fi FRRMEUJORK FOR
MODELING
FflTE RND EFFECTS
OF
TOHIC SUBSTRNCES
IN
MONROE HRRBOR, MICHIGRN
MARY 6ESSNER
AND
WILLIAM RICHARDSON
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ERL-DULUTH
LARGE LAKES RESEARCH STATION
GROSSEILE, MICHIGAN
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THE TITLE OF THIS PRESENTATION HAS BEEN CHANGED TO: A
FRAMEWORK FOR MODELING FATE AND EFFECTS OF Toxic SUBSTANCES IN
MONROE HARBOR, MICHIGAN. AND is AN OVERVIEW OF WORK BEING
CONDUCTED AT THE U.S. ERA'S LARGE LAKES RESEARCH STATION AT
GROSSE ILE. MICHIGAN.
THE MONROE HARBOR is LOCATED ON THE RAISIN RIVER AT MONROE,
MICHIGAN WHERE THE RIVER ENTERS WESTERN LAKE ERIE. THE
INTERNATIONAL JOINT COMMISSION HAS DESIGNATED THE MONROE HARBOR
AS ONE OF 18 CLASS "A" AREAS OF CONCERN AROUND THE GREAT LAKES
WHERE WATER QUALITY IS SIGNIFICANTLY DEGRADED AND BENEFICIAL
USES ARE SEVERELY IMPAIRED. THIS CLASSIFICATION OF MONROE
HARBOR WAS BASED ON:
- SUBSTANTIAL VIOLATIONS OF WATER QUALITY OBJECTIVES,
- SEDIMENTS HIGHLY POLLUTED BY HEAVY METALS, AND
- HIGH CONCENTRATIONS OF PCBS IN FISH (5-77 PPM).
OUR STUDY AREA INCLUDES AN APPROXIMATE *4 MILE (6.M KM)
STRETCH OF THE RIVER FROM tlONROE. MICHIGAN TO LAKE ERIE, WITH
PRIMARY EMPHASIS BEING PLACED ON THE LOWER 2.5 MILES (M.O KM).
THIS LOWER PORTION OF THE RIVER HAS ONLY 2 PRESENTLY ACTIVE
POINT-SOURCE DISCHARGES - MONROE WWTP AND A FORD MOTOR COMPANY
PLANT AND A DREDGED TURNING BASIN FOR COAL SHIPS. THE UPPER
RIVER RECEIVES AGRICULTURAL AND URBAN RUNOFF.
IN THE SPRING OF 1983, A STUDY WAS DESIGNED AND IMPLEMENTED
TO ADDRESS THE COMPLEX ISSUES OF TRANSPORT, EXPOSURE AND
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EFFECTS OF CONTAMINANTS IN THE TRIBUTARY AND NEARSHORE AREAS OF
THE GREAT LAKES. THE PRIMARY OBJECTIVES ARE:
A) TO MODEL CONTAMINANT IN THE RIVER FROM SOURCES THROUGH
EFFECTS. AND
B) TO MODEL TOXICITY AS A STATE VARIABLE.
SECONDARY OBJECTIVES OF THE STUDY ARE:
A) INVESTIGATE THE LONGEVITY AND IMPORTANCE OF IN-PLACE
POLLUTANTS.
B) PROVIDE INPUT INTO SURVEILLANCE DATA BASES, AND
c) DEVELOP A PROTOCOL FOR INVESTIGATING CHRONIC PROBLEMS
OF GREAT LAKES ESTUARIES.
IN ORDER TO ADDRESS THESE OBJECTIVES. AN INTEGRATED
ANALYSIS AND MODELING FRAMEWORK WAS DEVELOPED WHICH INCLUDES:
A) EXPOSURE MODELING - FATE AND TRANSPORT.
B) FOOD CHAIN MODELING - BIOACCUMULATION/BIOCONCENTRATION,
c) TOXICITY MODELING - CHEMICAL/EFFECTS CORRELATIONS.
THE FIELD AND LABORATORY RESEARCH. WHICH WAS DESIGNED TO
PROVIDE INPUT INTO MODEL DEVELOPMENT AND CALIBRATION. INCLUDES:
A) ANALYSIS OF CHEMICAL RESIDUES IN WATER, SEDIMENT AND
BIOTA, AND
B) MEASUREMENT OF TOXIC EFFECTS AT VARIOUS LEVELS OF THE
ECOSYSTEM.
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MONROE HflRBOR RESEflRCH PROJECT
PBIMBBV PURPOSES
0 MODEL SOURCES THROUGH EFFECTS
0 MODEL TOXICITY AS A STATE VARIABLE
SECONDflRV PURPOSES
0 LONGEVITY OF -|N-PLACE- POLLUTANTS
0 PROVIDE STATUS OF WATER QUALITY
0 PROTOCOL FOR GREAT LAKES ESTUARIES
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PROJECT SCHEMATIC
SAMPLING I
FOR FIELD >
VALIDATION I
ANALYSES FOR
CHEMICAL SPECIES
WATER COLUMN
SEDIMENT
MODEL I
APPLICATION \
AND (
DEVELOPMENT!
ANALYSIS FOR
CHEMICAL RESIDUES
IN
FOOD CHAIN
ORGANISMS
CHEMICAL
FATE/EXPOSURE
MODEL
WATER/SEDIMENT
ANALYSES FOR
TOXICITY TO
ECOSYSTEM
BACTERIA PHYTOPLANKTON
FISH ZOOPLANKTON
FOOD CHAIN
TRANSFER/DOSE
MODEL
WATER/SEDIMENT
TOXIC
EFFECTS
MODEL
WATER/SEDIMENT
TOXICITY
FATE/EXPOSURE
MODEL
WATER/SEDIMENT
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MONROE HARBOR PROJECT
PARTICIPANTS
MICHIGAN DEPARTMENT OF NATURAL RESOURCES
Biological Surveys, Historical Data, Point Source
Identification
CRANBRQQK INSTITUTE OF SCIENCE
Field Sampling, Laboratory Analyses, Bioaccumulation,
Toxicity Bioassays
CLARKSON COLLEGE
Characterization of Sediment and Partitioning of
Toxicants
UNIVERSITY OF MINNESOTA
Effects of Toxicants on Bacteria, Phytoplankton,
Zooplankton
OHIO STATE (CLEAR)
Distribution and Pathology of Fish Larvae
OHIO STATE (COASTAL ENGINEERING)
Fine Scale Transport Measurements
UNIVERSITY OF CALIFORNIA, SANTA BARBARA
Resuspension Physics and Modeling
MANHATTAN COLLEGE
Mathematical Modeling, Data Synthesis
EPA. GREAT LAKES NATIONAL PROGRAM OFFICE
Coordination with Regulatory Community and IJC
EPAr OFFICE OF RESEARCH AND DEVELOPMENT, LARGE
LAKES RESEARCH STATION
Research Planning, Administration, and Coordination,
Quality Assurance Data Base Development, Statistical
Analysis Modeling
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DURING 1983, THREE (3) INTENSIVE FIELD SURVEYS WERE
CONDUCTED TO DEFINE CHEMICAL GRADIENTS ALONG THE RIVER, AND TO
DEVELOP A MASS BALANCE MODEL FOR IMPORTANT CHEMICALS.
CONCURRENTLY, IN-SITU AND LABORATORY TOXICITY STUDIES WERE
CONDUCTED IN AN ATTEMPT TO CORRELATE SPATIAL VARIABILITY OF
WATER QUALITY WITH BIOLOGICAL EFFECTS. SINCE ALL THREE OF THE
1983 SURVEYS WERE CONDUCTED DURING PERIODS OF RELATIVELY LOW
RIVER FLOW, A FOURTH SURVEY WAS CONDUCTED AS' EARLY AS POSSIBLE
AFTER ICE-OUT IN THE SPRING OF I98M, WHICH TURNED OUT TO BE
APRIL 2-5.
THIS TABLE SHOWS THE WATER QUALITY PARAMETERS MEASURED
DURING THESE M SURVEYS. BASICALLY. GENERAL CHEMISTRY,
NUTRIENTS, METALS AND OR6ANICS. BIOLOGICAL TESTS, WHICH WERE
CONDUCTED DURING THESE SURVEYS ADDRESSED THE FOLLOWING
ENDPOINTS:
- BACTERIAL UPTAKE OF ACETATE - DECOMPOSER ECOSYSTEM
FUNCTION,
- PHYTOPLANKTON PHOTOSYNTHESIS - PRIMARY PRODUCTIVITY
ECOSYSTEM FUNCTION,
- ZOOPLANKTON REPRODUCTION, SURVIVAL AND GRAZING -
SECONDARY PRODUCTIVITY,
- LARVAL FATHEAD MINNOW SURVIVAL AND GROWTH,
- GROWTH AND PATHOLOGY OF RESIDENT LARVAL FISH.
- ACCUMULATION OF CONTAMINANTS BY CAGED CLAMS AND FISH AND
RESIDENT FISH.
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MONROE HARBOR PARAMETERS
GENERAL CHEMISTRY
WATER TEMPERATURE
DISSOLVED OXYGEN
TRANSPARENCY (SECCHI DEPTH)
PH
SPECIFIC CONDUCTANCE
ALKALINITY
CHLORINE (TOTAL, FREE AND COMBINED RESIDUAL)
AMMONIA
NITRITE
HARDNESS
CHLORIDE
SUSPENDED SOLIDS
METALS
CHROMIUM (TOTAL AND DISSOLVED)
COPPER (TOTAL AND DISSOLVED)
ZINC (TOTAL AND DISSOLVED)
ORGANICS
PCB (TOTAL AND DISSOLVED)
PESTICIDES (TOTAL AND DISSOLVED)
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O
O
EFFECTS END POINTS
BACTERIAL4JPTAKE OF ACETATE
PHYTOPLANKTON PHOTOSYNTHESIS
ZOOPLANKTON REPRODUCTION.
SURVIVAL AND GRAZING
O LARVAL FATHEAD MINNOW SURVIVAL
AND GROWTH
GROWTH AND PATHOLOGY OF RESIDENT
LARVAL FISH
ACCUMULATION OF CONTAMINANTS BY
CAGED CLAMS AND RESIDENT FISH
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A PRELIMINARY MASS BALANCE ESTIMATE BASED ON DATA COLLECTED
DURING THESE CRUISES INDICATED THAT TOTAL PCB IN THE WATER
COLUMN OF THE LOWER RIVER COULD NOT BE ACCOUNTED FOR BASED ON
THE MEASURED INPUTS (UPSTREAM, WWTP, FORD. LAKE €RIE).
POSSIBLE SOURCES OF THE UNACCOUNTED FOR PCBs, WHICH WE
CONSIDERED, INCLUDED:
- SEDIMENT RESUSPENSION,
- SEDIMENT DIFFUSION,
- GROUNDWATER LEACHING FROM ADJACENT LANDFILLS,
- CLANDESTINE DICHARGE.
SEDIMENT ANALYSES FROM THE 1983 FIELD SEASON INDICATE THAT
RELATIVELY HIGH LEVELS OF PCBS DID OCCUR AT NUMEROUS POINTS
ALONG THE RIVER BOTTOM, ESPECIALLY DOWNSTREAM OF THE TURNING
BASIN.
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Water ColumnTotal PCB
(NG/D- October 1983
16
LAKE ERIE
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CHLORIDE MASS BALANCE
Balance chloride mass to confirm transport for
October 25, 1983 Assumed/simplified transport
Q
KNOWNS:
Qus
Qw =
Qr =
247 cfs
18.2 cfs
MASS BALANCE
IN
us
le
out Le us wwtp Le2
mg/1
= Cle2
(estimated)
Cr.(Qu+
OUT
Solving for 0
Le
QLe= 132 cfs
• *
Qr= 379 cfs
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N
Surficial Sediment PCBs
(ug/kg)-1983
o>.330
70t> LAKE ERIE
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MANY OF THE BIOLOGICAL SAMPLES ARE STILL BEING ANALYZED.
BUT THE LIMITED DATA WE DO HAVE INDICATE FAIRLY HIGH LEVELS OF
CONTAMINATION (PARTICULARLY PCBs) IN MONROE HARBOR BIOTA. SIX
ADULT CARP, WHICH HAVE BEEN ANALYZED AS INDIVIDUAL, WHOLE BODY
SAMPLES HAD TOTAL PCB BODY BURDENS RANGING FROM 6.3 - T08.3
PPM. THE MEAN AND MEDIAN VALUES FOR THIS DATA SET ARE 38.3
AND.3M.OfPM, RESPECTIVELY. ADDITIONAL SAMPLES INCLUDING
FILLETS AND WHOLE BODIES OF CARP, WALLEYE, AND SMALLMOUTH BASS
ARE BEING ANALYZED NOW.
LARVAL GIZZARD SHAD SAMPLES COLLECTED FROM THE LOWER RAISIN
RIVER OVER A SIX-WEEK PERIOD IN 1983 HAD TOTAL PCB BODY BURDENS
RANGING FROM 65 - 3500 PPB. PATHOLOGICAL EXAMINATION OF LARVAE
COLLECTED AT THE SAME TIME HAS REVEALED CONSISTENT PRESENCE OF
LESIONS OF KIDNEY, GILL AND EPITHELIAL TISSUES, AND VERTEBRAL
ANOMALIES IN THE SPECIMENS. THESE DATA ARE STILL BEING
ANALYZED AND WE DO NOT KNOW IF THE PRESENCE OF ABNORMALITIES
CAN BE ACCOUNTED FOR BY ANY PARTICULAR WATER DUALITY
CONDITIONS.
IN ORDER TO DETERMINE WHICH EFFECT VARIABLES ARE EXPLAINED
BY WHICH CAUSE VARIABLES, MULTIPLE REGRESSION ANALYSES HAVE
BEEN CONDUCTED ON SOME OF THE LABORATORY TOXICITY RESULTS AND
VARIOUS WATER QUALITY PARAMETERS. A RELATIONSHIP BETWEEN MEAN
YOUNG/ADULT CERIODAPHNIA AND DISSOLVED ZINC AND HARDNESS WAS
DISCOVERED. 701 OF THE VARIANCE IN MEAN YOUNG/ADULT WAS
EXPLAINED BY CHANGES IN HARDNESS AND DISSOLVED ZINC FOR THE TWO
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TOTflL PCB IN MONROE HflRBOR CHRP
SfiMPLE NO.
1
2
3
4
5
6
LENGTH
(mm)
446
401
420
398
397
357
WEIGHT
<9>
1232
915
996
860
801
706
PCB
(M9/g)
34
36
108
11
6
33
MEDIAN = 34 yg/g
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TOTRL PCB IN MONROE HRRBOR
GIZZRRO SHRR—1983
SflMPLE NO DRTE COLLECTED PCB (»g/kg»
1
2
3
4
5
6
7/14/83
7/14/83
7/21/83
8/18/83
8/18/83
9/01/83
65
540
3500
530
1100
2600
XIPCB= 1389jjg/kg
MEDIAN = 820 jig/kg
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SURVEYS TESTED. IN BOTH CASES, DISSOLVED ZINC IS NEGATIVELY
CORRELATED WITH REPRODUCTION AND HARDNESS IS POSITIVELY
CORRELATED WITH REPRODUCTION. IT IS LOGICAL THAT ZINC SHOULD
HAVE A NEGATIVE EFFECT AND HARDNESS SHOULD HAVE A POSITIVE
EFFECT. IT IS A WELL'KNWON PHENOMENON THAT AS HARDNESS
INCREASES. THE TOXICITY OF SOME METALS IS REDUCED. ZOOPLANKTON
SURVIVAL DID NOT CORRELATE WITH THE TESTED WATER QUALITY
PARAMETERS. THE SURVIVAL OF ZOOPLANKTON WAS. IN GENERAL.
QUITE GOOD FOR THE SEVEN DAYS OF THE BIOASSAY AND IT MAY BE
THAT THE ORGANISMS WOULD HAVE TO :BE EXPOSED LONGER FOR A LETHAL
EFFECT TO BE DETECTED. REGRESSION ANALYSES FOR PCBS AND
PESTICIDES HAVE NOT BEEN COMPLETED.
IN-SITU BIOACCUMULATION STUDIES WERE CONDUCTED IN THE FALL
OF 1983 USING 2 SPECIES OF NATIVE CLAMS (LAMPSILIS RADIATA AND
ANODONTA GRANDIS). CAGED CLAMS WERE SUSPENDED IN THE WATER
COLUMN AT 5 RIVER STATIONS - I UPSTREAM CONTROL AND M IN THE
LOWER STRETCH OF THE RIVER. CLAMS WERE RETRIEVED AFTER 2M DAYS
OF EXPOSURE AND ANALYZED FOR PCBS AND ORGANOCHLORINE
PESTICIDES. CONCENTRATIONS OF TOTAL PCBs SHOWED A DEFINITE
INCREASING TREND FROM .05 PPM AT OUR CLEAN UPSTREAM SITES. TO
.2 NEAR THE WWTP AND WERE HIGHEST ( I PPM) AT THE TURNING
BASIN. LEVELS DECREASED AGAIN, TO O.I FURTHER DOWNSTREAM.
LEVELS OF ACCUMULATION WERE VERY SIMILAR FOR MALE AND FEMALE
LAMPSILIS RADIATA. AND SOMEWHAT LOWER IN ANODONTA GRANDIS.
INCREASING LEVELS OF PCBs WERE ALSO SEEN IN THE MEAN WATER
CONCENTRATIONS FOR THE EXPOSURE PERIOD AT 3 OF THE STATIONS.
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REGRESSION flNflLVSIS FOR
CERIODRPHNIR RETICULRTfl:
MEflN VOUN6 PER flDULT, DISSOLUED ZINC,HRRDNESS
EXPERIMENT I * EXPERIMENT 11» *
0.69694
VARIABLES:
CONSTANT 14.611
STANDARD ERROR (1.4404)
DISSOLVED ZINC -.25005
STANDARD ERROR (.055418)
0.69614
5.7837
(2.8428)
-1.5634
(.52598)
HARDNESS 0.14219 0.19307
STANDARD ERROR (0.0046934) (0.044918)
MEAN YOUNG
ADULT
MEAN YOUNG
ADULT
EQUATION I
14611 - .25005 (DIS. ZN) + 0.014219 (HARDNESS)
EQUATION II
5.7837 - 1.5634 (DIS. ZN) + 0.19307 (HARDNESS)
* EXCLUDES STATION 8, MASON RUN.
** EXCLUDES THE INTAKE PIPE, ST. 00
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* DAM ELEVATION FT ABOVE MSL
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CLAM BODY BURDENS - MONROE HARBOR - 1983
T
0
T
A
L
P
C
B
n
G
/
K
G
1.4 -
1.2 -
1 .
0.8 -
0.6 _
0.4 .
0.2 .
0
MALE L. RADIATA
FEMALE L. RADIATA
A. GRANDIS
CONTROL
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500
X TOTAL UATER
T
0
T
A
L
P
C
B
N
G
400 .
300 .
200 .
100 .
0
STA. 1
I
STA. 3
I
STA. 4
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RANGING FROM 20 PPB UPSTREAM TO ABOUT MOO PPB IN THE TURNING
BASIN.
BASED ON THE RESULTS OF THE FIRST M SURVEYS. 6 ADDITIONAL
SURVEYS WERE CONDUCTED THIS PAST SPRING AND SUMMER TO DEFINE
TEMPORAL VARIABILITY OF CHEMICAL AND TOXICITY GRADIENTS IN THE
HARBOR. THE SAME WATER QUALITY SAMPLING AND TOXICITY TESTS
WERE CONDUCTED AS IN PREVIOUS STUDIES. BUT SAMPLING WAS DONE
flORE FREQUENTLY (ONCE EVERY.2 WEEKS). IN RESPONSE TO SOME OF
THE RESULTS WE HAVE SEEN SO FAR, WE HAVE DONE MORE EXTENSIVE
SEDIMENT SAMPLING AND DID 'SOME PRELIMINARY SEDIMENT TOXICITY
STUDIES. THE SEDIMENT TOXICITY WORK WAS DONE BY MODIFYING
ELUTRIATE TEST METHODS DEVELOPED AT ERA'S ENVIRONMENTAL
RESEARCH LABORATORY AT CORVALLIS, FOR USE WITH THE 7-DAY
CERIODAPHNIA AND FATHEAD MINNOW RENEWAL METHODS DEVELOPED AT
ERL-DULUTH.
AN IN-SITU BIOACCUMULATION STUDY USING CAGED CLAMS. FATHEAD
MINNOWS, AND CHANNEL CATFISH WAS DONE IN ORDER TO COMPARE
DIFFERENCES IN CONTAMINANT UPTAKE BETWEEN SPECIES. REPLICATE
CAGES WERE SUSPENDED IN THE WATER COLUMN AND ON THE RIVER
BOTTOM TO COMPARE DIFFERENT EXPOSURE REGIMES.
MORE EXTENSIVE INVESTIGATION OF SEDIMENT RESUSPENSION
EVENTS AND THE EFFECT OF DIFFERENT SHEER STRESSES ON SEDIMENT
RESUSPENSION ARE BEING CONDUCTED IN ORDER TO PREDICT THE
FREQUENCY AND MAGNITUDE OF RESUSPENSION EVENTS. EVENTUALLY, WE
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HOPE TO BE ABLE TO PREDICT WHAT EFFECTS RESUSPENSION OF
IN-PLACE POLLUTANTS WILL HAVE ON THE SURROUNDING ECOSYSTEM.
DATA ANALYSIS AND MODELING ARE INCOMPLETE AT THIS TIME, BUT
WE HOPE TO DEVELOP AN INTEGRATED MODELING FRAMEWORK TO ADDRESS
PROBLEMS AND POSSIBLE REMEDIAL ACTIONS FOR THE RIVER AND HARBOR
AREAS OF CONCERN AROUND THE GREAT LAKES.
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MODELING
OUR OBJECTIVE, AS STATED IN THE BEGINNING, IS TO DEVELOP A
PREDICTIVE MODEL OF TOXICITY.
THE ABILITY TO PREDICT OR SIMULATE TOXICITY DEPENDS ON THE
ASSUMPTION THAT WE CAN FIRST PREDICT EXPOSURE CONCENTRATIONS OF
IMPORTANT CHEMICALS IN THE WATER COLUMN.
PREVIOUS RESEARCH AT LLRS AND MANHATTAN COLLEGE HAS SHOWN
THE FEASIBILITY OF THIS FOR METALS AND PCB'S AND ASSOCIATED
-SUSPENDED SOLIDS.
A SIMILAR APPROACH IS BEING APPLIED IN THE RAISIN ESTUARY -
FIRST BYi I) CALIBRATING TRANSPORT BY SIMULATING TEMPERATURE
AND CONDUCTIVITY,
SECONDLY 2) SIMULATING SUSPENDED SOLIDS INCLUDING SETTLING
AND RESUSPENSION FROM SEDIMENTS,
THIRDLY 3) SIMULATING TOTAL, DISSOLVED, AND PARTICULATE
FRACTIONS OF IMPORTANT CHEMICALS, I.E. ZINC.
PCBS.
PRELIMINARY RESULTS AS SUPPLIED BY DITORO AND WINFIELD AT
MANHATTAN COLLEGE SHOWS THAT AVERAGE CONCENTRATIONS FOR CRUISE
AVERAGES CAN BE SIMULATED BY A STEADY STATE MODEL.
THE MODEL INCLUDES A TWO-LAYERED SEGMENTATION SCHEME WHICH
ALLOWS REPRESENTATION OF THE STRATIFIED FLOW IN THE ESTUARY.
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PRELIMINARY SIMULATIONS ARE SHOWN T.N THESE FIGURES WITH THE
SOLID LINE REPRESENTING THE TOP LAYER AND THE DOTTED LINE THE
LOWER LAYER FOR CONCENTRATIONS ALONG THE LENGTH OF THE STUDY
SITE.
THE DATA ARE REPRESENTED BY THE MEAN SURVEY CONCENTRATIONS
AND STANDARD DEVIATIONS.
THE EVENTUAL PLAN WILL BE TO ENCORPORATE THE TOXICITY
CORRELATIONS INTO THE MODEL SO THAT TOXICITY CAN BE PREDICTED
DIRECTLY.
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