as chemical bonding of the
metallic species (11), particle size of the substrate (12), valence
state and humic acid availability (13), synergistic and antag-
onistic mechanisms all relate to the reactivity of a given metal.
The toxicity in terms of LD^o °f various metals has been well
documented (3, 4, 5) and large scale outbreaks of metal poisoning
(6, 7, 8, 9, 10) illustrate the potential health hazard of these
substances. The relationship between acute high level doses to
test organisms under laboratory conditions versus chronic low
level, long term effects in the environment remains a question.
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1-4
Even though the mechanism of exchange from the physical to the
biological is unclear there can be no doubt that such a mechanism
exists. The implications of this exchange is important as it relates
to the impact of dredging and open water disposal of dredged spoil.
At present, all dredged spoil from the Southern Branch of the
Elizabeth River is disposed of in a specially constructed dyked area -
Craney Island (36). Drifmeyer and Odum (1975) investigated dredge
spoil as a possible source of metals uptake by salt marsh biota
using Craney Island as one of the study areas. The spoil itself
was classified as polluted, highly organic (9-6 % loss on ignition)
and as a silt-clay complex (Vj). Marsh grasses showed significantly
higher levels of Fb and Zn in the spoil area compared to the control
area. Fb and Mn were also higher in grass shrimp from the spoil
area. Fb values in fish were higher in the spoil ponds. Drifmeyer
concluded that dredge spoil, even though disposed of in a contained
area, may act as a source of certain heavy metals that are potentially
toxic to the biota
For reference purposes the toxicity of some heavy metals is
presented in Appendix IV, Tables 21 and 22.
Sampling programs spanning several years have been carried ouc
by various private and public institutions. Each of these studies
has provided valuable data for the area studied. This study is an
effort to provide a synoptic picture of the metals accumulation in the
Elizabeth River sediments.
-------
II-l
SUMMARY AND CONCLUSIONS
1. This report provides an inventory of present conditions relating
to metals contamination of Elizabeth River sediments.
2. Concentrations of all metals analyzed in the Elizabeth River
sediments were two (2) to ten (10) times greater than sediments
from the mid-Chesapeake Bay.
3. Distribution of metals generally reflected the inputs from
heavy industrial, commercial and domestic sources which the
Elizabeth River receives.
k. Metal concentration ratios between the Elizabeth River sediments
and Chesapeake Bay sediments follow a pattern (Cu > Fb > Cd > Zn)
suggesting that in black colored sediments from the Eastern and
Southern Branches, Cu, Pb, Cd, and Zn may exist as sulfides since
the order for solubilities of divalent sulfides exhibits the
same pattern. In the Main Branch the ratio pattern in black
sediments suggests that these metals are probably present in
forms other than sulfides. Provided the metal sulfide solubilities
are low, the deposition as a sulfide would be one mechanism of
the sediment acting as a "sink". Additionally, so long as the
metals are tightly bound in the sink, their bioavailability would
be lessened and the metals would therefore be unavailable for
introduction into the biological segment assuming that the system
is not disturbed.
5. Non-linear relationships between metal and aluminum/metal ratios
suggest that Cu, Cr, Pb and Fe are not associated with the clay
-------
II-2
mineral portion of the sediment.
6. No black sediment was found in the Western Branch. Being the
least industrialized of the various branches it does not receive
the quantities of organic materials, sulfides, etc. to which
the other branches are exposed. The black color has been related
to hydrotrolite which depends on the presence of sulfide and
poorly oxygenated water for its formation (23). Such conditions
apparently do not exist in the Western Branch.
7- Better than half of the total number of black sediments found in
the study area had distinct "air" pockets in the core when the
sample arrived at the laboratory for analysis. No gray samples
showed this phenomenon. It is possible that the black sediments
were evolving E~S which is characteristic of hydrotrolite. The
absence of gas in gray samples, the sulfide solubility pattern
and the correlation between water content and color support
this conclusion.
8. A pronounced difference in water content between the black and
gray sediments was evident. The correlation exists for the
entire study area, excluding the Western Branch which had no
black sediments, and is very pronounced in the Southern and
Eastern Branches. No explanation is offered for this phenomenon
although some references indicate that the presence of hydrotrolite
in some way contributes to the high water content found in
black sediments (23).
-------
II-3
9- Particle size can play a significant role in adsorption reactions
of metallic species. The appearance of the sediments was recorded
as the sample was removed from the core. The sediments of the
Elizabeth River appear to be of a silt-clay nature and were
uniform in appearance throughout the study area in terms of
size. Differences in color were noted and recorded.
10. Examination of the four major river divisions revealed the
following:
a. The entrance of the Elizabeth River at Craney Island
shows high concentrations of Cr, Fe, and Al, with lesser amounts
of Zn. Fb, Cu, Cd and Eg increase in concentration moving in
a southerly direction as the branches are approached.
b. The Eastern Branch has very high concentrations of
Cu, Fb and Fe, with slightly lesser, but still high concentrations
of Zn, Cr, Cd, and Al.
c. The western side of the Southern Branch showed very
high concentrations of Fb and Cu, with Cr, Zn and Cd also high.
The eastern side showed lesser amounts of all metals except
Cd and Hg which are equally distributed on both sides.
d. The Western Branch had several areas that were very
high in Al, Fe, Fb, Zn, Cd, Cu and Cr.
11. Comparison of the Elizabeth River with other estuaries revealed
the following:
a. Concentrations of all metals analyzed from the Elizabeth
-------
n-k
River were two (2) to ten (10) times greater than concentrations
found in the Chesapeake Bay.
b. The Elizabeth River showed three (3) times the Pb and Zn
concentrations found in the James River (river miles 0 - 84),
but slightly less Hg was found in the Elizabeth. The James River
shows little accumulation of Fb and Zn compared to the Chesapeake
Bay, although Hg was five (5) times greater than in Bay sediments.
c. The Elizabeth River concentrations for metals analyzed
were from two (2) to ten (10) times the concentrations reported
for the Potomac River.
d. The Delaware estuary shows consistently higher than
ambient levels that are similar to the levels found in the
Elizabeth River.
e. Average Zn and Cd concentrations in Baltimore Harbor
were twice (2) the levels found in the Elizabeth River. Baltimore
Harbor showed four (4), five (5) and eleven (ll) times the
concentrations of Pb, Cu and Cr, respectively, found in the
Elizabeth River.
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III-l
GEOGRAPHICAL DESCRIPTION
The Port of Hampton Roads, Virginia, including the cities of
Norfolk, Portsmouth, Chesapeake, Newport News, and Hampton, is the
largest port complex in Virginia, in fact, one of the finest natural
harbors in the world. The combined population of the cities located
around Hampton Roads was 725,62U in 1970 (lit-) . Hampton Roads is
located at the southern end of the Chesapeake Bay, approximately
in the middle of the Atlantic seaboard, 300 miles south of New York,
l80 miles southeast of Washington, D.C., and 20 miles west of the
entrance of Chesapeake Bay (Figure l).
Hampton Roads is the largest bulk cargo exporting port in the
United States, with bituminous coal being the principal export.
Tobacco and grain exports are also among the world's largest. The
following table lists the most common items exported from Norfolk
Harbor in 1971.
Principal
Commodity
Coal and lignite
Corn
Grain mill products
Wheat
Coke, petroleum products
asphalts , s ol vents
Tobacco
Iron and Steel Scrap
All others
1
Exports - Norfolk Harbor - 1971
Short Tons
25,047,03^
875,7^8
28k, kkO
135,981
}
122,205
101,856
96,911
989,678
fo of Total
90.60
3.16
1.02
0.49
O.kk
0.36
0.35
3.58
"Waterborne Commerce of the U.S.," Calendar Year 1971, Part 1,
Waterways and Harbors of the Atlantic Coast, Department of the
Army, Corps of Engineers, 266 p.
-------
III-.
ANNAPOLIS MO.
WASHINGTON D.C.
NEWPORT NEWS
HAMPTON ROADS
CRANEY ISLAND
STUDY AREA
PORTSMOUTH
-------
III-3
There are natural depths of 20 to 80 feet in the main part of
Hampton Roads, but the harbor shoals to less than 10 feet toward the
shores. Dredged channels lead to the principal ports. Federal
project depth is ^0 feet in the two main channels in Hampton Roads (15)
One leads southward along the waterfronts of Norfolk, Portsmouth,
and Chesapeake, following the Elizabeth River, and the other leads west-
ward to the waterfront of Newport News at the entrance to the James River.
The climate throughout the James River Basin, of wh..ch the
Elizabeth River is a part, is temperate, as determined by the latitude,
prevailing westerly winds, the influence of the Atlantic Ocean, and its
overall topography. The terrain is low-lying and flat with a maximum
elevation of 25 feet, except for isolated sand dunes along beach
areas (lU). Average annual weather factors are:
Precipitation: ^2.5 inches
Snowfall: 17 inches (about 1.7 inches of precipitation)
Temperature: 57°F
The eastern portion of the basin is sometimes subjected to the effects
of hurricanes in the summer and early fall. Average annual temperature
is generally higher near the ocean - 6l.7°F. The average velocity of
the wind is 8 to 10 MPH, but winds of 80 MPH may occur in storms (l6).
The currents in this area are influenced considerably by the
winds. The current velocity is 1.1 knots in Hampton Roads and .6 knots
in the Elizabeth River (15) Tides in the vicinity of Craney Island
(on the flats opposite the entrance of the Lafayette River which bisects
Norfolk from east to west) are primarily semi-diurnal with a mean
range of 2.6 feet and a spring range of 3-1 feet
-------
Ill-k
The Elizabeth River study area, a tributary of the James River
just above the Hampton Roads Tunnel, is formed by three main branches;
the Eastern Branch, the Western Branch, and the Southern Branch. Sampling
stations are shown in Figure k. A map indicating the location of the
various sewage treatment plants in given in Figure 2. Municipal
wastewater loadings for 1971 are presented in Table 1 and major
industrial dischargers and associated average wastewater flows are
given in Table 2 (52). In addition, the largest or most significant
mas,-? emission rates (ibs/day) are also given in Table 2. The inputs
of the various industrial dischargers are graphically presented
in Figure 3 (52). The three branches of the Elizabeth are characterized
by heavy industrial, commercial and domestic facilities with their
inherent problems. In addition to domestic waste discharged by
primary sewage treatment plants and toxic wastes discharged by a variety
of industrial concerns, the area is plagued by frequent oil spills
and waste discharges from the extensive shipyard and docking facilities.
The Eastern Branch has shipbuilding and drydock facilities,
an automobile assembly plant, an electric power plant, and several
shipping docks which contribute to the waste input of the river. The
Southern Branch, the most industrialized and longest branch of the
Elizabeth River, is characterized by a variety of industrial and
commercial concerns: cement plants, creosote treatment plants, ship-
building and drydock facilities, food processing plants, power plants,
chemical plants and U.S. Wavy shipyards. On the Western Branch,
the least industrialized branch of the Elizabeth River, are located a
-------
Ill
WESTERN
BRANCH
EASTERN
BRANCH
22 SOUTHERN
BRANCH
FIGURE k
ELIZABETH RIVER SEDIMENTS
SAMPLING STATIONS
NAUTICAL MILES
E
2
-------
Hampton
Roads
Lafayette
River
Kreat Bridge STP
Western
Branch STPO X /
t ^^.^^f\ f ,
^ yM
Eastern
Branch
? S=>wage Treatment Plant Locations
-------
111-7
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A HUMBLE OIL 8 REFIN'NG CO
B USN-CRANEY IS PjEL FAC
C VIRGINIA CHEMICALS INC.
D NORFOLK COCA COLA
D WESTERN BRANCH DIESEL
E N.8W RR.
F J H. MILES S CO
G NORFOLK COCA COLA
H CHEVRON ASPHALT CO.
H FORD MOTOR CO
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H SOUTHERN/NORFOLK SB 8DO.
H CPC INTERNATIONAL
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JUS GYPSUM CO
K NORFOLK NAVAL SHIPYARD
L PROCTOR a GAMBLE
M GULF OIL CO
N LONE STAR IND
,0 FS ROYSTER.CO
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Q CARG'LL. '\C
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W USN-WEAPONS STAT ;.«
X SV/iFT C'-EV.CALS
Y S.V,iTH-DC'J3LAS Ct-E
Z WEAVER nSTILIZES 0
Figure 3
111-10
Industrial Discharges
(52)
CUMULATIVE DISCHASGi
INCLUDE THOSE OF VE
ASGiS DO NOT
f \ \ \ NXNV-^:^
DEFGHIJ KLMNOPORSTU V WX Y Z
ABC
LEGEND
EA9IUM (8«)
TITANIUf (T()
COSALT (Co)
LEGEND
-WESTERN BRANCH
--EASTERN BRANCH
^«
*'^ff
LBS./DAY
MANGANESE (nn)
'LEAD (Pb)
CWESTERN BRANCH
--EASTERN BRANCH
- *RcTn
J"»e*
ABC
-------
LEGEND
Figure 3 Con't. IH-H
ZIKC (In)
CYANIDE (Cn~) _.
-WESTERN BRANCH
|~EASTERN BRANCH
LSS./DAY
Zu I Cn-
P.E.
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LEGEND
NICKEL (Nl)
A BC d E FG'H I'J'K'L MNO PbVsXTXU\ wV^rz
r-WESTERN BRANCH
' r-EASTERN BRANCH
P.E._
-------
111-12
chemical manufacturing plant and shipyards. The Main Branch houses
shipping terminals, coal loading yards, an oil terminal, and sewage
treatment plants (2). The navigable portion of the three branches
of the river is located within the boundaries of the cities of
Portsmouth and Norfolk (l).
-------
IV-1
EXPERIMENTAL
Samples were taken with a Phelger corer. The top five centimeters
representing substantial sediment-water interface were discarded and
the sediment between five and fifteen centimeters was taken as the
sample to be analyzed.
A portion of the well-mixed sediment was spread to dry at room
temperature for kQ hours. After drying, the sample was pulverized
using an agate mortar and pestle and again spread to dry for an
additional 2k-k8 hours. A 1.0000 gram sample was placed in a 125 ml
glass-stoppered erlenmeyer to which 25-50 ml of deionized-
distilled water and 21.5 ml concentrated HNO_ were added. The samples
were then heated at U8-50°C (17) for k-6 hours in a shaking
hot water bath. After digestion, the samples were cooled to room
temperature and filtered through a OA5 micron membrane filter and
the volume adjusted to 100 mis. Blank solutions were run throughout
the same extraction procedure (18, 19). This acid extraction
procedure is believed to be 80 - 90 % efficient in the removal of
sorbed and bound metals (40, ij-5, 5^).
The filtered acid extracts were analyzed for Cd, Cr, Cu, Fb,
Zn, Al and Fe, using a Varian Techtron AA-6 absorption spectrophotometer
equipped with a standard pre-mix burner. Air and acetylene were used
for all flame techniques, except for Al for which nitrous-oxide and
acetylene were used. The flame stoichiometry was established
Any volume between 20 and 25 mis can be used, the volume used
here was delivered from a dispenser with a fixed volume delivery head
that happened to deliver 21.5 mis. and was used for convenience sake.
-------
IV-2
as per manufacturers instructions for optimum working conditions.
Standard, operating parameters are shown in Table 3
Mercury was analyzed using an automated flameless atomic
absorption technique (20, 21, 22). Mercury analysis was performed
by a cold vapor technique employing the Coleman Mercury Analyzer
MA.S-50 and a Technicon AutoAnalyzer. Concentrated sulfuric acid
and potassium permanganate were added to oxidize the sample. Further
oxidation of organomercury compounds was assured through the
addition of potassium persulfate. Samples were then heated to 105°C
in a closed system. Hydroxylamine sulfate-sodium chloride was used
to reduce the excess permanganate. The mercury in the sample was
then reduced to the elemental state through the addition of excess
stannous sulfate and a large amount of air. The gaseous phase was
then analyzed in the MAS-50.
Other paramteres used in the interpretation and examination
of the metals results were determined as follows:
1. Water content - determined as per cent weight lost
after samples were dried (18, 19);
2. COD - dichromate reflux (18, 19);
3. Total volatile solids - weight loss associated with
ignition of sample in muffle furnace (18, 19);
k. Oil and grease - as hexane extractables (l8, 19); and,
5. TKN - semi-automated phenolate method (18, 19).
In general, for all parameters including metals, precision
of analysis was checked by duplication of 10 fo or more of the samples .
-------
IV-3
TABLE 3
OPERATING PARAMETERS
Metal
Cd
Cr
Cu
Fb
Zn
Al
Fe
Wavelength
228.8
357-9
32U.7
217.0
213.9
309-3
248.3
Slit
.5 nm
.2
.5
1.0
.5
5
.2
Lamp Current
3 ma
5
3
5
5
5
5
AA - Air /Acetylene
Flame
AA
AA
AA
AA
AA
NA
AA
Stoichiometry
Oxidizing
Reducing
Oxidizing
Oxidizing
Oxidizing
Reducing
Oxidizing
HA - Nitrous Oxide/Acetylene
-------
IV- k
Accuracy was checked by periodically spiking samples and calculating
% recovery.
-------
v-i
RESULTS AND DISCUSSION
The purpose of this study was to assemble an up-to-date inventory
of metals accumulation in the Elizabeth River. Ninety-six stations
(Figure 2) were sampled in February of 1974 and the surfaces (5-15 cm)
analyzed for Cd, Cu, Cr, Pb, Zn, Hg, Al and Fe.
The distribution of metals by geographical area is presented in
Table 4. The average concentrations of Cr, Cd, Al and Fe were
similar in all four divisions indicating that these metals are
fairly evenly distributed throughout the entire area with some
localized high spots. The Eastern Branch is highly contaminated
with Cu, Pb, and Zn; the Southern and Western Branches also exhibit
high levels of these metals. The Main Branch has somewhat less of
all the metals analyzed, with localized high concentrations along its
western side. The entire area is contaminated with Zn, Cr, and Cu
but the concentrations in the Southern and Eastern Branches are
greatest. High levels of Al and Fe found in the study area are
normal estuarine concentrations and represent natural levels due
to the relative abundance of both raetals and the chemistry of the
estuarine system. The remaining metals are expected to show the
impact of man through waste discharges into the river. Figures 5
through 12 graphically depict the distribution pattern of metals
in the Elizabeth River. Appendix I, Tables 5 through 12, lists the
concentration of each metal found at the sampling stations. The
concentrations for the remaining parameters are also listed in
Appendix I, Tables 14, 16, 23, 24, 28 and 29.
The data has also been compiled as frequency distributions to
illustrate the relative occurences for a given concentration range.
-------
V-2
Table k
GEOGRAPHICAL
Metal
Cadmium, mg/kg
Low
Average
High
Chromium, mg/kg
Low
Average
High
Copper, mg/kg
Low
Average
High
Lead, mg/kg
Low
Average
High
Zinc, mg/kg
Low
Average
High
Mercury, mg/kg
Low
Average
High
Aluminum, mg/kg
Low
Average
High
Iron, mg/kg
Low
Average
High
DISTRIBUTION
Main
Branch
< 1
1+.0-1+.2
26
9
UT
95
< 2
36.6-36.7
2U6
< 3
6U.5-61+.8
2k2
65
388
1690
< .01
.10
.65
1+790
13180
17990
10180
2871+9
3681+0
OF METALS
Eastern
Branch
< 1
2.9-3.0
6
17
U3
7^
27
11*0
221
35
179
280
73
1+22
81+1
< .01
37
2.73
9600
13539
16980
20560
26235
35330
IN ELIZABETH RIVER
Western
Branch
< 1
3.8-1+.1
22
19
l+l
110
10
70
233
< 3
79-8-80.1
366
80
^54
2380
.10
.21+
.vr
10960
15601+
17920
21670
33521+
i+oi+i+o
Southern
Branch
< 1
1.8-2.0
6
10
38
109
< 2
7U.8-71+.9
395
< 3
96.2-96.3
382
38
271+
1016
< .01
.38
1.1+9
3980
10656
11+290
7970
263^8
375^0
-------
WESTERN
BRANCH
EASTERN
BRANCH
FIGURE 5
ELIZABETH RIVER SEDIMENTS
CADMIUM MG/KG DRY
SOUTHERN
BRANCH
NAUTICAL MILES
3!
I 2
-------
v k
WESTERN
BRANCH
EASTERN
BRANCH
FIGURE 6
ELIZABETH RIVER SEDIMENTS
MG/KG DRY
SOUTHERN
BRANCH
NAUTICAL MILES
J £
I 2
-------
v-s
WESTERN
BRANCH
EASTERN
BRANCH
FIGURE 7
ELIZABETH RIVER SEDIMENTS
CHROMIUM
MG/KG DRY
SOUTHERN
BRANCH
NAUTICAL MILES
I 2
-------
v-6
WESTERN
BRANCH
EASTERN
BRANCH
FIGURE 8
ELIZABETH RIVER SEDIMENTS
MERCURY .MG/KG DRY
SOUTHERN
BRANCH
JJAUTICAL MILES
I 2
-------
V-7
WESTERN
BRANCH
EASTERN
BRANCH
FIGURE 9
ELIZABETH RIVER SEDIMENTS
LEAD MG/KG DRY
SOUTHERN
BRANCH
.NAUTICAL MILES
"" Si
2
-------
V-8
WESTERN
BRANCH
EASTERN
BRANCH
SOUTHERN
BRANCH
FIGURE 10
ELIZABETH RIVER SEDIMENTS
ZINC
I - 50
50 - 250
250- 1.000
> 1,000
MG/KG .DRY
jvlAUTICAL MILES
2
I 2
-------
v-9
WESTERN
BRANCH
EASTERN
BRANCH
SOUTHERN
BRANCH
FIGURE 11
ELIZABETH RIVER SEDIMENTS
IRON MG/KG DRY
0 - 10.000
10,000 - 20.000
20,000 - 30,000
> 30.000
NAUTICAL MILES
~~2
I 2
-------
V-10
WESTERN
BRANCH
EASTERN
BRANCH
SOUTHERN
BRANCH
FIGURE 12
ELIZABETH RIVER SEDIMENTS
ALUMINUM MG/KG DRY
0 - 10,000
10.000 - 15,000
> 15.000
NAUTICAL MILES
uf
I 2
-------
V-ll
This information is presented in histogram form in Appendix II,
Figures 13 through 20. It is interesting to note that all the metals
exhibit frequency distribution patterns that are skewed to the right
with the exception of Al and Fe which are skewed to the left. A skew-
ness value, "k", has been calculated for each distribution (Table 13),
and as expected only Al and Fe show negative skewness (37)- As
mentioned above, Al and Fe represent naturally occuring levels
which may account for the different distribution which they exhibit.
This difference in distribution pattern may be of use in
evaluating metal-sediment associations. Sommer (197*0 has discussed
the use of metal versus aluminum/metal concentration ratios as an
aid for just this purpose (38). Aluminum was used as an indicator
of clay mineral concentration in Sommers' Chesapeake Bay work since
aluminum is associated with clay minerals in Bay sediments. The
linear relationships found in his work for Cu and Al/Cu, Pb and Al/Fb,
Cr and Al/Cr, and Mn and Al/Mn suggested that the metals were associated
with the clay mineral portion of the sediment. Fe did not show a
linear relationship. Sommers suggested sulfides as a possible
alternate distribution mechanism for Fe. The occurences of high
carbon concentrations also suggested the importance of possible
organic matrices in which the metals might be held. The Elizabeth
River data was examined in a like manner to see if the relationships
exist in a similar manner for a highly industrialized estuary, as
compared to the Chesapeake Bay. No linear relationships were found
for any of the metals tested: Fe, Cr, Pb and Cu. Either Al is not
-------
V-12
Table 13
"k" Values for Skewness
Metal
Fe - 1.77
Hg 5-08
Al - 0.82
Zn 2.16
Fb 1.19
Cu 1.79
Cr 0.60
cd 3.M
-------
V-13
associated with clay minerals in the Elizabeth River as it is in
Bay sediments or non-linear relationships are indicative of man-made
sources rather than naturally occuring levels. Metallic speciation
may depend on the availability of anions such as sulfide or organic
complexes vhich are not normally encountered in great abundance in
non-industrial areas.
Changes in color from black to gray were noted in many of the
core samples. An attempt was made to describe the color and texture
of each sample as it was removed from the core for analysis. These
descriptions are presented in Appendix III. Aside from the organic
contribution to color, Biggs (23) and others (24, 25, 2.6, 27, 28, 29)
have attributed the color of black sediments to hydrotrolite
(FeS'nHpO), an amorphous ferrous sulfide. Black sediments will
evolve HpS when treated with acid if soluble sulfides are present,
gray sediments evolve no HpS. Sixteen (l6) of the thirty (30)
black sediments taken from the study area had "air" pockets which
may have been HpS and would indicate the presence of hydrotrolite.
Van Straaten (26) found that the monosulfide (hydrotrolite) converts
to the bisulfide (pyrite) with time. This conversion alters the
color from black to gray. During the drying process the color of
a.n samples that were black initially had changed to gray at the
end of the drying period.
It has been suggested (23) that the ability of the hydrotrolite
to precipitate is due to the condition of the overlying water: when
there is no oxygen, hydrotrolite precipitates, and conversely, when
the water oxygenated, it does not. The observed banding of black and
-------
gray could be the result of deposition in alternating oxygen-
deprived and oxygenated waters combined with the time dependent
conversion of hydrotrolite to pyrite. This banding phenomenon
was observed in 15 cores. Neilson (MO has observed periods of
stratification in the Elizabeth River that would tend to produce
periods with resultant oxygen deficient waters that would favor the
formation of hydrotrolite and thus account for the observed color
changes and banding.
Biggs (23) also found a marked correlation between water content
and sediment color. The samples analyzed in this study showed such
a relationship except in the Western Branch where no black sediments
were found. The relationship is particularly pronounced in the
Eastern and Southern Branches (Figures 21 through 2^). The more
separation that exists between the white and black areas on the
graphs, the greater the correlation to water content; the striped
area represents overlap. The actual water content at each station
is presented in Appendix I, Table 14.
The suspected evolution of HpS, the change in color from black
to gray on drying, the banding phenomenon, and the correlation between
water content and color certainly suggest the possible presence of
hydrotrolite and, therefore, a "sulfide-precipitation" mechanism
of metallic deposition in the Elizabeth River. Since the order
of solubilities for divalent sulfides is Hg < Cu < Fb < Cd < Ni < Zn,
Biggs (30) postulated that in black sediment the least soluble
sulfides would show the highest ratio in the Elizabeth River relative
-------
V-15
UO-,
30-
CO
*fi
CO
O
S-t
20-
10-
Figure 21
ko^
30 -
CO
0)
H
CO
20
0)
,9
10 -
123^56789 10 xlO
$ Water Content
Entire Area - 96 Samples
Figure 23
Black
Gray
Black and Gray I
1234567
°lo Water Content
Eastern Branch - Ik Samples
89 10x10
to
0)
CO
30-
20-
10-
Figure 22
Water Content
Southern Branch - 21 Samples
10 xlO
Water Content
Main' Branch - ^9 Samples
-------
V-16
to their abundance in the Chesapeake Bay. If there"is a greater
concentration of the element in the Elizabeth River and if the sulfide
is the least soluble chemical form which that element can be present
as, then the elements should be present in the following ratio:
Hg > Cu > Fb > Cd > Ni > Zn
Table 15 shows the order of the ratios between the Elizabeth River and
the Chesapeake Bay sediments.
Only one sample in the Main Branch exhibits the expected ratio,
exclusive of Hg. One of the criteria given above was that the Elizabeth
River value must exceed the Bay value in order for it to be used, since
this is not the case with the Elizabeth River, the mercury values
may be dropped from consideration. The metals in the Main Branch,
then, probably exist in some form other than the sulfide. All six
samples from the Eastern Branch follow the expected pattern. A
similar situation exists in the Southern Branch: all but one sample
conform to the pattern except for several inverted Zn and Cd values.
In general the metals seem to exhibit the pattern given above and
probably exist as sulfide in the Eastern and Southern Branches.
Using a technique developed by Ballinger and McKee (1971) to
characterize bottom sediments using organic carbon and organic
nitrogen data, the values from the Elizabeth River were tabulated
(Appendix I, Table 23 - $ TKW, Table 2.h - % Organic Carbon).
Organic nitrogen and organic carbon have been shown to correlate
well with known sources and permit the classification of deposits
into four general types (53). The four types are:
-------
V-17
Table 15
Metals Concentration Ratios Between Elizabeth
Bay Sediments
Station Branch
C-l Main
D-l
D-2
E-l
F-2
P-3
G-2
H-3
1-4
J-5
M-2
N-2
N-3
EB-2 Eastern
EB-3
EB-4
EB-7
EB-8
EB-10
SB- 5 Southern
SB-6
SB- 7
SB- 9
SB-10
SB-12
SB-13
SB-15
SB-18
SB-19
SB-20
Order of
Cu ?
Cu -
Cu 2
Zn -
Cu >
Cu ;
Cu x
Cu "
Cu x
Cd -
Cu x
Cu :
Cu x
Cu x
Cu x
Cu ^
Cu ;
cu ;
cu ;
cu ;
cu ;
cu ;
cu ;
cu :
cu ;
cu :
cu :
Cu ;
Cu ;
cu :
> Zn ^
> Zn >
> Zn >
> Cu 5
> Zn ^
> Zn ;
> Cd -
» Fb :
" Cd ^
> Zn ;
> cd ;
> cd :
> cd :
> Fb ;
> Fb ^
> Fb ;
> Fb :
> Fb ;
> Fb :
> Fb :
> Zn ;
> Fb ;
> Fb :
> Fb :
> Fb ;
> Fb :
> Fb :
> Fb :
> Fb :
> Fb :
River and Chesapeake
Decreasing Ratio
> Cd x
> Cd 5
> Cd -
> cd ;
> Cd ;
> Fb ^
> Zn :
> cd :
> Zn x
> cu ;
> Zn x
> Fb ;
> Fb ;
> Cd 5
> Zn ;
> cd ;
> Zn :
> Zn :
> Zn :
> Zn ;
> Fb :
> Zn ;
> Zn ;
> Zn ;
> Zn ;
> Zn :
> cd :
> cd :
> Zn :
> Zn :
> Cr x
> Cr ^
> Cr ^
> Fb ;
> Fb ;
> Cd :
> Fb ;
> Cr :
> Fb ;
> Fb ^
> Fb ;
> Zn ;
> Zn ;
> Zn ;
> cd ;
> Zn ;
> Cr ;
> Cr :
> cd :
> Cd :
> cd :
> cd ;
> cd :
> cd :
> cd ;
> cd :
> Cr ;
> Zn ;
> Cr ;
> cd ;
> Fb
> Fb
> Fb
> Cr
> Cr
> Cr
> Cr
> Zn
> Cr
> Cr
> Cr
> Cr
> Cr
> Cr
> Cr
> Cr
> Cd
> Cd
> Cr
> Cr
> Cr
> Cr
> Cr
> Cr
> Cr
> Cr
> Zn
> Cr
> Cd
> Cr
-------
V-18
I. Inorganic or aged, stabilized organic deposits;
II. High carbon, little N~ contribution, slow 0~ demand;
III. Nitrogenous, substantial W contribution, further
stabilization likely, and;
IV. Actively decomposing sediments, high potential Np
release and high Op demand.
Figure 25 shows the plotted Elizabeth River data. The type
of bottom sediment associated with each station is presented in Table
26. The Main Branch is predominantly Types I and II; the Eastern
Branch appears to have equal amounts of all four types; the Western
Branch is predominantly Type I, as is the Southern Branch. It is
interesting to note that the Western Branch had no Type IV sediments,
which may explain the absence of black sediment noted earlier. The
Western Branch has little industry and would appear to be relatively
stabilized.
A further extension of this work is the product of organic
nitrogen times organic carbon or OSI (Organic Sediment Index), which
has been used to classify the bottom sediments into four categories
which are:
I. OSI (0.0 - O.h8) - sand, clay, old stable sludge;
II. OSI (0.48 - 1.0) - organic detritus, peat, partially
stabilized sludge;
III. OSI (l.O - 5-0) - sewage sludge, decaying vegetation,
pulp and paper wastes, sugar beet wastes, and;
IV. OSI (5.0 - > 10.0) - actively decomposing sludge,
fresh sewage, matted algae, packinghouse wastes.
The numeric OSI values for the Elizabeth River are depicted
graphically in Figure 26, and are presented by type of sediment in
-------
-£-:--n-T
__;_-i } :- - - ; -i : AJ _'j _;
I '"- 1 2 1 3 ' 'U
_l -r:, -.. L->4'.s$-\--a )**-,
-------
V-20
TABLE 26
BOTTOM SEDIMENT CLASSIFICATION.
Location
A 1
2
3
k
B 1
2
3
h
C 1-
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
li
5
6
7
Type
I
I
I
I
II
II
I
I
II
I
I
I
IV
III
I
I
II
I
NS
I
I
II
IV
I
II
I
II
I
I
I
II
I
II
I
I
II
II
II
I
I
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
k
5
6
7
8
9
10
11
12
13
Ik
WB 1
2
3
4 '
5
6
7
8
9
10
11
12
Type
II
I
II
II
I
I
II
I
IV
II
II
IV
IV
II
III
II
I
IV
I
IV
IV
I
III
III
I
I
I
I
III
I
I
II
I
II
III
I
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
1U
15
16
17
18
19
20
21
22
-
Type
I
I
I
I
III
I
rv
NS
in
i
i
IV
I
I
III
I
I
I
III
IV
I
III
NS - No Sample
-------
V-21
-------
V-22
Table 27. It is interesting to note that the sharp peaks in Figure
26 (which represent high OSI values in Table 27) are in many cases at
or near the location of a sewage treatment plant (by superimposing
Figures 2 and k, the following sampling stations are at or near
STPs: D 1-k, E 1-4, G 1-3, J 1-7, and SB 15-22 - see Figure 27).
As expected from the calculated OSI values, the bottom at these
locations shows some impact from the presence of the sewage treatment
plants.
The bottom sediment classification and OSI values are useful
tools for examining the nature of the sediments from the Elizabeth
River and have shown the possibility of an "organic matrix
mechanism" of deposit and exchange, as an alternate or co-mechanism
to sulfide precipitation and other forms of deposition and transport.
Another factor in evaluating the concentrations of metals in
addition to their distribution and the form in which they may exist,
is the particle size of the sediment. High surface area and adsorption
capacity make clays a perfect scavenger for metallic substances.
Given the absence of other contributing causes, particle size can
be indicative of the metallic concentration of sediments (12).
Before comparing one system to another, the particle size differences
or similarities between the two should be accounted for so that particle
size does not distort the interpretation of the data. Wo actual
determination of particle size was possible in this study, however,
the texture of each sample was recorded as the core was prepared for
analysis. The sediments for the most part resembled those taken from
-------
V-23
TABLE 27
OSI CLASSIFICATION
Location
A 1
2
3
U
B 1
2
3
k
C 1
2
3
, k
D 1
2
3
h
E 1
2
3
k
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
J^
5
6
7
Class
I
II
I
I
I
III
I
I
III
I
I
I
III
III
I
I
II
II
NS
I
I
II
III
I
III
I
III
I
II
I
II
I
III
I
I
III
I
II
I
I
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
Ik
W3 1
2
3
U
5
6
7
8
9
10
11
12
Class
II
II
III
II
I
II
III
I
III
II
III
III
III
III
II
III
II
III
I
III
III
II
III
II
I
I
I
II
II
II
I
III
I
II
II
I
Location
SB 1
2
3
k
5
6
7
8
9
10
11
12
13
1U
15
16
17
18
19
20
21
22
-
Class
I
I
I
I
III
I
III
NS
II
II
I
III
II
I
III
I
I
I
III
III
II
III
NS - No Sample
-------
Figure 27 Sampling Locations at or near STPs
Hampton
Roads
Lafayette
River
J Western^.
[Branch STP
Oreat Bridge STP
Eastern
Branch
v Mr)
T
-------
V-25
the Baltimore Harbor in an earlier study (31), being of a silt or
clay nature with no large sand particles or pebbles. In addition,
Drifmeyer (1975) has indicated that Elizabeth River sediment is
primarily a silt-clay complex and highly organic (45). Because the
comparisons to follow are based on fairly large numbers of determinations
that have been converted to overall averages for each system, it is felt
that particle size is not likely to be a contributing factor in
evaluating the distribution patters between one area and another.
Assuming that particle size will not bias the comparison of the
Elizabeth River to other systems, (This assumption is based on 1) visual
observations, 2) Drifmeyer's findings (45), 3) the averaging procedure
used, and 4) comparisons are made between estuarines in fairly close
geographic proximity.) an attempt has been made to define the degree of
metallic pollution in the Elizabeth River. In attempting to evaluate
the degree of metals contamination in the Elizabeth River, comparisons
of concentrations found in the Elizabeth River were made to those found in:
1) the Patapsco River (Baltimore Harbor), a tributary of
Chesapeake Bay in Maryland, representing another highly industri-
alized estuary (Table 17);
2) the open regions of the mid-Chesapeake Bay (Table 18);
3) other estuarine environments, in this case, the
Delaware, Potomac, and James River estuaries (Table 19); and,
4) the earth's crust (average values at best) (Table 20).
The Elizabeth River is similar to the Baltimore Harbor in that it,
too, supports a highly industrialized port facility. Table 17 provides
a comparison of Cd, Cr, Cu, Pb, Zn and Hg levels in these two harbors.
-------
V-26
Table 17
METALS IN ELIZABETH RIVER AND BALTIMORE HARBOR SEDIMENTS
Metal Elizabeth River Baltimore Harbor
Copper, mg/kg
Low < 2 < 1
Average 65.1-65.2 3*4-2
High 395 2926
Lead, mg/kg
Low < 3 < 1
Average 91.0-91.2 3^1
High 382 13890
Zinc, mg/kg
Low 38 31
Average 379-1 888
High 2380 6040
Cadmium, mg/kg
Low < 1 < 1
Average 3.3-3-5 6.3-6.6
High 26 654
Chromium, mg/kg
Low 9 10
Average hk.4 492
High 110 57^5
Mercury, mg/kg
Low < .01 < .01
Average .22 1.1J
High 2.73 12.20
villa, 0. and P.G. Johnson, "Distribution of Metals in Baltimore
Harbor Sediments," Environmental Protection Agency Region III
Technical Report Ho. 59, Annapolis Field Office, (Jan. 1974).
-------
V-27
Average Zn and Cd concentrations in Baltimore Harbor were
twice the levels found in the Elizabeth River. Baltimore Harbor
showed four, five and eleven times the concentrations of Pb, Cu and
Cr, respectively, found in the Elizabeth River. For all the
metals compared, Baltimore Harbor had considerably higher "high"
values than the Elizabeth River.
Table 18 is a comparison of Elizabeth River values with those
found in the open Chesapeake Bay (approximately five miles from the
Magothy River, in mid-bay, to Cove Point). For all metals compared
the average and "high" values found in the Elizabeth River exceeded
the open Bay values. The Hg, Cd, Cr, Pb, and Zn were two to four
times the average in the Bay; while the average Cu value was ten
times the Bay value.
The Delaware, Potomac and James estuaries provide additional
opportunities to evaluate the Elizabeth River data. While none of
these three estuaries have the concentrated industrial complex to
the extent that Baltimore Harbor and the Elizabeth River do, they
provide for comparisons primarily with an industrialized tidal
system (Delaware), an estuary with mainly municipal inputs (Potomac),
and a third system with a lesser degree of both municipal and industrial
inputs (James). The James River, being physically adjacent to the
Elizabeth River, provides an interesting contrast: the sediments
of the James contain the least amount of Zn and Pb, and in fact,
the average values of the James (Table 19) are similar to the Bay
values (Table 18). Potomac estuary sediments exhibit greater ranges
of values than the James but are no more than two times greater than
Bay concentrations.
-------
V-28
Table 18
METALS IN ELIZABETH RIVER AND CHESAPEAKE BAY SEDIMENTS
Metal
Copper, mg/kg
Low
Average
High
Lead, mg/kg
Low
Average
High
Zinc, mg/kg
Low
Average
High
Cadmium, mg/kg
Low
Average
High
Chromium, mg/kg
Low
Average
High
Mercury, mg/kg
Low
Average
High
Elizabeth River
< 2
65.1-65.2
395
< 3
91.0-91.2
382
38
379
2380
< 1
3.3-3-5
26
9
kk
110
< .01
.22
2.73
Chesapeake Bay
< 1
6.4-7.0
22
9
27
86
33
128
312
< 1
< l
< 1
18
25
42
< .01
.061-. 067
.31
Annapolis Field Office, unpublished, 1972-1973
-------
V-29
Table 19
METALS IN ELIZABETH
POTOMAC RIVER AND
Metal
Copper, rag/kg
Low
Average
High
Lead, rag/kg
Low
Average
High
Zinc, rag/kg
Low
Average
High
Cadmium, mg/kg
Low
Average
High
Chromium, mg/kg
Low
Average
High
Mercury, mg/kg
Low
Average
High
Elizabeth
River
< 2 '
65.1--65.2
395
< 3
91.0-91.2
382
38
379
2380
< 1
3.3-3-5
26
9
hk
110
< .01
.22
2.73
RIVER, DELAWARE RIVER,
JAMES RIVER SEDIMENTS
Delaware
River
1+
73
201
26
1^5
805
137
523
136^
< 1
2.9-3.1
17
8
58
172
< .01
1.99
6.97
Potomac
River 2
10
--
60
20
--
100
125
--
1000
< 1
.60
20
--
80
.01
--
.03
James
River
NO
--
DATA
I).
27
55
10
131
708
NO
--
DATA
NO
--
3
DATA
.
.
1.
02
32
00
Annapolis Field Office, unpublished, 1972-1973.
"Houser, M.E., and M.I. Fauth, "Potomac River Sediment Study,"
Naval Ordnance Station, Indian Head, Maryland (1972).
Pheiffer, T.H., et al., "Water Quality Conditions in the
Cheaspeake Bay System," Environmental Protection Agency Region III
Technical Report No. 55, Annapolis Field Office (August 1972).
-------
v-30
The Delaware estuary shows consistently higher levels than the
James or Potomac and is quite similar to the Elizabeth River values.
Table 20 shows average concentrations of heavy metals in the
earth's crust. As can be seen these concentration ranges are far
less than those found in the Elizabeth River. Those values from
the Chesapeake Bay and the James River are just slightly higher than
the values in Table 20. For the Potomac sediments, Pb, Zn and Cd
are in excess of the averages, while Cr, Cu and Hg are within the
specified ranges.
An inventory of existing metals concentrations in Elizabeth
River sediments has been presented and evaluated in terms of
distribution. Factors such as sulfide precipitation and organic
matrices and others have been addressed as possible mechanisms of
transport and distribution.
-------
V-31
Table 20
CONCENTRATION OF HEAVY METALS IN EARTH'S CRUST, AVG. RANGE1'2
Metal Range, mg/kg
Chromium .10 - 100.00
Copper 4.00 - 55.00
Lead 7.00 - 20.00
Zinc 16.00 - 95.00
Cadmium .05 - 0.30
Nickel 2.00 - 75-00
Manganese 50.00 - 1100.00
Mercury .03 - 0.^0
"TBowen, H.J.M., Trace Elements in Biochemistry, Academic
Press, N.Y. (1966).
2Green, J., "Geochemical Table of the Elements for 1959,"
Bulletin of the Geological Society of America, 70,
pp. 1127-1184 (1959JT
-------
APPENDIX I
-------
VI-1
TABLE 5
Location
A 1
2
3
1*
B 1
2
3
If
C 1
2
3
If
D 1
2
3
U
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
1+
J 1
2
3
U
5
6
7
CADMIUM ELIZABETH
mg/kg
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
3
< 1
< l
< 1
if
3
< 1
1
7
1
NS
< 1
1
2
2
1
7
1
Jf
1
1
3
4
3
10
U
3
3
23
26
9
7
Location
K 1
2
L 1
2
3
M 1
2
- N 1
2
3
EB 1
2
3
If
5
6
7
8
9
10
11
12
13
1U
WE 1
2
3
4
5
6
7
8
9
10
11
12
RIVER SEDIMENT
mg/kg
If
If
7
6
2
3
9
3
9
11
U
6
6
5
4
4
1
1
< 1
k
3
1
1
1
2
5
1
5
22
< 1
2
5
< 1
< 1
3
l
STUDY
Location
SB 1
2
3
Iv
5
6
7
8
9
10
n
12
13
1^
15
16
17
18
19
20
21
22
mg/kg
1
2
< 1
< 1
4
3
6
NS
1
2
1
If
U
1
If
1
2
< 1
1
< 1
1
1
NS - No Sample
-------
VI-2
TABLE 6
COPPER ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
mg/kg
13
4
2
3
19
4
4
< 2
4o
3
< 2
12
43
40
4
4
50
46
ws
13
24
28
47
56
65
3
52
7
30
13
41
43
71
18
7
11
60
66
25
22
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
mg/kg
32
40
246
90
15
49
87
3
112
128
137
169
204
141
192
112
189
195
27
221
198
74
30
74
15
32
13
212
232
18
27
130
16
18
122
10
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
6
83
55
3
192
74
395
US
30
91
< 2
165
149
24
112
27
9
24
96
52
27
32
NS - No Sample
-------
VI-3
TABLE J
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
1
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
T
CHROMIUM
mg/kg
39
H
58
ho
60
46
50
25
75
45
29
12
86
75
35
9
82
40
WS
10
39
23
51
23
82
9
43
25
25
ho
hh
32
81
32
32
26
88
92
24
20
ELIZABETH RIVER
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
SEDIMENT
mg/kg
48
41
81
72
19
39
94
40
95
95
26
55
67
32
20
17
53
53
30
74
73
27
41
40
39
51
35
19
110
32
36
40
30
35
39
31
STUDY
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
18
23
17
10
78
45
109
WS
30
48
25
99
77
23
71
36
11
16
43
24
13
26
US - No sample
-------
vi-k
TABLE 8
MERCURY ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
k
B 1
2
3
k
C 1
2
3
4
D 1
2
3
k
E 1
2
3
k
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
mg/kg
.60
.18
< .01
< .03.
< .01
< .01
< .01
< .01
< .01
.1*1
< .01
.10
< .01
< .01
< .01
< .01
< .01
.23
NS
.15
< .01
< .01
< .01
.15
.60
< .01
.15
< .01
< .01
< .01
.16
.30
.28
.15
.22
< .01
< .01
< .01
< .01
< .01
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
k
5
6
7
8
9
10
11
12
13
Ik
WB 1
2
3
k
5
6
7
8
9
10
11
12
mg/kg
< .01
< .01
.65
< .01
< .01
.33
< .01
< .01
.23
< .01
< .01
< .01
< .01
< .01
< .01
< .01
.13
^3
< .01
< .01
2.73
52
.85
.14.3
.10
.25
.23
.2k
-25
.10
^5
47
23
.11
30
.11
Location
SB 1
2
3
k
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
.07
33
-15
< .01
57
31
NS
.13
1.49
< .01
.46
52
.52
.17
< .01
.05
.24
73
.22
.80
NS - No Sample
-------
VI-5
TABLE 9
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
j 1
2
3
4
5
6
7
mg/kg
35
3
2
3
in
3
< 3
< 3
76
6
3
32
9
8
6
10
153
67
NS
6
29
48
70
130
130
< 3
86
22
60
35
80
89
156
44
16
2
226
191
35
51
LEAD ELIZABETH
Location
K 1
2
L 1
2
3
M 1
2
. N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
RIVER SEDIMENT
mg/kg
67
64
19U
162
< 3
100
162
13
19^
242
275
251
242
188
280
181
183
169
41
235
207
99
35
12.8
10
64
< 3
143
366
10
35
156
6
13
145
10
STUDY
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
41
92
102
< 3
382
108
344
NS
51
150
6
184
165
60
114
51
3
29
86
56
48
44
NS - No Sample
-------
vi-6
TABLE 10
ZINC ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
1*
5
6
T
mg/kg
249
80
86
71
237
87
72
53
564
83
68
271
541
V55
120
155
961
427
NS
65
230
Ma
373
198
885
39
367
73
107
212
217
186
1023
161
87
95
1660
1690
314
153
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
n
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
mg/kg
440
476
999
7^7
122
197
934
80
920
934
^56
67^
841
402
289
240
402
377
73
776
801
207
1^5
230
94
397
91
470
2380
105
334
841
103
80
467
83
Location
SB 1
2
3
4
5
6
7
8
9
10
n
12
13
14
15
16
17
18
19
20
21
22
mg/kg
38
349
179
132
747
532
1016
NS
168
255
60
665
507
122
337
120
54
80
255
152
108
159
WS - Wo Sample
-------
VI-7
TABLE 11
IRON ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
k
5
6
7
mg/kg
24020
33^60
35^60
27390
33120
35520
36690
16240
34440
35960
28420
11710
3^390
35320
28520
10420
36840
27200
NS
10180
319^0
17520
29910
31600
31060
14630
33270
28770
30580
31850
35080
31600
33220
28670
34240
27200
30320
35220
22700
31HO
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
mg/kg
27740
18490
33750
33950
33560
33^60
35900
33^60
31010
31600
26300
27430
30040
30430
27820
35330
29960
20560
28450
NSQ
28760
27440
29080
29890
377^0
21670
38440
26450
30190
29250
28350
387^0
385^0
35840
36640
40440
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
27210
16120
10070
7970
335^0
36540
375^0
NS
25540
351^0
29250
29140
28530
18770
29620
27330
21500
13970
26070
27380
22220
23500
NS - No Sample
NSQ- Not sufficient quantity
-------
VI-8
TABLE 12
ALUMINUM ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
k
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
k
J 1
2
3
k
5
6
7
mg/kg
10660
16040
15900
13210
12450
15900
16090
7990
17^20
16900
12120
5170
16370
15710
10940
4790
17530
11290
NS
5800
14080
6790
13170
13120
13690
6220
13670
12370
14160
13330
15030
12560
13040
11770
13870
13240
13^70
16730
11460
13830
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
mg/kg
13930
9880
14880
14360
13170
15250
17990
15710
16320
16340
9600
13670
13180
13280
11480
13730
12250
13030
13760
16700
14640
13^30
13820
16980
16720
10960
16540
13530
14500
15390
13700
17010
16480
18030
17920
16470
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
^750
6930
4740
3980
12380
10800
14290
US
9980
12820
10770
12930
12080
8120
13460
11460
8520
6710
13920
12790
11260
10440
NS - Wo Sample
-------
VT-9
TABLE
WATER CONTENT ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H i
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
*
Wet Wt.
45.04
58.89
55-05
51.29
56.06
54.30
53.00
39-^0
68.10
53.20
51.30
32.30
71-90
68.00
46.30
30.80
69-40
56.00
NS
28.70
67.10
48.50
69.40
57.60
71.80
31.00
64.50
53.90
55-20
61.10
63.80
58.30
66.60
57.60
60.70
56.30
58.40
66.60
52.30
53-80
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
I
Wet Wt.
61.10
49.50
63.80
58.60
50.10
62.30
70.20
49.80
69.40
65.20
56.60
68.70
68.40
66.60
55.90
61.50
66.60
64.40
56.70
71.80
69.80
61.90
62.20
59-80
47-30
45.30
49.80
53-50
59-00
55-40
55-20
60.60
54.00
60.00
60.50
55.20
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
1o
Wet Wt.
37-20
56.00
31.50
21.40
66.80
65.10
70.00
NS
63.60
67.50
52.30
71.80
68.40
48.90
70.40
58.90
39-20
47.60
66.40
67.80
54.00
49.00
NS - No sample
-------
VI-10
TABLE 16
COD ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
mg/kg
86440
126080
98330
89960
210110
209910
69430
85580
225890
58730
62530
38040
404880
119030
110580
64410
134970
121410
NS
18060
116520
206310
194540
107740
294540
9970
209310
66530
86260
114500
134410
95850
303350
127730
120890
263500
168800
155870
120310
107990
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
VB 1
2
3
4
5
6
7
8
9
10
11
12
mg/kg
187570
91540
152900
129880
21160
98l4o
268260
61690
153790
136720
173410
175690
175920
240720
82810
158180
126320
228200
80920
128320
172480
111550
106560
106790
35650
56510
58470
123720
91540
73900
61340
152260
64040
138320
99490
70830
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
36390
68040
74130
153000
122860
64610
310430
NS
61510
116950
75350
158650
90440
51960
116300
61290
22720
38470
118510
190370
110230
10494
NS - No Sample
-------
VI-11
TABLE 23
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
; 1*
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
T
% Org. C
3-2
^. 6
3.7
3-5
7-9
7.8
2.6
3-2
8.5
2.2
2.3
1.4
15-2
4.4
4.1
2.4
5-0
4.5
NS
.7
4.4
7-7
7.3
3.4
n.o
.4
10.9
2.5
3-2
4.3
5-0
3.6
11.4
4.8
4.5
9-9
6.3
5-8
4.5
4.0
% Organic
Location °jo
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
W3 1
2
3
4
5
6
7
8
9
10
11
12
Carbon
Org. C
7-0
3.4
5-7
4.9
.8
3-7
10.0
2.3
5.8
5-1
6.5
6.6
6.6
9-0
3-1
5-9
4.7
8.5
3-0
5-1
6.5
4.2
4.0
4.0
1.3
2.1
2.2
4.6
4.4
2.8
2.3
5-7
2.4
5-2
3-7
2.6
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
,
% Org. C
1.4
2.5
2.8
.6
4.6
2.4
7.0
NS
2-3
4.4
2.8
5.9
3-4
1.9
4.4
2.3
.8
1.4
4.4
7.1
4.1
3-9
NS - No Sample
-------
VI-12
TABLE 2k
Location
A 1
2
3
4
B 1
2
3
4
C 1-
2
3
> 4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
TKN
.087
.11*6
.064
.074
.050
.142
.068
.048
.159
.057
-151
.051
.246
.231
.054
.049
.193
.129
NS
.030
.074
.068
.269
.110
.188
.033
.096
.078
.188
.086
.131
.078
.136
.026
.057
- .136
.074
.123
.027
.050
%
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
W3 1
2
3
4
5
6
7
8
^ 9 -
10
11
12
TKN
TKN
.080
.146
.229
.100
.090
.172
.129
.092
.223
.162
.177
.295
.247
.190
.303
.192
.205
.198
.149
.264
.253
.179
.302
.208
.107
.134
.142
.178
.212
.179
.127
.195
.155
.145
.217
.152
'Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18 -
19
20
21
22
'
% TKN
.055
.077
.085
.024
.281
.160
.413
NS
.238
.189
.116
.325
.190
.098
.252
.166
.052
.092
.246
347
.200
.260
WS - No Sample
-------
VI-13
TABLE 25
Location
A 1
2
3
4
B 1
2
3
4
C 1
2
3
-, 4
T> 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
Organic Sediment Index
OSI
.28
.67
.24
.26
.40
l.ll
.18
.15
1.35
.12
.35
.07
3-7^
1.02
.22
.12
.96
58
NS
.02
.32
52
1.96
37
2.07
.01
1.05
.20
.60
.37
.66
.28
1.55
.12
.26
1.35
.47
.71
.12
.20
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
Ik
WB 1
2
3
4
5
6
7
8
9
10
11
12
OSI
.56
50
1.30
.^9
.07
.64
1.29
.21
1.29
.83
1.15
1.94
1.63
1.71
94
1.13
.96
1.68
.45
1-35
1.64
.75
1.21
.84
.14
.28
31
.82
93
50
.29
l.ll
.37
75
.80
.40
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
,
OSI
.08
.19
.24
.01
1.29
.38
2.89
NS
.55
.83
-32
1.92
.65
.19
l.ll
.38
.04
.13
1.08
2.46
.82
1.01
WS - No Sample
-------
TABLE 28 Total Volatile Solids ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
4
B 1
2
3
1+
C 1
2
3
4
D 1
2
3
4
E 1
2
3
4
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J 1
2
3
4
5
6
7
mg /kg
38000
54500
50300
51300
54600
51+000
50200
27700
85100
52000
44700
27500
95000
89400
44600
26000
81700
53100
NS
34500
69400
44500
98000
80600
95500
27300
78800
60900
89500
64200
78600
68800
81100
63300
57100
50000
63300
81800
58600
55500
Location
K 1
2
L 1
2
3
M 1
2
N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
rag/kg
61400
49900
79600
68700
55500
75100
89400
57200
91700
90100
87500
100500
100500
121100
109200
94700
107900
109200
72400
104300
101400
82300
82200
80500
52400
40000
52600
66700
71800
55900
51500
75600
57000
65600
75600
57000
4680
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
46800
36200
27200
12700
904oo
80000
111200
NS
73100
98800
72100
101700
85300
51500
100300
93900
34200
61300
99300
129100
80600
ioo4oo
NS - No Sample
-------
TABLE 29
Oil and Grease ELIZABETH RIVER SEDIMENT STUDY
Location
A 1
2
3
k
B 1
2
3
k
C 1
2
3
4
D 1
2
3
k
E 1
2
3
4
p 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
4
J l
2
3
4
5
6
7
mg/kg
8TO
70
110
ND
40
320
50
ND
80
130
200
410
390
90
690
850
3120
1870
NS
410
1330
1190
3220
1370
2840
150
1820
1600
2030
1820
2550
2450
1790
1220
950
250
770
3050
230
1720
Location
K 1
2
L 1
2
3
M 1
2
- N 1
2
3
EB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
WB 1
2
3
4
5
6
7
8
9
10
11
12
mg/kg
3100
3580
3610
3130
1160
1980
4o6o
520
3560
4710
2260
4460
4670
4400
2560
700
4390
2590
1140
3220
2620
1050
2340
800
1740
630
2290
2180
840
1060
1160
1330
430
1270
1420
890
Location
SB 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
mg/kg
840
370
70
380
7970
5020
8410
NS
2700
7800
1540
7960
4920
530
1580
1210
720
950
2860
8600
1100
1650
NS - Wo Sample
ND - Non-detectable
-------
APPENDIX II
-------
VII-1
f as
100 -
90 -
80 -
70 -
60 -
50
40 -
30 -
20
10 -
Figure 13
Cadmium
2 4 6 8 10 12 14 16 13 20 22 24 26 28 30 32
mg/kg dry
f as
100 -.
90 .
80 -
70-
60 -
50 -
40 -
30-
20 -
10 -
jpigure J.H
Chromium
r~T -T-r-n->-r-j
mg/kg dry
-------
VII-2
f as
100
90
80
TO
60
50
40
30
20
10
Figure 15
Copper
-v
I 1
LTN O LTN O
CM LT\ N- O
1 1
-]{-
ir\ O
OJ LT\
H H
LT\O LP\O LT\O >r\ O LT\O
t^-OCVI ir\t~-OOJ LAC~-O
HCVjOJOJOlroroooroJ-
mg/kg dry
f as
100
90
80
70
60
50
kO
30
20
10
Figure lo
Lead
IT\
-------
VII-3
f as
100 -
90 -
80 -
70 -
60 -
50
hO -
30
20 -
10 -
Figure 17
Zinc
1 r T~U,
oooooooooooo
ITS O L^ O LP\ O tr-> O vrs O i/> O
H rn -=t VQ t- 0\ 0 CM ro LO vD CO
H r t, H I I .1 i i
mg/kg dry
1 ' i r
O O O O
LT\ O U~\ O
OS H OJ -3"
H OJ CVI 0)
f a.s
100
90
80
70
60
5°
1*0
30
20
10
Figure 18
Aluminum
L=L i. i r: H r. 1
i
. In. ,
§§§§§§§§§§§§§
_^L^vOI>-oOCrNOHa|ro^t;Lr\^
iI iI iI ii
H H H
O O
O O
O O
r-, H
mg/kg dry
-------
VI1-
f as
100 -
90 -
80 -
70 -
60 -
50
ho -
30
20 '
10 -
Figure 19
Mercury
r i ! . i > . . . P=I . _
OJ
HHHrHHOJOJOJOJOJroro
mg/kg dry
f as
100
90
80
TO
60
5°
ho
30
20
10
Figure 20
Iron
r
i
0
o
LTA
-L_
V
0
o
0
0
H
i r~
0 0
0 O
ur\ O
I 1 1 1
-i r~
i
O 0
0 0
ir\ O
^ o
H OJ
1
1
O O O O
o o o o
LT\ O ir\ O
OJ ir\ t O
OJ r
mg
^J OJ 00
/kg dry
1
o o o
000
LT\ O l-T\
OJ LTN t
OO OO OO
1 ,
o o
0 O
O '-^N
O OJ
-* "*
o
0
o
LT\
-^
-------
-------
APPENDIX III
-------
VIII-1
NORFOLK, VIRGINIA DREDGING SITES
Sample
Number
71*020701
02
03
ok
05
06
07
08
09
10
11
12
13
Ik
15
16
17
18
19
20
21
22
23
2k
25
26
27
28
29
30
31
32
33
3k
35
36
37
38
39
Station
Location
A 1
2
3
k
B 1
2
3
k
C 1
2
3
k
D 1
2
3
li
E 1
2
li
F 1
2
3
G 1
2
3
H 1
2
3
I 1
2
3
li
J 1
2
3
U
5
6
7
Core
Description
dark gray
medium gray - slight clay
medium gray clay
medium gray clay
medium/dark gray - dark bands & medium gray bands
medium gray clay - some shells
gray clay - some shells
- light gray - some sand
black - distinct air pockets
medium gray clay - some shells
medium gray clay - some sand
core of 3" - total core - taken as sample
sand, worms, large pieces of shell, pebbles
black - air pockets
black - air pockets
gray clay - small pebbles, shells
core of k" - total core - taken as sample
medium gray, sand
black - dark band & medium gray band - sample taken
from dark band
medium gray/black sand - distinct air pockets
core of k" - total core - taken as sample
light gray clay - very dry, extremely low moisture
medium gray
black - some sand - air pockets
black - air pockets
dark gray
black - air pockets
core of 5" - total core - taken as sample
medium gray with sand - hard
medium gray
dark gray - varying shades of gray bands
black with shells - low moisture
medium gray
medium gray
dark gray
black - air pockets
medium gray
medium gray
medium gray - some sand
dark gray with sand
black - air pockets - heavy gray bottom of core
sample contains heavy brown clay - some sand -
medium gray band and dark gray band
medium gray - some sand
-------
VIII-2
Sample Station Core
Number Location Description
K 1 dark gray/medium gray/dark gray bands -
core from first dark band
hi. 2 dark gray with sand - pulverized dry sample
contained fish scales (identity confirmed
by AFO biology section)
1*2 LI dark gray
k3 2 dark gray
hh 3 core of 6" - total core - taken as sample
medium gray
1*5 Ml dark gray - alternating medium, dark gray
and black bands, about h" each
1*6 2 black - air pockets
1*7 N 1 medium gray clay with sand, shells
1*8 2 black/ dark gray/ medium gray bands -
sample taken from black band - air pockets
1*9 3 black
-------
VIII-3
NORFOLK, VIRGINIA DREDGING SITES
Sample
Number
7k02lkOI
02
03
Ok
05
06
07
08
09
10
11
12
13
lit
15
16
17
18
19
20
21
22
23
2k
25
26
27
28
29
30
31
32
33
3k
Station
Location
EB 1
2
3
k
5
6
7
8
9
10
11
12
13
111
₯B 1
2
3
ii
5
6
7
8
9
10
11
12
SB 1
2
3
k
5
6
7
9
Core
Description
dark gray, some sand, small pebbles
black, some shell
black/dark gray/light gray bands - sample from
black band - light gray portion has definite
orange streaks
black
dark gray, some sand
dark gray/black bands - ss.in.ple from dark gray band
black
black/dark gray bands - sample from black band
dark gray, some sand and -shell
black, air pockets
dark gray, air pockets
dark gray
dark gray, some sand
dark gray, small pebbles
medium gray, very low moisture
medium gray, sand and pebbles
medium gray, low moisture
medium gray, many shells & organic debris, some sand
3" core - total taken as sample - dark gray,
organic debris
medium gray, some sand & shell
3" core - total taken as sample - dark gray,
organic debris
dark gray
medium gray, some sand
medium gray
medium gray
medium gray
medium gray-brown/light brown bands - sample from
medium gray-brown band - difficult to get sample
well-mixed - extremely hard and brittle - almost
solid clay - yellow-brown sandy center of core
dark gray with lots of sand
k" core - total core taken as sample - dark gray,
much sand, small pebbles, organic debris
light gray with orange streaks - yellow-brown sandy
center of core - greenish cast when mixed
black
black, center is gray granular
black, air pockets
black mixed with light gray clay
-------
Sample Station Core
Number Location Description
SB 10 black, air pockets
36 11 medium gray, organic debris (hunk of decaying wood)
some sand
37 12 black
38 13 black, air pockets
39 Ik dark gray with sand and shell
lj.0 15 black, air pockets
ki 16 medium gray/brown with sand
1^2 17 medium gray clay
k3 18 black, light gray granular center, sand
kk 19 black, air pockets
k$ 20 black/brown, some sand, bottom 2" of core sandy brown
k& 21 brown with sand, sulfide odor
hi 22 brown, large amount of organic debris, some sand
-------
-------
APPENDIX IV
-------
IX-1
Table 21
TOXICITY OF METALS TO MARINE LIFE
Metal
Arsenic
Cadmium
Chromium
Copper
Mercury
Lead
Nickel
Zinc
Chemi cal
Symbol
As
Cd
Cr
Cu
Hg
Pb
Ni
Zn
Range of Concentrations that have
Toxic Effects on Marine Life
(mg/1 or ppm)
2.0
0.01 to 10
1.0
0.1
0.1
0.1
0.1
10.0
"National Estuarine Pollution Study, U.S. Dept. of the Interior,
FWPCA, i'-:,i_. II, Page IV, 3p6 (Nov. 3, 1969)
-------
IX-2
TABLE ?2
TRACE METALS - USES AND HAZARDS
Metals
Industrial Use
Health Effects
Arsenic coal, petroleum, deter-
gents, pesticides, mine
tailings
hazard disputed, may cause
cancer
Barium paints, linoleum, paper,
drilling mud
muscular and cardiovascular
disorders, kidney damage
Cadmium batteries, paints, plas-
tics, coal, zinc mining,
water mains and pipes,
tobacco smoke
high blood pressure, ster-
ility, flu-like disorders,
cardiovascular disease and
hypertension in humans
suspected, interferes with
zinc and copper metabolism
Chromium alloys, refractories,
catalysts
skin disorders, lung can-
cer, liver damage
Lead
batteries, auto exhaust
from gasoline, paints
(prior to
colic, brain damage, con-
vulsions, behavioral dis-
orders, death
Mercury coal, electrical batter-
ies, fungicides, elec-
trical instruments, paper
and pulp, pharmaceuti-
cals
birth defects, nerve dam-
age, death
Nickel diesel oil, residual oil, dermatitis, lung cancer
coal, tobacco smoke, chem- (as carbonyl)
icals and catalysts,
steel and nonferrous al-
loys, plating
-------
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-------
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-------
EFFECTS OF OCEAN DUMPING ACTIVITY
MID-ATLANTIC BIGHT - 1976
INTERIM REPORT
July 1977
-------
-------
EPA 903/9-77-029
EFFECTS OF OCEAN DUMPING ACTIVITY
MID-ATLANTIC BIGHT - 1976
INTERIM REPORT
Compiled and Edited by
Donald W. Lear
Marria L. O'Malley
Susan K. Smith
U.S. Environmental Protection Agency
Region III
Annapolis Field Office
Annapolis, Maryland 21401
July 1977
Project Officer
William C. Muir
U.S. Environmental Protection Agency
Region III
6th and Walnut Streets
Philadelphia, Pennsylvania 19106
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This report has been reviewed by Region III, EPA, and
approved for publication. Approval does not signify
that the contents necessarily 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.
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CONTENTS
LIST OF FIGURES iv
LIST OF TABLES x
ACKNOWLEDGEMENTS xiii
CONCLUSIONS xiv
INTRODUCTION 1
METHODOLOGY 6
REGIONAL MONITORING PROGRAM
Hydrography 8
Metals in Sediments 18
Temporal Trends of Metals in Sediments 45
from 1973 until 1977
Total Organic Carbon in Sediments 57
Organohalogens in Sediments 59
Apparent Mortalities of Arctica islandica 64
Effects of Anoxic Condition 68
INTENSIVE GRID MONITORING PROGRAM 70
Bathymetry 78
Metals and Total Organic Carbon in Sediments 81
Comparison of Intensive Grid with Regional Grid 117
Temporal Trends of Metals in Sediments 124
Distribution of Infauna in Intensive Grid 128
Incidence of Diseased Organisms 156
BACTERIOLOGY 158
REFERENCES 167
i i i
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LIST OF FIGURES
Page
1 Area of Study 4
2 Historical Stations, Intensive Grid, 5
EPA Ocean Disposal Monitoring Program
3 Historical Station Locations 10
4 Distribution of Temperature - Operation Touchstone 11
Cruise 75-VI, December 1975
5 Distribution of Salinity - Operation Touchstone 12
Cruise 75-VI, December 1975
6 Distribution of Temperature - Operation Pickup 13
Cruise 76-1, June 1976
7 Distribution of Salinity - Operation Pickup 14
Cruise 76-1, June 1976
8 Distribution of Temperature - Operation Hotspot 15
Cruise 76-11, August 1976
9 Distribution of Temperature - Operation Mogul 16
Cruise 77-1, February 1977
10 Distribution of Salinity - Operation Mogul 17
Cruise 77-1, February 1977
11 Total Organic Carbon in Sediments (mg/kg) 23
Operation Touchstone, December 1975
12 Iron in Sediments (mg/kg) - Operation Touchstone 24
December 1975
13 Nickel in Sediments (mg/kg) - Operation Touchstone 25
December 1975
14 Lead in Sediments (mg/kg) - Operation Touchstone 26
December 1975
15 Chromium in Sediments (mg/kg) - Operation 27
Touchstone, December 1975
16 Copper in Sediments (mg/kg) - Operation Touchstone 28
December 1975
iv
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Page
17 Zinc in Sediments (mg/kg) - Operation Touchstone 29
December 1975
18 Total Organic Carbon in Sediments (mg/kg) 32
Operation Hotspot, August 1976
19 Nickel in Sediments (mg/kg) - Operation Hotspot 33
August 1976
20 Lead in Sediments (mg/kg) - Operation Hotspot 34
August 1976
21 Chromium in Sediments (mg/kg) - Operation Hotspot 35
August 1976
22 Zinc in Sediments (mg/kg) - Operation Hotspot 36
August 1976
23 Total Organic Carbon in Sediments (mg/kg) 39
Operation Hotspot, August 1976
24 Nickel in Sediments (mg/kg) Operation Mogul 40
February 1977
25 Lead in Sediments (mg/kg) - Operation Mogul 41
February 1977
26 Chromium in Sediments (mg/kg) - Operation Mogul 42
February 1977
27 Copper in Sediments (mg/kg) - Operation Mogul 43
February 1977
28 Zinc in Sediments (mg/kg) - Operation Mogul 44
February 1977
29 Temporal Distribution of Iron in Sediments, Mean, 51
Standard Deviation and Range
30 Temporal Distribution of Nickel in Sediments, Mean, 52
Standard Deviation and Range
31 Temporal Distribution of Chromium in Sediments, Mean, 53
Standard Deviation and Range
32 Temporal Distribution of Zinc in Sediments, Mean, 54
Standard Deviation and Range
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Page
33 Temporal Distribution of Lead in Sediments, Mean, 55
Standard Deviation and Range
34 Temporal Distribution of Copper in Sediments, 56
Mean, Standard Deviation and Range
35 Temporal Distribution of Total Organic Carbon in 58
Sediments, Mean, Standard Deviation and Range
36 PCB (Arochlor 1254) in Sediments, Mean, Standard 63
Deviation and Range
37 Arctica islandica. Apparent Recent Mortality 66
38 Live Arctica and Clappers 67
39 Areal Extent of Oxygen Depleted Bottom Water 69
(<2 ppm 02) Mid-September 1976 (NMFS, Sandy
Hook, New Jersey, Unpublsihed data.
40 Distribution of "Dark" and "Clean" Sediments 73
Operation Touchstone, December 1975
41 Distribution of "Dark" and "Clean" Sediments 74
Operation Hotspot, August 1976
42 Distribution of "Dark" and "Clean" Sediments 75
Operation Mogul, February 1977
43 Distribution of "Dark" and "Clean" Sediments 76
Operations Touchstone, Hotspot and Mogul
44 Bathymetry of Intensive Grid Area, Depths in Feet 80
Operation Mogul, February 1977
45 Grid Station Lcoations, Operation Touchstone 89
December 1975
46 Total Organic Carbon (mg/kg dry wt) Operation 90
Touchstone, December 1975
47 Chromium (mg/kg dry wt) Operation Touchstone 91
December 1975
48 Zinc (mg/kg dry wt) Operation Touchstone 92
December 1975
49 Iron (mg/kg dry wt) Operation Touchstone 93
December 1975
vi
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Page
50 Copper (mg/kg dry wt)-Operation Touchstone 94
December 1975
51 Nickel (mg/kg dry wt) - Operation Touchstone 95
December 1975
52 Lead (mg/kg dry wt) - Operation Touchstone 96
December 1975
53 Cadmium (mg/kg dry wt) - Operation Touchstone 97
December 1975
54 Intensive Grid, Loran C Locations and Station 101
Numbers - Operation Hotspot, August 1976
55 Total Organic Carbon in Sediments (mg/kg) 102
Operation Hotspot, August 1976
56 Nickel in Sediments (mg/kg) - Operation Hotspot 103
August 1976
57 Lead in Sediments (mg/kg) - Operation Hotspot 104
August 1976
58 Chromium in Sediments (mg/kg)-0peration Hotspot 105
August 1976
59 Zine in Sediments (mg/kg) - Operation Hotspot 106
August 1976
60 Intensive Grid, Loran C Locations and Station 110
Numbers, Operation Mogul -February 1977
61 Total Organic Carbon in Sediments (mg/kg) 111
Operation Mogul -February 1977
62 Nickel in Sediments (mg/kg) - Operation Mogul 112
February 1977
63 Lead in Sediments (mg/kg) - Operation Mogul 113
February 1977
64 Chromium in Sediments (mg/kg) - Operation Mogul 114
February 1977
65 Zinc in Sediments (mg/kg) - Operation Mogul ^15
February 1977
66 Copper in Sediments (mg/kg) - Operation Mogul 116
February 1977
vii
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Page
67 Distribution of Infauna - Operation Touchstone 131
December 1975 - Protodrilus sp.
68 Distribution of Infauna - Operation Touchstone 132
December 1975 - Nematodes
69 Distribution of Infauna - Operation Touchstone 133
December 1975 - Goniadella gracilis
70 Distribution of Infauna - Operation Touchstone 134
December 1975 - Parapionosyllis longicirrata
71 Distribution of Infauna - Operation Touchstone 135
December 1975 - Sphaerosyllis erinaceus
72 Distribution of Infauna - Operation Touchstone 136
December 1975 - Aglaophamus circinata
73 Distribution of Infauna - Operation Touchstone 137
December 1975 - Stauronereis caecus
74 Distribution of Infauna - Operation Touchstone 138
December 1975 - Spiophanes bombyx
75 Distribution of Infauna - Operation Touchstone 139
December 1975 - Minuspio japonica
76 Distribution of Infauna - Operation Touchstone 140
December 1975 - Exogone hebes
77 Distribution of Infauna - Operation Touchstone 141
December 1975 - Potamilla neglecta
78 Distribution of Infauna - Operation Touchstone 142
December 1975 - Lumbrinereis impatiens
79 Distribution of Infauna - Operation Touchstone 143
December 1975 - Lumbrinereis acuta
80 Distribution of Infauna - Operation Touchstone 144
December 1975 - Aricidea jeffreysii
81 Distribution of Infauna - Operation Touchstone 145
December 1975 - Aricidea suecia
82 Distribution of Infauna - Operation Touchstone 146
December 1975 - Aricidea neosuecia
vm
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83
84
85
86
87
88
89
90
91
92
93
Distribution of Infauna - Operation Touchstone
December 1975 - Byblis serrata
Distribution of Infauna - Operation Touchstone
December 1975 - Trichophoxis epistomis
Distribution of Infauna - Operation Touchstone
December 1975 - Apelisca vadorum
Distribution of Infauna - Operation Touchstone
December 1975 - Praxillella "B"
Distribution of Infauna - Operation Touchstone
December 1975 - Number of Species
Distribution of Infauna - Operation Touchstone
December 1975 - Number of Individuals
Distribution of Infauna - Operation Touchstone
December 1975 - Simpson's Index
Distribution of Infauna - Operation Touchstone
December 1975 - Species Richness
Distribution of Infauna - Operation Touchstone
December 1975 - Shannon-Weaver Index
Cancer irroratus with Lesions
Flow Diagram of the Col i form Analysis Methodology
Page
147
148
149
150
151
152
153
154
155
156
166
Operation Mogul, February 1977
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LIST OF TABLES
Page
1 Metals in Sediments, Total Organic Carbon, Iron, 20
Nickel - Operation Touchstone, Cruise 75-VI -
Duncan's Multiple Range Test, Historical Stations
2 Metals in Sediments, Lead, Chromium, Copper - 21
Operation Touchstone, Cruise 75-VI - Duncan's
Multiple Range Test Historical Stations
3 Metals in Sediments, Zind - Operation Touchstone, 22
Cruise 75-VI - Duncan's Multiple Range Test,
Historical Stations
4 Metals in Sediments, Total Organic Carbon, 30
Chromium - Operation Hotspot, Cruise 76-11 -
Duncan's Multiple Range Test, Historical Stations
5 Metals in Sediments, Nickel, Lead, Zinc - 31
Operation Hotspot Cruise 76-11 - Duncan's
Multiple Range Test, Historical Stations
6 Metals in Sediments, Total Organic Carbon, 37
Chromium, Nickel - Operation Mogul, Cruise 77-1 -
Duncan's Multiple Range Test
7 Metals in Sediments, Copper, Lead, Zinc - 38
Operation Mogul, Cruise 77-1 - Duncan's Multiple
Range Test
8 Metals in Sediments, Historical Stations 47
9 PCB (Arochlor 1242, 1254) in Ocean Sediments 61
10 Chi-square Analysis of "Dark" and "Clean" Areas With 72
Organic Carbon Concentrations
11 Repeat Observations of "Dark" and "Clean" Areas, Grid 77
12 Metals in Sediments, Total Organic Carbon - Operation 82
Touchstone, Cruise 76-VI - Duncan's Multiple Range
Test, Grid Stations
13 Metals in Sediments, Chromium - Operation Touchstone, 83
Cruise 76-VI - Duncan's Multiple Range Test, Grid
Stations
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Page
14 Metals in Sediments, Zinc - Operation Touchstone, 84
Cruise 75-VI - Duncan's Multiple Range Test,
Grid Stations
15 Metals in Sediments, Iron - Operation Touchstone, 85
Cruise 75-VI - Duncan's Multiple Range Test,
Grid Stations
16 Metals in Sediments, Copper - Operation Touchstone, 86
Cruise 75-VI - Duncan's Multiple Range Test,
Grid Stations
17 Metals in Sediments, Nickel - Operation Touchstone, 87
Cruise 76-VI - Duncan's Multiple Range Test,
Grid Stations
18 Metals in Sediments, Lead - Operation Touchstone, 88
Cruise 76-VI - Duncan's Multiple Range Test,
Grid Stations
19 Metals in Sediments, Total Organic Carbon - 98
Operation Hotspot, Cruise 76-11 - Duncan's
Multiple Range Test, Grid Stations
20 Metals in Sediments, Nickel and Zinc - Operation 99
Hotspot, Cruise 76-11 - Duncan's Multiple Range
Test, Grid Stations
21 Metals in Sediments, Chromium and Lead - Operation 100
Hotspot, Cruise 76-11 - Duncan's Multiple Range
Test, Grid Stations
22 Metals in Sediments, Copper and Total Organic 107
Carbon - Operation Mogul, Cruise 77-1 - Duncan's
Multiple Range Test, Grid Stations
23 Metals in Sediments, Nickel and Chromium - Operation 108
Mogul, Cruise 77-1 - Duncan's Multiple Range Test,
Grid Stations
24 Metals in Sediments, Zinc and Lead - Operation Mogul, 109
Cruise 77-1 - Duncan's Multiple Range Test, Grid
Stations
25 Metals in Sediments, Total Organic Carbon, Operation 118
Mogul, Cruise 77-1 - Duncan's Multiple Range Test,
All Stations
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Page
26 Metals in Sediments, Chromium - Operation Mogul, 119
Cruise 77-1 - Duncan's Multiple Range Test,
All Stations
27 Metals in Sediments, Nickel - Operation Mogul, 120
Cruise 77-1 - Duncan's Multiple Range Test,
All Stations
28 Metals in Sediments, Copper - Operation Mogul, 121
Cruise 77-1 - Duncan's Multiple Range Test,
All Stations
29 Metals in Sediments, Lead - Operation Mogul, 122
Cruise 77-1 - Duncan's Multiple Range Test,
All Stations
30 Metals in Sediments, Zinc - Operation Mogul, 123
Cruise 77-1 - Duncan's Multiple Range Test,
All Stations
31 Metals in Sediments, Intensive Grid Area 125
32 Correlation of Benthic Infauna with Environmental 130
Parameters, Spearman's Rank Correlation
33 Bacteriological Data - Operation Hotspot, 160
August 1976
34 Bacteriological Data - Operation Mogul 164
February 1977
xn
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ACKNOWLEDGEMENTS
The U.S. Environmental Protection Agency, Region III, wishes to
acknowledge the many persons and institutions who have participated
in these multi-faceted monitoring studies.
Special acknowledgement must go to the director and staff of the
Annapolis Field Office, EPA Region III; Patricia Johnson made the many
metals determinations, Norman Fritsche the total organic carbon analyses
and R. Sigrid Kayser the organohalogen determinations. Margaret Munro
willingly typed the many tables and text of the manuscript.
The EPA Environmental Research Laboratory, Narragansett, Rhode
Island, has provided personnel for cruises and initiated special studies.
The EPA Wheeling Field Office assisted in these cruises. Chris Ostrom,
Maryland Department of Natural Resources, and Robert Davis, EPA Region
III, were especially effective participants on cruises. Capt. James
Verber, Cdrs. Adams and Gaines, U.S. Food and Drug Administration,
Davisville, Rhode Island, provided expertise in bacteriological analyses
and sampling.
Special thanks must go to the officers and crew of the U.S. Coast
Guard Cutter ALERT, Cape May, New Jersey, for their willing support and
excellent navigation in oceanographic operations. Cdr. Michael O'Brien
and his successor, Cdr. Donald Ramsden were especially helpful in
conduct of the field phases.
It is difficult to completely list all persons to whom grateful
acknowledgements are due, and many others not listed have materially
contributed to the program.
xiii
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CONCLUSIONS
1. Significantly high concentrations of metals known to be
present in City of Philadelphia sewage sludge can be found on
occasion at points in the sediments in and near the sludge release
site. Several bands with consistently high concentrations of metals,
in association with high organic carbon, have been partially identified
and have persisted for at least fourteen months in and adjacent to the
southern part of the sludge release site.
2. Ambient concentrations of the metals in question have been
derived by statistical comparisons over a three year period.
3. Polychlorinated biphenyls (PCB's) were widely distributed
in concentrations that may be inimical to marine organisms. The time
distribution indicated cyclical inputs, possibly from the coastal zone.
Localized areas of high impact, associated with other parameters from
sewage sludge, have been identified.
4. Mortalities of the mahogany clam, Arctica islandica. were
indicated at loci in and near the ocean dumping activity.
5. The large areas of anoxic waters off New Jersey in summer 1976
apparently did not extend into this study area, judging from relative
mortalities of macrobenthic fauna.
6. Detailed bathymetry of the persistently impacted area south
of the sludge release site indicates gentle geomorphic features may
affect the aggregation of dumped materials.
xiv
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7. Statistically significant changes of the benthic infaunal
communities are occurring in the impacted area south of the sewage
sludge release site.
8. A preliminary indication of diseased macrofauna associated
with the impacted area was found in February 1977.
9. Molluscan shellfish in the vicinity of the sewage sludge
site appear to harbor bacteria of sanitary significance.
xv
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INTRODUCTION
The ecological effects of a populous technological society on
the environment became incerasingly pronounced and obvious in the
past two decades. Legislation in the early 1970's was passed to
recognize and control deleterious effects on the environment.
The Marine Protection, Research and Sanctuaries Act of 1972
(PL 92-532, the "ocean dumping act") was passed to regulate ocean
dumping activities. One requirement of this legislation is a knowl-
edge of the ecological effects of ocean dumping activities as a
condition for the issuance of permits.
EPA Region III, in May 1973, initiated a field monitoring program
on two active dumpsites located approximately 40 miles east of the
Delaware-Maryland seacoast. A program was designed with emphasis on
the longer term, more persistent effects, especially on the benthic
environment, as contrasted to the more transient effects in the water
column. EPA research laboratories in Narragansett, Rhode Island, and
Corvallis, Oregon, were instrumental in the initial efforts. Many
other persons and institutions, as noted in the acknowledgements, have
participated.
The site locations of the area of study are shown in Figure 1.
Station locations are shown in Figures 2 and 3.
Several reports have been issued by EPA on the earlier phases of
this program (Palmer and Lear, 1973; Lear, Smith and 0'Mailey, 1974;
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Lear, 1974; Lear and Pesch, 1975) as well as summaries of program
results at ocean dumping permit hearings, which information is
available at EPA Region III, Philadelphia, Pa.
Several reports related to these studies have recently become
available. Forns (1977) has described the phytoplankton and zoo-
plankton findings from these cruises. Palmer et al. (1976) have
described the results of recording current meter observations and
inferred bedload transport in this area. Demenkow and Wiekramaratne
(1976) have developed a mathematical model of dispersal and settling
of sewage sludge into this environment. Klemas et al. (1976) have
reported on circulation studies in this area, conducted with radar-
tracked drogues. Marine Research, Inc. (1975, 1975, 1976, 1976) has
produced a series of reports, under contract with EPA Region III,
with detailed identification, enumeration and relationships of the
benthic infauna of this area. Interstate Electronics Corp. (1977)
under contract to EPA, has compiled an extensive and exhaustive data
bank pertinent to this area, from many sources.
This report will be primarily concerned with results of the most
recent four cruises (Operation Touchstone, December 1975; Operation
Pickup, June 1976; Operation Hotspot, August 1976; Operation Mogul,
February 1977) covering the span of time from winter 1975 to date.
In the past year several noteworthy events have been noted on
the continental shelf of the Mid-Atlantic Bight:
1. An insurgence of interest on the Mid-Atlantic continental
shelf as an ecosystem was engendered by the prospects of oil production.
2
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The results of the necessary environmental studies are beginning to
become available, with substantially increased information expected
in the next year or so.
2. There was a cessation of dumping of industrial acid wastes
at the nearby site in October 1976.
3. The track of Hurricane Belle indicated the eye of this small,
fast moving storm passed approximately over the dumpsite in August 1976.
4. A major area of dissolved oxygen depletion was noted, involving
thousands of square miles off the New Jersey coast.
5. The winter of 1977 was atypically cold, and some measured
parameters indicate the effects of this weather could be found on the
continental shelf.
The data presented herein do not represent all of the studies in
this ocean dumping monitoring program. Many samples remain archived
awaiting analysis, and many other data have not yet been plotted and
analyzed. This report summarizes some of the more salient aspects
of these investigations, primarily during the calendar year 1976.
This report is, in essence, a progress report. Field investigations
and summarization of data are continuing.
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FIGURE 1
AREA OF STUDY
76-
38'
37'
40T
77'
76'
75"
74'
SCALE IN MILES
O 10 20 30 40 30
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FIGURED
32
-, f\t
-38* 30
20
6-19
23
14
.30
33
9/
F
HISTORICAL STATIONS ; INTENSIVE GRID-'
EPA OCEAN DISPOSAL .MONITORING PROGRAM-
o
o
-38" 00'-
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METHODOLOGY
Sampling on all three cruises was from the USCGC ALERT, a 210'
Cutter based at Cape May, New Jersey and modified for oceanographic
operations. Navigation was done with the Coast Guard "Sealad" modifi-
cation of Loran C, with digital readout in yards from preassigned
location. Depth recordings were made on the ship's EDO recording
fathometer.
Hydrographic determinations were made using a mechanical BT
for temperature and depth and/or conductivities, temperature and
salinity by a Beckman RS-5 field induction salinometer. Salinity
values were verified in the laboratory with random grab samples run on a
Beckman RS-7C bench top salinometer.
Water samples for bacteriological analyses were taken by a Niskin
hinge sampler with sterile PE bags.
Bottom grabs at historical monitoring stations were made using a
Shipek sediment sampler. Four replicates were taken at each station.
The first grab was sacrificed for bacteriological subsamples and
organohalogens. Sediment for organohalogen determination was put in
hexane washed quart jars with teflon lids and stowed for laboratory
analysis.
Three grabs were sampled for metals, sediment size, total organic
carbon,and the remainder for infauna.
A small polyethylene cup was filled with sediment for metals analyses,
a small glass vial for TOC. These were then quick frozen on dry ice. A
6 oz. whirlpak was partially filled for sediment size and stowed.
6
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The remainder of the sample was placed in a gallon polyethylene
jar, preserved with 10% buffered formalin and stowed for subsequent
infauna sorting and identification.
At stations in the intensive grid one Smith-Mclntyre grab was
made at each station and three replicates for each parameter sampled
from the single grab.
Macrofauna was collected using a Fall River rocking chair dredge.
Laboratory methods can be found in Palmer and Lear (1973), Lear
and Pesch (1975) and Marine Research, Inc. (1975).
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REGIONAL MONITORING PROGRAM
HYDROGRAPHY
Station locations and the planar depth presentation of hydro-
graphic data are shown in Figure 3.
The distribution of temperature in December 1975 is shown in
Figure 4, with cooler surface waters intruding into the area from the
northwest. No vertical stratification was evident.
The distribution of salinity (Figure 5) indicates the input of
fresher waters from the coast at this season.
The distribution of temperature in June 1976, Operation Pickup,
shows the typical thermocline development and orientation of isotherms
approximating the isobaths (Figure 6). Warmer surface waters were
evident inshore. Temperatures below the thermocline were typical for
this season.
Salinities showed very little variation laterally or with depth,
and were generally slightly greater than 32 °/00 (Figure 7). One
station at the southeast portion of the study area showed anomalously
high values.
In August 1976 the waters were at midsummer temperatures, with
thermocline developed, and surface waters with no distributional
patterns (Figure 8). The thermocline was 16 to 20 meters, as usually
found.
The winter of 1977 was atypically cold in the eastern United States.
This was reflected on the continental shelf with water temperatures of
less than 3°C extending out on the shelf. The warmest waters were again
found at the southeast corner of the study area (Figure 9).
8
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The distribution of salinity showed the typically higher values
characteristic of winter conditions. A tongue of slightly fresher water
was indicated extending from the shore in center of the study area. No
pronounced stratification with depth was noted (Figure 10).
These observations indicate that in the time span noted, hydro-
graphic features were those characteristic of this area (Bumpus, 1974).
The presence of the major Delaware estuary was noted with the tongue
of fresher surface water penetrating the study area. The winter of 1977
was atypically cold, and the inshore waters were especially affected by
the meteorological phenomenon.
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FIGURE 3
HISTORICAL STATION LOCATIONS
38°50''
»G19
14
38' 30'
^ ~*
SURFACE
10 METER*
20 METER
30 METEF
40 METE
10
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FIGURE 4
DISTRIBUTION OF TEMPERATURE
Operation Touchstone - Cruise 75-VI
December 1975
38
10.8
11.3 411.6
11.0
SURFACE
38*30'
»10.8
11.0 »10'8 10.8 ',-,
. i n *fi L '
lore
.10.9 *11.3
.11.3
11.2 *
13.6
10 METERS
11.7
20 METERS
10.9
10'9.11.0
.11.1
11.5
12.5
11.9
30 METERS
,11.1
11.0'
11.8
12.9
,12.1
40 METERS
11
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FIGURE 5
DISTRIBUTION OF SALINITY
Operation Touchstone - Cruise 75-VI
8o5Q, December 1975
31.1
32.0
.32.0
32.6
38'30'
32
932.2
32.6* ,? s
#2$9' »32-8
32-8 .33.6
.33.1
SURFACE
32'° .33.5
32.0
40 METER5
12
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FIGURE 6
DISTRIBUTION OF TEMPERATURE
Operation Pickup - Cruise 76-1
June 1976
14.5
40 METERS
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FIGURE 7
DISTRIBUTION OF SALINITY
Operation Pickup - Cruise 76-1
June 1976
38°50'
32. 1
»31.7
32. 3
32.6
.32.6
31.6*32<2.32.0 .31.9
32.6
31.5
32.0
SURFACE
38* 30
20 METERS
033.3
.32.5
32.if
c£2.6
«32.5
032.2
.32.3
30 METERS
,32.
^3.0
40 METERS
14
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N
xf.
FIGURE 8
DISTRIBUTION OF TEMPERATURE
Operation Hotspot - Cruise 76-1
August 1976
38°50' ^BT Observations)
.23.6o-
.24.4
>3.9
24.4
23.6
SURFACE
^3 8* 30'
30 METERS
A0.6
.8.3
40 METERS
15
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FIGURE 9
DISTRIBUTION OF TEMPERATURE
Operation Mogul - Cruise 77-1
February 1977
SURFACE
IS 5^
3
/
5
/
40 METERS
16
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FIGURE 10
DISTRIBUTION OF SALINITY
Operation Mogul - Cruise 77-1
February 1977
38° 50
40 METERS
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REGIONAL MONITORING PROGRAM
HISTORICAL STATIONS - METALS IN SEDIMENTS
A major component of the monitoring of this continental shelf
environment was the determination of the maximum temporal and spatial
extent of measurable inputs of pollutants on the sea floor. The
routine monitoring station grid (historical) stations, covering
2
approximately 40 x 50 mile (2000 mi ) area, was designed to determine
the ambient levels of parameters, to identify areas impacted, to
estimate the extent of trans!ocation of deposited materials, and to
determine other possible inputs to the area.
A series of tables and figures (Tables 1-7 and Figures 11-28)
show the distribution of metals in sediments on cruises Touchstone
(December 1975), Hotspot (August 1976) and Mogul (February 1977).
The tables display results of analysis by Duncan's new multiple range
test, with three sample replications (Steele and Torrie,1960). Lines along
the ranked columns of concentrations include sets statistically related
at the 0.05 probability level.
Considering the data for this period, Stations A and D showed no
elevations of concentrations of any metal on any of the three cruises.
Station A, the northernmost of the monitoring stations, was probably
outside the influence of dumping activity, with known circulation
patterns primarily to the northeast and southwest from the release
sites.
18
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Station D, between the acid waste site and the sludge site, is
located on one of two fairly prominent small elevations known to the
fishermen as the "sausages". As indicated in the discussions on
bathymetry, such elevations are probably more readily swept clean of
such materials as may be deposited thereon.
The stations with most evidence of increased concentrations of
metals were 9, 20, 22, G-19, G-34, C, and F. Stations 9, 22, G-34
and F were generally south of the dumping activity, in the path of
known net water movement. Stations C and 20 were on the western sector.
of the industrial acid waste release site. Station G-19, first occupied
in June 1975, has consistently shown evidence of a catastrophic impaction
of metals and mortalities of mahogany clams.
The metals in sediments at these stations indicate intermittent
residence of high concentrations of metals on the benthos at sites over
a wide area, most commonly to the westerly and southerly directions
from the release sites. Certain areas, such as the aforementioned
Stations C, G-19, 20, 9, G-34, and F showed consistently higher concen-
trations of metals than other stations. This may be as a result of a
local more permanent residence of materials or possibly multiple input
events.
19
-------
TABLE 1
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f^.
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-------
TABLE 2
3
CJ
C
o
J3
to
M
CO
ocviLor^cooocOiiocoocM«d-rcnco COLO
i i i i i i i CVJCMCMCOCOCO'Sfr-.OO iCM
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v
CM
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c\ii
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r
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0)
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5
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r-.
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21
l i
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«^ f~"\ CO ' ' * 00 CT> r-. ii CM ***"* CM CM ^J" CTi ^* CO C_5 *^
CO i CO CMCOi CMCMi
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CVJ OO LT> CT>
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0)
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CO
00
X)
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c
£
r-
3
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CO
^
LO
CO
LO
~
O
1
21
-------
TABLE 3
in
CO 3 O) CO
I S- 01 C
^ o c o
LU n3 T-
Q O) 0) +->
LU C i CO
CO O Q.
-t->-r- i
Z to +J rO
i i -C i O
O 3 -r-
00 3 S S-
1 O O
«=C I to +J
\ - to
LU C C T-
s: o to re
i- O
4-> C
fO 3
S- Q
O)
ex
o
CO
t/1
E
C\J
c
M
-i cr>i r^coi CMO
o
to
CO
CM
CO If)
CM
CO
CO LO
a)
cu
a
O)
co
to
to
+->
CO
CO
CMCM
CM CO
22
i co
i i
CJ3 CJ3
U- O
-------
TOTAL ORGANIC CARBON IN SEDIMENT
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
*single observation
23
-------
° -> f\<
38° 30
IRON IN SEDIMENTS(mg/kg)
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
*single observation
-------
NICKEL IN SEDIMENTS (mg/kg)
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
*single observation
-------
LEAD IN SEDIMENTS (mg/kg)
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
*single ovservation
-------
Chromium in Sediments (mg/kg)
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
*single observation
-------
-38° 30'
COPPER IN SEDIMENTS (mg/k
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
* single ovservation
-------
ZINC IN SEDIMENTS (mg/kg)
29
OPERATION TOUCHSTONE
Cruise 75-VI
December 1975
*single observation
o
o
-------
TABLE 4
₯
*
1JD
LO
kO
CM
E
o
.E:
o
o
Q
UJ
CO
I OJ fJ
i CO
+> Q-
O M- i
Z Q--l-> (O
i i 13 -r-
uo o s: i-
_l ^ O
ct W -4->
I C - 10
LU O C T-
s: -r- (o a:
4J O
(O C
-------
TABLE 5
o
CD1-1
I -P
co
r^ococoocooooocococooocof^r^co
CO CM .
C\JCOC\J
CO
I
CD
CM
I
CD
u_
in
£
O
^
~°
CO
o
co
CO
«^-
CO
o
co
CTi
CM
^
C
O)
0)
-p
co
f~
I
fj
1
3
I
i
co
0^
co
co
en
^_
43
o
1
O)
CO (/)
t i (O
O I
o
co
o
1
CM
!
C
OJ
r-
3
1
I
O
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CO
CM
CO
CO
r
(O
-P
O
H-
O
p
co
CM CO CM r CO
I
CD
CM
CD
31
O
Z
0
if)
4-
TD
O
0
UD
CO
CM
CO
0
O
00
VO
_
c
O)
O)
s
-p
a>
CQ
i
CM
O
o
LO
^1-
d
UD
CM
C
r
C
4->
i
2
,
1
Lf>
CM
1
r^
CO
r^
(O
-p
o
h-
-------
38° 30'
>TOTAL. ORGANIC CARBON IN SEDIMENTS
OPERATION HOTSPOT
Cruise 76-11
August 1976
-------
3° 30'
NICKEL IN SEDIMENTS (mq/kg)
OPERATION HOTSPOT
Cruise 76-11
August 1976
-------
LEAD IN SEDIMENTS (mg/kg)
OPERATION HOTSPOT
Cruise 76-11
August 1976
34
O
o
-------
-38° 30'
(6.27;
CHROMIUM IN SEDIMENTS (mg/kg)
OPERATION HOTSPOT
Cruise 76-11
August 1976
-------
-38° 30'
ZINC IN SEDIMENTS (mg/kg)
OPERATION HOTSPOT
Cruise 76-11
August 1976
o
o
36
-------
TABLE 6
O)
o o o o o o o i
CM CM CO
CO
CM
coi coesji
CO CM i '
I I
03 CJ3
(/)
0)
co cu cu w
I 10 CD C
2: -r- c o
LU 3 -P S-
I o - =s
Q-O
o
oo
r iCMCMCMCMCMCMCMCMCMCMCM COCOCOCO«!d"l0
CS1CM
CM CO CM r- i CO CO
0
3
QJ
OQ
CO
O
in
0
un
co
c:
x:
5
en
CM
CO
10
un
(O
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.
k ..
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10
E
t/5
o
4_
-o
cn
oo
f__
V0
CM
LO
^J-
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=1-
^
<~
C
cu
cu
2
-4_)
cu
co
10
vo
0
cn
00
in
CM
cn
co
c
r-
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4-)
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c
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>i LOCOOICTII
r 10
CO
CD
CO
CM r- CO
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r CM CM r CM
C-D
37
0
^^
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u_
00
E
10
o
q_
-a
00
00
CM
CO
cn
co
LTJ
00
CM
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10
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cu
cu
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r
1
X)
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kO
CM
x>
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cn
CM
00
CO
c
f
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1
2
cn
o
cn
,i
00
cn
10
Lf)
r
rO
O
1
-------
TABLE 7
CT1
CT
E
A
O
c
1
t j 1 %
i to
r^ cu
i
OO CD CU to
1 l/> CD C
2: T- C O
UJ 3 f<3 T-
s: s_ a: -t->
i i O rC Ol
Q T -M *"*
UJ 1 i OO
ooo.cn
r~~ "f" '~ E
^- 3 "*~ ro
I-H CJ* r~ w **
o 3 -r- -a
00 2! S S- (0
1 O CU
et C to »-> _1
1 O - ">
m- ^~ «_^
r* \fm *^
res u
CU 3
OuO
o
C
1
o
4J
oo
c:
(O
cu
sr
<^
C
O
1 %
fO
oo
«c
___ o
coco-d-^^.d-^-^mtoiotoi^r-i^oooocnco
CMCO CM i r COCO r CM CM
1 i
CD O
^£
±»
< i
^. _ ^y
OJi COCOCM COCM CMi
1 |
VI
to
to
^_
a
u_
(St
E
t/i
o
to
<4_
"°
?-
^^~
vo
^o
UJ
CO
CO
1
c
CU
0)
-M
CU
CO
(
KOO
LO
CM
LO
cn
CVJ
uo
^
co
LO
00
1
cu
1
4->
CU
CD
^~
O
ro
c
r
^:
s
cj*
o
LO
₯^
^t
CO
ro
c
r~
^
5
o**
rt
^^
tn
ro
to
LO
03
-p
0
i
^>
LO
LO
cn
LO
LO
0
I
2
Ol
S-
OJ
Q.
Q.
en
OC3CDCDC>OOCDOOCDOOOOOO
COCM
^rLl-OOCM^d-aj cnCMO
CM coco en. CMCM
38
Li_
to
to
O
o
LO
o
LO
*d-
o
cn
oo"
oo
c
cu
a>
cu
«d-
o
=i-
00
co
£=
JC
3
CO
00
cn
to
LO
rC
0
h-
-------
TOTAL ORGANIC CARBON IN SEDIME
OPERATION MOGUL
Cruise 77-1
February 1977
(mg/kg)
39
o
o
o
^
r-
-------
,'.3.60.
NICKEL IN SEDIMENTS (mg/kgj
OPERATION MOGUL
Cruise 77-1
February 1977
-------
LEAD IN SEDIMENTS (rag/kg)
OPERATION MOGUL
Cruise 77-1
February 1977
41
o
o
o
^t
r-
-------
CHROMIUM IN SEDIMENTS (mg.
OPERATION MOGUL
Cruise 77-1
February 1977
9)
o
o
42
-------
(1 97}
COPPER IN SEDIMENTS (mg/kg)
OPERATION MOGUL
Cruise 77-1
February 1977
-------
ZINC_IN_SEDIMENTS (mg/kg)
OPERATION MOGUL
Cruise 77-1
February 1977
a
o
44
-------
TEMPORAL TRENDS OF METALS IN SEDIMENTS
Considering temporal trends of metals on the continental shelf,
Table 8 shows a summary of mean concentrations of metals at these
stations since the inception of the program. Figures 29 , 30, 31, 32,
33 , and 34 show plots of mean, standard deviation and range as a
function of time. Cadmium was not graphed because concentrations were
generally indeterminate. The means reflect ambient levels of metals
in this environment, and show no consistent fluctuations with season
or general increases as a function of time. The standard deviations
are an index of the normal variation to be expected. The ranges
plotted are particularly instructive for discriminating external
inputs to the environment, noting the atypical variations are nearly
always towards high concentrations. These may affect the means and
standard deviations to some extent, but when present such influences
can be taken into account.
As has been shown in previous reports (Lear and Pesch, 1975), the
metals, with possible exception of lead, show significant linear regres-
sions with iron, which further indicates a relatively stable ambience
of these parameters.
The concentrations of iron in sediments, shown in Figure 29, show
means of the order of magnitude of 1500-2500 mg/kg dry wt., which
probably represents the ambient concentrations. Loadings greater than
approximately 3500-4500 mg/kg can be regarded as atypical, and should
be further investigated.
45
-------
Nickel in sediments (Figure 30) shows mean concentrations of the
order of magnitude of 1.0-2.0 mg/kg dry wt., and concentrations greater
than approximately 2.5 mg/kg should be viewed with suspicion.
The ambient concentrations for chromium in sediments (Figure 31 )
were indicated to be 2.0-4.0 mg/kg.
Zinc in sediments in this region apparently ranged from 4.0 to
7.0 mg/kg, with aberrant concentrations above levels of approximately
8 mg/kg.
Lead concentrations generally averaged between 2.5 and 3.5 mg/kg,
and concentrations greater than 4.5 mg/kg may indicate unusual inputs
to this system.
The means of copper concentrations showed more variation than
the other metals (Figure 34) but no apparent cyclical or temporal
trends were evident. The ambient sediment concentrations would,
however, be approximately in the range of 0.5 to 2.0 mg/kg.
Cadmium concentrations, not graphed but shown in Table 8 , were
generally found to be less than 1 mg/kg. On the one cruise (Deep Six,
August 1974) with actual determinations, the mean at these stations
was 0.08 mg/kg dry wt., giving an estimate of ambient levels.
46
-------
tation A
Cd
TABLE 8
METALS IN SEDIMENTS
Historical Stations
Cr
Cu
Fe
Ni
Pb
Zn
etch
des
eep Six
id watch
ouchstone
otspot
ogul
tation B
etch
des
eep Six
id watch
ouchstone
otspot
ogul
! tation C
:etch
:des
Jeep Six
lidwatch
"ouchstone
totspot
togul
Station D
retch
:des
Deep Six
lidwatch
Touchstone
-lotspot
'fogul
Station E
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
-------
Station F
Cd
TABLE 8 (cont.)
METALS IN SEDIMENTS
Historical Stations
Cr
Cu
Fe
Ni
Pb
Zr
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station G-19
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station G-34
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 2
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 8
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
<1
0.12
<0.06
<0.05
-
-
-------
TABLE 8 (cont.)
METALS IN SEDIMENTS
Station 9
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 14
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 17
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 20
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 22
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Cd
<1.00
<1.00
0.06
<0.06
0.08
-
-
<1.00
<1.00
0.10
<0.06
0.06
-
-
<1.00
<1.00
0.08
<0.06
<0.05
-
-
<1.00
0.08
<0.06
0.05
_
-
<1.00
0.06
<0.06
0.23
_
-
Historical Stations
Cr Cu Fe
1.00
1.20
1.52
2.17
2.99
4.35
3.73
3.00
3.00
1.70
2.54
5.38
3.00
2.73
2.00
3.00
0.76
3.03
3.01
1.53
1.77
5.00
2.50
4.69
4.82
6.27
6.17
_
5.00
2.61
3.09
3.58
3.67
4.37
<1.00
<1.00
0.12
0.65
0.17
-
0.97
<1.00
<1.00
0.13
0.53
0.15
-
0.50
<1.00
<1.00
0.06
6.12
0.18
-
0.40
1.00
0.91
1.49
<1.00
-
1.97
_
<1.00
0.06
0.89
<0.10
-
1.13
49
2103
1162
1678
1644
1070
-
2350
1505
2484
2185
1302
-
1640
1607
2101
2097
1084
-
-
3016
3365
3792
2518
-
-
_
2637
2923
2643
1164
-
-
Ni
<1.00
2.20
0.78
2.57
0.94
0.97
2.53
1.00
<1.00
1.02
1.06
1.22
0.43
1.40
1.00
2.00
0.43
1.78
0.82
<0.1
1.00
3.00
2.44
2.71
1.87
1.63
3.60
_
3.00
1.22
1.27
2.88
0.37
1.83
Pb
3.00
3.60
1.61
2.15
2.12
0.97
2.67
3.00
2.50
2.96
2.12
3.11
1.05
<.05
3.00
1.00
1.88
2.42
4.08
<0.50
1.33
5.00
4.38
4.52
1.77
2.20
3.30
m^
4.50
3.23
2.97
5.95
0.57
2.60
Zn
4.00
3.20
3.52
3.39
3.16
5.50
9.13
6.00
4.00
4.04
5.14
3.56
' 3.00
5.07
4.00
4.00
2.79
4.41
2.94
2.30
4.97
11.00
8.60
10.25
9.15
11.63
' 13.77
__
8.00
4.67
6.23
3.09
4.20
8.80
-------
TABLE 8 (cont.)
METALS IN SEDIMENTS
Historical Stations
Station 23 Cd Cr Cu Fe Ni Pb
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 24
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 32
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station 33
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
Station
Fetch
Ides
Deep Six
Midwatch
Touchstone
Hotspot
Mogul
<1.00
-
<0.06
0.08
-
-
<1.00 .
0.06
<0.06
0.10
-
-
0.10
<0.06
0.11
_
0.06
<0.06
<0.05
-
-
3.00
-
2.54
3.91
3.33
2.50
6.50
1.30
2.47
3.88
2.77
2.37
1.30
2.53
3.27
2.67
3.37
_
1.43
2.36
2.37
3.30
2.73
<0.10
-
0.43
0.22
-
0.37
7.50
O.06
0.51
0.26
-
0.57
0.12
0.30
0.41
io.70
I
_
0.43
0.59
0.30
_
0.27
1992
-
2004
1338
-
-
6196
2102
2038
1887
_
-
2189
1833
1296
m
2531
2195
1458
_
-
3.00
_
0.50
1.92
<0.1
0.80
8.50
0.78
0.68
1.14
0.43
1.23
0.69
0.79
0.67
<0.1
1.20
1.16
0.97
0.52
0.37
0.97
4.00
2.47
3.67
1.77
0.85
8.50
2.96
4.46
4.19
1.60
2.03
1.21
1.72
1.20
<0.50
1.60
1.32
2.30
2.89
<0.50
1.77
5.
4.
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2.
4.;
17.!
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3.{
5.(
4.<
2.2
3.6
4.2
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7.1
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2.£
4.7
4.2
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FIGURE 29
r-
r*.
\
CM
r-
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00
OJ
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h-
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<£>
c\j
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00
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r^-
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in
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51
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FIGURE 30
e
e
LU
N.
OJ
oo
35 £
fe >
&5
il
>i
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in
r-
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(VJ
IT)
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CD
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/Cup 6>|/6ui
52
CD
-------
FIGURE 31
CD
id
CD
LO
CD
IM /Cup 6>|/6ui 1
53
CD
csi
-------
FIGURE 32
to
\
00
in
m
m
CO
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54
-------
FIGURE 33
LU
x
CM
x
00
w
i
f ^
p^
c o
H 1
Si
Q
1
£3
P
H-
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55
-------
FIGURE 34
I T 1 1 1 i '
1 _^x__ i
i ~-
r\l
z=5 LU
fe?
f£ £
CO WJ
Q %
i-
00
vn
(VJ
m
h-
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co
in
r-
Is-
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m
/Cup 65|/6iii 'H3ddOO
56
-------
TOTAL ORGANIC CARBON IN SEDIMENTS
Total organic carbon determinations in sediments were made using
similar sampling and statistical treatments as were metals, and were
consequently shown with the metals in sediments data. The stations
with statistically significant elevations of concentrations of metals
were also the stations with statistically significant increases of
organic carbon. The interpretation of these data in this context,
without qualitative knowledge of the carbon compounds, is difficult.
Increased carbon could be derived from sludge deposition, from accumu-
lations of dead organisms from the water column in consistently impacted
areas, or from increased populations of opportunistic benthic organisms,
among other causes. The association of the high organic carbon concen-
trations do, however, suggest these are related to ocean dumping
activity.
The distribution of TOC as a function of time, Figure 35, indicates
ambient concentrations in the order of magnitude of 300 to 800 mg/kg
dry wt.
57
-------
FIGURE 35
f-
\
rvj
oo
m
m
r^
\
CO
OJ
00
\
6>(/6iu 'NoayvD oiNvoyo ivioi
58
-------
ORGANOHAL06ENS IN SEDIMENTS
Analyses of the sewage sludge released into this environment
showed several organohalogens to be consistently present, consequently
checks were made in bottom sediments to determine ambient levels and
possible impaction areas. The data for polychlorinated biphenyls (PCB)
are shown in Table 9 as Arochlor 1252 and 1254, by station. These
data indicate the ambient levels on this shelf environment at a given
time, and obviously high concentrations may potentially indicate more
direct inputs. These may be related to ocean dumped materials by
association with other parameters, such as metals (Lear and Pesch, 1975).
When these data are examined as a function of time (Figure 36 ),
by expressing as mean, standard deviation and range, a cyclical plot
results. As these represent the larger scale monitoring grid, it
would appear that concentrations of PCB's fluctuate in the entire region
with atypically higher concentrations localized in specific areas.
Further computations are in progress to examine relationships with
salinity differences, reflecting possible inputs from runoff.
Regardless of source, the levels found are potentially deleterious
to the marine organisms in the area. Stalling and Mayer (1972) report
that levels of 0.94 yg/1 archlor 1254 were lethal to immature pink
shrimp, and levels of 5 yg/1 produced mortalities in the estuarine
fish, Lagodon rhomboides and leiostomus xanthurus. Moreover, these
authors report concentration factors in the order of magnitude of
40,000 times.
59
-------
These data indicate levels of PCB in this Mid-Atlantic Bight
in concentrations that can potentially be detrimental to the marine
organisms. Ocean dumping activities may contribute locally with even
greater impacts.
60
-------
TABLE 9
PCB (AROCHLOR 1242 and 1254) IN OCEAN SEDIMENTS (ppb)
Station
1
2
5
8
11
13
14
17
E
A
9
C
19
24
26
28
33
M- 3
M- 5
M- 7
M- 9
M-12
M-14
C-12
F
22
C- 1
30
D- 1
1-14
27
G-52
G-53
D
201
212
215
222
223
32
206
219
224
226
228
242
Composite
Midwatch Dragnet Touchstone
2-75 6-75 12-75
1254 1254 1254
2.52
1.39
0.68 20.5,15.4,13.6
2.19
29.2,14.8, 5.6
2.67
11.1,14.1,16.0
2.08
1.95
1.38
1.88
0.40
0.59
0.85
1.20
1.56 21.6,17.0,20.2
1.57
1.53
2.25
3.33
3.58
1.36
23.2
15.2,22.6
2.4,13.7, 9.6
102, 103, 104, 114, 115, 117 50.0
136, 144, 145, 146, 151, 152 80.0
Hot spot Mogul
8-76 ~2-7T
1254 1254
11.1
8.6
31.0
21.2
3.8
3.2
1.8 20.0
1.6
0.7 25.4
13.3
17.6
18.8
14.6
28.7
17.5
61
-------
TABLE 9 (cont.)
PCB IN OCEAN SEDIMENTS (ppb)
Quicksilver
5-73
1242 1254
Station
1 26 12
2 3 1
5 3 0.9
8 3 0.8
11 3 0.6
13 3 1
14 2 0.6
17 23 14
E
A
9
C
19
24
26
28
33
M- 3
M- 5
M- 7
Fetch Ides Deep Six
11-73 3-74 8-74
1242 1254 1242 1254 1242 1254
5.8 9.1
ND ND 33.0 28.7 <0.2 <0.2
1.4 2.1
0.5 0.4 <0.2 <0.2
1.9 3.1
2.5 ND <0.2 1.1
5.2 0.9
0.8 1.7 <0.2 1.7
0.3 3.5
b.6 1.7 4.5 4.3
6.1 5.0 1.9 4.7 <0.2 1.4
6.5 4.8
49.0/86.0 172.4/560
14.3 11.0 <0.2 1.0
-------
FIGURE 36
r-
rvj
g
»-^
tc
CO
v.
fVJ
CM
GO
qdd «WZl
63
-------
APPARENT MORTALITIES OF CLAMS
A gross index of apparent mortalities of the mahogany clam,
Arctica islandica, is the relative incidence of live, intact clams
compared with empty hinged valves, or "clappers". Individual shells,
not hinged, are not considered.
The data presented in Figure 37 are the total numbers of live
clams and clappers found in duplicate dredge hauls, not percentages.
Percent mortalities do not reflect the standing crops of available
clams, consequently may bias towards higher indicator numbers.
The low standing crops at Stations A, 32, 22, 23, and 9, all
near the 20-fathom isobath, reflect the natural distribution of this
organism which was generally found between the 20-and 30-fathom isobaths.
Stations F and G-34 are deeper than 30 fathoms and are generally sparser
in Arctica.
The data shown indicate apparent recent mortalities on several
cruises and at several locations. Stations G-19, C, 14, and 2 show
such indications.
Stations 2 and C are wtthin dumpsites. Station G-19, approximately
20 nautical miles northwest of the dumpsites, has consistently shown
significantly high concentrations of metals, indicating an impact.
Station 14 is approximately 20 nautical miles east of the dumpsites,
and shows indications or mortalities and has shown significantly high
concentrations of chromium and lead.
The data show no indications of seasonal mortalities.
64
-------
These data may also give some indication of the time required
for hinge ligaments to rot, whereby "clappers" become individual
valves. If the assumption is made that a single incident was respon-
sible for a major mortality at Stations G-19 and 2, a plot of the
incidence of "clappers" against time may give an order of magnitude
estimate. Such a plot, shown in Figure 38, indicates 12 to 14 months.
The apparent increase in numbers of live clams at Station 2 may
indicate a repopulation of an area once impacted.
Station G-19 indicates a mortality previous to June 1975, and
no evidence of recovery.
65
-------
>
Ij
<
FIGURE 37
8
ro
OJ
QQ
CD
QC
I-
UJ
-------
FIGURE 38
150
100
LJ
>
50
A
LIVE ARCTICA AND CLApPERS
o
\
\
\
\
VI
l$75
\
O
300
V)
££
UJ
a
a
u
200
100
A.2 CLAPPERS
A 2 LIVE
O GI9 CLAPPERS
GI9 LfVC
XII
VI
1976
67
xii
1977
-------
EFFECTS OF ANOXIC CONDITION
A major catastrophic oxygen depletion was noted off the New Jersey
coast by other investigators in summer 1976 (Sharp, 1977). This caused
major fish kills along some resort communities at the peak of the
summer season. This oxygen depletion apparently originated in the
apex of the New York Bight, and was at least partially due to pollution
from the New York metropolitan area. The extent of this anoxic area
was reported to extend nearly to the Delaware-Maryland dumpsite area
(Figure 40).
As one function of the February 1977 cruise (Operation Mogul)
comparative sampling at stations known to be affected by this condition
were occupied, to compare with the stations regularly visited in this
program.
Samples of macrobenthos were taken by measured mile with the rocking
chair dredge at stations marked Cl, Cl and N3. Massive mortality of
Arctica clams were found, as indicated by "clappers". There were four
live Arctica clams and one small (1-1/2" rock crab, Cancer irroratus,
in the sample at Station N3.
In comparison, the stations regularly visited (historical stations)
showed patterns of organisms and mortalities as has been regularly
experienced in this program. It is concluded, therefore, that the
effects of the anoxic area, if present in the study area at all, were
not reflected in the macrobenthos sampling. Infauna samples have been
archived, waiting analysis.
68
-------
Figure 39 Areal extent of oxygen depleted bottom water (<2 ppm 02)
mid-September 1976 (NMFS, Sandy Hook, unpublished data).
69
-------
INTENSIVE GRID MONITORING PROGRAM
An intensive bottom sampling grid, with stations one mile apart,
was initiated in December 1975 immediately south of the sewage sludge
site. This was occasioned by the detection on earlier cruises of
benthic biological community aberrancies at two of the monitoring
stations in the area. Areas of atypically discolored sediments were
found distributed in this grid sampling area.
The investigation of the intensive sampling area was facilitated
by the fact that sediments high in pollutants generally showed an
evident "dark" coloration, in contrast to the "clean" sands found
elsewhere. To test this hypothesis, chi square analyses were run
comparing total organic carbon concentrations greater than and less
than the mean of all grid stations, 'with visual observations noted at
time of collection. For the three cruises in December 1975, August 1976,
and February 1976, the results of such calculations are shown in Table 10.
These data indicate that such field observations can be useful for rapid
tentative identification of the areas with higher levels of pollutants.
The distributions of the "clean" and "dark" sediments are shown
in Figures 40, 41, and 42 for three cruises. A composite is shown in
Figure 43 These data indicate the full area! extent of the dis-
colorations has not yet been found, in spite of increased areas of
search on subsequent cruises.
The areas revisited, however, appear to be consistent and persistent.
Table 11 shows the findings of stations in common on the three cruises.
70
-------
With one exception, all areas noted as "dark" on the initial survey
remained "dark", while some "clean" areas subsequently became "dark".
This indicates this area of impaction is increasing. On the February
1977 cruise, Operation Mogul, two stations at the northwest corner
of the grid were found to be layered with "dark" bands interspersed
with "clean" sediment, possibly as a result of burial by storm
activity.
71
-------
Touchstone
Hotspot
Moqul
TABLE 10
Chi-Square Analysis of Dark and Clean
Areas with Organic Carbon Concentrations
Dark sediment
Clean sediment
Dark sediment
Clean sediment
Dark sediment
Clean sediment
TOC
> mean
30
8
X4
TOC
> mean
8
2
X2
TOC
> mean
10
2
TOC
< mean
12
45
= 30.98**
TOC
< mean
3
16
= 11.47**
TOC
< mean
11
14
X = 5.1V
72
-------
IN)
FIGURE 40
D
t i
00
DO
o z:
o
n> o
-s TI
o o a>
fD -S rfr =
O C -" O
(D _i. O J=
3 to 3 70
cr (D ;*:
0> -H =
-S ^J O
tn c 1>
i i o z:
to -c =r o
11i
en c+ =
o o
3 r
o> m
00
n
O
r i:; 11 is
o'
o
73"
-------
03
(V)
oo
ro
in
FIGURE 41
00
o
O -n
o
3=.
C (/>->
en ft) O
liD I O O
--J ii rt-
CTi ii 00 =
t3 O
O I
CO
m
a
o
O
74
-------
-------
FIGURE 43
I I
I '
I I
2 OC -H
000
i -^j
»-sj CT> en
< \
'
>. \
\
/.''/'<-1* rv;:-\/-<'--
*
;' '' \./ V- :/A--X vV'-V'\ y /
v- f\-'-/-' s \x. - v.. /; ^ //
vVV'X -/-^.v>\;W/-/ ^x
v - \v -/: /. . vvvV-.'. /
\. -x- ';-/.\v*<\'-'.-S/
V ""*':-
v.
V -V-
A
i \
-\ *
\.
\. -'.;. '
> v- -.7/.-..
\»/* * *
V"V* -' ' "
:-/-.. .x.-:--
V/..-;-.- /.::
> .-.»..
co
O.
n>
to
co
DO
O
a
n>
o &
-5 r+
o c -.
-j. O
o
3 73
fl, 7|
-S ^>l O
cn c j»
i n 2
ua < 3- o
^J II W
c+ =
o o
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n m
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m
o
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76
-------
TABLE 11
Repeat Observations of Dark & Clean Areas
Grid
Loran C
10490
70500
70510
70520
70530
70540
70550
70560
52300
52275
52250
52225
ccc
CCD
C-C
CCC
ccc
-CD
-DD
-CD
CCD
ODD
ODD
ODD
ODD
-DD
-DD
-CC
ODD
ODD
CCC
ODD
ODD
-DD
-CC
CDC
CCC
CCC
CCC
CCD
-CC
-CD
C = clean
D = dark
77
-------
BATHYMETRY
The stability of the high organic carbon areas south of the sludge
site led to specualtions on why such accumulations occur. Inspection
of the available bathymetry on the standard navigational chart of the
area showed no apparent depressions coincident with the organic carbon
areas. Previous bathymetry by EPA on the first cruise in May 1973,
limited to the boundaries of the release site, showed no apparent
depressions. A chart, "Bathymetry of the Virginia Sea," by V. Goldsmith
and C. H. Sutton at the Virginia Institute of Marine Science, shows a
small basin at approximately the southern boundary of the sewage sludge
site, but insufficient relief to account for the configurations found.
One facet of the February 1977 (Operation Mogul) cruise was a
bathymetric survey of the area to the south of the sludge site, using
the recording depth finder available on the U.S. Coast Guard Cutter ALERT.
The resultant fathograms were plotted at approximately one-half nautical
mile intervals. This interpretation resulted in a contoured plot of
the intensive grid area with very subtle relief features evident (Figure 44).
Several features not evident on other charts were discernable, but consis-
tent with the known northeast-southwest ridge and swale topography
characteristic of the Mid-Atlantic shelf.
The northeast corner of the area showed a fairly gentle slope, 40
feet over 10 miles, leading to a basin-like depression, with relief of
15 feet over approximately 3 miles. Small ridges and troughs were e
evident on the northeast and southwest sides, and another minor depres-
sion suggested towards the southern end of the area. The southeast
corner seemed to grade off towards a known steep slope or scarp.
78
-------
Super-imposition of the distribution of the organic carbon areas
on a chart with the derived geomorphologic features indicates that
the flat, gently sloped or depressed areas are higher in organic
carbon, and the slight ridges are generally cleaner. This suggests
that the materials are not so much trapped in depressions as the
ridges are swept clean by the current regimes. The implications here
are that, while organic carbon areas with concomitant metallic pollu-
tants have been consistently found in characteristic distribution in
this area, the usual hydraulic regime is sufficiently energetic to
keep the ridges cleaned off. The converse, of accumulation in these
minor depressions, must be viewed with caution, however, for high
energy events such as storm surges may be capable of redistributing
these materials. That such case may be true are observations of
intermediate layering of dark bands with clean bands of sediment in
the sampler, found on the slope on the northwest side of the area
during the past cruise. This indicates a cataclysmic activity, rather
than biological reworking. As this area is described as geologically
non-depositional, but as a palimpsest, the strength of evidence to
date would be insufficient to conclude the organic carbon area is
stabilized in the locations so far described.
If further materials were added to the area, it can be hypothesized
that the organic carbon area would increase to the seaward, less
energetic side.
79
-------
FIGURE 44
80
-------
METALS AND TOTAL ORGANIC CARBON IN SEDIMENTS - INTENSIVE GRID AREA
The distribution of metals and organic carbon in the intensive
grid area was determined statistically using Duncan's new multiple
range test. This procedure objectively selects the stations statis-
tically related at a selected level, in this case the 0.05 probability
level. The data are shown in tabular form (Tables 12 through 26) and
plotted in Figures 45 through 66 with the statistically highest subsets
encircled by broken lines. Cadmium is shown on chart only, for there
were too many indeterminate values for statistical comparison.
These plots show the distribution of the contaminant organic
carbon and metals fall statistically into similar patterns, indication
of a common source. As these materials are major components of the
sludge, as shown by analysis of the barged materials, it can be
concluded that this was an accumulative area for such dumped materials.
81
-------
TABLE 12
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
TOC
Station Maan lcv ocn
1 02 380
115 405
117 410
114 426
104 440
138 450
179 453
103 460
133 463
161 463
196 470
180 493
134 506
111 510
121 520
112 530
178 533
162 566
135 570
139 585
140 586
173 600
101 613
106 636
131 640
130 650
177 653
182 663
125 670
168 676
132 686
116 710
155 713
181 720
188 733
113 743
107 746
142 750
105 750
165 753
148 756
153 760
143 766
119 773
134 775
120 796
170 810
195 826
147 850
I V/ Uv/VS
174 860
160 866
163 896
156 930
190 956
164 963
141 980
189 1006
169 1023
154 1046
172 1053
191 1076
149 1080
157 1105
124 H20
183 n^fi
1 08 11 36
187 1160
193 1163
194 1170
166 1170
158 1190
185 1230
186 1233
192 1233
159 1240
171 1333
137 1363
175 1376
176 1385
109 1396
110 1436
118 1450
128 1470
150 1546
123 1605
122 1610
126 1720
129 1956
127 2226
152 2290
136 2333
151 2396
144 2556
145 2570
146 2373
82 df
1 Between 95
Within 183
IMIIIIIIIIINI II Total 278
III Illllll III
i I i 1 1 1 |
ANOVA
sos ms F 1
83104560 874784 8.0^
17915833 97900 !
101020394 1
-------
TABLE 13
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
Cr
Station
142
196
105
101
115
103
125
139
140
132
104
143
124
112
133
120
117
138
106
131
113
180
160
134
153
130
119
116
114
102
135
154
126
155
165
141
147
172
189
156
149
177
121
181
162
159
178
107
111
194
182
Mean
0.98
0.99
1.02
1.08
1.13
1.22
1.29
1.29
1.29
1.31
1.36
1.37
1.40
1.43
1.46
1.48
1.51
1.53
1.56
1.58
1.60
1.67
1.71
1.75
1.75
1.79
1.80
1.80
1.86
1.89
1.89
1.91
1.92
1.94
1.94
1.96
1.97
2.07
2.09
2.18
2.19
2.20
2.21
2.24
2.26
2.29
2.32
2.37
2.40
2.43
2.45
Station Mean II M Ml "
137 2750"!
167 2.54
123 2.56
168 2.58
170 2.58
152 2.60
148 2.63
195 2.66
118 2.66
169 2.68
179 2.69
158 2.73
174 2.76
193 2.82
173 2.83
127 2.88
150 2.92
122 2.93
171 2.96
188 2.96
129 2.99
157 3.01
190 3.08 1
186 3.12 1
183 3.18
144 3.22
166 3.30
163 3.33
151 3.38
110 3.39
192 3.43
184 3.45
187 3.53
136 3.55
175 3.55
108 3.56
109 3.65
176 3.67
145 3.74
M1II|H|II II
128 3.92
191 4.14
161 4.22
164 4.53
146 4.77
ANOVA
df sos ms F
Between 94 221.32 2.35 4.29*'
Within 187 102.65 0.549
Total 281 323.98
83
UMiiiiliMMMIIIIlUlll
-------
TABLE 14
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
Zn
Station
194
128
123
196
117
105
114
101
152
161
140
120
139
180
132
142
125
143
118
115
153
119
165
131
182
113
133
154
138
134
169
167
136
168
147
127
135
106
148
149
103
177
155
160
102
112
156
124
121
Mean
0.92
1.35
1.71
1.89
2.21
2.27
2.37
2.40
2.40
2.42
2.45
2.47
2.64
2.65
2.67
2.69
2.74
2.77
2.84
2.86
2.94
2.96
3.00
3.01
3.02
3.09
3.14
3.24
3.24
3.32
3.33
3.35
3.35
3.36
3.42
3.49
3.50
3.53
3.55
3.65
3.60
3.66
3.68
3.68
3.70
3.79
3.91 1
4.02
4.07
Station Mean ||||||ll III |l
162 4.09
116 4.23
172 4.25
188 4.32
111 4.32
178 4.47
181 4.48
126 4.50
189 4.65
130 4.84
173 4.89
141 4.92
159 5.17
195 5.19
137 5.34
107 5.40
104 5.50
179 5.63
170 5.67
158 5.67
157 5.68
184 5.89
190 6.07
183 6.60
187 6.79
150 6.90
191 6.96
171 6.98
166 7.04
122 7.11
174 7.22
192 7.35
175 7.41
144 7.78
186 7.79
185 8.00
151 8.04
163 8.08
176 8.11
109 8.31
193 8.34
129 8.35
145 8.52
164 9.05
146 9.31
108 9.42
110 9.73 ANOVA
84
-------
Station
104
105
101
180
117
103
196
115
106
118
142
113
140
161
139
102
132
114
120
112
116
124
147
143
165
160
126
138
119
153
107
182
133
125
141
134
188
131
181
m
177
154
152
156
189
155
148
167
184
178
168
Mean
720
732
862
865
868
893
896
933
966 1
1045
1055
1117
1120
1140
1146
1156
1156
1159
1199
1222
1231
1233
1244
1267
1287
1303
1329
1354
1366
1393
1400
1403)
1443
1444
1483
1497
1497
1511
1539 |
1574
1586 1
1636
1654
1661 |
1669
1674
1685
1711
1726 1
1808 1
1823
1
1
TABLE 15
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
Iron
Station
85
UNI minium
162
135
121
179
172
187
169
109
183
195
149
158
159
190
186
173
130
123
150
170
no
137
185
191
144
108
174
151
136
192
157
193
129
122
127
166
146
194
145
171
175
164
163
176
128
18231
1842
1859
1866
1888
1892
1913
1939
1941
1983
2025 1
2034
2045 1
2056
2058
2064
2071
2130
2134 1
2180
2256
2262
2265
2267
2270 1
2310 |
2377 1
2404
2408
2439
2475
2494
2503
2535
2617
2740
2749
2771
2822
2826
2935
3072
3135
3308
3331
ANOVA
df sos ms F
Between
Within
Total
95 111868617 1177564 9.7**
187 22627719 121004
282 134496336
-------
TABLE 16
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
Cu
Station Mean
165
167
115
180
117
161
183
120
130
196
168
101
189
118
125
114
153
148
182
184
121
134
150
142
131
135
119
162
139
112
103
132
154
147
140
188
143
138
149
102
141
116
124
176
177
133
178
156
157
.05
.05
.09
.09
.11
.12
.14
.15
.17
.18
.19
.20
.21
.23
.23
.23
.23
.24
.26
.26
.27
.28
.28
.29
.30
.30
.30
.30
.31
.32
.33
.33
.34
.35
.35
.36
.36
.38
.39
.40
.41
.42
.42
.42
.42
.42
.42
.45
.45
/iiimii
Station
172
155
113
111
195
152
160
104
105
171
169
181
190
158
107
185
106
170
159
187
174
179
194
173
126
163
192
151
129
166
193
191
109
123
175
164
144
137
110
108
145
146
122
127
186
128
136
86 r~
Meani | 1 1 1 1 1
1 II
.46
.46
.47
.48
.48
.49
.49
.49
.50
.52
.52
.53
.56
.56
.57
.61
.62
.63
.63
.70
.71
.72
.72
.74
.76
.77
.78
.79
.79
.80
.85
.88
.95
.96
.98
1.02
1.06
1.07
1.07
1.08
1.12
1.15
1.19
1.20
1.23
1.85
T-96 ANOVA
df sos ms F
Between 95 56.74 0.597Z 7.35T
Within 177 14.37 0.081
Tota
1 272 71.11
-------
TABLE 17
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
Ni
Station Mean Station Mean II III llll III! lit II
117 0.15
149 0.28
133 0.39
119 0.41
120 0.45
105 0.46
104 0.49
113 0.55
101 0.55
134 0.58
116 0.58
114 0.59
118 0.60
130 0.63
132 0.64
106 0.65
110 0.65
115 0.65
138 0.67
112 0.68
103 0.69
165 0.72
180 0.74
139 0.74
131 0.80
142 0.83
196 0.84
124 0.86
147 0.86
121 0.87
140 0.92
102 0.93
111 0.93
125 0.94
152 1.00
169 1.04
141 1.07
1 54 1.10
148 1.11
161 1.14
T60 1.20
155 1.21
167 1.23
182 1.23
177 1.29 1
172 1.31
107 1.33
1 26 1 . 34
162 1.35
143 1.38
183 1.38
135 1.40
150 1.52
168 1.52
184 1.54
159 1.56
181 1.57
156 1.59
173 1.59
108 1.61
158 1.66
195 1.74
188 1.79
170 1.82
189 1.82
178 1.83
137 1.94
164 2.05
157 2.08
1 171 2.08
, 190 2.12
145 2.21
123 2.22
129 2.24
| 146 2.28
122 2.33
127 2.34
166 2.34
144 2.38
194 2.43
186 2.50
109 2.55
175 2.56
192 2.65
187 2.66
174 2.71
185 2.80
179 3.01
163 3.07
1 128 3.09
191 3.12
151 3.20
153 3.31
136 3.33
176 3.35
193 3.38
1
ANOVA
df sos ms F
87 Between 95 205.03 2.16 3.
Within 186 126.66 0.68
'IIMIIIIIIIIIIHI
-------
Station
117
196
105
180
118
101
111
135
182
113
120
114
115
165
119
110
104
112
102
167
161
106
132
125
134
103
189
143
154
140
133
181
138
153
139
142
124
116
160
192
177
188
195
183
155
184
130
123
170
121
107
131
Mean
0774"
1.02
1.18
1.25
1.43 I
1.56
1.68
1.79
1.81
1.91
1.92
1.93
1.93
1.96
2.01
2.12
2.23
2.30
2.34
2.43
2.45
2.50
2.55
2.56
2.57
2.57
2.63
2.66
2.67
2.68
2.73
2.73
2.76
2.84 1
2.89 j
2.99
3.01
3.02
3.09
3.10
3.11
3.12
3.16
3.19
3.24
3.28
3.42
3.45
3.45
3.48
3.53
3.77
i
TABLE 18
METALS IN SEDIMENTS
Operation Touchstone - Cruise 75-VI
Duncan's Multiple Range Test
Grid Stations
Pb Station
Mean HI IIHII11 Hi
168
179
169
172
158
178
190
191
156
126
149
162
148
147
144
157
173
174
193
108
187
159
129
194
141
145
176
175
171
151
127
163
122
109
137
186
152
150
166
146
128
136
164
185
3.79 1
3.88
3.91
3.93
3.94
4.06 1
4.06
4.09
4.11
4.11
4.22
4.40
4.49
4.51
4.53
4.53
4.54
4.56
4.60
4.86
5.08
5.08
5.10
5.14
5.15
5.19
5.22
5.24
5.25
5.29
5.38
5.39
5.53
5.57
5.73
5.73
5.75
5.93
5.96
6.55
6.89
7.02
7.59
10.28
|
1
i
i
ANOVA
Between
Within
Total
df
95
187
282
SOS
723.54
628.65
1352.19
ms
7.61
3.36
F
2.26*'
88
-------
FIGURE 45
(7)
00
-------
FIGURE 46
-------
FIGURE 47
91
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FIGURE 48
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FIGURE 49
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FIGURE 50
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-------
TABLE 22
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
Grid Stations
Station Mean
Copper
237
236
234
205
209
235
220
227
238
202
224
225
208
212
216
223
213
228
207
241
204
219
242
239
217
210
211
222
215
206
240
226
214
218
221
203
201
0.20
0.23
0.27
0.30
0.33
0.37
0.40
0.40
0.40
0.47
0.47
0.47
0.53
0.60
0.63
0.63
0.67
0.67
0.70
0.73
0.83
0.83
0.90
0.97
0.97
0.97
1.00
1.00
1.30
1.33
1.43
1.63
1.90
2.20
2.57
2.63
3.27
ANOVA
TOC
Between
Within
Total
df
35
76
111
SOS
55.59
8.79
64.38
ms
1.59
0.13
F
13.73*
Station
209
212
205
234
213
236
207
237
242
224
216
202
227
228
235
225
220
208
223
219
211
210
204
241
217
238
215
240
206
239
214
222
201
218
226
203
201
Mean
275
287
316
333
383
433
470
493
600
613
665
686
693
747
783
787
793
827
873
913
933
963
980
1010
1077
1103
1227
1400
1623
1687
1700
2007
2376
2433
3060
3150
4250
ANOVA
Between
Within
Total
df
36
72
108
SOS
86211348
10706433
96917781
ms
2394760
148700
F
16/
1*
107
-------
Nickel
TABLE 23
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
Grid Stations
Station
234
236
209
205
237
235
228
238
208
213
227
207
202
220
225
223
212
204
216
240
219
224
222
217
210
239
211
241
242
206
214
203
215
226
201
218
221
Mean
0.40
0.50
0.57
0.63
0.70
0.80
0.83
0.87
1.03
1.10
1.10
1.13
1.17
1.17
1.17
1.23
1.33
1.37
1.60
1.90
1.93
1.97
2.17
2.37
2.37
2.40
2.40
2.60
2.60
2.60
2.63
2.73
2.90
3.00
3.07
3.13
3.53
Chromium
ANOVA
Between
Within
Total
df
36
H
110
SOS
81.19
4.61
85.80
ms
2.25
0.62
F
36.17*
Station
220
236
238
228
202
234
237
209
204
213
205
225
216
235
224
207
240
223
208
219
212
227
239
241
222
217
210
242
211
203
226
215
214
206
218
221
201
Mean
T733
1.43
1.73
1.73
1.80
1.80
1.87
1.90
1.93
1.97
2.07
2.17
2.27
2.33
2.33
2.37
2.47
2.47
2.50
2.60
2.67
2.70
2.87
3.00
3.00
3.13
3.30
3.33
3.50
3.53
3.53
3.57
3.83
3.97
4.23
4.53
5.33
ANOVA
Between
Within
Total
df
35
75
110
SOS
91.33
7.03
98.35
ms
2.61
0.094
F
27.85*
108
-------
TABLE 24
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
Grid Stations
Zinc
Station Mean
236
234
237
238
235
202
228
209
205
223
220
225
227
213
212
208
204
207
216
240
224
219
241
217
239
210
242
211
222
226
215
206
214
218
203
221
201
1.73
2.53
2.63
2.73
3.07
3.63
3.63
3.83
3.90
3.93
4.06
4.10
4.30
4.30
4.67
4,67
5.47
6.17
6.83
7.23
7.57
7.87
8.27
8.30
8.40
8.63
8.93
8.97
8.97
9.67
10.53
11.07
11.63
12.73
13.43
14.67
15.20
ANOVA
Between
Within
Total
df
36
74
110
SOS
1428.26
53.56
1481.81
ms
39.67
0.72
F
54.81*^
Station
Mean
Lead
238
235
236
202
234
237
209
208
225
220
207
204
212
227
205
228
240
216
239
223
211
210
241
215
222
226
219
217
224
242
206
201
214
218
221
203
0.40
1.03
1.10
1.20
1.25
1.25
1.30
1.43
1.77
1.90
1.93
2.00
2.20
2.20
2.23
2.30
2.30
2.37
2.40
2.60
2.97
3.13
3.13
3.27
3.33
3.37
3.37
3.50
3.57
3.73
4.20
5.03
5.23
5.60
6.20
6.73
ANOVA
Between
Within
Total
df
36
74
no
SOS
201.28
53.47
254.74
ms p
5.59 7.74*^
0.72
109
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116
c\j
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-------
COMPARISONS OF INTENSIVE GRID WITH REGIONAL GRID
The data from the regional monitoring stations were pooled with
the data from the intensive grid from the February 1977 cruise,
Operation Mogul, and subjected to the new Duncan multiple range test.
The results are shown in Tables 25 through 30.
Total organic carbon was significantly higher in concentration
in the impacted areas of the intensive grid than on the surrounding
shelf regions. Station 20, in the acid waste site, had concentrations
at levels found in the intensive grid. The metal parameters, chromium,
nickel, copper, lead, and zinc showed a similarity with organic carbon
of stations with significantly elevated concentrations.
117
-------
TABLE 25
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
All Stations
TOO
Station Mean
Station Mean
G-34
D
33
9
209
212
A
205
234
213
2
23
17
32
236
E
207
B
8
237
14
242
224
216
202
227
C
228
77
156
176
250
275
287
290
316
333
383
386
386
393
413
433
453
470
486
493
493
593
600
613
665
686
693
713
747
235
225
220
F
208
24
223
219
211
210
204
241
22
217
238
G-19
215
240
206
20
239
214
222
201
218
226
203
201
783
787
793
820
827
850
873
913
933
963
980
1010
1036
1077
1103
1176
1227
1400
1623
1680
1687
1700
2007
2376
2433
3060
3150
4250
ANOVA
Between
Within '
Total 1
df
55
10
65
SOS
10618056.
1258623.
11876679.
0
3
3
ms F
193055.5 16.87**
11442.0
118
-------
TABLE 26
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
All Stations
Chromi um
Station Mean
260
236
238
228
E
17
202
234
237
209
204
213
2
205
8
225
D
A
216
235
224
24
207
G-34
240
223
23
208
219
1.33
1.43
1.73
1.73
1.77
1.77
1.80
1.80
1.87
1.90
1.93
1.97
2.02
2.07
2.13
2.17
2.17
2.23
2.27
2.33
2.33
2.37
2.37
2.40
2.47
2.47
2.50
2.50
2.60
Station Mean
II
6-19 2.631
212 2.67
227 2.70
14 2.73
33 2.73
239 2.87
F 2.97
241 3.00
222 3.00
217 3.13
210 3.30
242 3.33
32 3.37
C 3.47
211 3.50
203 3.53
226 3.53
215 3.57
9 3.73
B 3.80
214 3.83
206 3.97
218 4.23
22 4.37
221 4.53
201 5.33
20 6.17
ANOVA
Between
Witnin
lotal
df
bb
112
167
SOS
154.34
15.52
169.86
ms
2.81
0.14
F
20.25*
119
-------
Station Mean
234
236
209
205
237
E
23
235
2
8
228
238
B
D
33
17
208
213
227
207
202
220
235
32
A
24
223
TABLE 27
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
All Stations
Nickel
0.40
0.50
0.57
0.63
0.70
0.70
0.80
0.80
0.83
0.83
0.83
0.87
0.90
0.97
0.97
1.00
1.03
1.10
1.10
1.13
1.17
1.17
1.17
1.20
1.20
1.23
1.23
Illl
Station Mean
14
212
C
G-34
F
22
240
219
224
222
217
210
239
211
9
241
242
206
214
6-19
203
215
226
201
218
221
20
ANOVA
III
1.401
1.60 1
1.73
1.73
1.77
1.83
1.90
1.93
1.97
2.17
2.27
2.37
2.40
2.40
2.53
2.60
2.60
2.60
2.63
2.63
2.73
2.90
3.00
3.07
3.13
3.53
3.60
Between
Within
Total
df
55
112
167
SOS
121.26
9.45
130.71
ms
2.20
0.08
F
26.11*
120
-------
Station Mean
237
236
234
D
33
205
209
235
23
B
17
220
227
238
202
224
225
A
14
208
C
2
24
212
F
216
223
213
0.20
0.23
0.27
0.27
0.27
0.30
0.33
0.37
0.37
0.40
0.40
0.40
0.40
0.40
0.47
0.47
0.47
0.50
0.50
0.53
0.56
0.57
0.57
0.60
0.63
0.63
0.63
0.67
TABLE 28
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
All Stations
Copper
Station Mean
228
207
8
32
G-34
E
241
204
219
242
239
217
210
9
6-19
211
222
22
215
206
240
226
214
20
218
221
203
201
0.67
0.70
0.70
0.70
0.70
0.73
0.73
0.83
0.83
0.90
0.97
0.97
0.97
0.97
0.97
1.00
1.00
1.13
1.30
1.33
1.43
1.63
1.90
1.97
2.20
2.57
2.63
3.27
ANOVA
Between
Within
Total
df
55
112
167
SOS
68.72
7.48
76.20
ms
1.25
0.066
F
18.71
r*
121
-------
TABLE 29
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
All Stations
Lead
Station tfean
238
23
235
D
236
202
234
237
209
14
208
32
33
225
220
A
207
204
24
212
227
205
228
240
8
216
2
G-34
0.40
0.85
1.03
1.05
1.10
1.20
1.25
1.25
1.30
1.33
1.43
1.60
1.77
1.77
1.90
1.90
1.93
2.00
2.03
2.20
2.20
2.23
2.30
2.30
2.35
2.37
2.40
2.40 J
Station Mean
239
B
22
223
9
F
E
211
210
241
215
C
20
222
226
219
217
224
242
G-19
206
201
214
218
221
203
limn
2.40
2.50
2.60
2.60
2.67
2.80
2.83
2.97
3.13
3.13
3.27
3.27
3.30
3.33
3.37
3.37
3.50
3.57
3.73
4.07
4.20
5.03
III
5.23
5.60
6.20
6.73
ANOVA
Between
Within
Total
df
53
99
152
SOS
247.53
90.69
338.22
ms
4.67
0.92
F
5.09*
122
-------
TABLE 30
METALS IN SEDIMENTS
Operation Mogul - Cruise 77-1
Duncan's Multiple Range Test
All Stations
Zinc
Station Mean
236
234
237
238
235
D
202
228
8
209
205
223
220
225
23
33
227
213
212
208
2
A
24
17
14
E
204
207
1.73
2.53
2.63
2.73
3.07
3.43
3.63
3.63
3.77
3.83
3.90
3.93
4.06
4.10
4.23
4.23
4.30
4.30
4.67
4.67
4.70
4.73
4.97
4.97
5.07
5.27
5.47
6.17
Station Mean
B
F
216
32
G-34
240
224
C
219
241
217
239
210
6-19
22
242
211
222
9
226
215
206
214
218
203
20
221
201
Hill
6.30HI
6.67 1
6.83 |
7.10
7.23
7.23
7.57
7.83
7.87
8.27
8.30
8.40
8.63
8.70
8.80
8.93
8.97
8.97
9.13
9.67
10.53
11.07
11.63
12.73
13.43
13.77
14.67
15.20
ANOVA
Between
Within
Total
1
1
df
55
12
67
SOS
1784.
107.
1892.
73
51
25
ms
32.
0.
45
96
F
33.
80*
123
-------
TEMPORAL TRENDS OF METALS IN THE INTENSIVE GRID
Table 31 shows a summary of metal concentrations at stations in
the intensive grid area common to the December 1975, August 1975 and
February 1977 cruises. No consistent trends of increasing or decreasing
concentrations are immediately apparent with any parameter. However,
stations marked with an asterisk were significantly the highest in
concentrations in the respective cruises, indicating these two clusters
of stations show consistently elevated levels, and are probably the
most severely impacted.
124
-------
TABLE 31
METALS IN SEDIMENTS
Intensive Grid Area
Stations in Common
Touchstone
117
120
*122
124
133
*135
138
140
149
*152
154
156
165
167
170
172
181
184
*186
188
Hotspot
228
201
202
235
203
204
205
227
206
207
208
209
211
212
213
214
215
216
217
*218
219
220
*221
222
223
224
225
*226
Mogul
234
228
201
202
235
203
204
205
227
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
Touchstone
1.08
1.92
5.53
3.01
2.73
1.79
2.76
2.68
4.22
5.75
2.67
4.11
-
3.16
5.14
3.93
2.73
3.28
5.73
3.12
Pb
Hotspot
4.13
3.23
0.93
3.33
3.60
1.20
-
4.03
1.43
<0.5
<0.5
-
1.93
1.70
<0.5
1.80
1.90
2.70
0.80
2.30
1.80
0.45
1.67
1.60
2.00
1.00
3.37
3.70
Mogul
1.25
2.30
5.03
1.20
1.03
6.73
2.00
2.23
2.20
4.20
1.93
1.43
1.30
3.13
2.97
2.20
<0.5
5.23
3.27
2.37
3.50
5.60
3.37
1.90
6.20
3.33
2.60
3.57
1.77
3.37
Touchstone
1.51
1.48
2.93
1.40
1.46
1.89
1.53
1.29
2.19
2.60
1.91
2.18
1.94
2.54
2.58
2.07
2.24
3.45
3.12
2.96
Cr
Hotspot
5.57
4.73
2.60
5.27
3.43
2.47
-
4.20
2.33
2.67
1.60
2.40
3.97
2.90
2.20
4.03
4.43
3.57
2.47
6.07
3.87
1.80
4.23
4.00
3.07
2.57
2.87
4.53
Mogul
1.80
1.73
5.33
1.80
2.33
3.53
1.93
2.07
2.70
3.97
2.37
2.50
1.90
3.30
3.50
2.67
1.97
3.83
3.57
2.27
3.13
4.23
2.60
1.33
4.53
3.00
2.47
2.33
2.17
3.53
125
-------
TABLE 31 (cont.)
METALS IN SEDIMENTS
Intensive Grid Area
Stations in Common
Touchstone Hotspot
117
120
122
124
133
135
138
140
149
152
154
156
165
167
170
172
181
184
186
188
228
201
202
235
203
204
205
227
206
207
208
209
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
Mogul
234
228
201
202
235
203
204
205
227
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
:hstone
0.15
0.45
2.33
0.86
0.39
1.40
0.67
0.92
0.28
1.00
1.10
1.59
0.72
1.23
1.82
1.31
1.57
1.54
2.50
1.79
Ni
Hotspot
1.67
1.67
<0.1
1.37
1.60
0.30
-
1.57
0.25
0.30
0.45
0.24
1.33
0.67
0.47
1.33
1.70
1.17
0.30
2.43
1.13
0.40
1.80
1.37
0.90
0.33
0.50
1.77
126
Mogul
0.40
0.93
3.07
1.17
0.80
2.73
1.37
0.63
1.10
2.60
1.13
1.03
0.57
2.37
2.40
1.33
1.10
2.63
2.90
1.60
2.27
3.13
1.93
1.17
3.53
2.17
1.23
1.97
1.17
3.00
Touchstone
2.21
2.47
7.11
4.02
3.14
3.50
3.24
2.45
3.65
2.40
3.24
3.91
3.00
3.35
5.67
4.25
4.48
5.89
7.79
4.32
Zn
Hotspot
12.83
11.50
3.43
9.87
9.23
2.43
-
8.87
3.03
2.73
2.90
3.27
7.73
4.50
2.77
7.87
8.40
6.47
3.17
11.60
7.37
2.53
10.50
7.20
5.47
2.57
3.27
9.03
Mogul
2.53
3.63
15.20
3.63
3.07
13.43
5.47
3.90
4.30
11.07
6.17
4.67
3.83
8.63
8.97
4.67
4.30
11.63
10.53
6.83
8.30
12.73
7.87
4.06
14.67
8.97
3.93
7.57
4.10
9.67
-------
TABLE 31 (cont.)
METALS IN SEDIMENTS
Intensive Grid Area
Stations in Common
Touchstone
117
120
122
124
133
135
138
140
149
152
154
156
165
167
170
172
181
184
186
188
Hotspot
228
201
202
235
203
204
205
227
206
207
208
209
_
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
Mogul
234
228
201
202
235
203
204
205
227
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
Cu
Touchstone
<0.10
0.15
1.19
0.42
0.41
0.30
0.38
0.35
0.39
0.49
0.34
0.45
<0.10
<0.10
0.61
0.52
0.53
<0.10
1.23
0.36
Mogul
0.27
0.67
3.27
0.47
0.37
2.63
0.83
0.30
0.40
1.33
0.70
0.53
0.33
0.97
1.00
0.60
0.67
1.90
1.30
0.63
0.97
2.20
0.83
0.40
2.57
1 00
1 \J\J
0.63
0.47
0.47
1.63
127
-------
DISTRIBUTION OF INFAUNA IN INTENSIVE GRID
Previous reports (hearing testimony, City of Philadelphia; ocean
dumping permit hearing, Georgetown, Delaware, April 1976) have indicated
changes in the benthic infaunal community as a function of ocean dumping
activity. These conclusions were based on observations of data from
the regional wide area monitoring (historical) stations.
More detailed examination of data in the intensive sampling (grid)
areas associated with the high organic carbon and metal deposits is
currently in progress. Figures 67 through 85 show the distribution
of the dominant organisms from the December 1975 cruise (Operation
Touchstone). Numbers shown are the mean of three replicates.
Visual inspection of the data indicate the distribution of the
archiannelid Protodrilus did not appear to be affected by any of the
parameters measured. Similarly the nematode distribution showed no
obvious positive or negative associations with the "clean" or "dark"
areas.
The polychates showed a wide range of response. Goniadella gracilis,
Parapionsyllis longicirrata, Praxilella "B", Sphaerosyllis erinaceus, and
Aglaophamus circinata were intolerant of the materials deposited. Stauro-
nereis caecus was apparently indifferent. Spiophanes bombyx. Minuspio
japonica, Exogone hebes, and Potomilla neglecta population densities
were apparently stimulated by the inputs to this habitat. Within some
polychaete general Lumbrinereis impatiens was stimulated while Lumbrinereis
acuta was intolerant of these conditions. Aricidea jeffreysii was in-
tolerant, while Aricidea sueria and Aricidea neosuecia were apparently
indifferent.
128
-------
Of the amphipods dominating this environment, Byblis serrata
and Trichophoxis epistomis seemed to be indifferent, while Ampelisea
vadorum populations were stimulated in the high organic areas.
Preliminary statistical examination of these data indicated the
benthic populations were not normally distributed, but fitted a negative
binomial distribution. Consequently a nonparametric statistical method,
Spearman's rank correlation, was selected to determine whether the
apparent distributions were in fact statistically sound (Table 32).
The polychaete, Spiophanes bombyx, was apparently stimulated in
numbers in the areas of high organic carbon at this time, as indicated
by positive and significant correlation coefficient. Mean grain size
was not significant in its distribution, but the percent fines was
correlated at a lesser level.
Sphaerosyllis erinaceus and Lumbrinereis acuta were significantly
excluded from the areas of high organic carbon and nickel, were inde-
pendent of mean grain size, but were negatively correlated with percent
fine fraction. Goniadella gracilis was excluded from the high organic
carbon and nickel areas, and was negatively correlated with mean phi
and percent fine fractions.
Data analyses are continuing on this aspect, but the indications
to date are that sewage sludge disposal is significantly altering the
distribution of the benthic infauna, causing aberrant increases of
some opportunistic species, and lethal to the pollution sensitive
species.
129
-------
TABLE 32
Correlation of Benthic Infauna with Environmental Parameters
Spearman's Rank Correlation
rs,t
Mean 0 % Fines TOC Ni
Spiophanes bombyx 0.44 0.58 0.54 0.67
1.73 2.52 5.85** 5.20**
Goniadella gracilis -0.56 0.47 -0.62 -0.67
2.38* 1.89* 8.99** 5.20**
Sphaerosyllis erinaceus 0.02 -0.62 -0.50 -0.49
0.07 2.79** 6.32** 6.46**
Lumbrinereis acuta -0.22 -0.71 -0.52 -0.76
0.79 3.50** 5.51** 14.04**
* Significant p <0.05
** Significant p <0.01
130
-------
FIGURE 67
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RIBUTION OF
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131
o
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132
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133
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09
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CD
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AU
DISTRIBUTION OF
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Cruise 75-VI
ra
re
i-
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134
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in
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en.
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DISTRIBUTIO
Ol
c
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Cruise
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to
CD
c
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138
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^ o o*
₯ *-<
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Cruise 75-VI
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140
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xf>
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152
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153
O
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155
O
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ION OF INFAU
Operation Touchstone
Cruise 75-VI
DISTRIBUT
X
CD
TD
C
S-
01
>
(O
CD
I
c
o
c
c
ra
.c
to
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o
CM
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CO
CO
o
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-------
DISEASES OF MARINE ORGANISMS
Visible necrotic conditions or abnormalities or marine organisms
have been described from known polluted areas, including the New York
Bight. It has been a function in the cruise plans of the Region III
monitoring expeditions to note abnormalities, lesions, growth,
deformities, etc. In the wide area coverage, no obvious aberrancies
were noted.
In the February 1977 cruise, while sampling with the rocking chair
dredge in the intensive grid, adjacent and immediately south of the
sewage sludge site, a live rock crab, Cancer irroratus, was noted with
obvious lesions (Figure 92). As this sampling was for collection for
other parameters further investigations were not accomplished on that
cruise. More detailed collections in the intensive survey area are
planned, based on this observation.
Macroscopic observations are obviously but a gross index of
organic or infectious diseases. Samples of Arctica have regularly
been collected, preserved and archived for histopathological deter-
minations at the EPA National Marine Water Quality Laboratory,
Narragansett, Rhode Island.
156
-------
FIGURE 92
Cancer irroratus with Lesions
157
-------
BACTERIOLOGY
Operation Hotspot - Cruise 76-11
August 1976
M. L. O'Malley
During Operation Hotspot, August 1976, 32 sediment samples and
3 shellfish samples were analyzed for total coliforms and fecal coli-
forms. All stations sampled were within the intensive sampling grid.
(Figure 54 ). Sediments were subsampled from an undisturbed Smith-
Mclntyre bottom grab using a flame-sterilized 2.7 ml cylindrical
scoop. This was introduced into a French square containing 100 ml
of sterile distilled water and treated as a normal bacteriological
sample. The French square was vigorously shaken and the sediment
allowed to settle out over 2-3 minutes. The sample was split and run
through both the total coliform and fecal coliform procedures as out-
lined in Standard Methods for the Examination of Water and Wastewater
(1976). Incubation for coliforms was 24 hours at 35°C in a dry air
incubator and at 44.5°C for fecal coliforms in a shaker water bath.
Results were negative for both total coliforms and fecal coliforms for
all sediments sampled as shown in Table 33.
A Fall River "rocking chair" dredge was deployed at Station 201
to obtain shellfish for bacteriological analyses. Two Arctica islandica
clams and one horse mussel, Modiolus modiolus were tested. Each was
shucked, weighed and ground in a sterile blender to facilitate handling.
Standard total coliforms and fecal coliforms MPN's were estimated
following procedures listed in "Standard Methods". A 3-tube, 3-dilution
158
-------
schema was employed using aliquots of 10.0, 1.0 and 0.1 ml of blended
shellfish meat. MPN's for shellfish are also shown in Table 33. All
shellfish tested contained both coliforms and fecal coliforms with the
mussel, Modiolus, having the highest values for both.
Sediment samples showed no influence from municipal waste disposal,
however the shellfish sampled contained coliforms and fecal coliforms.
This indicated bacteriological studies should continue.
159
-------
TABLE 33
BACTERIOLOGICAL DATA
Operation Hotspot - August 1976
GRID STATIONS
Station Date Time
201 8/08/76 1615
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
232
235
201
201
201 8/C
1645
1110
1552
1710
1140
1535
1730
1042
1203
1515
1750
1014
1224
1447
1810
0953
1303
1423
1830
0920
1333
1338
1847
1845
2014
2218
2128
2240
V 2240
18/76 2240
Depth
(Fathoms) Samp
Col i form F. Col i form
le plate cts./50 ml
25 Sediment <1 <1
/TV. 'N /x
27
27
28
29
29
27
29
27
30
29
30
25
25
34
32
25
32
33
32
32
33
33
35
i
i
i
i
j
I
35 I
37
i
25 -^ ^/ "J'
26 Sediment <'
MPN/100 gm MPN
25 Arctica 3
25 Arctica 15
25 Modiolus 29
-------
BACTERIOLOGICAL ANALYSES
Operation Mogul - February 1977
Capt. Willard N. Adams
USPHS - Davisville, R. I.
The comments expressed in this section are the interpretations
of bacteriological (coliform) analysis performed aboard ship during
calm and rough seas and good and inclement weather conditions. The
ship was not equipped to perform laboratory work, which required
modifications of existing ship compartments and temporary laboratory
installations. The ship's helicopter shack was used as an incubator
room, which required an electric heater to maintain ambient tempera-
ture for the desired incubator operation during Operation Mogul.
Temporary 4 x 6 x 8 ft. laboratory shacks were lashed to the railing
of the ALERT. It was necessary to keep an electric heater operating
in the temporary lab shacks to keep membrane filter (MF) apparatus
(tubing) from freezing. Thirty-five mm slides of facilities and
operations are available at North East Technical Services.
The results of coliform analysis of bottom waters, sediments and
mahogany clam (Arctica islandica) samples are presented in Table 34
Figure 93 represents a flow diagram of the coliform analysis methodo-
logy employed aboard ship. These methods generally follow APHA
Recommended Procedures for the Examination of Sea Water and Shellfish,
4th edition, 1970. However, some procedures were difficult to follow
aboard ship such as gravametric procedures that require weighing a
portion of sediment or shellfish homogenate. A special balance is
161
-------
required (not available during these studies) that will record weighings
and compensate for ship movement. Volumetric measurements of shellfish
homogenate were therefore made based on the equivalence of one ml to
one gram of homogenate. Sediment measurements were made with a sterile
wooden applicator, four approximate 2.5 g portions were estimated to
represent a ten-gram amount of sediment. The temperature of the air
incubators ranged between 35° to 37° C. rather than the 35±0.5°C recom-
mended by APHA Recommended Procedures for the Examination of Sea Water
and Shellfish, 4th edition, 1970. All other procedures, except those
discussed above, for MPN and MF analysis were generally in agreement
with the Recommended Procedures and Standard Methods.
The results expressed in Table 34 showed that of 20 water samples
only 3 contained detectable MPN and MF coliform concentrations and only
one sediment sample contained a detectable coliform MPN concentration.
Water samples from Stations G-34, 205 and 207 had coliform MF concen-
trations of 0.6/100 ml, 1/100 ml and 0.2/100 ml respectively. The
sediment coliform MPN concentration at Station 207 was 22/100 g.
Table 34 also shows that speciation of coliform bacteria isolated
from water and sediment samples were not fecal coliforms. Escherichia
coli was not isolated in these samples, but rather secondary coliforms
such as Enterobacter, Citrobacter and Pseudomonas which are perhaps
more resistant to the the marine environment than £. coli.
The significance of these results suggest that even though the
coliform isolates are not specifically associated with fecal contamination
they are associated with a hetrotrophic terrestrial environment and are
162
-------
present in sewage. They are foreign to marine waters especially at
the ocean depths salinity and temperature from which these samples
were obtained.
Table 34 also shows the clams, Arctica islandica, to have a
relatively higher concentration of coliforms than was indicated by
water or sediment samples. Of the seven clam samples examined the
MPN coliform count ranged from 36/100 g to 2400/100 g, and the fecal
coliforms from 36 to 73 per 100 grams.
Speciation of the coliform isolated from clam samples, with the
exception of Station 17-1, were not E_. coli. Enterobacter, Klebsiella
and Pseudomonas genera were isolated and identified from clam homo-
genates. The increased concentrations of these coliforms in the clams
is probably caused by the filter-feeding habits of clams. A clam
sample from Station 17-1 had an MPN concentration for coliform and fecal
coliform of 9 /100 g, which was speciated to be £. coli. indicating a
potential for more recent sewage deposition at this station.
The bacteriological results from Operation Mogul suggest that the
count levels of secondary coliform indicator bacteria obtained from
clam samples indicate concentration of these bacteria in the filter-
feeding clams. Also speciation of coliforms isolated and identified
from clam, sediment and water samples suggests that they are probably
coming from sewage dumping. Additional studies in surrounding ocean
areas out of the disposal site are required to establish background
information presently lacking on the concentrations and speciation of
bacteria present in the clams, sediment and water.
163
-------
TABLE 34
BACTERIOLOGICAL DATA
OPERATION MOGUL
February 1977
Station
32
G-34
G-34
24-1
8
8
8
17-1
234
234
201
201
236
236
205
205
203
203
207
207
227
227
238
238
240
240
Sampl e
Sediment
Water
Sed.
Clam
Clam
Sed.
Water
Clam
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
MPN MF MPN
Total Total Fecal
Col i forms/ Col i forms/ Col i forms/
100 ml Count 100 ml 100 ml API Speciation
<22
<2.2 0.6+ <1 Ent. agglomerams 4 ea
<22
36 <36 Kl . pneumoniae
Ent. aerogenes
2400 73 Ent. cloacae - 3 ea
Kl . pneumoniae - 4 ea
<22
<2.2 <1
91 91 E. coli - 2 ea
<22
<2.2 <1
<22
<2.2 <1
<22
<2.2 <1
<22
<2.2 <1 1 C. freundii
<22
<2.2 <1
22/<22 <22 Ps. mal tophi lia
<2.2 0.2+ <1 Ent. Cloacae
<22
<2.2 <1
<22
<2.2 <1
<22
<5.7 <1 ]64
Date
2/16/77
2/17
11
"
"
"
11
II
11
"
"
11
"
11
11
"
"
2/18
"
11
"
11
"
n
11
11
-------
TABLE 34 (cont.)
Station Sample
210
210
212
212
213
213
215
215
220
220
221
221
223
223
225
225
242
242
218
218
Grid #1
209 - 1
mile SW
Grid #2
218 - 1 mi
toward 215
Grid #3
206 - 1 mi
toward 203
Grid #4
237 - 1 mi
toward 236
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Sed.
Water
Clam
Clam
Clam
Clam
MPN MF MPN
Total Total Fecal
Col i forms/ Col i forms Col i forms
100 ml Count 100 ml 100 ml API Speciation Date
<22
<2.2 <1
<22
<2.2 <1
<22
<5.7 <1
<22
<5.7 <1
<22
<5.7 <1
<22
<5.7 <1
<22
<5.7 <1
<22
<5.7 <1
<22
<5.7 <1
<22
<5.7 <1
230
36/<36
2400
91
2/18/77
11
n
n
11
11
11
n
2/19/77
n
n
11
"
11
"
"
11
11
11
11
36 Ent. cloacae - 2 ea "
<36 Ps. aeruginosa "
73 Kl . pneumoniae - 3 ea "
Ent. cloacae 2 ea
Ent.aerogenes
<36 Kl . pneumoniae "
Ent. aerogenes
165
-------
FIGURE 93
FLOW DIAGRAM OF COLIFORM PROCEDURES EMPLOYED IN OPERATION MOGUL
SAMPLES COLLECTED FROM PHILADELPHIA DISPOSAL SITE
Bottom Sea Water
(SW)
Bottom Sediment
(Sed)
Sea Clams-Homogenized
Liquor + Meats
Membrane Filter Procedure
(MF) HC Mi Hi pore Filter
Most Probable Number
(MPN)
Procedure
I
Sample Filter Volumes (SFV) were
500 and 100 ml aliquots. MF's
containing filtrates were placed
in contact with pads saturated
with lauryl tryptose broth (LST)
and incubated for 3 hrs. at 35°C
Recessitated MF's were transfer-
red from LST pads to m-Endo Agar
LES with continued 35°C incu-
bation for 21 hrs. Pick pink to
dark red colonies with metallic
sheen (typical coliform morpho-
logy) to BGBB for confirmation.
Colony count equated to 100 ml
of SFV represents the total
coliform concentration.
5 tubes of double strength
LST presumptive broth are
inoculated with 10 ml of
SW and/or 10 ml of 10% sus
pension of Sed in sterile
phosphate buffer solution
(PBS). Incubate for 24 to
J48 hrs. at 35°C. Positive
tube indicated by the
[presence of gas.
V
3-tube 3-dilution
presumptive LST
broth tubes are
inoculated with
10 ml, 1 ml and
0.1 ml of a 10%
suspension of
clam homogenate.
This amount of
inoculum repre-
sents 1 g, 0.1 g.
and 0.01 g por-
tions. Incubate
at 35°C for 24 to
48 hrs. Positive
tubes indicated
jby the presence
jof gas.
Confirm total coliform counts by transferring from positive presumptive
tubes or m-Endo colony picks to brilliant green bile broth tubes.
Incubate at 35°C for 24 to 48 hrs. Positive gassing tubes are scored
and total coliform concentrations are recorded as MPN/100 ml SW or 100 qri
of Sed or Shellfish homogenate. Direct MF counts are equated to typical
coliform colony counts/100 ml SFV.
Streak positive BGBB tubes on EMB plates and incubate for 24 hrs. at 35°C.
Pick typical coliform colonies (nucleated green metallic sheen) to nutrient
(BHI) agar slants and incubate for 18 to 24 hrs. at 35°C. Speciate with APF
20 biochemical Enterobacteriacae tests. IMViC classification is included
in test with the addition of MR test. Also EC lactose broth tube is inclu-
ded to determine fecal coliform concentrations (gas production at 44.5°C in
24 hr. water bath incubation). Positive EC tubes are scored and appropriate
MPN/100 ml concentrations are recorded.
Information available:
Total and Fecal Coliform concentrations
by MF and MPN methods in parallel.
Speciation of coliforms in the Entero-
bacteriacae family.
IMViC classification.
166
-------
REFERENCES
American Public Health Association. 1976. Standard Methods for the
Examination of Water and Wastewater, 14th Edition. APHA, Washington,
D. C.
American Public Health Association. 1970. Recommended Procedures
for the Examination of Sea Water and Shellfish, 4th Edition. APHA,
Washington, D. C.
Bumpus, D. F. 1974. General Circulation Over the Baltimore Canyon
Area. In Marine Environmental Implications of the Offshore Oil and
Gas Development in the Baltimore Canyon Region of the Mid-Atlantic
Coast. Estuarine Research Federation, Wachapreague, Virginia.
Demenkow, J. W. and P. Wiekramartane. 1976. Far Field Sewage
Release Simulations. Raytheon Corporation, Portsmouth, Rhode Island.
Forns, J. M. 1977. Phytoplankton and Zooplankton Taxonomic Investi-
gations of the Interim Ocean Dumpsites. Westinghouse Ocean Research
Laboratory, Annapolis, Maryland.
Interstate Electronics Corporation. 1977. Environmental Protection
Agency, Region III Ocean Dumpsites Data Base, IEC, San Diego, Cali-
fornia. (Unpublished)
Klemas, V., G. R. Davis and D. J. Leu. 1976. Current Drogue and
Waste Observations at the DuPont Waste Disposal Site. CRS-3-76.
University of Delaware, College of Marine Studies, Newark, Delaware.
Lear, D. W., S. K. Smith and M. L. O'Malley (Eds.) 1974. Environ-
mental Survey of Two Interim Dumpsites, Middle Atlantic Bight. U. S.
Environmental Protection Agency, Region III. EPA-903/9-74-010A.
Lear, D. W. 1974. Environmental Survey of Two Interim Dumpsites,
Middle Atlantic Bight, Supplemental Report. U. S. Environmental
Protection Agency, Region III. EPA-903/9-74-010B.
Lear, D. W. and G. G. Pesch. 1975. Effects of Ocean Disposal Activities
on Mid-Continental Shelf Environmental Off Delaware and Maryland. U. S.
Environmental Protection Agency, Region III. EPA-903/9-75-015.
Marine Research, Inc. 1975(a) Analysis of Operation "Deep Six" Benthic
Invertebrates. Marine Research, Inc., Falmouth, Massachusetts.
167
-------
Marine Research, Inc. 1975(b) Analysis of Operation "Midwatch"
Benthic Invertebrates. Marine Research, Inc., Falmouth, Massachusetts.
Marine Research, Inc. 1976(a) Analysis of Operation "Dragnet"
Benthic Invertebrates. Marine Research, Inc., Falmouth, Massachusetts.
Marine Research, Inc. 1976(b) Analysis of Operation "Touchstone"
Benthic Invertebrates. Marine Research, Inc., Falmouth, Massachusetts.
Palmer, H. D. and D. W. Lear (Eds.) 1973. Environmental Survey of
An Interim Ocean Dumpsite, Middle Atlantic Bight. U. S. Environmental
Protection Agency, Region III. EPA-903/9-73-001A.
Palmer, H. D., J. R. Guala and J. L. Nolder. 1976. Current Meter Data
Reduction With Comments On Bedload Sediment Transport: Middle Atlantic
Bight. Westinghouse Ocean Research Laboratory, Annapolis, Maryland.
Sharp, J. H. (Ed.) 1976. Anoxia On the Middle Atlantic Shelf During
the Summer of 1976. IDOE/NSF. University of Delaware, College of
Marine Studies, Lewes, Delaware.
Stalling, D. L. and F. L. Mayer. 1972. Toxicities of PCB's to Fish
and Environmental Residues. Environmental Health Perspecitves,
pp. 159-164.
Steel, R. G. D. and J. H. Torrie. 1960. Principles and Procedures of
Statistics, McGraw Hill, New York, N. Y.
168
-------
Annapolis Field Office
Region III
Environmental Protection Agency
Statistical Analysis
of
Dissolved Oxygen Sampling
Procedures Employed by the
Annapolis Field Office
TECHNICAL PAPER 14
July 1976
Joseph L. Slayton
Robert B. Ambrose, Jr.
Elizabeth Fowler Nyhan
-------
-------
I. INTRODUCTION
The Annapolis Field Office began using pumps to obtain dissolved
oxygen samples during water quality surveys in 1967. Testing of
results obtained at the time indicated that the pumps were sufficiently
accurate for use in the surveys. Furthermore, tests on submersible
pumps reported in the literature supported this conclusion.. Two
types of pumps have been used by AFO crews to sample for dissolved
oxygen: the Rule Master 1300 (submersible, push) and the Tee! 1P580
(mounted, pull).
During the August 1975 Delaware Intensive Survey, the AFO loaned
the Philadelphia Water Department a Rule Master high speed pump.
Following this survey, the Water Department performed a series of tests
comparing DO samples from the Rule Master pump and DO samples by an
2
APHA sampler. These tests indicated that their pumped samples had
been significantly aerated at DO levels between 1 and 6 mg/1
(corresponding to DO deficits between Z and 7 mg/1). It was not
determined whether the aeration resulted from improper use of the pump.
Common errors include failure to completely clear the pumo hose before
filling the DO bottle, failure to adequately restrict the flow from
the high speed pump hose thus allowing splashing in the DO bottle,
and failure to allow water in the DO bottle to overflow 2-3 volumes
before capping. It was recommended that AFO review its sampling
procedure and conduct a similar study.
The mention of trade names or commercial products in this report
is for illustration pruposes and does not constitute endorsement or
recommendation by the U. S. Environmental Protection Agency.
-------
-------
II. THEORETICAL CONSIDERATIONS
First, the potential sources of extraneous oxygen in the pumps
were considered. For a submerged pump, such as the Rule Master,
aeration could result from (1) transient air initially caught in the
pump and hose, (2) splashing of the sample stream in the DO bottle,
or (3) air leaks in the hose. The first problem should be eliminated
by clearing the lines by pumping through at least three gallons of
water before taking a sample. The second problem should be eliminated
by crimping the hose to reduce the velocity of the stream, by inserting
the hose well into the DO bottle, and by allowing the DO bottle to
overflow three volumes before removing the hose and capping. The
third problem should be eliminated by regular inspections of the hose.
All of these problems, then, should be controllable.
For a surface mounted pump, such as the Tee!, the same potential
problems and solutions are applicable. In addition, however, is the
potential introduction of air through the pump itself during operation.
This could result from a loose casing and/or extra strain on the pump
caused by excessive crimping of the hose (by restricting the flow of
water through the apparatus, the volume displacement pump could pull
air through the casing). This problem should be minimized with careful,
experienced handling and periodic inspections of the pump.
If aeration is occurring due to faulty pumps or handling
techniques, the amount of dissolved oxygen added to the sample should
be proportional to the partial pressure gradient in the gas phase and
-------
-------
3
the concentration gradient in the liquid phase. This is similar
to reaeration in streams described by the following equation:
= i^ (r r}
dt L V lts L>
where
K[_ = the interfacial oxygen transfer coefficient
A = surface area through which transfer occurs
V = volume of the sample
C = saturation value of DO
C = concentration of DO in the sample
The oxygen transfer coefficient itself is a function of the diffusivity
of oxygen in water D^ and the rate of surface renewal r, itself a
function of flow regime:
K!
The terms describing the gas phase and air-water interface are usually
lumped in a volumetric coefficient Ka, which is a weak function of
temperature:
K-
aT
where 0 = 1.025 (1.016 - 1.040).
Thus, for a constant temperature,
dt" ~ Ka (Cs ~ c) >
and, over a small period of contact time,
A DOD = K, x DOD x At,
a
-------
-------
where DOD is the DO deficit of the water being sampled, C - C.
Assuming a constant volumetric oxygen transfer rate K and contact
a
time t, then the dissolved oxygen deficit of the sample DOD should
be related to the deficit of the water by
DOD = DOD (1-K At).
s a
As one consequence of this relationship, a linear regression of DOD
versus DOD should give an intercept of 0 and a slope less than or
equal to 1.0. Because K is a positive exponential function of
a
temperature, DOD versus DOD should yield progressively smaller slopes
at higher temperatures. Variations in pump operation would probably
mask this effect in experimental situations, however, allowing the
grouping of data taken throughout a moderate temperate range.
-------
-------
III. EXPERIMENTAL PROCEDURE
The subsequent steps were followed during all experiments
reported in this paper.
1. A plastic 75 gallon drum was filled with tap water.
2. Oxygen was monitored with a YSI submergible probe,
YSI 5419, and a model 51 A YSI meter. The
YSI equipment had been previously calibrated using
the azide modification of the Winkler dissolved
oxygen method, APHA 1975, pp. 143-4484.
3. An A. H. Thomas 8590-H20 stirrer was employed to
maintain an adequate current for the YSI probe and
to minimize a dissolved oxygen gradient. Homogeneinty
of this system was established in a preliminary exper-
iment in which 24 samples were siphoned from the
drum and assayed (Appendix A).
4. Prepurified nitrogen and/or oxygen was bubbled through the drum
using a gas dispersion tube, Kimax 28630, until the
desired D.O. was obtained.
5. Stirring was maintained and the temperature was recorded.
6. The Rule Master 1300 or the Teel 1P580 pump line
was placed in the drum and three gallons of v/ater were
pumped out to free the lines of entrapped air.
7. The delivery hose of the pump was crimped to restrict
the flow from the pump until splashing was minimized.
8. The hose was placed at the bottom of a 300cc BOD
type bottle. Twelve bottles were over filled with
approximately three times their volume. This was
-------
-------
achieved by filling the bottles over an empty plastic
bucket of predetermined volume.
9. The pump was stopped and twelve replicate bottles
were siphoned from the tank using tygon tubing
(1/4" O.D.). Over-filling was not deemed necessary
since the flow was very slight and no splashing was
observed.
10. All bottles were capped after being filled and
immediately "fixed" as outlined in APHA 1975, p. 443.
11. All samples were immediately assayed using a Fisher Model 41
Auto Titralyzer. Fisher P-340, 0.025 N Potassium
Biodate was used as the primary standard and twenty
duplicate biodate standards were used to establish
the precision of this instrument, (Appendix A).
-------
-------
RESULTS AMD DISCUSSION
Prior to experimentation with the pumps, the precision of
both the analytical method and of the siphoning procedure was determined.
Twenty replicates of 0.025N Potassium biodate standards were run on
o
a Fisher Titralyzer, giving a variance of 0.0025 (mg/1) DO (S = .05 mg/1).
Twenty-four replicate samples were siphoned from the tank, giving a
2
variance of 0.0049 (mg/1) DO (S = .07 mg/1). Thus the variance added by
siphoning alone was approximately twice the variance due to the analytical
procedure. Assuming perfect accuracy in sampling and analysis,
95 of 100 siphoned samples should lie within 0.12 mg/1 from the
correct value. Both the analytical procedure and the siphoning technique
were considered precise enough to proceed with the experiments.
Nine experiments at DO levels ranging from 1.1 - 5.6 mg/1 (DOD
from 4.5 - 9.1 mg/1) were run by an AFO chemist, to compare the samples
collected by the Rule Master pump with those obtained by siphoning.
Nine similar experiments were performed with the Teel pump at DO
levels from 1.0 - 5.0 mg/1 (DOD from 4.1 - 8.8 mg/1). [To check the
sensitivity to technique involved in sampling, the following pump
operators were tested: A field technician and an AFO chemist not
experienced in the operation of the pump; and an experienced field
technician.] Twelve replicates from the pump and the siphon were
analyzed during each experiment. Variances were tested for homogeneity
using the F-test at the a = .01 level. Means were tested for equality
using the one-tailed student's t-test for unpaired data at the a = .01 level.
-------
-------
TABLE 1
Summary of Experiments
Number
trument
erator Repl
e Master
rated
lab
mist
or Avg.
1
rated
lab chemist
: or Avg.
il operated
inexper.
'Id tech.
: or Avg.
si operated
exoer.
fid tech.
: :r Avg.
of
icates
12/12
12/12
11/12
12/12
12/12
12/12
12/12
12/12
12/11
12/12
12/12
12/12
12/12
12/12
12/12
12/12
12/12
12/12
12/12
12/12
12/12
12/12
Siphon
DO
(mg/1)
5.6
5.6
4.5
3.3
3.1
2.6
2.3
1.1
1.2
3.1
2.7
1.0
5.0
3.1
1.6
1.8
1.9
1.7
'emp
o C)
15
15
16
15
15
15
16
15
14
16
16
16
17
11
17
11
16
16
Siphon
DOD
(mg/1)
4.5
4.5
5.4
6.8
7.0
7.5
7.6
9.0
9.1
6.8
7.2
8.9
4.7
7.9
8.1
9.2
8.0
8.2
Pump
DOD
(mg/1)
4.5
4.5
5.0
6.7
6.9
7.5
7.6
9.0
9.0
5.7
7.1
8.8
4.1
7.1
7.7
8.2
8.1
8.2
Homogeneous Equal
Variance Means
(ct = .01) (a - .01)
x
x
X
0
X
X
X
X
0
X
6
Prob of not det
0.1 mg/1 dif.(p)
(a = .01)
.07
.07
.11
.17
.05
0
.31
.12
.11
.36
.07
.21
In this first experiment performed, the
cleared before sampling.
pump line was not sufficiently
-------
-------
The probability of not detectino a mean difference of 0.1 mo/1 (the 3-error)
was computed from the sample size, pooled standard deviation, and the
a level (.01). Data from each experiment are listed in Appendix A,
and a summary is provided in Table 1.
Of the nine experiments on the Rule Master pump operated by a
laboratory chemist, all but the first passed the test for homogeneous
variances. In the first experiment, the pump line was not sufficiently
cleared before sampling, and aeration of the samples occurred due to residual
air in the pump and hose. In subsequent experiments at least 3 gallons of
water were pumped through the hose before collecting samoles. Subject to
adequate clearing of the hose, the Rule Master pump is a sufficiently precise
sampling instrument.
Eight experiments with the Rule Master pump and the siphon were tested
for equality of means. Although two experiments did result in statistically
significant differences, the average differences were all less than 0.1 mg/1.
The probability of not detecting a 0.1 mg/1 difference in means averaged 11%.
A linear regression between pumped D.O. deficits (DODp) and siphoned deficits
(DODs) gave a slope of .991, an intercept of 0.063 mg/1 DODp and a correla-
tion coefficient exceeding 0.999. It is concluded that, with adequate handling,
the Rule Master pump is a sufficiently accurate sampling instrument.
Of the nine experiments on the Teel pump, seven were operated by
inexperienced operators, and none of these seven experiments passed the
test for homogeneous variances. In two of these experiments, the average
differences between pump and siphon were 0.08 and 0.11 mg/1, respectively
giving marginally unacceptable accuracies. Generally, however, the Teel
-------
-------
pump with inexperienced operators is neither a sufficiently precise nor
sufficiently accurate sampling instrument.
The two experiments on the Tee! pump with an experienced operator
passed both the test for homogeneous variances and the test for equal
means. Average differences between pump and siphon were 0.0 and 0.03 mg/1,
respectively. In the latter experiment, both the precision and the accuracy
of the pump seemed to exceed that of the siphon. The Tee! pump with an
experienced operator, then, can be both a sufficiently precise and sufficiently
accurate sampling instrument.
-------
-------
CONCLUSIONS
1. The Rule Master pump is sufficiently precise and accurate to use
for sampling D.O. at deficits as high as 9 tng/1 (this covers all D.O.
concentrations at temperatures exceeding 20°C, and down to 1 mg/1 D.O.
at 15°C).
2. The Tee! pump can be operated by experienced personnel in a manner
sufficiently precise and accurate to use for sampling D.O. at deficits
as high as 8 mg/1.
3. The Teel pump operated by inexperienced personnel can result in imprecise
and inaccurate D.O. measurements.
4. The Rule Master pump is preferable to the Teel pump because it is less
sensitive to variations in operating procedures.
-------
-------
REFERENCES
1. Whaley, R. C., "A Submersible Sampling Pump," Limnology and Ocenography,
Vol. 3, No. 4, October, 1958.
2. Blair, D. D., "Statistical Analysis of Two Dissolved Oxygen Sampling
Procedures", Technical Report prepared by the Philadelphia Water Depart-
ment, December 10, 1975.
3. O'Connor, D. J. et al , "Mathematical Modelling of Natural Systems," notes
for a course given in May, 1975.
4. Standard Methods for the Examination of Hater and Wastewater, 14th Edition,
American Public Health Association, Inc., 1975.
-------
-------
APPENDIX A
EXPERIMENTAL DATA AND STATISTICS
-------
-------
Preliminary Experiment: Uniform D.O.
Twenty-four 0.0. bottles were siphoned from the tank and assayed via the
Azide-Modification of the Winkler Method,APHA 1975 pp. 443-448. The
following D.O. concentrations (ppm) were obtained:
4.3 4.2
4.3 4.2
4.2 4.1
4.2 4.1
4.1 4.1
4.3 4.1
4.2 4.2
4.1 4.1
4.2 4.1
4.2 4.2
4.2 4.1
4.1 4.1
N = 24
S = 0.07
-------
-------
Preliminary Exoeriment: Precision of Fisher Auto Titralyzer
Twenty duplicate standards were prepared using: 10 ml of 0.025 N Potassium
biodate, 284 ml of distilled water; 2 ml of cone. H2S04; 2 ml of APHA*
Manganese sulfate; and 2 ml of APHA* Alkali-iodide-Azide reagent. These
standards were titrated using the Fisher model 41 titralyzer and the follow-
ing concentrations (ppm) were obtained:
4.9
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.1
5.0
5.0
5.0
5.0
4.9
5.0
4.9
4.9
with N = 20 and S = 0.05
* APHA 1975, p. 443
-------
-------
Experiment 1
Dissolved Oxygen Range 4.3 - 5.6 mg/1
Temperature 16°C
Rule Master Pump
4.7
5.6
5.0
4.9
5.0
4.7
4.7
4.7
4.8
4.8
4.7
Chemist 2/23
Siphon
4.5
4.5
4.5
4.3
4.5
4.4
4.4
4.5
4.4
4.5
4.5
4.4
X-|=4.873
Si2=.0722
X2=4.467
S22=.00455
H0: a i2 = 02 a - .01 Fa = 4.23
F - 15.8641 Reject - Variances are not homogeneous
X-j - X2 = 4.87 - 4.47 - 0.40
Comments:
Pump line not completely cleared before running experiment (only 1 gal water
running experiment (only 1 aal water was pumped prior to experiment)
-------
-------
Experiment 2
Dissolved Oxygen Range 2.5 - 2.7 mg/1 Chemist 3/17
Temperature 15°C
Rule Master Pump Siphon
2.6 2.6
2.6 2.5
2.7 2.5
2.7 2.5
2.6 2.6
2.6 2.5
2.6 2.6
2.5 2.6
2.6 2.6
2.6 2.5
2.6 2.6
2.6 2.5
n2 = 12 n-j = 12
= 2.608 JT-j = 2.55
s| = .00265 sf - .00273
o 2
H0: cr-j = a2 a = .01 Fa = 4.47
._ Si? _ 1.0292 Accent - variances are homogeneous
p =-i^ -
52
H0 - y-j - vz = 0 a = .01 Ta = 2.508
T = 2.7529
Reject - there is a significant difference between means
X"i - X~2 = 2.61 - 2.55 - 0.06
d* -
n2 s where 6 = the mean difference
to be detected = 0.1 mg/1
d* - .9848 6 = .05
-------
-------
Experiment 3
Dissolved Oxygen Ranae 1.1 - 1.4 mg/1 Chemist 3/17
Temperature 14°C
Rule Master Pump Siphon
1.2 1.2
1.3 1.2
1.3 1.1
1.3 1.1
1.3 1.1
1.2 1.3
1.4 1.3
1.3 1.2
1.3 1.2
1.2 1.2
1.3 1.2
1.3
n2 - 12 m - 11
X~2 = 1.2833 JC, - 1.1909
S2, - .00334 S? = .00491
HQ: a^ = 02 a = .01 Fa = 4.23
F = 1.4714 Accept - variance are homogeneous
H0: y-j - y2 = 0 a = .01 Ta = 2.518
T = 3.4643
Reject - there is a significant difference in means
X-| - X"2 = 1.28rl .19 = 0.09
d* - .7993 3 = .12
-------
-------
Experiment 4
Dissolved Oxygen Range 5.5 - 5.7 mg/1 Chemist 4/2
Temperature 15°C
Rule Master Pump Siphon
5.6
5.5
5.6
5.6
5.6
5.6
5.7
5.7
5.7
5.6
5.5
5.6
n1 = 12
5.5
5.7
5.6
5.6
5.6
5.6
5.6
5.7
5.6
5.6
5.6
5.6
n2 =
X1 = 5.6083 X2 = 5.6083
S^ - .00447 $! - .00265
2 2
HQ: o-| = 02 a = .01 Fa = 4.47
F = 1.6849 Accept - variance are homogeneous
HQ: y-j - y2 = ° a = .01 Ta = 2.508
T = 0 Accept - no significant difference in means
X"-, - X"2 = 5.61 - 5.61 - 0
d* - .8561 8 - .07
-------
-------
Experiment 5
Dissolved Oxygen Range 5.5 - 5.7 rng/1 Chemist 4/2
Temperature 15°C
Rule Master Pump Siphon
5.6 5.7
5.6 5.6
5.6 5.6
5.6 5.6
5.6 5.6
5.6 5.6
5.7 5.7
5.6 5.6
5.7 5.5
5.6 5.6
5.5 5.6
5.7 5.5
n2 = 12 n-, = 12
X"2 = 5.6167 X"-, - 5.6
S2 = .00333 S^ = .00364
H0: a-,2 = a22 a = .01 Fa = 4.47
F = 1.9309 Accept - variance are homogeneous
H0: yi - y2 = 0 a = .01 Ta = 2.508
T = .6934 Accept - no significant difference in means
X"-j - X"2 = 5.62 - 5.60 - .02
d* = .8658 3 = .07
-------
-------
Exoeriment 6
Dissolved Oxygen Range 2.2 - 2.4 mg/1
Chemist 4/2
Temperature 16 C
Rule Master Pump
2.3
2.3
2.3
2.4
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
n2 = 12
X"2 = 2.3083
$2 = .000833
Siphon
2.3
2.3
2.2
2.3
2.2
2.3
2.3
2.3
2.3
2.3
2.3
2.3
n-| = 12
jf| - 2.2833
= .00152
Ho: °
= a2 a = -01 Fa = 4'47
F = 1.8182 Accept - variances are homogeneous
- y2 = 0 a = .01 Ta = 2.508
T = 1.7868 Accept - no significant difference in means
HQ:
-]
= 2.31 - 2.28 = .03
d* = 1.4905
3=0
-------
-------
Experiment 7
Dissolved Oxygen Range 0.9 - 1.2 mg/1 Cheinist 4/2
Temperature 15.5°C
Rule Master Pump Siphon
H a
1.0
1.1
1.1
1.1
1.1
1.0
1.0
1.1
1.1
1.0
1.1
1.2
n2 = 12
X"2 = 1.075
2
$2 = .00386
2 2
, = 02 a = .01
F = 2.5098 Accept - variances
H0: y-j - M2 = 0 a = .01
T = .2479 Accept - no sign
1.1
1.0
1.0
1.2
1.1
1.2
1.0
1.1
1.0
1.2
0-9
1.0
nl =
_ n
1
_
S^ = .00!
Fa - 4.47
are homog<
Ta =
ificant dr
X~] - X2 = 1 .08 - 1 .07 = . 01
d* - .6203 6 = .31
-------
-------
Dissolved Oxygen Ranqe 3.0
Temperature 15°C
Experiment 8
3.2 mg/1
Rule Master Pump
H0: a-, = a2
F = 1.1525
Siphon
3.0
3.2
3.1
3.1
3.2
3.2
3.1
3.2
3.2
3.2
3.2
3.2
n2 = 12
X~2 = 3.1583
£ = .00447
3.1
3.2
3.1
3.1
3.2
3.1
3.1
3.0
3.1
3.2
3.2
3.0
ni = 12
JT-j - 3.11
S? = .0051
67
5
Chemist 1/4
H0:
T = 1.4685
a = .01 Fa = 4.47
Accept - variances are homogeneous
a - .01 Ta = 2.508
Accept - no significant difference in means
X1 - X2 - 3.16 - 3,12 - .04
d* = .736
= .17
-------
-------
Experiment 9
Dissolved Oxygen Range 3.2 - 3.4 mg/1
Chemist 4/4
Temperature 15 C
Rule Master Pump
3.3
3.3
3.4
3.4
3.5
3.4
3.3
3.3
3.4
3.4
3.4
3.4
n2 = 12
X> 3.375
s| = .00386
Siphon
3.3
3.2
3.3
3.3
3.4
3.4
3.3
3.3
3.4
3.3
3.4
3.4
n-, = 12
JT-j = 3.3333
? 2
Ho: a] = °2
F = 1.0984
0
S| - .00424
a = .01 Fa - 4.47
Accept - variances are homogeneous
- y2 = 0 a = .01 Ta = 2.508
T = 1.6041 Accept - no significant difference in means
X"-, - 5f = 3.38 - 3.33 - .05
d* = .8026 B = -11
-------
-------
Experiment 10
Dissolved Oxygen Range 3.1 - 3.2 mq/1 Chemist 3/26
Temperature 16°C
Teel Pump Siphon
4.9
5.3
4.5
4.5
5.9
5.1
3.2
3.3
3.3
3.7
3.2
3.7
3.2
3.1
3.2
3.1
3.1
3.1
3.1
3.1
3.2
3.2
3.1
3.1
n-| = 12 n2 = 12
X] = 4.2167 X~2 = 3.1333
S2 = .8815 Sg = .00242
HQ: a-,2 - a22 a = .01 Fa = 4.47
F = 364.2562 Reject - variances are not homogeneous
X"-, - X"2 = 4.22 - 3.13 = 1.09
-------
-------
Experiment 11
Dissolved Oxygen Range 2.6 - 2.8 mg/1 Chemist 3/26
Temperature 16°C
Teel Pump Siphon
nl
X 1 -
s?-
H0: a
2.7
2.6
2.7
2.7
2.6
2.6
2.7
2.7
2.8
2.7
3.3
3.3
= 12
2.7833
.0615
9 2
1 = a2
2.7
2.8
2.7
2.7
2.7
2.7
2.8
2.6
2.7
2.7
2.7
2.6
n2 =
JT2 = 2
12
.7
S2 = .00364
a = .01 Fa
= 4
F = 16.8956 Reject - variances are not homogeneous
X] - 5T2 = 2-78 - 2-70 = °-n8
-------
-------
Experiment 12
Dissolved Oxygen Range 0.9 - 1.2 mq/1
Temperature 16°C
Chemist 3/26
H0: a-,2 = a22
F = 7.1127
f>?el Pump
a = .01
Siphon
1.1
1.1
1.0
1.0
1.0
1.1
1.9
1.2
1.0
1.0
1.0
1.3
n} - 12
X"-, = 1.1417
S2 - .06629
1.0
1.2
1.2
1.0
0.9
1.0
1.0
1.1
1.0
0.9
1.0
1.0
n2 = 12
X~2 = 1.025
S2 = .00932
Fa - 4.47
Reject - variances are not homogeneous
TT ~"T0 = 1.14-1 .03 - 0.11
-------
-------
Experiment 13
Dissolved Oxygen Ranqe 4.9 - 5.1 mgl
Temperature 17°C
Tee! Pump
HQ: a-,2 = a22
Inexperienced Field Technician 4/1
S'ohon
4.9
6.1
8.3
7.1
5.5
5.0
5.0
5.0
4.9
4.9
4.9
5.0
n-] = 12
)F| = 5.55
S2 = 1.1973
5.0
5.0
5.1
5.0
5.0
4.9
5.1
5.0
5.0
5.0
5.0
5.0
n2 =
X"2 = 5
S2 -
b2 - .
12
.0083
00265
a - .01 Fa - 4.47
F = 451.8113 Reject - variances are not homogeneous
Xi - Xj? = 5.55 - 5.01 = 0.54
-------
-------
Experiment 14
Dissolved Oxygen Range 3.0 - 3.3 mg/1 Inexperienced Field Technician 4/1
Temperature 11°C
Tee! Pump Siphon
4.9
4.8
4.2
3.5
3.7
3.8
4.1
3.4
3.7
3.4
3.3
3.5
n] = 12
JT-j = 3.8583
S2 - .2899
« 2 2
°1 = a2
3.2
3.2
3.0
3.1
3.2
3.3
3.0
3.0
3.3
3.0
3.0
3.0
n2 = 12
X~2 = 3.108
SJj = .0154
a = .01
HQ: a-, - a2 a = .01 Fa = 4.47
F = 18.8247 Reject - variances are not homogeneous
X"l - X"2 = 3.85 - 3.11 - 0.74
-------
-------
Experiment 15
Dissolved Oxygen Range 1.8 - 1.9 mg/1
Temperature 11°C
Tee! Pump
3.7
2.8
2.6
1.9
1.8
1.9
1.8
1 .8
2.6
1.9
1.8
1.8
ni - 12
77" _ o O
S2 = .3636
1.9
1.9
1.8
1.8
1.9
1.9
1.8
1.8
1.8
1.8
1.9
n2
h-
S2 = .
= 12
1.8455
00273
H0: a-,2 - a22
Inexperienced Field Technician 4/1
Si p hon
a = .01
Fa - 4.4
F = 133.2 Reject - variances are not homogeneous
I-, - 12 = 2.20 - 1.85 = 0.35
-------
-------
Experiment 16
Dissolved Oxygen Range 1.5 - 1.7 ng/1 Inexperienced Field Technician 4/1
Temperature 17.5°C
Teel Pump Siphon
5.4
4.6
4.2
1.7
1.9
1.6
2.3
2.2
2.2
1.6
1.6
2.0
1.5
1.5
1.6
1.7
1.5
1.5
1.5
1.6
1.6
1.6
1.7
1.6
n-| =12 n2 - 12
X"., - 2.6083 X"2 = 1.575
S^ - 1.7699 S^ - .00568
o 2
Ho: al ~ °2 a - .01 Fa = 4.47
F = 311.5024 Reject - variances are not homogeneous
X"-| - 3T2 = 2.61 - 1 .58 - 1 .03
-------
-------
Experiment 17
Dissolved Oxygen Range 1.6 - 1.8 mg/1
Temperature 16.5°C
Tee! Pump
1.6
1.8
1.8
1.7
1.7
1.6
1.7
1.8
1.7
1.7
1.7
1.7
n] - 12
3f-| = 1 .7083
S? = .00447
Experienced Field Technician 4/2
Siphon
1.7
1.6
1.7
1 .7
1.8
1.7
1.7
1.7
1.7
1.8
1.7
1.7
n2 = 12
X2 - 1.7083
3? - .00265
H0:
: a-, = a2 a = .01 Fa - 4.47
F = 1.6858 Accept - variances are homogeneous
Ta - 2.508
T = 0
no significant difference
d* - .856
= .07
-------
-------
Experiment 18
Dissolved Oxygen Range 1.8 - 1.9 mg/1
Temoerature
Tee! Pump
HO-
i^ =12
X] = 1.8333
\ = .0115
2
Experienced Field Technician 4/2
Siphon
2.0
2.0
1.9
1.8
1.8
1.7
1.9
1.9
1.8
1.7
1.8
1.7
1.9
1.8
1.8
1.9
1.8
1.8
1.9
1.9
1.9
1.9
1.8
1.9
n2 - 12
X2 = 1 .8583
S| = .00265
a2- a = .01 Fa = 4.47
F = 4.3396 Accept - variances are homogeneous
H0: y] - y2 - 0 a = .01 Ta = 2.508
T - .728 Accept - no significant difference in means
X-| - X2 = 1.83 - 1 .86 - 0.03
d* - .607
- .36
-------
HERBICIDE ANALYSIS
OF
CHESAPEAKE BAY WATERS
June 1977
John Austin
Annapolis Field Office
Region III
U.S. Environmental Protection Agency
-------
-------
BACKGROUND
During the first week of June 1976, surface water samples
were collected along a longitudinal axis from eleven stations of
the water quality monitoring network maintained by the Environ-
mental Protection Agency, Annapolis Field Office, Annapolis,
Maryland. These samples represent mid-channel surface waters of
the main body of the Bay. They were screened for the herbicides
Alachlor, Atrazine, and Simazine by gas chromatography following
an appropriate organic extraction procedure.
-------
-------
METHOD
One liter samples were extracted with methylene chloride.
Subsequently a hexane keeper was added and the samples evaporated
to one milliliter utilizing a Kuderna-Danish assembly. Qualitative
and quantitative analyses were then performed utilizing gas chro-
matography. Fifty microliter samples were injected onto a one
percent Carbowax 20 M column maintained at 160°C with a 60 ml/min
Helium flow. A Hall detector operated in the nitrogen specific mode
at an attenuation of 1x10 was employed for maximum sensitivity.
Under these conditions a 10 percent of full scale response was
obtained with samples containing either .069 ppb Alachlor, .07 ppb
Atrazine, or .10 ppb Simazine.
-------
-------
DISCUSSION
Alachlor, which was detected at only one station, was the only
one of the three herbicides analyzed that failed to show wide dis-
tribution. Simazine seemed to show even distribution whereas Atrazine
appeared to be associated with high solids emanating from freshwater
runoff into the upper Chesapeake Bay.
There is no known report documenting the existence of these
compounds in open waters of the Chesapeake Bay. In that this is the
first data generated on the distribution of these herbicides in the Bay,
it is hard to comment on their possible distribution due to the
limited geographical coverage of this study, or their significance to
aquatic life since little bioassay work has been conducted at these
low levels. The half life of these compounds in water and sediment and
their potential for bioaccumulation are not known. Degradation products
of these compounds present another unknown factor which should be
investigated. Although the levels found in the Chesapeake Bay were
generally less than 100 parts per trillion, it is disconcerting to note
that PCB's and widespread chlorinated insecticides are found at only
the 1 to 10 parts per trillion level in the same waters. While the
triazine herbicides are not as persistent as PCB's in the environment,
the impact of such levels should be investigated, especially in regards
to effects on aquatic vegetation and the biological food chain.
-------
-------
Micrograms/liter (PPB)
Lab No. Date Station Alachlor Atrazine Simazine
76060160
76060158
76060159
76060121
76060122
76060827
76060828
76060829
76060830
76060831
76060832
6-1-76
6-1-76
6-1-76
6-1-76
6-1-76
6-8-76
6-8-76
6-8-76
6-8-76
6-8-76
6-8-76
20
T2
T7
F2
Ml
M2
M3
M4
M5
H2
12
.069
<;07
<;07
<.07
LA
<.07
<.07
<.07
<.07
<.07
<.07
.12
.35
.08
.02
LA
.06
.08
.07
.05
.03
.05
.03
<.03
.05
<.03
LA
.05
.05
.05
.04
.03
.03
L. A. - Lab Accident
-------
-------
-V/ESTM
BALTIMORE
m
MARYLAND
HAVRE DE GRACE S
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%%
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^^:^0:l^i^S^^^^^ -i"-^-. '.;'! ' -"-'.i.-V -/^§sKs *
s. ', :v^
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SSIkiSli^S^
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&&
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^jl
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A* .- -
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-------
EPA 903/9-79-003
CARBONACEOUS AND NITROGENOUS
DEMAND STUDIES OF THE
POTOMAC ESTUARY
(Summer 1977)
Annapolis Field Office, Region III
Environmental Protection Agency
Joseph Lee Slayton
E. R. Trovato
-------
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.
-------
TABLE OF CONTENTS
Page
Tabulation of Tables iii
Tabulation of Figures iv
I. Introduction 1
II. Conclusions 4
III. Procedure 6
IV. Oxygen Demand in The Potomac River Samples
A. Biochemical Oxygen Demand - Carbonaceous
1. General Discussion 7
2. Standard BODs Test 7
3. CBOD/First Order Kinetics 8
4. Thomas Graphical Determination of
BOD Constants 10
5. Temperature Effect Upon Reaction Rates 14
6. Nature and Distribution of CBOD 19
B. Biochemical Oxygen Demand - Nitrogenous
1. General Discussion 27
2. Bacterial Growth Requirements 28
3. Lag Phase and Growth Characteristics 29
4. Stoichiometry of Nitrification 30
5. Nitrification Kinetics 43
6. Nature and Distribution of NOD 43
V. Oxygen Demand in the Potomac STP Effluent Samples
A. CBOD 51
B. NOD 51
C. Loadings Characteristics 54
-------
TABLE OF CONTENTS (con't)
Page
References 67
Appendix:
A. N-Serve/NOD Determinations 69
B. Alternative Methods 70
C. Study Data 72-84
11
-------
TABLES
No . Page
1. Station Locations 3
2. Thomas Graphical Determinations of k^Q, and Lo>
for river CBOD's 12
3. Thomas Graphical Determinations of k^o» and Lo>
for river BOD's 15
4. Chlorophyll a_ vs CBOD 26
5. NOD2Q vs (TKN-N x 4.57) 32
6. Thomas Graphical Determinations of kjo* Lo, and r
for river NOD's 44
7. Ratios of NOD5/BOD5 and NOD20/BOD2o 48
8. Thomas Graphical Determinations of kiQ, Lo, and r
for STP CBOD's 52
9. Thomas Graphical Determinations of k^o> Lo, and r
for STP NOD's 55
10. Summary sheet of % [NOD20/NOD Ultimate] for STP's 60
11. STP Loadings of CBOD2Q. NOD Ultimate, and BOD5 61
12. Proportion of Total STP Demand Expressed as NOD 63
13. N02-N Concentration and the Resulting NOD Error 65
14. Potomac River Long-Term BOD Survey Data 72-84
111
-------
FIGURES
No. Page
1. Study Area 2
2. Depletion Curve for BOD and CBOD 17
3-8. BOD2o> CBOD20 and NOD2Q vs River Mile Index (RMI) 20-25
9. Plot of NOD2Q vs (TKN-N x 4.57] 35
10, 12-16. Plot of NOD2Q and (TKN-N x 4.57) 36, 38-42
11. NH3-N, N02-N, N03-N and TKN-N vs RMI 37
17. NOD Depletion Curves 46
18-20. BOD, NOD, and CBOD Oxygen Depletion Curves 57-59
IV
-------
I. Introduction
During the summer of 1977 an intensive survey of the middle reach
of the Potomac River (Figure #1) was undertaken by the A.P.O. All
samples were collected under slack tide conditions. As part of this
work, 20-day B.O.D. analyses were performed on selected stations
(Table #1) to help define the major oxygen demand inputs and establish
their effect upon the river. The fraction of the B.O.D. associated
with nitrogenous oxygen demand was determined using an inhibitor to
nitrification. To afford a more meaningful intrepretation of the
results, a discussion is included on the B.O.D. test; nitrification;
and the nature and action of the inhibitor employed.
-------
Figure 1. Study Area
Potomac Estuary
-------
Table #1
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
Station
Number
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
Stations
for
Long Term
BOD/NOD
X
X
X
X
X
X
X
X
X
X
Stations
for
Long Term
BOD/NOD
X
X
X
X
X
X
X
X
Station Name
Chain Bridge
Windy Run
Key Bridge
Memorial Bridge
14th Street Bridge
Hains Point
Bellevue
Woodrow 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
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
RMI
0.0
1.9
3.4
4.9
5.9
7.6
10.0
12.1
13.6
15.2
18.4
22.3
24.3
26,9
30.6
34.0
38.0
42.5
45.8
52.4
58.6
62.8
67.4
^ RMI*
18.4
5.9
11.1
12.4
12.8
20.0
22.3
24.5
Buoy Reference
C "1"
FLR-23' Bell
C "87"
N "86"
FL "77"
FL "67"
R "64"
FL "59"
N "54"
R "44"
N "40"
N "30"
G "21"
N "10"
C "3"
* The RMI's are approximate since the STP's are often located on embayments
-------
II. Conclusions
1. CBOD of the Potomac River samples followed first order kinetics
with an average ke=0.14 day'1.
2. In August, a significant increase in CBOD, between Gunston Cove
and Possum Pt., correlated (r=.94) with an algae bloom of
Oscillatoria.
3. NOD of Potomac River samples between Mains Point and Ft. Washington,
(peak NOD area) followed first order kinetics with an average
ke=0.14 day"1. The exceptional samples had significant lag times
resulting in S-shaped or consecutive S-shaped D.O. depletion
curves. These samples were limited to the algal bloom area and to
samples from the Chain Bridge area which had low NOD2Q (2.0 ppm average)
4. In general, the NOD,- represented about one-third of the BOD$ of the
river samples and therefore, estimates of CBODs from BODg values
are prone to error unless a nitrification inhibitor is employed.
5. The CBOD2Q represented 68% of the river demand2Q-
6. The CBOD of the STP effluents followed first order kinetics with
an average ke=0.17 day~l.
7. The CBOD2Q represented 31% of the STP effluent demand2o-
8. The NOD for the STP effluents had a significant lag time resulting
in S-shaped or consecutive S-shaped depletion curves. This lag time
was probably an artifact, since nitrification in the receiving
waters was immediate.
9. The NOD20 observed for river samples did not significantly differ
from (TKN-N x 4.57) which suggests:
-------
II. Conclusions (con't)
a. Nitrification was essentially complete after 20 days
of incubation.
b. The nitrification inhibitor 2-chloro-6 (trichloromethyl)
pyridine (common name nitrapyrin), gave accurate NOD results.
c. The NOD observed was due to autotrophic bacteria since
the inhibitor was specific for Nitrosomonas spp.
10. The relation CBOD20 =1.85 CBOD5 held consistently for the Potomac
River samples and, with the use of nitrapyrin, short term experiments
may yield adequate estimates of ultimate demand via the relation:
UBOD * 1.85 CBOD5 +4.57 (TKN-N).
-------
Ill.Procedure
BOD: The BOD test employed was that outlined in Standard Methods
APHA 14th edition1. Dilutions were made for the S.T.P.
samples using BOD bottles, that were within ± 1% of 300 ml,
as volumetric flasks. S.T.P. samples were diluted with APHA
dilution water; seeded using 1 ml per bottle of stale raw-
settled S.T.P. influent; and dechlorinated. All samples were
purged for 15 seconds using purified oxygen and a Fisher gas
dispersion tube to obtain an initial DO of 10-15 ppm.
DO: All dissolved oxygen measurements were made using a YSI BOD
probe #5750 and a YSI model #57 meter. These were calibrated
against the Winkler (azide modified) method1.
Nitrification: The nitrification inhibitor (Hach Chemical Co. #2533)
was dispensed, using a powder dispenser, directly into the BOD
bottles. This allowed quick and uniform additions of the
inhibitor. Two bottles were filled with each sample; one
received the inhibitor and represented CBOD and the uninhibited
bottle expressed total BOD. The NOD was determined by difference.
Nitrogen-Series: TKN-N was analyzed by the automated phenate method1.
The N02-N + NOj-N was analyzed by the automated cadmium
reduction method1.
-------
IV. Oxygen Demand in the Potomac River Samples
A. Biochemical Oxygen Demand-Carbonaceous
1. General Discussion
Biochemical oxygen demand is a bioassay procedure concerned with
the utilization of oxygen in the biochemical oxidation (respiration)
of organic material. This test is one of the most widely used
measures of organic pollution, applied both to surface and waste
waters. The BOD test has been relied upon in the design of waste
treatment plants and to establish standards for effluent discharges.
One of the primary disadvantages of this test is that as a bioassay
it reflects biological variability. The test is not a relatively
simple assay whereby pure strains of bacteria interact with a well-
defined media, but involves monitoring a complex and changing
population of microorganisms (bacteria, protozoa, fungi, algae, etc.),
as they respire in a changing mixture of organic matter. Interlaboratory
studies have established its precision on synthetic samples to be
± 20% at 2i 200 ppm BOD2. The accuracy of the test is difficult to
assess since the results obtained for "standard solutions" vary
markedly with the seed employed .
2. Standard BOD5 Test
The standard method of BOD measurements, adopted by APHA ,
is a five-day test at 20°C in the dark. The five-day incubation period
was selected to maximize that portion of the oxygen demand associated
with heterotrophic respiration (oxidation of carbon compounds)
and, at the same time, minimize the oxygen demand of autotrophic
organisms, primarily nitrifying bacteria. The basis for this method
-------
IV. Oxygen Demand in the Potomac River Samples (con't)
selection rests upon the generally observed 10-15 day lag in oxygen
uptake associated with the growth of nitrifying bacteria in sewage
samples. This assumption was found to be erroneous for Potomac
River samples.
The standard BOD5 test was designed to provide the biota with
the macronutrients and oxygen necessary for growth, such that the
rate of utilization of organic material will be limited only by the
amount and nature of the organic material present. In comparison
to a long-term test of 20 or 30 days, the short-term test is more
severly dependent upon the number and type of biota introduced (seed)
and the temperature of incubation. These factors will affect the
kinetics of respiration. In essence the standard BOD5 test for
sewage effluents was not designed to give accurate rate estimates,
but its use as a best estimate remains because of the absence of an
alternative. BOD tests of river water involved no dilution nor seeding
and may have the best correlation with actual river rates, since the
least manipulation of the sample is involved. Because the kinetics
of the process are largely avoided when measuring plateau values,
which are not measureably affected by seed conditions or temperature
value between 4 and 20°C , the ultimate oxygen demand has been cited
as a more practical parameter for judging the potential pollution load .
3. CBOD/First Order Kinetics
The kinetics of the carbonaceous BOD observed during this study
were first order. The observed oxygen utilization fell off exponentially
with time, and approached an ultimate asymptote. The first order
-------
characteristic is thought to be the summation of many different
reaction rates of the gamut of material expected in waste and river
samples.
The expression relating the remaining oxygen demand L, at time
t is given by:
-dL = k Lo equation #1
dt
such that the rate at any instant is proportional to the amount of
BOD yet to be expressed. Lo is the intial remaining oxygen demand (at t=o)
or ultimate demand and k is the deoxygenation rate constant, day" .
Rearranging and integrating equation #1
L
Lo
where t0 = 0,
= -(In L-ln Lo) = kt
or In L = In Lo - kt equation #2
The - kt term can be expressed as In e'^tf since In ex = X, and equation #2
becomes
In L = In Lo + In e"kt
or the familar expression
L = Lo e~ equation #3
However, the BOD test actually involves the measurement of oxygen
consumption rather than the amount left to be depleted, so a new variable
-------
10
y (oxygen depletion) is introducted such that
y = Lo -L
and substitution into equation #3 yields
y = Lo (l-e~kt) equation #4
The average ke value reported ^ for the Thames River STP effluent
samples was 0.234 day"-'- which results in
y/ - (l-ef--234^)
/Lo
or Lo = 1.45 y
or BOD ultimate = 1.45 x BOD5
It should be cautioned that the equivalent expression
y = Lo (l-10"klt) equation #5
is often employed with k=k'x2.303
The observed Potomac River samples' CBODs and CBOD20 data, included
in Table #2, gave the following best fit function:
CBOD20 =1.85 CBOD5
with a correlation coefficient of 0.945 based upon 53 data pairs.
4. Thomas Graphical Determination of BOD Constants
All data points (6 or 7 readings per sample over the 20 day
incubation period) were also used to give the best available estimate
of kjQ and L by using the Thomas Graphical Determination^'7. This
method relies upon the observation that the relation (l-10"kt) is
-. t~
such that by using equation #5
very similar to 2.3 kt [l + (2-.3) kt]
6
y = LQ2.3 kt [1 + C^3-) kt]-3
-------
11
or
1 (2.3k)2//5 t equation #6
=(2.3L0k) + (6L0)!/3
A plot of/t/X1/3 vs t yields a linear relation with slope
m = (2.3k)2/3 and intercept b = 1
- r - 1/3
(2.3kL0)
BOD k}Q and L values can be determined from equation #6 as follows:
(2.3k)2/3 slope
C6L0)V3
m =
b"
(2.3kLn)1/3 intercept
m _ (2.3)2/3 x (2.3)1/3 x k2/3 x
b 6
or
k = 2.61m
b
Also since b =( 1 \ 1//3 it follows that L0= L
2 . 3kL/ 2.3b3k
The end result is that the two variables L0and k^g are related to
a close approximation to y and t by two simple equations which
allow their solution.
To facilitate the calculation of Thomas constants, a computer
program was written to compute the k^g an<3 LQ-
The results are compiled in Table #2. The average (n=43) k1Q
value observed for river CBOD's was kj,Q = 0.062 days"1 or ke = 0.14 days"1
The correlation coefficients (.30-.99):
y = L0 Cl-10'kt) = 2.3kt (1+ 2-3kt)'
suggests first order kinetics. The value predicted by the
Q
Dynamic Estuary Model (DEM) for the deoxygenation rate constant,
ke, of CBOD's at 20°C was 0.17 days"1.
-------
TABLE # 2
CBOD RIVER
12
THOMAS GRAPHICAL DETERMINATION
DATE -
July 20
July 27
Aug. 3
Aug. 24
STA
- P8
1
3
4
5
6
7
8-A
10
11
- P8
1
3
4
5
6
7
8-A
10
11
- 1
3
4
5
6
7
8-A
10
11
- P8
1
3
4
5
6
7
8-A
10
11
fclO
0.070
0.049
0.057*
0.065
0.062
0.035*
0.053
0.073
0.069
0.051
0.058
0.067
0.056
-
0.041
-
0.001*
0.065
0.020*
.071
.018*
.066
.066
.083
.055
.060
.055
.057
.059
.078
.067
.075
.066
.065
.052
.032*
.032*
.012*
LO
5.41
6.76
8.67
6.51
8.40
11.78
8.80
6.85
6.69
7.99
3.85
5.62
4.67
-
10.18
-
15.60
5.61
7.91
4.39
10.51
7.04
5.93
5.98
7.31
8.26
7.02
6.43
6.15
4.68
4.46
6.19
9.28
8.66
10.40
20.93
23.78 -
22.38_j~
1 lag phase
1 lag phase
1 lag phase
1 lag phase
8/24 bloom
300 ppb chlcn
CBOD 5
3.0
3.0
5.2
2.6
4.4
5.3
4.2
4.0
3.8
3.8
1.8
3.0
2.3
3.0
4.0
3.1
3.0
1.9
2.3
3.0
3.7
3.2
3.5
3.6
3.9
3.2
2.9
3.1
2.6
2.2
3.6
5.2
4.3
4.6
7.6
6.6
2.8
CBOD20
5.0
6.0
8.2
5.9
7.6
9.7
7.9
6.2
6.2
6.9
3.5
5.1
4.1
5.1
8.9
6.4
5.1
4.6
4.1
5.1
6.6
5.2
5.3
6.5
7.8
6.4
6.2
5.8
4.3
4.2
5.7
8.6
8.0
9.4
15.4
17.3**
9.0**
_
Algae major contributor
-------
TABLE # 2 (con't)
CBOD RIVER
13
DATE - STA
Aug. 31 - P8
1
3
4
5
6
7
8-A
10
11
Sept. 8 - P8
1
3
4
5
7
8-A
10
11
THOMAS GRAPHICAL DETERMINATION
*10 L
.058
.061 4.65
.014* 13.80 1 lag phase
o
4.17
.053
.091
.062
.050
.055
.059
.043
.069
.056
.081
.056
.071
.065
.018*
.035*
7.59
8.17
10.00
12.54
12.98
9.48
5.25
4.91
5.31
8.01
9.76
4.80
6.35
14.66
8.72
CBOD5
2.1
2.4
3.2
3.8
3.7
5.2
5.1
5.2
6.3
4.6
CBOD20
3.8
4.3
5.7
6.5
6.7
7.2**
9.2
11.1
11.9
8.7
1 lag phase
2.0
2.6
2.5
4.8
4.8
2.6
3.2
3.9
3.1
4.5
4.5
5.0
7.4
8.8
4.5
6.1
7.3
6.9
* Not included in calculation of average kjQ due to their exceptionally
low correlation coefficients and lag periods in growth
** Deleted from calculation of CBOD5/CBOD20
K10:
n
average
s.d.
43
.062
.010
-------
14
The total BOD for the river samples (Table #3) also followed
first order kinetics with correlation coefficients over the range
"1
of (1.000 to .156) with an average (n=50) kio of 0.054 day
This rate corresponds to an expression of 47% of the ultimate BOD
after 5 days such that: BOD2Q = 2.1 x BODs
An oxygen depletion curve is included in Figure #2.
5 . Temperature Effects Upon Reaction Rates
Any statement concerning the observed B.O.D. reaction rates
should take into consideration the potential error due to fluctuation
in the incubation temperature. If it is assumed that over a narrow
range biochemical reaction rates tend to increase, as do strictly
chemical reactions (endothermic) , with increasing temperature,
then the effect of temperature upon the rate of these reactions may
be approximated by the Arrhenius equation" : k = Ae~ '
were A is the frequency factor or pre-exponential factor (time ) ;
Ea is the activation energy, (energy/mole) ; T is temperature in
°Kelvin and R is the ideal gas constant (energy x temp x mol" ).
Taking the natural log:
-Ea
In k = _ * In A
RT
and differentiating with respect to temperature:
d In k = d In A - d E_a
d T d T _ RJ_
d T
but A, Ea and R are all constant with respect to T.
or: d In K = -Ea d T"1 = Ea_
d T R d T RT2
-------
15
TABLE # 3 BOD RIVER
DATE - STA
July 20 - P8
1
3
4
5
6
7
8-A
10
11
July 27 - P8
1
3
4
5
6
7
8-A
10
11
Aug. 3 - P8
1
3
4
5
6
7
8-A
10
11
Aug. 24 - P8
1
3
4
5
6
7
10 !oiO* 68^80 1 ill Phased al§ae % 30° ?Pb
H _ nn/i* _t.7. T.Z i , ~" J chloro a
kio
.037
.032
.058
.027
.049
. 036*'
.040
.058
.048
.051
.023*
.047
.060
.057
.047
.059
.041
003*
.053
.023
.105
.081
.063
.079
.080
.045
.030
.049
.039
.042
.045
.047
.072
.081
.063
.059
.049
.011*
.010*
.004*
LO
9.10
10.95
13.27
18.31
21.14
24.5 1 lag phase
14.71
10.74
10.59
10.53
-2.99 2 lag phases
5.73
8.50
10.60
11.87
16.45
14.08
100.0 1 lag phase
7.95
12.75
2.38
5.85
13.99
12.14
11.08
9.45
11.50
13.12
12.50
9.17
9.52
7.83
9.01
10.99
12.99
13.00
14.45
62.48 1 lag phasT)
68.80 1 lag Phaser algae
-63.35 | linear"! _J chl'
r=.999
m=.673
b=-.232
-------
16
TABLE # 5 Ccon't) BOD RIVER
DATE - STA k1Q L0
Aug. 31 - P8 .063 5.73
1 .056 5.97
3 -054* 14-76 1 lag phase
4
5 .073 12.77
6 .075 12.96
7 .071 14.80
8-A .059 17.89
10 .045 19.62
11 .044 15.66
Sept. 8 - P8 .016 13.04
1 .039 8.11
3 .066 10.39
4 .060 18.65
5 .060 22.81
6 .066 12.60
8-A .062 9.84
10 .026* 15.10 1 lag phase
11 .023 16.12
* Not included in calculation of average k due to their exceptionally
low correlation coefficients and lag periods in growth
k!0:
n = 50
average = .054
s.d. = .017
-------
17
Figure #2
20-
18-.
§ Ht
H
s *
I lot
0)
X
o
Depletion Curve for BOD and CBOD
July 20, 1977
Broad Creek Sta. 6
i
12
BOD
CBOD
8 10
Time (days)
14
16
18
20
10.0
8.0
6.0
G
(1)
IS
2.0
Sept. 8, 1977
Possum Point Sta. 11
BOD
CBOD
_,
12
10
Time (days)
16
18
20
-------
18
Integrating over temperature and rate
d In k =
Ea d T
RT2
\L O
T"2 d T
/T^
*.o J.I1 K. i ~ "
R Tl>
In /k
/k2\ - Ea /]. - l_^
\kl/ R \T1 T2;
or In/k2\ = Ea C*2 ~ Tl\ equation #7
Because the original assumption is that only a limited temperature
range be considered, Tj x T2 (in K ) is essentially constant. Let
Ea = 8, which has been termed the temperature coefficient.
Substitution of 6 into equation #7.
In /k?/ \ ^
Experimentally determined 9 values have been found to be reasonably
constant over narrow temperature ranges with the average value for
temperature coefficient over the range 5-25°C being reported ' as
0.056 °C~1 and 0.047 "C"1. The observed difference between experimental
1 T S'U
(ke = 0.143 day"1) and classical (ke = 0.234 day"1) rates cannot
be explained based soley on fluctuation in incubation temperature. This
can be shown by substituting these values into equation #7
ln(:234\ = 0.056 (20-T1°C) Equation^
V-143/
-------
19
and solving for
= n°
A 9°C variation in temperature is necessary to explain the difference
in rates. The observed fluctuation of the Jordon Model #818 BOD
incubator was 20 +_ 1°C (measured with an NBS certified thermometer)
during the course of the Potomac Survey. Therefore it may be
concluded that the observed rate cannot be explained by temperature
fluctuation.
6. Nature and Distribution of CBOD
The distribution of the CBOD20 vs RMI and STP locations are
compiled in figures 3-8. The peak(s) CBOD area extended from the
Memorial Bridge to Gunston Cove, which corresponds to the locations
of the major STP's: Arlington; Blue Plains; Alexandria; Westgate;
Piscataway; Hunting Creek; Dogue and Pohick.
A second CBOD peak area was observed on August 24 (figure 6)
which corresponded to an algal bloom with a chlorophyll a concentration
of ^ 300ppb. The chlorophyll a. and CBOD data for stations 8-A, 10, and 11
are compiled in Table #4. The high correlation obtained (r=.94 and
n=18) suggested this second peak demand area was largely attributable
to algal decomposition and/or respiration. The kinetics of the CBOD
process for stations 8-A, 10, and 11 were first-order exponential but
were abnormally slow (Table #2) . These data points were not included
in the calculated ke of 0.143 day"1.
The average CBOD2Q entering the study area at Chain Bridge was
4.6 ppm while the average NOD2Q was 2.0 ppm. Figures 3 thru 8 reveal
-------
Figure #3
xD
000
CM CM CM
a Q a
o o o
03 03 Z
u
f-
t--
01
o
CM
o
O
H
c
H
rt
f-»
u
3
O
r-H
-------
Figure #4
oxD
o o o
CM (M CN
c c c
c o c
ffl ea z
CJ
*-:
21
-------
Figure #5
oxD
o o o
(Nl CM (N
O C C.
o c c
efl 02 z
00
t-O
t-o
CM
to
. o
oo
CM
CM
(N
CM
O
CM
-00
CO
I
CM
-------
Figure #6
23
-------
Figure #7
24
-------
Figure #8
>xD
o o o
CM CN (N
CCQ
O C O
cc ca z:
u
oo
?H
25
-------
26
TABLE # 4
Date
July 20
July 27
Aug. 3
Aug. 24
Aug. 31
Sept. 8
Station #
8-A
10
11
8-A
10
11
8-A
10
11
8-A
10
11
8-A
10
11
8-A
10
11
n=18
r=.942
m= . 046
b=1.907
Name
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Chlorophyll a
ppb
86.2
81.0
90.0
123.0
129.0
112.5
103.5
76.5
85.5
306.0
312.0
168.0
187.5
195.0
148.5
85.5
100.5
120.0
CBOD20
ppm
6.2
6.2
7.2
6.4
5.1
4.6
7.8
6.4
6.2
15.4
17.3
9.0
11.1
11.9
8.7
6.1
7.3
6.9
-------
27
that CBOD is in general more significant than the NOD for the river
samples. This may be attributed to the greater masses of carbon
in the system8. The average NOD2o/BOD2o (Table #7) was 0.38, (n=58) .
The algal bloom area exhibited the same trend which reflects the algae
C/N ratio of 4.6 found by elemental analysis. The few exceptions
to the dominant CBOD pattern were restricted to river locations
adjacent to the sewage plants in the reach from the 14th Street
Bridge to Broad Creek. Nitrification was largely completed above
the algal bloom area.
B. Biochemical Oxygen Demand - Nitrogenous
1. General Discussion
Nitrification is the conversion of NH3 to NO^ by biological
respiration. This type of respiration is employed by seven genera
of autotrophic nitrifyers as listed in Bergey's manual12. However,
only Nitrosomonas spp and Nitrobacter spp are regularly reported by
in situ nitrification studies . In general, the treatment of
nitrifying river samples with inhibitors specific to Nitrosomonas
and Nitrobacter can be expected to stop all appreciable nitrification ,
It should be noted that heterotrophic nitrification can also occur
whereby N02 and NO- are formed by reactions that do not involve
oxidation. The contribution due to these organisms was not found to
be significant in the Potomac River, since a close correlation was
observed between the expected NOD (associated with TKN-N) and the
measured NOD which was specifically limited to autotrophic bacteria.
-------
28
2. Bacterial Growth Requirements
Nitrifying bacteria prefer temperatures of 35-40°C but can
survive well over the range of 4-45°C . The rate of nitrification
increases with increasing temperature throughout the range of 5-35°C .
Nitrifying bacteria are more temperature sensitive than heterotrophic
bacteria and their contribution to B.O.D. will vary more markedly
with temperature. BOD samples assayed during winter months should
incorporate a nitrification inhibitor to yield results more relevant
to river conditions. The temperature ranges observed during this
summer's Potomac survey were very narrow:
Date Temperature Range °C
July 20 31-29
July 27 28-25
Aug. 3 28-27
Aug. 24 26-27
Aug. 31 30-28
Sept. 8 28-27
14
Nitrifyers can generally tolerate a pH range of 6-10 . The "ideal"
values seems to vary with the particular environmental conditions
from which the tested bacteria were selected but in general a
slightly basic pH seems ideal (^8.0). At pH levels below 7,
Dissolv
5,13,14
14
the rate of maximum growth was decreased by more than 50% . Dissolved
oxygen does not seem to affect the rate of their growth above O.Sppm.
The average temperature and pH measured over the course of this study
were 27.0°C and 7.6 respectively.
The reactions involved in nitrification are as follows:
NH4+ + 1% Q2Nitrosomonas>2H+ + N02" + H20 equation #9
}2
N0~ + % n2 Nitrobacte^ N0^~ equation
-------
29
An average pH of 7.6 was found in the Potomac River long term BOD
samples. The pka of ammonia at 25 °C is 9.26 . These factors
combined with the Henderson-Hasselbach equation:
pH = pka + log base
acid
establish that NH4 should be used in the preceeding equations and
that ammonium (NH^"*") represents 98% of all ammonia species present.
3. Lag Phase and Growth Characteristics
Nitrosomonas have a maximum growth rate less than that of
Nitrobacter and heterotrophic bacteria in general have a maximum
growth rate nearly double that of autotrophic bacteria (doubling time
of 30/hr)13. For STP effluent samples an NOD lag time of 10-15
days often occurs due to the slow growth of nitrifying bacteria and
the small population initially present. For this reason, nitrogenous
oxygen demand is often termed second stage BOD.
Nitrifiers not only have a slower growth rate but also are more
fragile than heterotrophic bacteria, resulting in more sporadic
results from an NOD experiment than from CBOD tests . The growth
of nitrifiers are inhibited by a wide variety of substances as :
halogens; thiourea and thiourea derivatives; halogenated solvents;
heavy metals; cyanide; phenol; and cresol.
A study of 52 such compounds known to inhibit nitrification revealed
that the inhibition of Nitrobacter is less severe than that of
Nitrosomonas; Nitrosomonas representing the weak link in nitrification
Nitrification is a surface phenomenon with much of nitrification
occurring in clear, shallow rivers on the surfaces of mud (aerobic),
-------
30
plants, slime, etc . Laboratory experiments involving the incubation
of clear-shallow stream samples would not be expected to reflect
the extent of in situ nitrification. However in a turbid estuary,
such as the Potomac, the surface area of the suspended material is
expected to exceed that of the river bed, such that nitrification
would be expected to be more significant in the water column. Tests
of such water samples should estimate the extent of nitrification
actually occurring in the estuary.
4. Stoichiometry of Nitrification
The Stoichiometry of the nitrification reactions , equations #9 § #10
dictate that the conversion of 1 gram of nitrogen from ammonia to
nitrite utilizes 3.43 grains of oxygen and the conversion of 1 gram of
nitrite-nitrogen to nitrate involves the utilization of 1.14 grams of
oxygen. However, nitrifying bacteria are autotrophic and as such
utilize a portion of the energy derived from nitrogen oxidation to
reduce CC>2, their primary source of carbon. The net result is a
reduction in the amount of oxygen actually consumed. Short term
10 in OA
(0-5 day) experiments, JJ employing cultures of Nitrosomonas
and Nitrobacter have related the depletion of oxygen to the production
of nitrite and nitrate with the corresponding 0/N ratios of 3.22 and
1.11 determined. However in long term experiments, the decay of
these organisms would be expected to exert an oxygen demand approximately
equivalent to the oxygen originally generated, resulting in an overall
relation not significantly different from 4.57
-------
31
In Table #5, NC^g derived from long term incubation of river
samples was compared to a predicted value based upon 4.57 x TKN-N
initially assayed in the sample. A paired t-test established, at
a 95% confidence level, that no significant difference existed
between these methods of prediction with t=.7 at 57 degrees of freedom.
A plot of the predicted NOD (4.57 x TKN-N) vs that observed with
laboratory incubation is included in figure #9. The comparison of
NOD and TKN x 4.57 vs RMI is included in figures #10 and #12 - #16.
The close correlation suggests that:
1. Nitrification was essentially completed after 20 days
of laboratory incubation.
2. The inhibitor to nitrification employed, N-serve,
gave accurate NOD results.
3. The NOD observed was due to autotrophic bacteria since
the inhibitor was specific for Nitrosomonas.
Figures #3-8 include the found NOD vs River Mile Index and
indicate that nitrification occurs within a short span of the river,
between Hains Point and Fort Washington.
A second peak NOD area occurred, as with CBOD, at stations 8-A;
10 and 11 on August 3, 24, and 31. This was thought to reflect the
nitrogen contribution associated with the decay of the algae present
at these stations. A significant NOD lag time was observed in samples
obtained in the algal bloom area.
The changes in N02, N03, and W$ concentration with RMI
for samples obtained on July 20 are included in figure #11. They
illustrate the classical relation expected during the course of
-------
32
TABLE # 5 NOD20 vs (TKN-N x 4.57)
Date
July 20
July 27
Aug. 3
Station
P-8
1
3
4
5
6
7
8-A
10
11
P-8
1
3
4
5
6
7
8-A
10
11
P-8
1
3
4
r
O
RMI
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
NOD
(TC5$)
2.2
2.3
4.4
6.2
11.0
11.1
4.0
3.6
3.0
2.6
1.4
1.5
2.6
5.3
5.6
6.8
5.5
5.8
2.4
3.6
LA
1.4
7.3
4.8
5.0
TKN
.741
.705
.821
2.05
2.495
2.20
1.358
1.074
.853
.621
.461
.380
.582
.986
1.212
1.301
.897
.727
.606
.509
.438
.358
1.477
1.262
1.298
NOD
(4. 57) (TKN)
3.4
3.2
3.8
9.4
11.4
10.1
6.2
4.9
3.9
2.8
2.1
1.7
2.7
4.5
5.5
5.9
4.1
3.3
2.8
2.3
2.00
1.6
6.7
5.8
5.9
-------
33
TABLE # 5 (con't) NOD2Q vs (TKN-N x 4.57)
Date S
Aug. 3 (con't)
Aug. 24
Aug. 31
tation
6
7
8-A
10
11
P-8
1
3
4
5
6
7
8-A
10
11
P-8
1
3
4
5
6
7
RMI
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
NOD20
(TCMP)
3.3
4.4
4.0
3.8
1.8
3.0
2.7
4.0
4.4
3.4
4.1
3.5
6.6
6.8
4.2
1.6
1.2
7.1
4.7
5.1
4.9
4.3
TKN
1.083
.877
.734
.684
.546
.484
.484
.894
1.378
1.161
1.094
1.119
1.269
1.328
.802
.472
.400
1.760
1.392
1.264
1.092
.968
NOD
(4. 57) (TKN)
4.9
4.0
3.4
3.1
2.5
2.2
2.2
4.1
6.3
5.3
5.0
5.1
5.8
6.1
3.7
2.2
1.8
8.0
6.4
5.8
5.0
4.4
-------
34
TABLE # 5 (con't) NOD2Q vs CTKN-N x 4.57)
Date
Aug. 31 (con
Sept. 8
d = .0965
Sd = 1.1207
S3 = .1471
df = 57.00
t = 0.6560
Station
t)8-A
10
11
P-8
1
3
4
5
6
7
8 -A
10
11
RMI
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
n = 58
r = .876
m = .844
b = .774
NOD 20
(TCMP)
5.2
4.9
5.6
2.0
2.2
4.5
8.9
11.0
--
3.6
3.0
2.5
3.0
TKN
1.224
1.28
.816
.460
.406
1.056
1.43 *
1.83 *
--
.721
.451
.288
.388
NOD
(4. 57) (TKN)
5.6
5.5
3.7
2.1
1.9
4.8
6.5
8.4
3.3
2.1
1.3
1.8
* Not included in calculation of r or t
LA = lab accident
-------
35
Figure #9
NOD2Q (Inhibitor) vs NOD (TKNx4.S7) for River Water Samples
NOD
(TKN x 4.57)
mg/1
13 -
12 -
11 -
10 _
9 -
7 -
6 -
4 -
3
2
1 -
n = 58
r = .876
m = .849
b = .774
10 11 12
NOD (Inhibitor) mg/1
-------
Figure #10
36
-------
N-Series vs RMI
July 20, 1977
16 18
RMI
32 34
-------
Figure #12
CN
X
3
p
00
o
in
rf
X
2 O
I (N
c c
£S
c
CO
CL.
-------
en
to
oo
3
I
00
z: t---
c
00
to
CO
I
a.
Figure #13
O
z o
I (M
H Z
_ co
(M
to
o
to
oo
(Nl
\o
CM
O
CN
39
-------
Figure #14
o
o>
M
tn
3
<
00'
r-
LO
rr
X
Z O
I CM
Z Q
« O
E- Z
OO
CO
CM
to
o
10
00
(N
CM
CM
O
CM
CO
i
-------
Figure #15
o
z o
I CM
z c
fc^ O
t- Z
tO
00
I
C-
00
to
CM
to
o
to
00
CM
(N
(N
CN
O
CM
00
\o
CM
- \o
41
-------
Figure #16
o _
01
I
00
oo
i
a,
O
Z O
I (N
Z Q
bi O
H Z
_ o
oo
CM
CM
O
CS1
42
-------
43
nitrification. The NOD pattern for this slack run (figure #11) is
directly associated with a. decrease in NH3 and a corresponding
increase in NC>2~ and N03~.
5. Nitrification Kinetics
The kinetics of nitrification for river samples taken between
Hains Point and Ft. Washington, the peak area of nitrification
associated with the STP effluents, were found to be exclusively
first order. The average ke of 0.14 day'1 was observed with a
correlation coefficient of 0.91 for n=25 (Table #6). This k value is
consistent with the close correlation between NOD and TKN-N x 4.57,
since a ke of 0.14 day'1 predicts that 94% of the ultimate NOD will
be expressed after 20 days of incubation. The value predicted by
o
the Dynamic Estuary Model (DEM) for the deoxygenation constant of
NOD was 0.08 day'1. The standard deviation of 0.02 for the NOD ke (Table #6)
was twice that of the CBOn rate constant and reflects the fragile and
sporadic nature of nitrification.
6. Nature and Distribution of NOD
Bracketing the region of exponential NOD are the upper stations
at Chain and Key Bridges and lower stations from Gunston Cove to
Possum Point. Occasionally these stations had poor correlation to
Thomas Plots. The upper stations correspond to a region of low
NOD2n levels with an average of 2.0 ppm. The lower stations correspond
to a region of low NOD2Q or algal blooms. The data from these stations
was plotted as D.O. depletion vs time and two additional classes
of kinetics were observed (figure 17). A two-stage or consecutive
-------
44
TABLE # 6
NOD RIVER
DATE - STA
July 20 - P8
1
3
4
5
6
7
8-A
10
11
July 27 -
Aug. 3 -
Aug. 24 -
k!0
-.061
-.560
.031
.040
.038
.035
.029
.001
.051
LO
-0.178
-.016
5.19
8.03
13.47
13.07
4.71
65.45
2.46
P8
1
3
4
5
6
7
-A
10
11
1
3
4
5
6
7
-A
10
11
P8
1
3
4
5
6
7
-A
10
11
--
.107
.042
.058
--
.071
--
-.000
.102
.027
.103
.083
.094
.090
.024
.030
0.033
-.052
-.025
.015
-.022
0.076
0.089
0.053
0.045
0.030
0.023
0.009
0.002
__
1.49
3.47
5.93
-_
7.36
__
-361.09
1.93
5.16
1.53
8.00
5.23
5.20
4.60
6.21
5.13
4.08
-1.02
5.56
-1.63
4.55
4.83
3.79
4.54
4.75
-4.08
-13.38
45.92
r
-.747
-2.39
.83
.784
.966
.942
.875
.048
.871
.897
.700
.992
.991
CURVE
CODE
S
S
E
E
E
E
E
S
E
E
E
E
(see figure #17
Low NOD
009
901
855
949
982
961
928
793
944
895
746
704
740
823
992
991
959
972
700
263
188
022
S
E
E
E
E
E
E
E
E
E
C
S
C
S
E
E
E
E
E
S
S
C
Low NOD
Low NOD
Low NOD
Algae
-------
45
TABLE # 6 (con't)
NOD RIVER
DATE - STA
Aug. 31 - P8
1
3
4
5
6
7
8-A
10
11
Sept. 8-1
3
4
5
7
8-A
10
11
k!0
.068
.077
.095
.043
.090
.073
.009
.014
.056
.077
.036
.063
.067
.054
.039
.011
1.60
7.81
5.
5.
4,
5.
.60
.41
.95
.63
15.59
9.92
-.22
5.12
12.37
13.00
3.79
3.51
2.73
-5.63
r
.871
.964
.989
.900
.992
.935
.229
.487
.654
.997
.714
.925
.930
.981
.734
.305
CURVE
CODE
E
E
E
E
E
C
c
s
E
E
E
E
E
C
S
(see figure #17)
Algae 200ppb
Low NOD
The average was limited to Hains Point to Fort Washington stations,
because these stations represented the primary area associated with
nitrification and the kinetics were limited to "E" Kinetics.
cio-
n = 25
y = .059
s.d. = .023
ke = .14
n = 25
y = .91
r = .09
-------
Figure #17
NOD Depletion Curves
46
Oxygen
Depletion
mg/1
exponential
s-shaped
(lag + exponential)
consecutive
(2 lags + exponential curves)
time
-------
47
pattern was bbserved in which exponential growth occurred after a lag
phase in each of two distinct processes. This may involve the separation
of Ntiq+»N02~ and NC>2~^NO?* by a lag stage. In the majority of
the "exceptional" NOD stations an S-shaped pattern was observed with
a lag time probably occurring for the Nitrosomonas conversion of NH^
to N02~. Nitrosomonas is considered the weak link in nitrification.
All samples from the peak algal bloom period displayed a lag time
with a. resultant poor correlation coefficient in Thomas Plots. This
suggests that the action of heterotrophic bacteria was necessary
to liberate the required ammonia.
A consequence of the lag-free first order NOD kinetics observed
for the majority of Potomac river samples is that the BOD^ contains a
significant NOD component. The average NOD5/BOD5 observed during the
study (Table #7) was 0.33 (n=S6).
-------
48
TABLE # 7
NOD5/BOD5 and NOD2Q/BOD20
DATE - STA
July 20 - P8
1
3
4
5
6
7
8-A
10
11
July 27 - P8
1
3
4
5
6
7
8-A
10
11
NODs
0.2
0
1
2
4
4
0
1
0
1
-
1
1
3
2
4
-
1
1
1
.4
.4
.2
.6
.6
.8
.2
.7
.4
.0
.1
.1
.8
.6
--
.6
.4
.7
TBO
3.
3.
6.
4.
9.
9.
5.
5.
4.
5.
--
2.
4.
5.
5.
8.
--
4.
DS NODs/TBOD5
2 .063
4
6
8
0
9
0
2
5
2
-
8
1
4
8
6
-
7
4.4
3.6
.118
.212
.458
.511
.465
.160
.231
.156
.270
.357
.268
.574
.483
.535
.340
.318
.472
n = 56
y = . 33
s = .18
NOD?o
2.2
2
4
6
11
11
4
3
3
2
1
1
2
5
5
6
5
6
2
3
. 3
.4
. 2
.0
.1
.0
.6
.0
. 3
.4
.5
.6
.3
.6
.8
.5
.8
.4
.6
TBOD20 NOD2o/TBOD20
7.2 .306
8
12
12
18
20
11
9
9
9
5
5
7
/
9
10
14
14
10
7
8
.3
.6
.1
.6
.8
.9
.8
.2
.5
.4
.C
7
.4
.7
.9
.4
.2
.5
.2
.278
.349
.512
.591
.534
.336
.367
.327
.242
.259
.30
.337
.564
.523
.456
.382
.666
.32
.439
n =
y =
s =
58
.58
.11
-------
49
TABLE # 7 (con'tO NOD5/BOD5 and NOD20/BOD2o
DATE - STA NODs TBODs NODs/TBODs NOD20 TBOD20 NOD2n/TBODon
Aug. 3 - P8
1
3
4
5
6
7
8-A
10
11
Aug. 24 - P8
1
3
4
5
6
7
8-A
10
11
Aug. 31 - P8
1
3
4
0.9
5.6
3.7
3.1
0.9
1.6
1.3
1.1
0.3
0.9
0.4
2.9
3.4
1.8
2.1
0.9
0.4
0.0
0.5
0.7
0.9
6.0
4.7
3.2
8.6
7.4
6.3
4.4
5.2
5.2
4.3
3.2
4.0
3.0
5.1
7.0
7.0
6.4
5.5
8.0
6.6
3.3
2.8
3.3
9.2
8.5
.281
.651
.500
.492
.204
.308
.250
.256
.094
.225
.133
.569
.486
.257
.328
.164
.050
0
.152
.250
.273
.652
.553
1.4
7.3
4.8
5.0
3.3
4.4
4.0
3.8
1.8
3.0
2.7
4.0
4.4
3.4
4.1
3.5
6.6
6.8
4.2
1.6
1.2
7.1
4.7
5.5
12.4
11.4
10.2
8.6
10.9
11.8
10.2
8.0
8.8
7.0
8.2
10.1
12.0
12.1
12.9
22.0
24.1
13.2
5.4
5.5
12.8
11.2
.254
.589
.421
.490
.384
.404
.339
.372
.225
.341
.386
.488
.436
.283
.339
.271
.300
.282
.318
.296
.218
.555
.420
-------
50
TABLE # 7 (con't) NODs/BOD5 and NOD20/BOD20
DATE - STA NODs TBOD5 NOD5/TBODs NOD20 TBOD2Q NOD20/TBOD20
Aug. 31 -
(con't)
f
Sept. 8 -
i
5
6
7
5-A
10
11
P8
1
3
4
5
6
7
3 -A
10
11
3.9
2.8
3.7
4.5
2.6
1.7
0.0
0.1
2.8
4.6
7.0
2.0
1.8
1.0
0.5
7.6
8.0
8.8
9.7
8.9
3.3
2.0
2.7
5.3
9.4
11.8
4.6
5.0
4.9
3.6
.513
.350
.420
.464
.292
.515
0
.037
.528
.489
.593
.435
.360
.204
.139
5.1
4.9
4.3
5.2
4.9
5.6
2.0
2.2
4.5
8.9
11.0
3.6
3.0
2.5
3.0
11.8
12.1
13.5
16.3
16.8
14.3
6.5
6.7
9.5
16.3
19.8
8.1
9.1
9.8
9.0
.432
.405
.318
.319
.292
.392
.308
.328
.474
.546
.556
.444
.330
.255
.333
-------
51
V- Oxygen Demand in the Potomac STP Effluent Samples
A. CBOD
The CBOD kinetics observed for the sewage treatment plant effluents
were first order with an average ke = 0.17 (n=19, s=0.02) and a average
correlation coefficient of 0.86 (Table #8).
B. NOD
The NOD kinetics observed for the sewage treatment plant effluents
were all characterized by a lag period which generally lasted for the
first 10 to 15 days of incubation. The NOD expressed within five days,
though relatively small compared to the NOD expressed after 10 to 12
days was significant and is included in Table #12. The average (n=30)
NOD5/BOD5 value was 0.26 with considerable noise in the data, s=0.21.
This relationship corresponded to an average CBODs/BODs ratio of 0.74.
The observed carbonaceous kinetics of ke = 0.17 dictated a CBOD ultimate
to CBODs ratio of 1.75 and together with the observed ratio suggests:
CBOD (ultimate) = BOD5 * ±-
The relation CBOD ultimate = BOD5 x 1.45 is based upon the classical
kinetics, ke=.234 associated with sewage effluents and assumes an
insignificant nitrification contribution. However, the factor 1.45
is not unsatisfactory for the Potomac STP effluents since it predicts
CBODu;Ltimate values not significantly different from those predicted
by the 1.30 factor. An STP effluent with a BODs of 30.0 mg/1 would
yield CBODu|t^mate values of 39.0 mg/1 based upon the 1.3 factor and
43.5 mg/1 based upon the 1.45 factor. This is within the error
2
associated with the BOD test" and provides a conservative estimate of
the carbonaceous oxygen demand.
-------
TABLE # 8
CBOD - STP
52
DATE - STA
July 20 - SI
S2
S3
S4
S5
S6
S7
S8
Aug. 24 - SI
S2
S3
S4
S5
S6
S7
S8
Aug. 31 - SI
S2
S3
S4
S5
S6
S7
S8
Name
Pi scat away
Arlington
Blue Plains
Alexandria
West gate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
kio
.105
.075
.076*
.061
.074
.069
.050
.055
--
.101
.072
.092
.012 *
.064
.080
.037
--
.012*
.101
.101
--
--
.063
.076
LO
5.66
10.09
26.40
108.17
21.68
22.79
16.95
34.16
--
20.21
44.04
84.27
58.17
22.43
21.68
22.7
--
9.97
32.52
57.59
--
_-
9.97
16.04
r
.997
.998
.844
.997
.991
.996
.983
.979
--
.998
.992
.992
.257
.998
.997
.621
--
.588:
.997
.997
--
--
.976
.997
1 lag phase
2 lag phases
2 lag phases
588} linear r=.991
m=.370 b=-.23
-------
53
TABLE #_8_ (con't) CBOD - STP
DATE -
Sept. 8
STA
- SI
S2
S3
S4
S5
S6
S7
S8
Name
Piscataway
Arlington
Blue Plains
Alexandria
West gate
Hunting Creek
Dogue Creek
Pohick Creek
.009* 29.30
__
__
.069 94.97
.047 28.59
.053 24.94
.034* 20.49
.007* 89.88
k:
n=19
r
.019 1 lag phase
--
--
.985
.995
.989
.799 2 lags
.469} linear r=.991
m=1.294 b=.824
r :
n=26
k~=.017 f=.86
s=.020 s=.26
-------
54
The Thomas correlation coefficients for NOD are listed in Table #9. The
negative correlation consistently observed resulted from the lag in
NOD. The oxygen depletion plots (figures 18, 19 § 20) were restricted
to "S-shaped" and "consecutive S-shaped" patterns.
The fraction of the potential NOD, TKN-N x 4.57, expressed after
20 days is included in Table #10. The low recovery is related to
the long lag phase observed for the NOD. Since the receiving waters
have lag-free, first order kinetics, it is likely that the consistent
NOD lag phase observed in STP samples is artifical and is perhaps
due to the lack of nitrifying bacteria.
C. Loading Characteristics
The average flows and loadings based on: CBOD2Q5 TKN-N x 4.57 (NOD)
and BOD5 are presented in Table #11. The ratio of NOD20 to BOD2Q
for the STP effluents is compiled in Table #12 with an average value
of 0.69 (n=27; s=0.11). The effluent loadings were therefore
predominantly NOD, and as pointed out previously, the river samples
were dominated by the CBOD. The predominant nitrogen form, in the
STP effluents, (nearly to the exclusion of all other oxidation states)
was ammonium (Table #13). This suggested that a portion of the
discharged ammonium was being lost from the system, since nitrification
would be expected to be very efficient for ammonia. A mechanism
for this loss may be sorption of ammonia onto clays and organic
colloids in sediments and loss to the bottom by sedimentation. On
the bottom denitrification would be expected to predominate" .
-------
TABLE # 9 (con't)
NOD - STP
55
DATE - STA
July 20 - SI
Aug. 24 -
Aug. 31 - SI
:A
si
S2
S3
S4
S5
S6
S7
S8
SI
S2
S3
S4
S5
S6
S7
58
SI
S2
S3
S4
S5
S6
S7
S8
Name
Piscataway
Arlington
Blue Plains
Alexandria
West gate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
fcio
-.005
-.0464
-.089
-.024
-.034
-.064
-.014
-.063
-.025
-.089
-.098
-.098
-.076
-.050
-.082
-.066
-.004
-.063
-.051
-.012
.008
-.011
LO
-77.76
-5.68
-1.85
-30.13
-5.240
-3.35
-25.8
-2.59
-10.70
-.89
-.606
-.739
-1.43
-6.61
-.989
-2.09
-176.6
-3.98
-3.91
-4.46
109.17
-81.8
r
-.098
-.758
-.743
-.428
-.627
-.811
-.220
-.912
-.437
-.927
-.825
-.863
-.986
-.895
-.797
-.894
-.083
-.730
-.547
-.1058
.117
-.388
Curve
Type (see fig.20)
1 lag stage
1 lag stage
2 lag stages
2 lag stages
1 lag stage
2 lag stages
2 lag stages
1 lag stage
2 lag stages
1 lag stage
2 lag stages
-------
56
TABLE # 9 (con't) NOD - STP
Curve
DATE - STA Name kjg L0 r T>Te Csee fig-2
Sept. 8 - SI
'A
SI
52
S3
S4
S5
S6
S7
S8
Name
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
kio
-.021
-.044
-.026
-.027
-.074
-.057
LO
-24.59
-14.30
-13.44
-17.4
-2.38
-6.89
r
-.526
-.899
-.406
-.591
-.689
-.897
2 lag stages
2 lag stages
2 lag stages
-------
57
Figure #18
Oxygen Depletion Curves
Aug. 31, 1977
Dogue STP S-7
§ 30
H
-P
30
G
OJ
S? 10
T-
2
CBOD
1-
6
T~
8
10 12
Time (days)
16
18 20
Sept. 8, 1977
Piscataway STP S-l
60-
50
c 40
o
30
G
-------
Figure #19
100 t-
Oxygen Depletion Curves
58
0
BOD
NOD
10 12
Time (days)
Aug. 24, 1978
16
18
20
BOD
NOD
8 10 12
Time (days)
lo
18
20
-------
59
Figure #20
STP Oxygen Depletion Curves
NOD (consecutive)
2 lag phases
NOD (exponential)
1 lag phase
time
-------
60
TABLE* 10 Summary Sheet of % (NOD20/NODultimate) for STP's
Station
Sl-Piscataway
S2-Arlington
S3-Blue Plains
S4-Alexandria
S5-Westgate
S6-Hunting Creek .469
S7-Dogue Creek
S8-Pohick Creek
* NOD20 = NOD determined with the inhibitor
7/20
.747
.549
.873
.961
.24
.469
.214
.417
8/24
.85
.56
.78
.82
.61
.55
.41
.62
8/31
.52
.57
.68
.32
.53
9/8
.92
1.06
.40
.32
.42
.66
ave.
y
.84 ±
.54 ±
.74 ±
.88 ±
.42 ±
.45 ±
.34 ±
.56 ±
std.
dev.
s
.09
.02
.16
.17
.19
.12
.10
.11
NODultimate = TKN"N x 4'57
-------
TABLE # 11
61
STP Loadings of CBOD20, NOD Ultimate, and
DATE - NAME
ly 20-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
ly 27-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
I. 3-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
Flow
(MGD)
12.48
21.00
280.00
19.40
11.63
3.90
2.28
14.26
16.00
19.90
251.00
19.73
11.51
3.75
2.28
13.79
7.50
20.20
261.00
19.09
11.15
4.17
2.16
14.18
20 -day TKNx4.57=
CBOD Loading NOD
(rag/1) (Ib/day) (mg/1)
4.8 499.9 24.05
9.1 1,594.8 85.14
27.6 64,491.4 81.78
99.0 16,027.7 98.61
19.2 1,863.4 95.73
20.4 663.9 110.64
15.0 285.4 157.30
31.2 3,712.8 139.50
39.15
61.67
66.10
81.98
77.55
84.57
73.49
97.86
19.63
73.20
65.43
98.56
83.01
92.42
90.38
110.42
Loading
(Ib/day)
2,504.7
14,920.6
191,090.7
15,964.6
9,291.0
3,600.9
2,992.9
16,600.8
5,227.4
10,241.5
138,455.3
13,498.0
7,448.9
2,646.6
1,398.3
11,261.7
1,228.6
12,339.5
142,512.1
15,701.5
7,724.0
3,216.2
1,629.1
13,066.5
BOD5
Loading
(Ib/day)
749.8
2,102.9
53,274.9
11,462.0
1,630.5
507.7
285.4
2,499.0
881.2
1,096.0
40,216.2
4,346.7
864.5
187.8
79.9
1,726.2
262.9
606.8
58,807.2
7,073.2
55S.3
229.7
54.1
994.0
-------
62
TABLE # 11 (con't)
STP Loadings of CBOD2o> NOD Ultimate, and
DATE - NAME
Aug. 24-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Cr-ek STP
Pohick Creek STP
Aug. 31-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
Sept. 8-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
* 18-dav BOD
Flow
(MGD)
10.99
19.30
282.00
19.24
10.43
4.04
2.09
13.70
12.13
20.80
297.00
20.18
10.59
4.09
2.15
13.91
10.95
20.80
313.00
19.44
10.44
4.00
2.63
14.24
Loading
20-day
CBOD
Og/1)
0
17.4
39.6
75.6
23.4
20.0
19.5
16.2
--
7.2
28.2
49.8
15.6*
14.4*
9.0
14.4
12.0
15.6*
132.0*
84.6
25.4
21.0
18.0
27.9
(Ib/day)
Loading
(Ib/day)
0
2,802.5
93,192.0
12,138.4
2,036.7
674.3
340.1
1,852.1
1,249.7
69,892.7
8,386.4
1,378.6
491.5
161.5
1,671.5
1,096.6
2,707.8
344,781.9
13,724.6
2,212.9
701.0
395.1
3,315.5
= BOD (n\i
TKNx4.57=
NOD
Crag/D
22.52
97.31
76.71
99.99
90.44
94.64
95.41
48.46
20.84
55.20
67.64
85.92
77.51
87.74
79.34
100.90
33.36
37.07
77.44
82.38
102.15
107.92'
105.80
115.74
;/l) x Flow
Loading
(Ib/day)
2,065.3
15,672.6
180,520.9
16,054.2
7,871.7
3,190.7
1,664.1
5,540.3
2,109.5
9,581.4
167,643.3
14,469.1
6,849.8
2,994.7
1,423.5
11,712.4
3,048.4
6,434.6
202,275.9
13,364.5
8,899.7
3,602.4
2,278.2
13,754.0
(MGD) x 2000
BOD5
Loading
(Ib/day)
27.5
2,415.9
57,890.9
8,959.1
1,557.8
505.7
230.2
1,714.9
0
208.3
69,892.7
6,971.8
1,537.7
512.0
495.2
2,577.0
1,069.1
2,707.8
344,781.9
11,193.6
1,672.7
560.8
322.6
1,853.8
239.66
-------
63
TABLE #12 Proportion of Total STP Demand Expressed as NOD
DATE - STA NOD5 BOD5 NOD5/BOD5 NOD2o BOD20 NOD2o/BOD2o
July 20 - SI . .. . -
Aug. 24 - SI
Aug. 31 - SI
SI
S2
S3
S4
S5
56
57
S8
SI
S2
S3
S4
S5
S6
S7
S8
SI
S2
S3
S4
S5
S6
S7
S8
3
6
1
14
3
2
7
3
1
0
2
1
3
Q
1
6
1
2
0
22
12
.0
.0
.8
.4
.6
.4
.2
.6
0
.2
.6
.4
.8
.6
.6
.8
-
0
.0
.8
.4
.6
.8
.4
7
12
22
70
16
15
15
21
15
24
55
15
15
13
15
1
28
41
17
15
27
22
.2
.0
.8
.8
.8
.6
.0
.0
0
.0
.6
.8
.6
.0
.2
.0
-
.2
.2
.4
.4
.0
.6
.2
.42
.50
.079
.20
.21
.15
.48
.17
-
.080
.024
.043
.12
.24
.045
.12
-
0
.21
.044
.14
.040
.83
.56
18
46
71
94
28
51
33
58
19
54
60
82
55
52
39
30
31
38
58
27
55
.0
.7
.4
.8
.8
.9
.6
.2
.2
.6
.0
.2
.8
.2
.0
.0
.2
.4
.8
-
-
.6
.8
22
55
99
193
48
72
48
89
19
72
99
157
79
72
58
46
38
66
108
-
-
36
70
.8
.8
.0
.8
.0
.3
.6
.4
.2
.0
.6
.8
.2
.2
.5
.2
.4
.6
.6
.6
.2
.789
.837
.721
.489
.600
.718
.691
.651
1
.758
.602
.521
.704
.723
.667
.649
.812
.576
.541
.754
.795
-------
64
TABLE #12 (con't) Proportion of Total STP Demand Expressed as NOD
DATE - STA
Sept. 8 - SI
A
SI
S2
S3
S4
S5
S6
S7
S8
NOD5 BOD5 NOD5/BOD5
6.3 11.7 .54
10.2 15.6 .65
42.0 132.0 .32
11.4 69.0 .17
7.2 19.2 .38
4.8 16.8 .29
6.3 14.7 .43
6.6 15.6 .42
n=30
x=.26
s=.21
NOD2Q BOD20 NOD20/BOI
42.0 54.0 .778
-
87.6 172.2 .509
41.2 66.6 .619
34.8 55.8 .624
44.0 62.4 .705
76.5 104.4 .733
n=27
x=.69
s=.ll
-------
TABLE # 15 N02-N Concentration and the Resulting NOD Error 6S
VTE/STA
ily 20
P-8
P-4
1
1-A
2
3
4
5
5A
6
7
8
8A
9
10
10B
11
12
13
14
15
ISA
16
SI
52
N03-N
Cmg/1)
N.D.
N.D.
N.D.
N.D.
N.D.
.174
.160
.162
.360
.535
.892
1.243
1.060
.893
.834
.618
.382
.164
.080
.144
.073
.046
N.D.
5.755
2.189
N02-N
Cmg/1)
N.D.
N.D.
N.D.
N.D.
N.D.
.107
.155
.222
.558
.606
.328
.126
.078
.055
.059
.063
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
.315
.241
1.14x
N02-N
N.D.
N.D.
N.D.
N.D.
N.D.
.1
.2
.2
.6
.7
.4
.1
.1
.1
.1
.1
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
.4
.3
NH3-N
(mg/1)
.087
N.D.
N.D.
N.D.
N.D.
.234
1.094
1.240
1.02
.800
.291
.186
.134
.071
.095
.092
.026
N.D.
N.D.
.128
.060
.094
.040
3.09
18.4
TKN-N
Cmg/1)
.741
.621
.705
.632
.632
.821
2.052
2.495
2.429
2.200
1.358
1.179
1.074
.842
.853
.726
.621
.600
.453
.474
.863
.442
.621
5.263
18.631
4.57x
TKN-N
3.4
2.8
3.2
2.9
2.9
3.8
9.4
11.4
11.1
10.1
6.2
5.4
4.9
3.8
3.9
3.3
2.8
2.7
2.1
2.2
3.9
2.0
2.8
24.1
85.1
0,
"0
Error
N.D.
N.D.
N.D.
N.D.
N.D.
2.6
2.1
1.8
5.4
6.9
6.4
1.8
2.0
2.6
2.6
3.0
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
1.6
.4
STA
P-8
P-4
1
1-A
2
3
4
5
5A
6
7
/
8
8A
9
10
10B
11
12
13
14
15
15A
16
SI
S2
RMI
0.0
1.9
3.4
4.9
5.9
7.6
10.0
12.1
13.6
15.2
18.4
22.3
24.3
26.9
30.6
34.0
38.0
42.5
45.8
52.4
58.6
62.8
67.4
STP
STP
-------
66
TABLE #13 (con't) N02-N Concentration and the Resulting NOD Error
'E/STA
y 20
S3
S4
S5
S6
S7
S8
N03-N
(mg/D
N.D.
N.D.
N.D.
1,557
.734
.048
N.D.
< .04
N02-N
Og/1)
N.D.
N.D.
N.D.
.213
.236
.044
N.D.
< .04
1.14x
N02-N
N.D.
N.D.
N.D.
.2
.3
.1
NHs-N
Cmg/1)
16.4
17.0
36.6
23.1
29.4
22.6
N.D.
< .02
TKN-N
Cmg/D
17.894
21.578
20.941
24.210
34.420
30.525
4.57x
TKN-N
81.8
98.6
95.7
110.6
157.3
139.5
%
Error
N.D.
N.D.
N.D.
.2
.2
.1
STA
S3
54
SS
56
57
S8
RMI
STP
STP
STP
STP
STP
STP
-------
67
References
1. "Standard Methods for the Examination of Water and Wastewater,"
14th ed., APHA, 1975.
2. Ballinger, D. G. and Lishka, R. J., "Reliability and Precision of
BOD and COD Determinations." J.W.P.C.F., p. 470-474, (May 1962).
3. Wang, L. K. and Wang, M. H., "Computer Aided Analysis of Environmental
Data Part II: Biochemical Oxygen Demand Model," 2jnd Annual Proceedings
Institute £f Envir. Science 1976.
4. Benedict, A. H. "Temperature Effects on BOD Stoichiometry,"
J.W.P.C.F., 48, p. 864-5, 1976.
5. Effects of Polluting Discharges on the Thames Estuary, p. 202-225,
Reports of the Thames Survey Committee and of the Water Pollution
Research Laboratory, Crown Copyright, 1964.
6. Thomas, H. A., "Grophical Determination of B.O.D. Curve Constants,"
Water and Sewage Works, p. 123-124, (March 1950).
7. 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.
8. Clark, L. J. and Jaworski, N. A., "Nutrient Transport and Dissolved
Oxygen Budget Studies in the Potomac Estuary," Technical Report 37,
AFO Region III, Environmental Protection Agency, 1972.
9. Daniels, F. and Alberty, R. A., Physical Chemistry, 4 ed., John
Wiley and Sons, Inc., 1975.
10. Streeter, H. W. and Pheips, E. B., Public Health Bull., Wash.,
No. 146, 1925.
11. Sawyer, C. N. and McCarty, P. L., Chemistry for Sanitary Engineers,
2nd ed., McGraw-Hill, 1967.
12. Breed, R. S., Murry E. G. D., and Kitchens, A. P., Sergey's
Manual of Determinative Bacteriology, 6th ed., The Williams and
Wilkens.
13. Srinath, E. G., Raymond, L. C., Loehr, M. and Prakasam, T.B.S.,
"Nitrifying Organism Concentration and Activity." J. of Env.
Engineering, p. 449-463, 1976.
14. Mattern, E. K., Jr., "Growth Kinetics of Nitrifying Microorganisms,"
CE 756A6 prepared for Office of Water Research and Technology.
15. Segel, I. H. Biochemical Calculations, John Wiley & Sons, Inc.,
New York, 1968.
16. 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. 74.
-------
68
References
17. Hockenbury, M. R., and Grady, C. R. Jr. "Inhibition of Nitrification
Effects of Selected Organic Compounds," JWPCF, p. 768-777, (May 1977).
18. Wezernak, C. T. and Gannon J. J., "Evaluation of Nitrification
in Streams," J. Sanitary Engineering Div., Proc. of .American
Soc. of Civil Engineers, p. 883-895, (Oct. 1968).
19. Wezernak, C. T. and Gannon, J. J., "Oxygen-Nitrogen Relationships
in Autotrophic Nitrification," Applied Microbiology, 15, p. 1211-1215,
(Sept. 1967).
20. Montgomery, H. A. C. and Borne, B. J., rrrhe Inhibition of
Nitrification in the BOD Test," J. Proc. Inst. Sew. Purif.,
p. 357-368, 1966.
21. Young, J. C., "Chemical Methods for Nitrification Control," 24th
Industrial Waste Conference, Part II. Purdue University,
pp. 1090-1102, 1967.
22. Allen, H. E. and Kramer, J. R., Nutrients in Natural Waters,
Wiley-Interscience Publication, New York, 1972.
23. Van Kessel, J. F. "Factors Affecting the Denitrification Rate
in Two Water-Sediment Systems,"Water Research, 11, pp. 259-267,
(July 1976).
24. Goring, C. A., "Control of Nitrification by 2-Chloro-6-(Trichloro-
methyl) Pyridine Soil Science, 93, p. 211-218, (Jan. 1962).
25. Mullison, W. R. and Norris, M. G., "A Review of Toxicological,
Residual and Environmental Effects of Nitrapyrin-and Its
Metabolite, 6-Chloropicolinic Acid," Down to Earth, 32, p. 22-27,
(Summer 1976) .
26. Redemann, C. T., Meikle, R. W. and Widofsky, J. G.," The Loss of
2-Chloro-6(Trichloromethyl) Pyridine from Soil," J. Agriculture
and Food Chemistry, 12, p. 207-209, (May-June 1964).
27. Young, J. C., "Chemical Methods for Nitrification Control," JWPCF,
45, 4, p. 637-646, (April 1973).
28. Laskowski, D. A., O'Melia E. C., Griffith, J. D. et al, "Effect of
2-Chloro-6(Trichloromethyl) Pyridine and Its Hydrolysis Product
6-Chloropicolinic Acid on Soil Microorganisms," J. of Env.
Quality, 4, p. 412-417, (July-Sept. 1975).
29. Bundy, L. G., "Control of Nitrogen Transformations," Ph.D.
Dissertation, Iowa State University, 1973.
-------
69
Appendix
A. N-Serve/NOD Determinations
The inhibitor incorporated was formula 2533 Nitrification
Inhibitor, a product of the Hach Chemical Company. The product
consists of 2-chloro-6(trichloromethyl) pyridine known as TCMP or
N-Serve. This compound is plated on a simple inorganic salt which
serves as a carrier and is soluble in water. The Dow Chemical Company,
Midland, Michigan, markets this chemical under the name N-Serve as a
23,24,25,26
fertilizer additive. Studies using N-Serve suggest that it acts as a
"biostat" at moderate concentrations to delay nitrification and aids
the retention of ammonia or urea fertilizers on crops by retarding the
conversion to the more highly leachable NC>3 . Ideally TCMP is slowly
biodegraded to 6-chloropicolinic acid which leaves the fields in
their original state, with no further inhibition to nitrification.
This allows long term (20-30 day) NOD assays without significant
21,27 28
inhibitor contribution to the carbonaceous demand. Extensive studies
were performed on the toxicity of this material, because of concern
for the environment. These have revealed it to be very selective
21,27
and effective at stopping nitrification at 10 ppm.
Although the mechanism of its action is still unclear, it is
restricted to Nitrosomonas. This selectivity is an advantage in that
it stops the process of nitrification at ammonia with little or no
79
effect on urea hydrolysist assuring an adequate nitrogen source for
the heterotrophic bacteria contributing to the CBOD. The disadvantage
of this selectivity is that Nitrobacter are not inhibited and N02 will
be oxidized to N03~. This limitation generally represents a small error
-------
70
since NC>2~ is generally much smaller than TKN in river water and
the demand associated with the NO? initially present is or one-
^ 4.57
quarter that associated with the TKN initially in the sample.
The Potomac intensive survey did not include the separate
determination of NC>2 and NO,, but incorporated cadmium reduction
technique whereby the sum concentration of N02 plue NOj was determined.
The initial run, however, was assayed for N02 separately to determine
the significance of the potential error associated with TCMP. This
data is compiled in Table #13 with a maximum potential error of 5 to 7%
associated with the NOD determination of 3 out of a total of 23 river
stations and 9 waste treatment effluents. This error was not considered
significant enough to justify the added time and cost involved in the
analysis of N02 throughout the course of this study.
B. Alternative Methods
Several other alternate approaches to determining NOD were
considered. In situ tests, where a segment of water is followed
and assayed for D.O. and states of nitrogen would give actual "river
rates" for NOD and CBOD. However; the flows of a large, complex, tidal
estuary are not adequately defined. Even if the segment of water
could be followed it is altered by diffusion and by the input of
effluents, resulting in a faulty estimate of the NOD rate.
Laboratory studies involving the incubation of samples with
analysis of sub-samples at timed intervals for all nitrogen states,
coupled with the determination of NOD based upon the stoichiometric
relation between oxygen utilization and nitrogen oxidation is a
second method for NOD determinations.
-------
71
A second approach to laboratory studies involves only D.O. analyses,
not the extensive laboratory committment associated with frequent
N-series determination. One such method involves killing all of the
bacteria present by pasteurization, chlorination, or acidification and
reseeding with populations containing few nitrifyers. However, these
methods involve the disadvantages associated with extensive sample
modification. A second D.O. method involves killing or inhibiting
the nitrifyers by addition of: methylene blue; thiourea; allylthiourea
ATU; and TCMP. Methylene blue interferes with Winkler D.O. determinations
as does thiourea. Further, only Temp has been found effective for
long term experiments, because the others were either degraded thus
contributing to the CBOD or Nitrosomonas quickly acclimated to their
21
effect and nitrification began.
-------
TABLE # 14
C. Study Data
Potomac River Long-Term BOD Survey Data-Summer 1977
72
Date: 7/20/77
STA #
P-8 T*
C*
N*
P-4 T
3.2
3.0
0.2
3.6
Days of Incubation
8 11 15 18 20
4.2 5.6 6.8 7.0 7.2
4.0 4.3 4.6 4.8 5.0
.2 1.3 2.2 2.2 2.2
1
1-A
2
3
4
5
T
C
N
T
T
T
C
N
T
C
N
T
C
N
3.4
3.0
0.4
3.7
4.0
6.6
5.2
1.4
4.8
2.6
2.2
9.0
4.4
4.6
4.9
4.0
0.9
7.7
5.2
2.5
9.7
4.4
5.3
12.8
5.5
7.3
6.1
4.6
1.5
8.3
5.2
3.1
11.0
5.1
5.9
14.1
6.5
7.6
7.4
5.2
2.2
10.8
7.6
3.2
11.7
5.5
6.2
17.1
7.0
10.1
8.0
5.8
2.2
11.2
8.0
3.2
12.0
.58
6.2
17.5
7.4
10.1
8.3
6.0
2.3
12.6
8.2
4.4
12.1
5.9
6.2
18.6
7.6
11.0
5-A T
6
7
T
C
N
T
C
N
8.1
9.9
5.3
4.6
5.0
4.2
0.8
11.4
5.0
6.4
8.0
5.5
2.5
11.8
5.0
6.8
9.8
6.0
3.8
17.0
8.6
8.4
11.1
7.3
3.8
19.3
9.4
9.9
11.5
7.7
3.8
20.8
9.7
11.1
11.9
7.9
4.0
3-A T
C
N
4.6
5.2
4.0
1.2
7.3
5.0
2.3
8.1
5.7
2.4
9.0
6.0
3.0
9.2
6.2
3.0
9.8
6.2
3.6
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
73
TABLE # 14 (con't)
Date: 7/20/77
10-B T
3.9
Davs of Incubation
STA #
9 T
10 T*
C*
N*
5
4.9
4.5
3.8
0.7
8
6.2
4.7
1.5
11
7.8
5.4
2.4
15
8.2
5.6
2.6
18
8.9
5.9
3.0
20
9.2
6.2
3.0
11
12
13
14
15
15-A
16
S-l
S-2
S-3
S-4
S-5
T
C
N
T
T
T
T
T
T
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
5
3
1
4
4
2
13
4
7
7
4
3
12
6
6
22
21
1
70
56
14
16
13
3
.2
.8
.4
.6
.5
.5
.2
.0
.8
.2
.2
.0
.0
.0
.0
.8
.0
.8
.8
.4
.4
.8
.2
.6
6
4
1
18
4
13
13
7
6
28
19
9
88
73
15
18
14
3
.1
.7
.4
.0
.6
.4
.8
.4
.4
.6
.0
.6
.0
.0
.0
.0
.4
.6
7.
5.
1.
20.
4.
IS.
16.
8.
7.
55.
18.
37.
102.
83.
18.
25.
18.
7.
1
7
4
4
8
6
0
3
8
4
0
4
3
5
8
2
0
2
8.2
6.3
1.9
22.8
4.8
18.0
33.0
8.7
24.3
66.4
17.0
49.4
117.6
94.0
23.6
26.2
19.0
7.2
9.
7.
2.
22.
4.
18.
54.
9.
45.
89.
26.
62.
153.
94.
59.
39.
19.
19.
3
0
3
8
8
0
7
1
6
1
7
4
6
0
6
0
2
8
9.5
7.2
2.3
22.8
4.8
18.0
55.8
9.1
46.7
99.0
27.6
71.4
193.8
99.0
94.8
48.0
19.2
28.8
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE # 14 (con't) 74
Date: 7/20/77
Days of Incubation
STA
S-6
S-7
S-8
#
T*
C*
N*
T
C
N
T
C
N
5
15.6
13.2
2.4
15.0
7.8
7.2
21.0
17.4
3.6
8
25.2
15.6
9.6
17.2
10.0
7.2
23.4
19.8
4.2
11
48.0
18.0
30.0
18.2
11.0
7.2
35.0
26.0
9.0
15
58.2
20.4
37.8
23.0
14.0
9.0
57.6
27.0
30.6
18
68.4
20.4
48.0
40.8
14.4
26.4
61.2
29.4
31.8
20
72.3
20.4
51.9
48.6
15.0
33.6
89.4
31.2
58.2
Date: 7/27/77
STA #
P-8 T
C
N
2
.3
5
1.5
--
--
8
1.1
1.1
0
11
2.2
2.2
0
15
4.5
3.2
1.3
18
5.1
3.8
1.3
20
5.4
4.0
1.4
P-4 T .7 2.2
1 T 1.0 2.8 3.5 3.7 4.2 5.0 5.0
C 1.0 1.8 2.5 2.7 3.2 3.5 3.5
N 0.0 1.0 1.0 1.0 1.0 1.5 1.5
1-A T 1.0 2.4
2 T 1.2 2.2
T
C
N
T
C
N
T
C
N
2.1
1.6
0.5
2.4
1.0
1.4
2.1
1.5
0.6
4.1
3.0
1.1
5.4
2.3
3.1
5.8
3.0
2.8
5.6
3.8
1.8
6.8
3.2
3.6
6.8
3.8
3.0
6.6
4.4
2.2
7.8
3.5
4.3
7.7
--
--
7.3
4.8
2.5
8.8
3.8
5.0
8.9
4.7
4.2
7.7
5.1
2.6
9.4
4.1
5.3
9.8
4.9
4.9
7.7
5.1
2.6
9.4
4.1
5.3
10.7
5.1
5.6
5-A T 3.3 7.5
6 T 3.9 8.6 10.5 12.2 13.6 14.6 14.9
C 1.7 4.0 5.5 6.5 7.2 8.0 8.9
N 2.2 4.6 5.0 5.7 6.4 6.6 6.8
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE #14 (con't)
75
Date: 7/27/77
Days of Incubation
STA #
7 T*
C*
N*
8 T
8-A T
C
N
9 T
10 T
C
N
10-B T
11 T
C
N
12 T
13 T
14 T
15 T
15-A T
16 T
S-l T
S-2 T
S-3 T
S-4 T
S-5 T
*T
*c
*N
3
2
1
2
0
0
0
1
1
1
0
1
1
1
0
0
1
0
1
1
3
9
12
3
- BOD
- CBOD
- NOD
2
.6
.1
.5
.6
.8
.4
.4
.6
.5
.5
.0
.5
2
.6
.6
.0
.7
.8
.2
.0
.1
.8
.6
.6
.0
. 3
Og/D
Cmg/1)
fmg/n
5
.51
--
--
5.6
4.7
3.1
1.6
4.2
4.4
3.0
1.4
3.7
3.6
1.9
1.7
2.7
2.2
1.9
3.4
1.2
2.6
6.6
6.6
19.2
26.4
9.0
8
5.
3.
2.
7.
3.
3.
5.
3.
1.
4.
2.
1.
10.
11.
22.
32.
15.
7
0
7
6
8
8
0
6
4
0
3
7
8
2
8
4
6
7
4
3
8
4
3
6
4
1
5
3
2
16
11
25
32
15
11
.5
.2
.3
.7
.9
.8
.0
.6
.4
.6
.2
.4
.2
.2
.8
.4
.6
9
5
4
9
5
3
6
4
1
7
3
3
27
12
45
32
15
15
.6
.6
.0
.0
.2
.8
.1
.7
.4
.2
.8
.4
.0
.0
.6
.4
.6
18
11.8
6.3
5.5
9.8
6.0
3.8
6.4
5.0
1.4
8.0
4.4
3.6
28.2
13.2
57.6
32.4
17.4
20
14.4
8.9
5.5
10.2
6.4
3.8
7.5
5.1
2.4
8.2
4.6
3.6
28.8
13.2
72.0
32.4
18.6
-------
TABLE #14 (con't)
Date: 7/27/77
Date: 8/03/77
76
Days of Incubation
STA #
S-6 T
S-7 T
S-8 T
2
5.4
2.4
7.8
5
6.0
4.2
15.0
8
12.0
12.0
21.6
11
12.0
12.0
21.6
15
13.2
12.6
22.2
18
18.0
14.4
26.4
20
22.8
16.8
28.8
STA
P-8
P-4
1
1-A
2
3
4
5
5 -A
6
7
#
T
T
T*
C*
N*
T
T
T
C
N
T
C
N
T
C
N
T
T
C
N
T
C
N
*T
*C
*N
2
1.3
1.4
2.2
1.3
0.9
2.6
2.9
3.2
0.5
2.7
4.1
1.9
2.2
4.2
1.5
2.7
3.8
2.6
2.0
0.6
2.3
1.5
0.8
- BOD (mg/1)
- CBOD (mg/1
- NOD (mg/1)
5
1.7
2.4
3.2
2.3
0.9
4.2
4.0
8.6
3.0
5.6
7.4
3.7
3.7
6.3
3.2
3.1
6.4
4.4
3.5
0.9
5.2
3.6
1.6
8
1.7
4.4
3.3
1.1
9.4
3.8
5.6
8.5
4.8
3.7
7.5
4.1
3.4
6.2
4.6
1.6
8.0
5.0
3.0
11
1.7
4.6
3.5
1.1
10.4
4.5
5.9
9.4
5.7
4.9
3.4
6.9
.0
.9
9.0
5.5
3.5
15
1.7
4.9
3.6
1.3
11.9
4.8
7.1
10.4
5.8
4.6
10.0
5.2
4.8
7.9
5.3
2.6
9.9
5.9
4.0
18
2.2
5.3
3.9
1.4
12.4
5.1
7.3
10.9
6.1
10.0
5.2
4.8
8.1
5.3
2.8
10.8
6.2
4.4
20
2.4
5.5
4.1
1.4
12.4
5.1
7.3
11.4
6.6
4.8
10.2
5.2
5.0
8.6
5.3
3.3
10.9
6.5
4.4
-------
TABLE # 14 (con't)
77
Date: 8/03/77
Days of Incubation
STA
8
8-A
9
10
10-B
11
12
13
14
15
15-A
16
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
#
T
T*
C*
N*
T
T
C
N
T
T
C
N
T
T
T
T
T
T
T
T
T
T
T
T
T
T
2
2.
3.
2.
0.
3.
2.
1.
0.
1.
1.
1.
0.
1.
0.
1.
1.
1.
1.
4.
3.
18.
31.
6.
0.
3.
8.
9
0
2
8
2
0
6
4
7
8
7
1
6
5
2
3
0
4
2
6
6
8
0
6
0
4
5
5
3
1
5
4
3
1
3
3
2
0
2
1
1
1
0
1
4
3
27
44
6
6
3
8
5 ' 8
.3
.2 7.4
.9 5.4
.3 2.0
.4
.3 7.0
.2 4.5
.1 2.5
.8
.2 4.8
.9 4.0
.3 0.8
.9
.3
.3
.9
.8
.6
.2
.6
.0
.4
.0
.6
.0
.4
11 15 18 20
8.8 10.6 11.1 11.8
6.3 6.8 7.1 7.8
2.5 3.8 4.0 4.0
7.8 9.1 9.7 10.2
5.3 5.6 6.0 6.4
2.5 3.5 3.7 3.8
5.9 6.6 7.2 8.0
4.7 5.3 5.4 6.2
1.2 1.3 1.8 1.8
*T - BOD
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE » 14 (con't)
78
Date: 8/24/77
STA #
P-8T*
C*
N*
P-4 T
2
2.0
1.6
0.4
1.3
5
4.0
3.1
0.9
2.9
Days of Incubation
8 10 15 18 20
4.8 5.8 7.0 8.0 8.8
3.6 4.4 5.0 5.4 5.8
1.2 1.4 2.0 2.6 3.0
1
1-A
2
3
4
5
5-A
6
7
8
8 -A
9
T
C
N
T
T
T
C
N
T
C
N
T
C
N
T
T
C
N
T
C
N
T
T
C
N
T
1.8
1.6
0.2
1.7
1.5
2.6
1.4
1.2
3.6
2.0
1.6
3.3
2.6
0.7
3.6
3.4
2.6
0.8
3.1
2.3
0.8
1.5
2.3
2.3
0
2.6
3.0
2.6
0.4
2.7
2.5
5.1
2.2
2.9
7.0
3.6
3.4
7.0
5.2
1.8
7.4
6.4
4.3
2.1
5.5
4.6
0.9
5.0
8.0
7.6
0.4
6.4
4
3
0
6
2
3
8
4
3
8
6
2
8
5
2
9
6
2
12
10
2
.1
. 3
.8
.5
.9
.6
.0
.2
.8
.8
.0
.8
.1
.6
.5
.2
.6
.6
.8
.2
.6
4
3
1
7
3
3
8
4
3
9
6
2
9
6
2
9
7
2
16
11
4
.8
.8
.0
.0
.4
.6
.7
.8
.9
.6
.8
.8
.1
.3
.8
.6
.0
.6
.2
.4
.8
6
4
2
7
3
4
9
5
3
10
7
2
10
7
3
11
8
3
19
13
5
.3
.0
.3
.6
.6
.0
.2
.3
.9
.8
.9
.9
.6
.3
.3
.4
.2
.2
.2
.3
.9
6.6
4.2
2.4
8.1
4.1
4.0
9.9
5.6
4.3
11.4
8.3
3.1
11.6
7.9
3.7
12.4
9.0
3.4
21.4
15.1
6.3
7.0
4.3
2.7
8.2
4.2
4.0
10.1
5.7
4.4
12.0
8.6
3.4
12.1
8.0
4.1
12.9
9.4
3.5
22.0
15.4
6.6
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE #14 (con't)
79
Date: 8/24/77
STA #
10 T*
C*
N*
10-B T
11 T
C
N
12 T
13 T
14 T
15 T
15-A T
16 T
S-l T
C
N
S-2 T
C
N
S-3 T
C
N
S-4 T
C
N
S-5 T
C
N
S-6 T
C
N
2
3.0
3.0
0
1.8
1.2
1.2
0
1.8
0.9
0.5
0.8
0.8
1.1
0
0
0
8.1
8.1
0
13.8
13.8
0
33.8
33.6
0.2
2.0
2.0
0
7.8
6.0
1.8
5
6.6
6.6
0
3.0
3.3
2.8
0.5
3.0
1.6
1.4
1.0
1.2
1.3
0
0
0
15.0
13.8
1/2
24.6
24.0
0.6
55.8
53.4
2.4
15.6
13.8
1.8
15.0
11.4
3.6
Days of Incubation
8 10 15
13.6 17.3 20.9
12.2 14.1 15.7
1.4 3.2 5.2
4.7
3.8
0.9
4.2
0
4.2
19.6
16.0
3.6
35.4
29.4
6.0
71.4
61.2
10.2
18.0
13.8
4.2
27.6
15.0
12.6
6.5
5.6
0.9
13.2
0
13.2
26.6
17.0
9.6
47.2
34.0
13.2
80.2
70.0
10.2
22.2
13.8
8.4
33.8
17.0
16.8
10.2
7.7
2.5
18.6
0
18.6
66.0
17.4
48.6
88.8
39.6
49.2
106.2
72.6
33.6
45.6
22.2
23.4
57.0
19.2
37.8
18
23.1
16.8
6.3
11.8
8.6
3.2
19.2
0
19.2
17.4
54.6
94.8
39.6
55.2
138.6
74.4
64.2
63.0
22.8
40.2
64.4
20.0
44.4
20
24.1
17.3
6.8
13.2
9.0
4.2
19.2
0
19.2
72.0
17.4
54.6
99,
39,
60.0
157.8
75.6
82.2
79.2
23.4
55.8
72.2
20.0
52.2
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE # 14 (con't)
80
Date: 8/24/77
Days of Incubation
STA
S-7
S-8
#
T*
C*
N*
T
C
N
2
7.6
7.0
0.6
2.6
2.0
0.6
5
13.
12.
0.
15.
13.
1.
2
6
6
0
2
8
8
22.6
16.0
6.6
20.4
13.2
7.2
10
29.0
18.2
10.8
26.8
16.0
10.8
15
44.
18.
26.
46.
16.
30.
4
3
1
2
2
0
18
58.
19.
39.
46.
16.
30.
S
S
0
2
2
0
20
58.5
19.5
39.0
46.2
16.2
30.0
Date: 8/31/77
STA #
P-8 T
C
N
2
1.7
1.0
0.7
5
2.8
2.1
0.7
8
3.4
2.6
0.8
12
4.6
3.2
1.4
15
4.8
3.4
1.4
18
5.1
3.7
1.4
20
5.4
3.8
1.6
P-4 T
2.1
3.0
1
1-A
2
3
4
5
5 -A
6
T
C
N
T
T
T
C
N
T
C
N
T
C
N
T
T
C
N
1.2
1.2
0
2.7
1.9
2.4
0.5
1.9
4.7
1.9
2.8
3.8
1.6
2.2
3.8
3.8
3.0
0.8
3.3
2.4
0.9
3.8
2.9
9.2
3.2
6.0
8.5
3.8
4.7
7.6
3.7
3.9
6.7
8.0
5.2
2.8
3
2
0
10
4
6
9
4
4
8
4
4
9
6
3
.8
.9
.9
.5
.3
.2
.6
.9
.7
.8
.6
.2
.4
. 3
.1
4
3
0
11
5
6
10
10
5
4
10
6
3
.6
.7
.9
.4
.1
.3
. 3
.1
.7
.4
.4
.9
.5
4
4
0
11
5
6
10
6
4
10
5
4
11
7
3
.9
.0
.9
.8
.2
.6
.5
.0
.5
.8
.9
.9
.1
")
^.
.9
4.9
4.0
0.9
12.2
5.5
6.7
10.8
6.3
4.5
11.7
6.8
4.9
11.4
7.2
4.2
5.5
4.3
1.2
12.8
5.7
7.1
11.2
6.5
4.7
11.8
6.7
5.1
12.1
7.2
4.9
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
81
TABLE #14 Ccon't)
Date: 8/31/77
STA # 2 5 " 8 12 15 18 20
7 T* 4.0 8.8 10.7 12.1 12.7 13.0 13.5
C* 2.5 5.1 6.8 7.8 8.4 8.7 9.2
N* 1.5 3.7 3.9 4.5 4.3 4.3 4.3
8 T 3.7
8-A T 4.0 9.7 11.7 13.6 14.9 15.5 16.3
C 2.8 5.2 7.2 9.0 10.3 10.7 11.1
N 1.2 4.5 4.5 4.6 4.6 4.8 5.2
9 T 3.5
10 T 3.3 8.9 11.2 13.7 15.0 16.0 16.8
C 2.9 6.3 8.3 10.0 10.- 11.4 11.9
N 0.4 2.6 2.9 3.7 4.3 4.6 4.9
10-B T 3.2
11 T 3.3 6.3 7.5 9.9 11.7 13.3 14.3
C 2.5 4.6 5.8 7.1 8.0 8.5 8.7
N 0.8 1.7 1.7 2.8 3.7 4.8 5.6
12 T 2.0
13 T 1.4
14 T 0.7
15 T 0.9
15-A T 0.8
16 T 1.3
S-l T 0.6 1.2 3.0 30.6 32.2 36.6 38.4
C 0.6 1.2 3.0 4.2 5.8 6.0 7.2
N 0 0 0 26.4 26.4 30.6 31,
S-2 T 19.0 28.2 36.8 39.6 58.8 66.6 66.6
C 13.0 22.2 26.0 27.0 28.2 28.2 28.2
N 6.0 6.0 10.8 12.6 30.6 38.4 38.4
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
Days of Incubation
5
8.8
5.1
3.7
9.4
9.7
5.2
4.5
9.1
8.9
6.3
2.6
7.9
6.3
4.6
1.7
4.2
2.8
1.7
1.6
1.8
2.6
1.2
1.2
0
28.2
22.2
6.0
8
10.7
6.8
3.9
11.7
7.2
4.5
11.2
8.3
2.9
7.5
5.8
1.7
3.0
3.0
0
36.8
26.0
10.8
12
12.1
7.8
4.5
13.6
9.0
4.6
13.7
10.0
3.7
9.9
7.1
2.8
30.6
4.2
26.4
39.6
27.0
12.6
15
12.7
8.4
4.3
14.9
10.3
4.6
15.0
10.-
4.3
11.7
8.0
3.7
32.2
5.8
26.4
58.8
28.2
30.6
-------
TABLE #14 (con't)
82
Date: 8/31/77
STA
S-3
S-4
S-5
S-6
S-7
S-8
#
T*
c*
N*
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
2
19.0
13.0
6.0
24.1
22.8
1.8
12.6,
10.2
2.4
1.2
0.6
0.6
4.8
3.0
1.8
4.8
4.8
0
Days of Incubation
5 8 12
28.2
22.2
6.0
41.4
39.6
1.8
17.4
15.0
2.4
15.0
14.4
0.6
27.6
4.S
22.8
22.2
9.8
12.4
36.8
26.0
10.8
67.0
46.6
20.4
18.8
15.6
2.4
15.0
14.4
0.6
28.8
6.0
22.8
32.2
11.2
21.0
39.6
27.0
12.6
67.2
48.0
19.2
31.6
15.6
16.0
15.0
14.4
0.6
31.2
7.8
23.4
34.9
13.5
21.4
15
58.8
28.2
30.6
91.2
49.8
41.4
45.0
15.6
29.4
19.2
14.4
4.8
36.6
9.0
27.6
60.0
14.0
46.0
18
66.6
28.2
38.4
107.6
49.8
57.8
52.8
15.6
37.2
19.2
14.4
4.8
36.6
9.0
27.6
69.6
14.4
55.2
20
66.6
28.2
38.4
108.6
49.8
58.8
55.8
--
--
19.2
--
--
36.6
9.0
27.6
70.2
14.4
55.8
Date: 9/08/77
STA #
P-8 T
C
N
3
1.4
1.4
0
5
2.0
2.0
0
7
3.0
2.6
0.4
10
4.0
3.3
0.7
15
5.3
3.7
1.6
17
6.4
4.4
2.0
20
6.5
4.5
2.0
P-4 T
2.0
2.6
1
1-A
2
3
T
C
N
T
T
T
C
N
2.2
2.0
0.2
1.2
1.6
3.9
1.8
2.1
2.7
2.6
0.1
1.8
2.4
5.3
2.5
2.8
3.5
3.3
0.2
7.0
3.2
3.8
5
3
1
8
3
4
.0
.6
.4
.0
.7
.3
5
4
1
8
4
4
.8
.2
.6
.7
.2
.5
6
4
2
9
4
4
.5
.4
.1
.1
.6
.5
6.7
4.5
2.2
9.5
5.0
4.5
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
Q T
TABLE # 14 (con't)
Date: 9/08/77
STA
4
5
5-A
6
7
#
T*
C*
N*
T
C
N
T
T
T
C
N
5
3
1
6
3
3
7
4
3
1
1
3
.5
.7
.8
.5
.1
.4
.0
.9
.8
.9
.9
5
9.4
4.8
4.6
11.8
4.8
7.0
11.2
6.6
4.6
2.6
2.0
Days
7
13.
5.
7.
16.
5.
10.
8.
5.
3.
2.
of Incubation
5
8
7
5
9
6
2
5
4
1
10
14.6
6.2
8.4
17.8
6.8
11.0
9.4
6.2
3.8
2.4
15
15.
6.
8.
19.
8.
11.
10.
7.
3.
3.
4
8
6
0
0
0
3
0
8
2
17
16.1
7.1
9.0
19.6
8.4
11.0
11.4
7.9
4.3
3.6
20
16.3
7.4
8.9
19.8
8.8
11.0
11.6
8.1
4.5
3.6
8 T 3.5 4.7
8 -A T
C
N
9 T
3.6
2.5
1.1
3.1
5.0
3.2
1.8
4.6
6.2
4.3
1.9
6.9
4.6
2.3
8.0
4.9
3.1
8.8
5.7
3.1
9.1
6.1
3.0
10 T 1.8 4.9 5.8 7.2 8.6 9.6 9.8
C 1.0 2.9 4.8 6.0 6.7 7.2 7.3
N 0.8 l.o 1.0 1.2 1.9 2.4 2.5
10-B T 3.2 4.9
11
12
13
14
15
15-A
T
C
N
T
T
T
T
T
2
1
0
2
2
1
1
0
.3
.8
.5
.2
.6
.3
.2
.6
3.
3.
0.
3.
3.
1.
1.
1.
6 4.7
1 3.6
5 1.1
1
4
6
8
2
7.2 8.8 9.6 9.9
4.8 5.8 6.6 6.9
2.4 3.0 3.0 3.0
*T - BOD (rng/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE #14 (con't)
84
Date: 9/08/77
Davs of Incubation
STA
16
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
#
T
T*
C*
N*
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
3
1.3
1.0
1.0
0
9.6
5.4
4.2
102.0
102.0
0
31.0
31.0
0
8.2
8.2
0
7.0
7.0
0
5.1
4.5
0.6
4.2
4.2
0.0
5
1.7
11.7
5.4
6.3
15.6
5.4
10.2
132.0
90.0
42.0
69.0
57.6
11.4
19.2
12.0
7.2
16.8
12.0
4.8
14.7
8.4
6.3
15.6
9.0
6.6
7
17.1
6.0
11.1
15.6
5.4
10.2
132.0
90.0
42.0
79.6
67.2
12.4
22.2
15.0
7.2
24.0
15.0
9.0
16.2
8.4
7.8
17.4
9.6
7.8
10
26.6
9.9
16.7
41.4
6.0
35.4
183.0
111.0
72.0
98.6
76.4
22.2
25.2
18.0
7.2
43.2
17.4
25.8
37.8
8.4
29.4
40.2
13.2
27.0
15
26.6
9.9
16.7
69.0
--
--
220.0
--
--
131.0
80.0
51.0
33.6
22.2
11.4
47.8
21.4
26.4
51.0
12.6
38.4
65.4
18.7
46.7
17
53.4
11.1
42.3
72.0
--
--
264.
--
--
171.6
83.3
88.3
63.6
23.4
40.4
55.8
21.4
34.3
59.4
16.2
43.2
101.4
22.8
78.6
20
54.0
12.0
42.0
72.6
--
--
270.
--
--
172.2
84.6
87.6
66.6
25.4
41.2
55.8
21.0
34.8
62.4
18.0
44.0
104.4
27.9
76.5
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD 9mg/l)
-------
TECHNICAL REPORT DATA
(Please read Instructions on tfic rcicrsc before eomnlenng)
REPORT NO. 2.
EPA 903/9-79-003
TITLE AND SUBTITLE
CARBONACEOUS AND NITROGENOUS DEMAND STUDIES
OF THE POTOMAC ESTUARY
AUTHOH(S)
J . L . Slayton
and S. R. Trovato
PERFORMING ORGANIZATION NAME AND ADDRESS
Annapolis Field Office, Region III
U.S. Environmental Protection Agency
Annapolis Science Center
Annapolis, Maryland 21401
2. SPONSORING AGENCY NAME AND ADDRESS
Seine
3 RECIPIENT'S ACCESSION NO.
5. REPORT DATE
Summer 1977
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/903/00
5. SUPPLEMENTARY NOTES
6. ABSTRACT
The biochemical oxygen demand of Potomac River and SIP effluent samples vas
determined during the summer of 1977. The fraction associated with N.O.D.
was measured using an inhibitor to nitrification and the oxygen depletion
7,'as monitored during long term incubation. The average, deo^/gsnation constants
for the river sample C.B.O.D. and N.O.D. were C.U lay"1 (l-O~ The N.O.D. --as
found to be a significant component of the 2.0.D.= for STF effluent and river
samples. The peak C.B.O.D. was associated with an algal bloom of Cscilletcria.
7. KEY WORDS AND DOCUMENT ANALYSIS
i. DESCRIPTORS
Biochemical Oxygen Demand
Nitrification
Nitrification Inhibitor
Respiration
IS. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
b. IDENTIFIERS/OPEN ENDED TERMS
Lag Time
Depletion Curves
Deoxygenaticn
Kinetics
19. SECURITY CLASS (Tins Report)
UNCLASSIFIED
20. SECURITY CLASS (This page)
UNCLASSIFIED
c. COSATI Field/Group
21. NO. OF PAGES
90
22. PRICE
.PA Form 2220-1 (C-73)
-------
-------
EPA 903/9-79-002
ALGAL NUTRIENT STUDIES OF THE
POTOMAC ESTUARY
(Summer 1977)
Annapolis Field Office
Region III
Environmental Protection Agency
Joseph Lee Slayton
E. R. Trovato
-------
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.
-------
TABLE OF CONTENTS
Page
I. Introduction 1
II. Conclusions 6
III. Experimental 7
IV. Discussion of Results 18
V. Recommendations 30
VI. References 31
-------
TABLES
Page
1. Stat ion Locat ions 3
2. Algal Growth/Assay Media 1C
3. Summary of Assay/Analysis Results 19
4. Ammonium Uptake Rates/Nitrogen Distribution 24
5. NS Fixation/Acetylene Reduction 26
6. Filtered vs Centrifuged Methods 29
-------
FIGUHES
1 . Map of Study Area ....................................... 2
2 . Sample Preparation Flow Chart ........................... 5
3. Standard Curve for Alkaline Phosphatase Activity ........ 13
4-7 . Chlorophyll a vs RMI ................................... 20-23
-------
-------
I. Introduction
During the summer of 1977 an intensive survey of the middle reach
of the Potomac River (Figure 1, Table 1) was undertaken by the A.P.O.
As part of this work the nutrient requirements of the phytoplankton
present were studied using the following laboratory tests: NH.-N
uptake; alkaline phosphatase enzyme activity; extractable surplus
orthophoshate; tissue analysis for carbon, nitrogen and phosphorus
content; and nitrogen fixation by acetylene reduction. These bio-
assays were conducted in the Potomac from Gunston Cove to Possum
Point during August and September 1977.
The ammonium uptake test was designed to assess the bio-avail-
ability of nitrogen to algae. Algae are spiked with ammonia and if
a rapid rate of absorption of nitrogen with time is observed this
signifies that nitrogen is limiting potential algal growth.
Algae have the ability to store phosphorus" when it is encountered
p
in amounts beyond the immediate biological need. Previous studies
have determined that this stored phosphorus is easily extracted and
is thought to be stored as orthophosphate; polyphosphate chains and/
or as very labile organic compounds which breakdown to orthophosphate
with heat (100°C). Algae containing significant luxury phosphate are
not limited in their growth by phosphorus.
When ambient bio-available phosphorus is depleted in the water
column, algae may activate the production of alkaline phosphatase
enzyme. This enzyme cleaves phosphate from the stored luxury phosphate
chains/compounds. The presence of significant alkaline phosphate enzyme
is indicative of algae limited in their potential growth by phosphorus
-1-
-------
Figure 1. Study Area
Potomac Estuary
-2-
-------
Station Number
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
Table 1
Station Name
Chain Bridge
windy Run
Key Bridge
Memorial Bridge
14th Street Bridge
Hains Point
Bellevue
Woodrow 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
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
RMI Buoy Reference
0.0
1.9
3.4
4.9
5.9
7.6 C "1"
10.0 FLR-23' 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
-------
and forced to draw upon reserve phosphate to meet their nutrient re-
quirements . If phosphorus was depleted to a critical level in the
estuary, measured concentrations of luxury phosphate would be expected
to decrease and the activity of alkaline phosphatase would be expected
to increase. Studies-' have found that these changes are not immediate
and a lag time occurs before the biological changes, related to phos-
phorus deficiency, are expressed.
Several species of algae, notably blue-green algae, have the ability
to meet their nitrogen requirement by reducing free nitrogen (Ng) from
the air and incorporating it into cellular organic compounds. Algae
grown in an environment containing adequate fixed nitrogen (NH^ or NOo)
do not fix No vrithout a preliminary starvation period during which the
nitrogenase enzyrr.es can develop.^ The triple bonds of N2 are extremely
stable and breakage of these bonds involved in nitrogen reduction dic-
tates that fixation requires considerable energy input. Cells capable
of fixing nitrogen will use NH, or NO" preferentially because less
energy is required.'*'''7
The nitrogenase enzyme complex is comprised of two major protein
components, Fe-protein and Mo-Fe-protein, each composed of several
12
subunits. Nitrogen is reduced by the enzyme complex to ammonia as
electrons flow from a reducing agent to the Fe-protein, then to the
Mo-Fe-protein and finally to nitrogen. The ammonia formed in these
processes is subsequently employed in amino acids, which are the
building blocks of protein. The nitrogen fixing activity of algae
is often restricted to specialized cells termed heterocysts. These
-L-
-------
are enlarged, clear (reduced pigmentation) cells, which apparently do
not produce CU since oxygen is thought to deactivate nitrogenase. ^
It has been found-^-3 that nitrogenase can reduce a variety of
multiple bond substances in addition to molecular nitrogen. These
include N02, N^, RCN, RNC, and RCCH. Acetylene is reduced by this
system to ethylene which is not further affected. Algae actively
fixing nitrogen will produce ethylene when incubated with acetylene.
Bulk elemental analysis of the phytoplankton standing crop gave
an indication of the carbon, nitrogen and phosphorus bound in algal
cells. This information when ratioed to chlorophyll a gives a means
of predicting algal C, N, and P from the more easily ir.easu.red
chlorophyll a concentration. To increase the comparability of these
elemental analyses to cells of different sizes, the cell concentrations
of C, N, and P were also reported on a dry weight basis. A problem
with the comparability of elemental analysis is the varying amount of
sheath material observed with different algal species. This problem
makes it difficult to establish a reliable relationship between elemen-
tal composition ratios measured and the nutrient status of the algae
being studied.
-5-
-------
II. Conclusions
A. The average composition of the phytoplankton present in the
study area was (mg/ug):
Org C/ =0.028; PO// = 0.002; TKN-N/ =0.007
/chlor a /chlor a /chlor a
The predominate phytoplankton species present during the study
period was the blue-green algae Oscillatoria sup.
B. No significant alkaline phosphatase activity was detected
during this study and together with the average luxury phosphate
of G.45 mg PO^/100 nig algae (dry) suggested that phosphorus was
not limiting growth.
C. "o significant nitrogen fixation was detected during the
study period.
D. Ammonium uptake rate varied markedly with station location
and a negative correlation, r = -.60 (n - 4), was determined
for ammonia absorption rate vs (NOj + NOo)-N concentration. The
absorption rate increased from 0.0 ug NH/-N/10 mg algae/hr. at a
(N02 * NOo)-N concentration of 0.352 mg/1 at Chapman Point to
7.5 ug NH ,-N/10 nig algae/hr. when the nitrate + nitrite-nitrogen
4
concentration became less than 0.0^ mg/1 at Possum Point. This
indicated that the reach from Chapir,an Point to Possum Point was
becoming nitrogen limited.
E. Approximately 50j? of the algal TKN-N was refractory to the
Technicon Autoanalyzer (phenolate/helix method) without preliminary
manual digestion.
F. Elemental analysis data for phosphorus was obtained by Millipore
filtration and by centrifugation. The results obtained were not
significantly different.
-c-
-------
III. Experimental
A. Chlorophyll a was determined on an untreated portion of the
sample via a 90% acetone extraction of a Millipore filtrate from,
100 ml of the sample.
B. Sairple. preparation procedures (Figure 2) required the exist-
ence of a significant bloom (>50 ug/1 chlorophyll a) so that
errors due to "non-agal particulate material" would be minimized
and so that sufficient algae could be concentrated to run the
necessary tests. The sample preparation procedures involved;
1. Centrifuge algal sample in 50 ml aliquots (3) at 3K RFM
for 5 minutes. The sample was stored at 4°C during this
procedure.
2. Collect 10 ml of supernatant as a blank from each
centrifuge tube in a 125 nil Erlenmyer flask stored on ice.
Discard all but a few drops of the remaining liquid in the
tubes.
3. Resuspend pellets in >_50 ml of river water blank (super-
natant). The volume of the sample centrifuged and the volume
to which the resultant algal pellet was diluted was recorded.
Microscopic examination revealed that no apparent morphological
damage was suffered by the predominant phytoplankton species
present.
C. Elemental Analyses
1. TKN-M (NH_ plus organic nitrogen): 5 ml of algal
suspension was diluted to 25 ml in a volumetric flask using
Super Q - Milli Ro deionized '.vater. A blank was run using
-------
Figure 2
Sample Preparation
Sample (stored on ice)
1-4 liters
Centrifuged (3K RFM - 5 minutes)
(stored on ice)
Algal Pellet
Supernatant Discarded
except for 100-500 ml)
Resuspension of Pellet with clear filtrate
\
Algal Suspension
ions
Elemental
Analysis
TKN-N TOC TP
Approoriate subsairples and diluti
Luxury \.
Phosphate N.
N
Absorption
-------
5 ml of supernatant river water diluted to 25 ml in Super Q -
Milli Ro deionized water.
These samples were then manually digested: 10 ml aliquot
of each was placed in reflux tubes and 8.0 ml of
digestion solution was added. The tubes were placed over
flame until boiling and reflux stopped. The contents of
the tubes were washed with deionized water and brought to
50 ml using a graduated cylinder.
The resultant digests were analyzed using the Technicon
Autoanalyzer phenolate method.
2. TOG; 5 ml of algal suspension was diluted to 25 ml in
a volumetric flask using Super Q deionized water. A blank
was run using 5 ml of supernatant river water diluted to 25
ml in Super Q deionized water. The TC and 1C were then
determined on a Beckman 915 TOC analyzer.
3. Total Phosphate; 25 ml of sample and blank were prepared
as above by dilution of 5 ml of sample 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 autoclaved at 15 psi for 30
minutes. The digests were then analyzed for total phosphate
by the Technicon automated ascorbic acid reduction method.
-------
D. Table 2
Growth Media^ used in laboratory studies:
Gorham's Gorham's Gorham's
Complete (Minus P) (Minus N)
Solution Solution Solution
mg
/1
mg/1
mg/1
Volume of Stock
ml per liter cone, stock
K2HPO,
NaNOj
MgS04-2H20
CaCl2-2H20
Na2Si03.9H20
Na2C03
Ferric Citrate
Citric Acid
(Na2)E.D.T.A.
39.0
496.0
75.0
36.0
53.0
20.0
6.0
6.0
1.0
0.0
496.0
75.0
36.0
58.0
20.0
6.0
6.0
1.0
39.0
0.0
75.0
36.0
58.0
20.0
6.0
6.0
1.0
1 ml
10 ml
1 ml
1 ml
10 ml
1 ml
i; mi
1 ml
1 mi
19.5g/500 ml
24.8g/500 ml
37.5g/500 ml
18.0g/5CO ml
2.9g/500 ir.l
10.Cg/500 ml
C.3g/5CC ~1
3.0g/5CO ~.l
l.Cg/500 ml
Luxury Phosphate^
1. Spin down two sets of 5 ml aliquots of algal suspension
at 3K RFM for 5 minutes and discard supernatant.
2. Lightly wash pellet with 10 ml of Gorham's (P-mir.us)
solution adjusted to pH 7 with acetic acid.
3. Pour off liquid and wash cells with Gorham's (P-minus)
pH 7 solution into an Erlenmyer flask to a total volume of 40 ml,
4, Cover with aluminum foil and place one flask into
boiling water for 50 minutes.
5. The other set is immediately centrifuged ana the super-
natant analyzed for PO^.
6. After one hour repeat step #5 for the first extracted set.
-1C-
-------
7. Calculate the net (by difference) extracted PO^/
100 mg algae (dry weight).
Definition: Extracted algae that give less than 0.03 mg PO^/
100 mg algae (dry weight) are considered to be
phosphorus limited.
F. Alkaline Phosphatase Activity^
1. Centrifuge 5 ml of algal suspension and discard supernatant.
2. Wash pellet with 10ml of Gorham's (P-minus) adjusted to
pH 9.0 with acetic acid.
3. Wash cells into Erlenmyer flask with 32ml of Gorham's
(P-minus) pH 9.0 solution.
4. Add 4 ml of 1M THIS solution which is also 0.01 M MgCl2
and adjust pH to 8.5 with acetic acid.
5. Add 4ml of p-nitrophenyl phosphate solution (30 irg/100 ml).
6. Incubate glass stoppered flask with mixing for 15 to 20
minutes at 35-37°C.
7. Stop when color is within standard curve by adding 0.5 ml
of orthophosphate (20 mg PO^/ml) stock solution.
8. Filter material through .45 u Millipore membrane filter and
analyze liquid.
9. Read absorbance at 395 nm in 2 cm cells with 2.0 nm slit.
10. Run standard curve of nitrophenol, (color is pH dependent)
with:
32ml Gorham's (P-minus) adjusted to pH 9.
4ml of the Tris Buffer.
4ml of standard solution.
-11-
-------
11. Standard curve concentrations (after reagent addition):
0; 0.5; 1.0; 1.5; 2.0; 2.5; 3.0 xlO"5M p-nitrophenol.
a. Preparation of standard solutions:
(1) Prepare a stock of p-nitrophenol of 1.3911g/l
(10-2M).
(2) 20 ml of this solution was diluted to 200 ml
with deionized water to generate a working stock.
(3) 5; 10; 15; 20; 25; and 30 ml of the working
solution is diluted to 100 ml with deionized water
to generate: 0.5; 1.0; 1.5; 2.0; 2.5; 3.0xlO~4M
solutions.
(4) When 4 ml of these solutions is diluted to ^0 nil
total with reagent, the standard curve at the 1C~".M
level is generated.
b. Characteristic Calibration Curve (Figure 3;
mg
Concentration
0
0
1
1
2
2
3
.0
.5
.0
.5
.0
.5
.0
X
X
X
X
X
X
10
10
10
10
10
10
-5
-5
5
"V
-5
-5
M
M
M
M
M
M
Absorbane
0
0
0
0
0
0
1
.coo
.193
.362
.536
.733
.902
.CP6
p-nitrophenol
C
n
1
2
2
3
4
.00
.70
.39
.08
.78
.45
.17
-12-
-------
H
II
M
B
-------
12. Determine mu moles of nitrophenol liberated/hr. per
milligram of algae (dry weight).
Definition:
a. 1 unit of enzyme activity is equivalent to 1.0 mu
mole of nitrophenol per hour per mg dry weight.
b. /^x 1000 enzyme units/jug algae/hour represent algae
considered phosphorus limited.
c. This test is generally a confirming test since
changes in enzyme activity per changes in nutrient level
are slow to occur.
A check standard of bacterial alkaline phosphatase
(12 units/mg from the Worthington Biochemical Corporation)
was run as a positive control check with each batch of samples
analyzed.
G. Ammonia Absorption Plate'''
1. Centrifuge 2 sets of 5 ml aliquots of algal suspension
at 3K RPM for 5 minutes. Discard the supernatant.
2. Pre-wash pellets with 10 ml of Gorham's N-minus, adjusted
to pH 8.0 with acetic acid and discard liquid.
3. Wash pellets into a flask with 30 ml of Gorhain's N-minus
adjusted to pH 8.0.
-4. Spike both sets with 0.5 mg NH4C1-N/1.
5. Centrifuge the first set Immediately and analyze super-
natant for NH^-N.
6. Incubate the other flask in the dark at 68°C with occa-
sional mixing for one hour.
-U-
-------
7. Centrifuge and assay supernatant for NH^-N.
Threshold Limit; Nitrogen-starved algal cells were found to
assimilate NH^-N 4 to 5 times more rapidly than normal cells
under optimum nitrogen conditions. The limit cited is that
algae are considered nitrogen limited if they absorb more than
"*" 7
15 ug NH,-N/10 mg dry algae per hour . This threshold rate,
however, was observed to vary from species to species. The
comparison of NH^-N assimilation rates measured for algae from
different locations in the Potomac River study area, associated
with different in situ nitrogen concentrations was thought to be
more meaningful. A drastic rate of increase (--4 or 5 times)
from one location to another was taken to indicate changes in the
availability of nitrogen for assimilation purposes and suggested
that nitrogen was limiting growth.
H. N2 Fixation8
1. Sample preparation:
a. Concentrate 2 liters of sample (770906-16, 17, 19)
for algae as described previously and bring to 25 ml
total volume with river water supernatant. (Blank)
b. Add 10 ml of each concentrate to two 40 ml septum
vials.
2. Seal the vials with an injectionable septum (air tight
pharmaceut ical type).
3. Inject 1.5 ml of acetylene (Cgf^) into each vial using a
5 ml disposable syringe.
4. Immediately inject 0.2 ml of 5N H2SO^ into one set to act
as a control blank.
-15-
-------
5. Shake all flasks and vent by pricking with a hypodermic
needle.
6. Incubate in a water bath in direct sunlight for 1 1/2
hours at 29°C (~ambient surface water temperature).
7. The reduction reaction was stopped by the injection of
0.2 ml of 5N HoSO^. The samples were stored at 4°C until
gas chromatographic analysis.
8. The G.C. and experimental conditions were as follows:
a. Column temperature: 50°C
b. Flow 25 ml/minute of Helium
c. Column: porapack N, 80-100 mesh, 6 ft. with 0.2 ram I.D.
d. Retention time:
Ethylene: 1.75 minute
Acetylene: 3.55 minute
e. Room temperature: 2<4°C; 30.13" Hg barometric pressure.
9. Chlorophyll a. concentration was determined as described
previously, and using the measured TKN-N/chlorophyll a. ratio
(0.007) the mg of algal TKN-N was determined and the results
were reported as ng acetylene reduction per mg algal TKN-N.
10. The volume of the vials (60.0 ml) was determined using
the weight of water at room temperature.
11. The procedure for diluting the stock ethylene was crude
but the reduction test was run more as a qualitative assay to
detect significant nitrogen fixation rather than a strictly
quantitative rate determination. The dilution and spikes
were as follows:
-16-
-------
a. Stock ethyler.e preparation (ir.w. 28.04 gm/mole)
(l) Ethylene TOS assumed an ideal gas or PV = nRT.
R = 0.082 1 at in K"1 mol"1
T = 24°C or 297.14 K
P = 30.13" Hg x 2.54 err/in x ^~ = 1.0070 AHA
V = 60 ml bottle or 0.060 1
in stock
(2) Inject 0.5 ir.l directly into 60 ml gas tight vial:
'°°260 Sl6S x '5 ml = °00021 moles or -57S n«
b. Dilute 5/60 by volume using a gas tight syringe and
gas tight bottle:
.00243 moles x g~ = .000207 moles in dilution
(1) Inject 0.5 ml directly:
.000207 moles x 0.5 ml = .00000173 mole or .049 irg
60 ml
(2) Inject 1.0 ml directly:
. 000207 moles x 1.0 ml = .0000034 mole or .095 irg
60 ml
c. Dilute 1/60 by volume using a gas tight syringe and
gas tight bottle:
.002Z3 moles x _1 = .0000413 moles in dilution
60 ml
Inject 0.5 ml directly:
.0000413 x 0.5 nl = .00000034 mole or .0095 mg
60
The area of the G.C. peaks for these standards was used
to determine the concentration in the unknown samples.
-------
IV. Discussion of Results
The elemental analyses and special bioassay results are compiled
in Table 3. The location and chlorophyll a distribution of the stations
sampled for this study are given in Figures 4-7. It should be empha-
sized that these results are based on the overall phytoplankton standing
crop. The alkaline phosphatase activity (^1000 enzyme units/mg algae/
hour)^ indicative of phosphorus starved algal cells was not encountered
in any of the study samples. The average luxury phosphate measured,
0.45 mg PO//100 mg algae (dry), was in excess of the established thres-
hold level for phosphorus limitation of 0.03 mg PO^/100 rag algae (dry).2
Little difference was observed in luxury phosphate measured at the up-
stream and downstream stations. The inorganic phosphate concentration
increased in the bloom area with an average cf 0.214 mg/1 FO^ measured
over the study stations. The alkaline phosphatase, luxury phosphate,
and ambient inorganic phosphorus data indicated that adequate phos-
phorus was present for maximum growth during the study period.
The inorganic nitrogen source for algal growth was limited to
(N02 + NO.J-N in the bloom area, Table 4. This was a result of the
rapid nitrification of the ammonia entering the river upstream of the
q
study area. The distribution of measured ammonium uptake rates
relative to (NOg + NO^)-N measured in the Potomac are also included
in Table 4. Though this data is sparse, a significant increase in
uptake rate occurred with (N02 + NO-^-N depletion on the August 29
analysis between Chapman Point (0.0 ug NH//10 mg algae/hour) and
Possum Point (7.5 ug NH^/10 mg algae/hour). This data (n = 4) was
used to generate the correlation coefficient of -0.3. The increased
-13-
-------
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Figure 6
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-22-
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Figure 7
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-23-
-------
Table 4
Ammonium Uptake Rates/Nitrogen Distribution
Location
Chapman Pt.
Guns ton Cove
Chapman Pt.
Indian Head
Chapman Pt.
Indian Head
Deep Pt.
Possum Pt .
Location
Guns ton Cove
Chapman Pt.
Indian Head
Deep Pt.
Possum Pt.
Sandy Pt.
Smith Pt.
Date Sta. ug NH^-N/10 mg Algae/hour mg
8-1-77 9 0.3
8-22-77 8-A 0.3
8-22-77 9 0.2
8-22-77 10 0.3
8-29-77 9 0.0
8-29-77 10 0.4
8-29-77 10-B 4.2
8-29-77 11 7.5
Date 8-1-77 8-22-77
Sta. *NHtt (NOo + NO-j)-N NHtf (NOp + NO^)-}
4 ' *- J £+\ £ 2
8-A .928 0.3 .181
9 .710 0.2 .130
10 0.3 .495 0.3 .089
10-B .378 ND
11 .122 ND
12 **ND .126
13 ND .317
NH^-N/ug Chi
0.4 x 10
0.5 x 10
0.2 x 10
0.5 x 10
0.0
8.0 x 10
12.2 x 10
23.7 x 10
. a/hour
-5
-5
-5
-5
-5
-5
-5
8-29-77
4 NH+7 (N02
0.0
0.4
A. 2
-.5
+ NO~)-N
.352
.110
ND
ND
ND
ND
Note: The NH^-N concentration was less than 0.02 mg/1 over these dates and
stations except for Sta. 13 on 8-22-77 which had an NH/-N concentration
of 0.052 mg/1.
*NH^t = ug NH*-N/10 mg Algae/hour
**ND = not detectable = <0.04 mg (N02 + NO,)-N/1
-24-
-------
rate of ammonium absorption (>7.5x) corresponded to a decrease in
inorganic nitrogen from 0.352 mg/1 (NC>2 < NOo)-N at Chapman Point to
less than 0.04 mg (N02 + NO^)-N/1 at Possum Point. The rate of NH^-N
absorption by algae and aquatic weeds in the dark has been shown to be
4-5 times greater for plants which are N-limited as compared to plants
' The
nitrogen fixation data is compiled in Table 5 and indicates that no
significant acetylene reduction (<.073 n moles C2H,/mg N/hour) was
measured although ambient inorganic nitrogen became non-detectable
between Deep Point and Sandy Point on September 6 when the acetylene
fixation procedure was carried out. Values of 126-230 n moles C2H//mg
N/hour have been reported as indicative of high efficiencies of
acetylene reduction, ^ and rates of 30-60 n moles CgHy/mg N/hour are
g
considered significant.
As a check on the laboratory procedures involved in centrifugation
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and sample concentration, dilution, etc., the elemental analysis results
were compared to a second method (filter method). The results are com-
piled in Table 6. The columns designated "total" represent analytical
results (C, N, and P) on the unaltered samples. The column labeled
"filtered" represents the elemental analyses of the filtrate after
filtration through 0.45 u Millipore filters. The algae were held on
the filter and the differences of filtered and unfiltered results were
taken as the algal material. A paired t-test of the phosphorus results
revealed that there was no significant difference at the 95$3 confidence
level and 9 degrees of freedom between the results of the two methods
with t = 1.195. The nitrogen data (Table 6) was consistently lower
for the filtered experiments. The TKN-N for the filtered data did
not incorporate the preliminary manual digestion used in the centrifuge
procedure. The results suggest that 5CJ§ of the algal nitrogen was
refractory to the TKN-N Technicon Autoanalyzer without preliminary
manual digestion. A paired t-test of filtered TKN-N data (corrected
for recovery) and centrifuged data established that there was no
significant difference at the 95% confidence level and 9 degrees of
freedom with t = 0.958. The good comparison between these experimental
approaches suggest that the analytical procedures were accurate and
precise. The basic assumption inherent in both Y/as that the primary
suspended material was algae. This assumption was not tested but algae
assays and analyses were limited to the peak-bloom area where the
assumption would be most reasonable.
-28-
-------
Table 6
FILTERED vs CENTRIFUGED METHODS
Total Filtered
org POz/Chl. a
Location
Chapman Pt.
Indian Head
Deep Pt.
Guns ton Cove
Chapman Pt.
Indian Head
Chapman Pt.
Indian Head
Deep Pt.
Possum Pt.
Date
8-1-77
8-1-77
8-1-77
8-22-77
8-22-77
8-22-77
8-29-77
8-29-77
8-29-77
8-29-77
Sta.
9
10
10-B
8-A
9
10
9
10
10-B
11
IP
.503 .
.472 .
.469 .
.764 .
.751 .
.736 .
.799 .
.759 .
.850 .
.846 .
Ei IE Ei
rag PO^/1
161
157
157
162
238
259
176
205
275
282
.204
.212
.210
.240
.243
.270
.256
.250
.279
.366
.102
.114
.120
.227
.170
.207
.122
.136
.290
.310
Chi. a
ug/1
60.0
66.0
76.5
306
264
283.5
261.0
300.0
294
199.5
X
Filter Centrifuge
.004
.003
.003
.002
.002
.002
.002
.001
.002
.002
= .002
V
t
r
*
*
*
9
003
002
002
003
002
003
001
001
001
002
002
= 9
= 1.152
= .50
Location
Chapman Pt.
Indian Head
Deep Pt.
Guns ton Cove
Chapman. Pt.
Indian Head
Champan Pt .
Indian Head
Deep Pt.
Possum Pt.
Total Flit'
Date Sta. TKN NH3 TKN
8-1-77
8-1-77
8-1-77
8-22-77
8-22-77
8-22-77
8-29-77
8-29-77
8-29-77
3-29-77
9
10
10-B
8-A 1
9 1
10 1
9 I
10 1
10-B 1
11
mg
.685 ND
.651 ND
.600 ND
.439 ND
.254 ND
.227 ND
.373 ND
.328 ND
.111 ND
.885 ND
N/l
.338
.313
.288
.344
.362
.353
.526
.426
.342
.334
ered
NH3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Chi.
ug/1
60.
66.
76.
306
264
283.
261.
300.
294
199.
N
org/Chl
j a.
a Filter Centrifuge
0 .006
0 .005
5 .004
.004
.003
5 .003
0 .003
0 .003
.003
5 .003
x = .004
V
4.
\J
r
*
*
*
,
008
013
009
008
006
008
003
003
004
005
007
Filter
x2
.012
.010
.008
.008
.006
.006
.006
.006
.006
.006
.007
= 9.00
= .958
= .67
-------
V. Recommendations
A. It is recommended that future work with algal bioassays be
split into two areas of concern. Algae from the peak bloom area
(highest chlorophyll a concentration) should be employed in the
elemental analysis work. This will ensure adequate phytoplankton
necessary for the required analyses. Limiting nutrient analyses
should be stressed in areas downstream from the peak bloom, where
algae are encountering less productive conditions.
B. It is recommended that future ^-fixation work involve con-
centration and incubation of phytoplankton in situ. In addition
to providing the natural setting for incubation, larger quantities
of algae should be obtained to insure that the TKN-N determinations
are in the optimal range of the test. The practice of reporting
acetylene reduction in terms of total Kjeldahl nitrogen limits
the test to some degree by the lack of sensitivity of the TKN-N
analysis relative to the gas chroiratographic determination of
ethylene.
-------
VI. References
1. O'Shaughnessey, J. C., McDonnell, Archie J., "Criteria for
Estimating Limiting Nutrients in Natural Streams". Inst. for
Research on Land and Water. Pennsylvania State University,
Res. Pub. No. 75.
2. Fitzgerald, G. P. and Nelson, T. C., "Extractive and
Enzymatic Analysis for Limiting or Surplus Phosphorus in Algae",
Journal of Phvcology. Vol, 2, 1966, pp. 32-37
3. Williams, L. R., "Heteroinhibition as a Factor in Anabaena
flos-aquae Waterbloom Production", Proceedings of Biostimulation
Nutrient Assessment Workshop. EPA - Corvallis, October 1973.
4. Fitzgerald, G. P., "Bioassay Analysis of Nutrient Availability",
Nutrients in Natural Waters. John Wiley and Sons, Inc., 1972.
5. Strickland, J. D. H., and Parsons, T. R., "A Manual of Sea
Water Analysis", Bulletin 125, Fisheries Research Board of Canada.
Ottowa, I960, p. 185.
6. Environmental Protection Agency, Methods for Chemical Analysis
of Water and Wastes. 1974, p. 182.
7. Fitzgerald, G. P., "Detection of Limiting or Surplus Nitrogen
in Algae and Aquatic Weeds", Journal of Phvcology. Vol. 4, 1968,
pp. 121-126.
8. Stewart, W. Df, Maque, T., Fitzgerald, G. P., and Burris, R. H.,
"Nitrogenase Activity in Wisconsin Lakes of Differing Degrees of
Euthrophication", New Phytol.. (1971), 70, pp. 497-509.
9. Slayton, J. L., Trovato, E. R., "Carbonaceous and Nitrogenous
Demand Studies of the Potomac Estuary", Annapolis Field Office,
EPA, 1979.
10. Carpenter, E. J., "Marine Oscillatoria (trichodesmium):
Explanation for Aerobic Nitrogen Fixation Without Heterocysts",
Science 191, March 1976, pp. 1278-1280.
11. Mague, T. H. and Burris, R. H., "Acetylene Reduction as an
Indicator of Biological Nitrogen Fixation in the Great Lakes",
Limnology and Oceanography.
12. Skinner, K. J., "Nitrogen Fixation", Chemical and Engineering
News. Oct. 4, 1976, pp. 23-35.
13. (Author unknown) "Reduction Point to ^ Fixation Mechanisms:
Nitrogen Fixing Enzymes Catalyze the Reduction of Acetylene, Azide,
Cyanides, Methyl isocyanide and nitrous oxide", Chemical and
Engineering News, Jan. 30, 19o7, p. 32.
-31-
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1. REPORT NO.
EPA 903/9-79-002
4. TITLE AND SUBTITLE
ALGAL NUTRIENT STUDIES OF
7. AUTHOR(S)
J. L. Slayton
and E. R. Trovato
9. PERFORMING ORGANIZATION NAME AT
Annapolis Field Office, Re
U.S. Environmental Protect
Annapolis Science Center
Annapolis, Maryland 214.03
2. 3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
Summer 19VV
THE POTOJ.1AC ESTUARY ' 6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
vlD ADDRESS 1 10. PROGRAM ELEMENT NO.
'gion III
ion Agency 11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS . 13. TYPE OF REPORT AND PERIOD COVERED
In House; Final
Same
14. SPONSORING AGENCY CODE
SPA/903/00-
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The nutrient requirements
studied curing the summer
NH^-N uptake, alkaline phc
orthophosphate; tissue ana
and nitrogen fixation by a
the bloom of Oscillatoria
was present.
17.
3. DESCRIPTORS
Algae
Nutrients
13. DISTRIBUTION STATEMENT
ZELZASE TO PUBLIC
of the phytoplankton of the Potomac Estuary were
of 1977 employing the following laboratory tests :
>sphatase enzyme activity; extra ctable surplus
.lysis for carbon, nitrogen and phosphorus content;
cetylene reduction. The results indicated that
,vas limited by nitrogen and that adequate phosphor-is
KEY WORDS AND DOCUMENT ANALYSIS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Luxury phosphorus
Ammonium uptake
Nitrogen fixation
Alkaline phosphates e
Elemental analysis
19. SECURITY CLASS (Tins Report) 21. NO. OF PAGES
UNCLASSIFIED 3fi
20. SECURITY CLASS (This page) 22. PRfCE
UNCLASSIFIED
EPA Form 2220-1 (9-73)
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