xv EPA
United States
Environmental Protection
Agency
Great Lakes National Program Office
77 West Jackson Boulevard
Chicago, Illinois 60604
EPA 905-R97-005
March 1997
Survey of Sediment
Quality In The
Duluth/Superior
Harbor:
1993 SAMPLE RESULTS
Minnesota Pollution Control Agency
i) MnraMtat \Mmmnutt unJoWitit of Lift
-------
Minnesota Pollution Control Agency
1111111^1*!^^;..,^^^^^
»•;'":•„::' :-•:,.; •- ••••-'•V
-------
SURVEY OF SEDIMENT QUALITY IN THE DULUTH/SUPERIOR
HARBOR: 1993 SAMPLING RESULTS
Submitted to
Callie Bolattino, Project Officer
Great Lakes National Program Office
U.S. Environmental Protection Agency
77 West Jackson Boulevard
Chicago, IL 60604-3590
Mary Schubauer-Berigan and Judy L. Crane
Minnesota Pollution Control Agency
Water Quality Division
520 Lafayette Road North
St. Paul, MN 55155-4194
March, 1997
-------
DISCLAIMER
The information in this document has been funded by the U.S. Environmental Protection
Agency's Great Lakes National Program Office. It has been subject to the Agency's peer
and administrative review, and it has been approved for publication as an EPA document.
Mention of trade names or commercial products does not constitute endorsement or
recommendation for use by the U.S. Environmental Protection Agency.
11
-------
TABLE OF CONTENTS
Disclaimer ii
List of Figures v
List of Tables vi
Acknowledgments viii
List of Acronyms and Abbreviations , ix
Executive Summary xii
1.0 Introduction 1
1.1 Background 1
1.2 Project Description 2
1.3 Project Objectives 3
2.0 Methods 5
2.1 Field Methods . 5
2.1.1 Preliminary Site Selection 5
2.1.2 Sediment Collection A 5
2.2 Laboratory Methods 6
2.2.1 Chemical Analyses 7
2.2.1.1 Established Methods 7
2.2.1.2 Screening Methods 7
2.2.2 Toxicity Tests 8
2.2.2.1 Benthic Invertebrate Tests 8
2.2.2.2 MicrotoxR and MutatoxR Tests 8
3.0 Results and Discussion 20
3.1 Site Locations and Field Observations 20
3.1.1 Site Locations, Water Depth, and Core Sections Analyzed 20
3.1.2 Sediment Core Depths 21
3.1.3 Sediment Physical Description 22
3.2 Chemical Analyses 23
3.2.1 Ammonia 24
3.2.2 Total Organic Carbon 25
3.2.3 Mercury 26
3.2.4 Other Heavy Metals 27
3.2.4.1 Atomic Absorption Spectroscopy 27
3.2.4.2 X-ray Fluorimetry 32
3.2.5 PCBs 33
3.2.5.1 GC/ECD Method 33
3.2.5.2 Immunoassay 35
3.2.6 2,3,7,8-TCDD/TCDF 36
3.2.7 Pesticides 38
111
-------
TABLE OF CONTENTS
3.2.8 PAHs 40
3.2.8.1 Gas Chromatography/Mass Spectrometry (GC/MS) 40
3.2.8.2 Fluorescence Screen 43
3.2.9 Tributyltin 45
3.3 Toxicity Tests 47
3.3.1 10-day Sediment Toxicity Tests 47
3.3.1.1 Acute Toxicity to Hyalella azteca 48
3.3.1.2 Acute Toxicity to Chironomus tentans 48
3.3.1.3 Chronic Toxicity to Chironomus tentans 49
3.3.4 Acute Toxicity to Photobacterium phosphoreum (MicrotoxR) 49
3.3.5 Genotoxicity to Vibrio fischeri (MutatoxR) 49
3.4 Cesium Dating of Sediment Cores 50
4.0 Composite Site Descriptions 115
4.1 Relative Contamination Factors ..115
4.2 Field Design Considerations. ' , 118
4.3 Compilation of Results. . . /. 119
5.0 Recommendations 128
6.0 References 130
Appendix A Database of Sediment Chemistry Data
Appendix B Sediment Toxicity Test Reports for Hyalella azteca and Chironomus tentans
IV
-------
LIST OF FIGURES
Figure 1-1. Site map of the St. Louis River AOC 4
Figure 2-1. Location of sediment sampling sites in the Duluth/Superior Harbor. ... 9
Figure 2-2. Detailed map of site locations in the vicinity of WLSSD and Slip C. . . 10
Figure 3-1. Distribution of surficial KCl-extractable ammonia at the sample sites. . 53
Figure 3-2. Distribution of surficial TOC at the sample sites 54
Figure 3-3. Distribution of surficial mercury at the sample sites 55
Figure 3-4. Depth profile of mercury at sites DSH 12 and DSH 24 56
Figure 3-5. Depth profile of mercury at sites DSH 25 and DSH 34 57
Figure 3-6. Depth profile of mercury at sites DSH 36 and DSH 40 58
Figure 3-7. Distribution of surficial arsenic at the sample sites 59
Figure 3-8. Distribution of surficial cadmium at the sample sites 60
Figure 3-9. Distribution of surficial chromium at the sample sites 61
Figure 3-10. Distribution of surficial copper at the sample sites 62
Figure 3-11. Distribution of surficial lead at the sample sites 63
Figure 3-12. Distribution of surficial nickel at the sample sites 64
Figure 3-13. Distribution of surficial zinc at the sample sites 65
Figure 3-14. Distribution of surficial, total PCBs at the sample sites 66
Figure 3-15. Depth profile of normalized, total PCBs at sites DSH 03 and DSH 12 . 67
Figure 3-16. Depth profile of normalized, total PCBs at sites DSH 20 and DSH 31 . 68
Figure 3-17. Depth profile of normalized, total PCBs at sites DSH 34 and DSH 40 . 69
Figure 3-18. Relationship between PCB immunoassay and GC/ECD method ...... 70
Figure 3-19. Distribution of surficial 2,3,7,8-TCDD at the sample sites 71
Figure 3-20. Distribution of surficial 2,3,7,8-TCDF at the sample sites 72
Figure 3-21. Distribution of surficial, total PAHs at the sample sites 73
Figure 4-1. Map of total relative contamination factors (RCFs) for surficial sediments
collected in the Duluth/Superior Harbor 121
-------
LIST OF TABLES
Table 2-1. Summary of site codes, descriptions, ami reasons for inclusion in the 1993
Duluth/Superior Harbor sediment assessment 11
Table 2-2. Summary of sediment analytical methods 14
Table 2-3. Summary of quality assurance parameters for sediment analytical methods . 16
Table 2-4. Summary of toxicology methods 18
Table 2-5. Summary of quality assurance parameters for sediment toxicology methods 19
Table 3-1. Approximate location of sites and depth of vibracore sections analyzed ... 74
Table 3-2. Water depth sampled and sediment core length 76
Table 3-3. Physical description of Ponar grab samples 77
Table 3-4. Physical description of sediment cores collected using the vibracorer 78
Table 3-5. KCl-extractable and porewater ammonia concentrations in surficial
(approximately 0-30 cm) sediments from the Duluth/Superior Harbor .... 80
Table 3-6. TOC concentrations in sediment cores from the Duluth/Superior Harbor. . 82
Table 3-7. Mercury concentrations in sediment cores from the Duluth/Superior
Harbor 83
Table 3-8. Heavy metal concentrations in surficial sections (0-30 cm) of sediment
cores from the Duluth/Superior Harbor, measured by cold vapor atomic
absorption spectroscopy 85
Table 3-9. X-Ray fluorescence determination of metals concentrations (mg/kg dry wt.)
from selected sites and core depths 87
Table 3-10. Comparison of metal determinations made by atomic absorption
spectroscopy (AAS) vs. x-ray fluorimetry (XRF), in surficial (< 30 cm)
sediments of the Duluth/Superior Harbor 88
Table 3-11. Total PCB concentrations in sediment cores from the Duluth/Superior
Harbor 89
Table 3-12. PCB immunoassay determinations in sediment cores from the
Duluth/Superior Harbor 91
Table 3-13. 2,3,7,8-TCDD/TCDF concentrations in surficial sediment core samples
from the Duluth/Superior Harbor 93
Table 3-14. Pesticide concentrations (/ig/kg dry wt.) in surficial sediment core samples
from the Duluth/Superior Harbor 95
Table 3-15. Comparison of toxaphene extracts analyzed by GC/ECD and GC/SIM. . . 97
Table 3-16. TOC-normalized pesticide analyses of Duluth/Superior Harbor sediments . 98
Table 3-17. PAH analyses, conducted October 1993, for samples collected during
September 1993 100
vi
-------
LIST OF TABLES
Table 3-18. TOC-normalized PAH results for samples collected during September 1993,
analyzed during October 1993 . 102
Table 3-19. PAH analysis on stored surflcial (0-30 cm) Vibracore samples (collected
September 1993 and analyzed July 1994) 104
Table 3-20. Comparison of split analyses of sediment samples collected during June
1993 and analyzed during either October 1993 or July 1994 106
Table 3-21. Location and description of surficial sediment samples (0-15 cm) collected
on June 11, 1994 107
Table 3-22. PAHs in surficial sediments (0-15 cm) from the Duluth/Superior Harbor
collected during June 1994 and analyzed during July 1994 108
Table 3-23. PAH fluorescence screen results for Duluth/Superior Harbor sediments
collected in September 1993 110
Table 3-24. Tributyltin (3-BT), monobutyltin (1-BT), dibutyltin (2-BT), and
tetrabutyltin (4-BT) concentrations in Duluth/Superior Harbor sediments. Ill
Table 3-25. Sediment toxicity to Hyalella azteca, Chironomus tentans, Photobacterium
phosphoreum (MicrotoxR) and Vibrio fischeri (MutatoxR) 112
Table 3-26. Sedimentation rates for sediment cores collected from the Duluth/Superior
Harbor, in cm/year 114
Table 4-1. Relative contamination factors (RCF) for surficial sediments collected in the
Duluth/Superior Harbor survey 122
Table 4-2. Summary of contaminant and toxicology data for 40 sites in the
Duluth/Superior Harbor 124
vu
-------
ACKNOWLEDGMENTS
This report was initially written by Mary Schubauer-Berigan, formerly of the Minnesota
Pollution Control Agency (MPCA) Water Quality Division. Judy Crane (MPCA) edited,
revised, and finalized this document. Mary Schubauer-Berigan, Dan Helwig, and Harold
Wiegner formed the primary MPCA project team responsible for designing this investigation.
Jerry Flom, Patti King, John Thomas, Karen Kroll, Jill Jacoby, Mary Arm Koth, Carolyn
Voelkers, Sandy Bissonnette, Judy Mader, Gary Simonsen, and Mark Stuart, all of the
MPCA Water Quality Division, assisted with sediment sampling. Steve Simmer, Heidi
Bauman, Katie Peukart, and Bob Beresford, all of the MPCA Duluth Regional Office, also
helped collect samples. Sampling assistance was also received from the following Wisconsin
Department of Natural Resources (WDNR) staff: Karen Plass, Nancy Larson, Kim Walz,
Scott Redman, Tom Janisch, and Frank Koshere. Personnel from the Great Lakes National
Program Office (GLNPO) operated GLNPO's Research Vessel (RAO: the Mudpuppy. The
use of the R/V Mudpuppy and GLNPd's vibracorer device was essential for collecting
sediment samples. '
Carol Hubbard, MPCA Water Quality Division, performed the sediment toxicity tests with
assistance from Harold Wiegner, Patti King, Jerry Flom, and Mary Schubauer-Berigan. The
analytical support of the University of Minnesota's Trace Organics Lab (Irene Moser and
Keith Lodge) and Natural Resources Research Institute (Rich Axler, Joe Schubauer-Berigan,
Chris Owen, Geri Tesser, John Ameel, Anastasia Bamford, Gloria Ely, and Kent Johnson),
AScI Corporation (Elliott Smith, Joe Rathbun, and Laura Huellmantel), St John's University
(Dan Steck), Texas A&M University (Terry Wade), and Twin City Testing (Deneen Walker)
contributed greatly to the study. Scot Beebe, of the MPCA Water Quality Division, assisted
with the analysis of data. James Beaumaster and Patti King, MPCA Water Quality Division,
provided graphical and spreadsheet support.
The Sediment Contamination Work Group of the St. Louis River Remedial Action Plan
provided valuable review comments of the draft report. Other review comments received by
the MPCA Site Response Team, WDNR (especially Tom Janisch), U.S. Steel, Minnesota
Power, and GLNPO were appreciated.
This project was funded by the U.S. EPA Great Lakes National Program Office through
grant number GL995636-01-0. Rick Fox and Gallic Bolattino provided valuable input as the
successive GLNPO project officers of this investigation.
vm
-------
LIST OF ACRONYMS AND ABBREVIATIONS
AAS Atomic Absorption Spectroscopy
AC Alternating Current
ACOE Army Corp of Engineers
AOC Area of Concern
ARCS Assessment and Remediation of Contaminated Sediments
As Arsenic
ASTM American Society of Testing and Materials
1-BT Monobutyltin
2-BT Dibutyltin
4-BT Tetrabutyltin
Cd Cadmium
cm Centimeter
Co Company
Cr Chromium >
137Cs Cesium 137 Radioisotope
Cu Copper
CV Coefficient of Variation
DC Direct Current
DDD Metabolite of DDT
DDE Metabolite of DDT
DDT Dichloro-diphenyl-trichloroethane
DSD Duluth Steam District
DSH Duluth/Superior Harbor
EC50 The median effective concentration causing an effect to 50% of test organisms
EPA Environmental Protection Agency
ft Feet
GC/ECD Gas Chromatography/Electron Capture Detection
GC/FPD Gas Chromatography/Flame Photometric Detector
GC/MS Gas Chromatography/Mass Spectrometry
GC/SIM Gas Chromatography/Selective Ion Methodology
GIS Geographic Information System
GLNPO Great Lakes National Program Office
GPS Global Positioning System
HCB Hexachlorobenzene
Hg Mercury
ix
-------
LIST OF ACRONYMS AND ABBREVIATIONS
IDL Instrument Detection Limit
IJC International Joint Commission
KCI Potassium Chloride
kg Kilogram
LaMP Lakewide Management Plan
LEL Lowest Effect Level
m Meter
MDL Method Detection Limit
mg Milligram
mm Millimeter
MN Minnesota
MPCA Minnesota Pollution Control Agency
MQL Method Quantitation Limits
N/A Not Applicable >
NC Not Collected
ND Not Detected
NEL No Effect Level
NH3+ Ammonia
Ni Nickel
NRRI Natural Resources Research Institute
NO Not Obtained
NOAA National Oceanographic and Atmospheric Administration
NT Not Toxic
OCS Octachlorostyrene
OMOEE Ontario Ministry of Environment and Energy
PAHs Polycyclic Aromatic Hydrocarbons
Pb Lead
PCBs Polychlorinated Biphenyls
pH Equal to the negative logarithm of the hydrogen ion concentration
PQTW Publicly Owned Treatment Works
ppb Part Per Billion
ppt Part Per Trillion
QA/QC Quality Assurance/Quality Control
QAPP Quality Assurance Project Plan
QC Quality Control
-------
LIST OF ACRONYMS AND ABBREVIATIONS
RAP Remedial Action Plan
RCF Relative Contamination Factor
R-EMAP Regional Environmental Monitoring and Assessment Project
RI/FS Remedial Investigation/Feasibility Study
RPD Relative Percent Difference
R/V Research Vessel
S South
SD Standard Deviation
SE Southeast
SOP Standard Operating Procedure
SQC Sediment Quality Criteria
SQOC Sediment Quality Objective Concentration
SRM Standard Reference Material
SW Southwest ,
1 Toxic
TBT Tributyltin
TCDD Tetrachlorodibenzo-p-dioxin (as in 2,3,7,8-TCDD)
TCDF TetracMorodibenzofuran (as hi 2,3,7,8-TCDF)
TOC Total Organic Carbon
Hg Microgram
UMD University of Minnesota-Duluth
W West
WDNR Wisconsin Department of Natural Resources
WI Wisconsin
WLSSD Western Lake Superior Sanitary District
wt. Weight
XRF X-ray Fluorimetry
Zn Zinc
XI
-------
EXECUTIVE SUMMARY
The Duluth/Superior Harbor has been designated as part of the St. Louis River Area of
Concern (AOC) by the International Joint Commission (IJC). Contaminated sediments
contribute to impaired uses hi this AOC. The degree of sediment contamination in
depositional areas outside the shipping channels is not well documented in the harbor, which
has a long history of industrialization. In order to obtain a cohesive dataset, a sediment
quality assessment was conducted hi the St. Louis River estuary during September 1993.
This study was designed to support the assessment goals of the Phase I sediment strategy for
the St. Louis River Remedial Action Plan (RAP).
This survey included the collection of sediment cores from 40 sites suspected to exhibit
contamination (Table 1, Figure 1). The U.S. EPA Research Vessel, the Mudpuppy, was
used to collect sediment samples between the Fond du Lac Dam and Duluth/Superior entries
during September 1993. A vibracore sampler (10 cm diameter) was used for collecting up to
3-ni deep cores. The surficial (0-30 cm) layer was analyzed for the following contaminants:
2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and 2,3,7,8-tetrachlorodibenzofuran (TCDF),
polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), thirteen
pesticides, mercury (Hg), lead (Pb), arsenic (As), cadmium (Cd), chromium (Cr), copper
(Cu), nickel (Ni), zinc (Zn), total organic carbon (TOC), and ammonia. Up to five sections
per core (at 30 cm increments) were analyzed for mercury, PCBs (congeners and Aroclors),
PCB immunoassay, PAH fluorescence screen, and TOC. Six of the 40 vibracore samples
were sectioned in 2 to 5 cm increments and dated using the radioisotopic tracer l37Cesium.
In addition, surface gravity cores were collected from six sites, selected by their proximity to
commercial, private or public shipyards, boat docks, and loading facilities; these samples
were analyzed for tributyltin and three other butylated forms of tin (i.e., mono-, di-, tetra-).
Surficial sediments, collected with a Ponar, were evaluated for acute toxicity to two benthic
invertebrates: the amphipod, Hyalella azteca (H. azteca), and midge, Chironomus tentans (C.
tentans). The Ponar samples were also evaluated for acute toxicity to the bacterium
Photobacterium phosphoreum (MicrotoxR test) and genotoxicity to the bacterium Vibrio
fischeri (MutatoxR). All analytical and toxicity test methods followed the data quality
objectives of the Quality Assurance Project Plan.
The distribution of surficial (i.e., 0-30 cm) contaminants varied widely throughout the
harbor. Color charts showing the distribution of mercury, PCBs, PAHs, 2,3,7,8-
TCDD/TCDF, toxaphene, p,p'-DDD -f o,p'-DDT, and heavy metals are given in Figures
xn
-------
2-15. The concentrations of mercury and PCBs varied with depth in the sediment cores.
Although the mercury concentrations at some sites (e.g., DSH 24 and DSH 34) rapidly
decreased below the surficial layer, other sites (e.g., DSH 12, DSH 36, DSH 25, and DSH
40) showed both declines and increases hi mercury concentrations at depth. For PCBs, the
sediment profiles for DSH 03, DSH 20, DSH 31, and DSH 40 showed PCB peaks below the
surface. Sites DSH 12 and DSH 34 had the greatest PCB concentrations in the surficial
sediments.
Acute toxicity to C. tentans was evident at three of the 40 sites. The H. azteca test only
passed quality assurance requirements for 12 sites; no acute toxicity was observed at these
sites. One-quarter of all sites were toxic to the microbe Photobacterium phosphoreum,
whereas about half the sites were genotoxic to the bacterium Vibrio fischeri. For the
sediment toxicity test results, there was little comparability between the C. tentans results
and the MicrotoxR and MutatoxR results.
The surficial sediment chemistry data for 17 contaminants and TOC were compared to
sediment quality guidelines developed by the Ontario Ministry of Environment and Energy
(OMOEE). The State of Minnesota has not developed sediment quality guidelines, and the
U.S. EPA has only developed draft sediment quality criteria for five organic contaminants.
The OMOEE guidelines provide a biologically-based benchmark that can be used to compare
to the results of this study. The OMOEE Low Effect Level (LEL) guidelines correspond to
the level of sediment contamination that can be tolerated by the majority of benthic
organisms, and at which actual ecotoxic effects become apparent. The OMOEE Severe
Effect Level (SEL) corresponds to the level at which pronounced disturbance of the sediment
dwelling community can be expected. Relative contamination factors (RCFs) were calculated
for 17 contaminants by normalizing the contaminant concentration by the respective LEL
value (i.e., RCF = Contaminant Concentration/LEL). The individual RCFs were summed
to yield a total RCF value for each site. Total RCF values that exceeded 17 indicated that
some ecotoxic effects may be present at the sampling sites.
Table 2 contains a summary table of the total RCF values, as well as the sediment chemistry
and toxicity test results. The table is organized with the total RCF values in descending
order. Thus, an indication of the most contaminated to least contaminated sites can be
derived from this table. It is important to note that correlations cannot be made between the
toxicity test results and sediment chemistry data; this is because the sediment chemistry
measurements were based on the upper 30 cm of the vibracore samples, whereas the toxicity
tests were run on approximately the upper 20 cm of sediments obtained using a Ponar
dredge.
xiii
-------
A number of sites exceeded the OMOEE LEL values for heavy metals, PCBs, and PAHs
(Table 2). PAH contamination was widespread in the harbor, and may have resulted partly
from the historical storage, shipment, and use of coal in the Duluth/Superior Harbor. Sites
in the Superior Harbor generally had relatively fewer exceedances of heavy metal, PCB, and
PAH LELs than sites in the Duluth Harbor. Some of this difference may be due to different
watershed inputs as the Nemadji River drains into the Superior Harbor, and the St. Louis
River drains into the Duluth Harbor. In addition, the Duluth Harbor watershed has a greater
industrial/commercial/residential base than the Superior Harbor watershed. Thus, there is a
greater probability of anthropogenic point and nonpoint sources of contamination in the
Duluth portion of the harbor. The Duluth portion of the harbor is also impacted by two
Superfund sites: USX and Interlake/Duluth Tar.
Table 2 also provides a qualitative priority for further study at each site. The USX
Superfund site was the most contaminated site evaluated in this study. This site, along with
the Interlake/Duluth Tar Superfund site, have been undergoing additional investigations as
part of the potentially responsible parties legal obligations. Other sites that were rated highly
for further study included the bay surrounding the Western Lake Superior Sanitary District
(WLSSD) and Coffee/Miller Creek outfalls, Eraser Shipyards, Minnesota Slip, area between
the M.L. Hibbard Plant/DSD No. 2 and Grassy Point, and in the old 21st Ave. West
Channel. Other areas, such as Slip C and off the Superior POTW outfall, were listed as
medium priority. It is important to note that this study was limited in scope and was not
meant to characterize large areas as to the extent of contamination. In addition, a sediment
hotspot investigation was carried out by the Minnesota Pollution Control Agency (MPCA)
during 1994 to further characterize several of the aforementioned priority sites. The results
of this hotspot investigation should be used to decide whether or not further site
characterization and/or remediation is needed at these sites.
xiv
-------
Table 1. Summary of site codes and descriptions of sites included in the 1993
Duluth/Superior Harbor sediment assessment. Sites in Wisconsin are bold and italicized,
whereas sites in Minnesota are in normal typeface.
Site
Number
Site Description
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
Burlington Northern Taconite facility (Superior)
Barkers Island Channel, East End (Superior)
Off Superior POTW
Public launch area, Minnesota Point
Off Superior Fiber Products former discharge
Base of East Gate Basin, Superior
Hoarding Island deep hole
Corps of Engineers vessel yard
Near Globe Elevators (Superior)
Interstate Island deep hole
WLSSD, just west of outfall
Old 21st Ave. W. Channel
DM&IR taconite storage facility
East of Erie Pier (Scrap yard at International
Welders & Machinists)
West of Incan Superior dock
North of M.L. Hibbard plant/Duluth Steam District
(DSD) No. 2
South of M.L. Hibbard plant/DSD No. 2
Loon's Foot Landing Inlet (Superior)
C. Reiss coal dock
Channel between Hearding Island and Park Point
Mouth of Stryker Embayment
Near Stryker Embayment, just west of current channel
Across channel from Tallas Island, east of buoy #28
Off Un-named Creek (USX Superfund site)
Near Wire Mill Settling Pond (USX Superfund site)
xv
-------
Table 1. Continued.
Site
Number
Site Description
DSH26
DSH27
DSH28
DSH29
DSH30
DSH31
DSH32
DSH 33
DSH34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
Mud Lake (near ME International)
Kimballs Bay (no known contaminant source)
Allouez Bay, Superior
Slip C (near end)
New Duluth (site of old paint factory)
Fraser Shipyards, first slip west of drydocks # 1 and 2
Across Howard's Bay Channel from Fraser Shipyards Slip
305 m S-SW of WLSSD outfall
91 m SE of WLSSD outfall
24 m W of Rice's Point, E of 21st Ave. W. Channel
61 m S of Coffee Creek outfall and near Miller Creek Outfall
Slip C, in front of Superwood plant
Slip C, near Great Lakes Towing Co.
Slip C, just up from Cutler Magner Co.
Minnesota Slip, near William Irvin ore boat
xvi
-------
1993 Sediment
Sampling Sites
Hearding Island
N
A
Duluth, MN
Lake Superior
Kilometers
1BHP
vfflse
Figure 1. Location of sediment sampling sites in the Duluth/Superior Haitxar.
-------
Mercury: Surficial Samples
• ND
© 0.005-0.19 mg/kg
O 0.20-1.9 mg/kg "
• 2.0-2.3 mg/kg
Mnnesota Slip
SlipC
Mller Creek
Mercury (mg/kg dry wt.)
Mean = 031
Median = 0.22
Minimum = 0.005
Maximum = 2.3
Heardng Island
Duluth, MN
A
Notes:
Ontario LEL = 0.2 nrg/kg
Ontario SEL= 2 mg/kg
i
2
F
Kilometers
3
-i
Lake Superior
Figure 2 Distribution of surficial mercury c»ncaitrations (mg/kg dry wt) in the Duktth/Superior Harbor
xviii
-------
Total PCBs: Surficia! Samples
• ND
O 4.0-9.9
• 10.0-69,9
O 70.0-450
Duluth, MN
Mller Creek
WLSSD
Total PCBs (ng/kg dry wt.)
Mean = 99.7
Median = 68.0
Minimum = 4.3
Maximum = 439
Lake Superior
KJmballs Bay
Superior, Wl
Notes:
Ontario NEL=_1 pug/kg
Ontario
Est. Ontario SEL = 19/10% g/kg (at 3.6% OC)
1 0 1 234
i=r i =r— t—^^—
Kilometers
'*nrtemaoMflriCarrt^gTcy
Figure 3. Distribution of surficial total PCB concaitrations (ng/kg dry wt.) in the Duluth/Superior Harbor
xix
-------
Total PAHs: Surficial Samples
• ND
© 30-3,900 jjg/kg
O 4,000-185,OOOMg/kg
Minnesota Slip
SlipC
Mller Creek
Duluth, MN
Total PAHs ((.ig/kg dry wt.)
Mean = 11,900
Median = 4,180
Minimum = ND
Maximum = 185,000
Lake Superior
Grassy Point
N Interlake Steel Superfund Site
A
Hearding Island
Clough
Island
AllouezBay
•
USX Superfund Site
Notes:
Ontario LEL = 4,000ng/kg
Ontario SEL = 360.000 n g/kg (at 3,6% OC)
Figure 4 Distribution of surficial total PAH concentrations (ng/kg dry wt.) in the Duluth/Superior Harbor.
xx
-------
TCDD: Surficial Samples
• ND
• NQ
O <10ng/kg
O > 10 ng/kg
TCDD (ng/kg dry wt,)
Mean = 6.4
Median = 8.9
Minimum = ND
Maximum = 13.0
Duluth, MN
101234
Kilometers
Lake Superior
Figure 5. Distribution of surficial TCDD concentrations (ng/kg dry wt) in the Duluth/Superior Harbor.
xxi
-------
TCDF: Surficial Samples
• ND
• NQ
© <10ng/kg
O >10ng/kg
TCDF (ng/kg dry wt.)
Mean = 8.3
Median = 9.1
Minimum = ND
Maximum = 15.0
Duluth, MN
W.SSD
N
A
Kilometers
Lake Superior
Figure 6. Distribution of surficial TCDF concentrations (ng/kg dry wL) in the Duluth/Supaior Harbor.
-------
Toscaphene; Surficial Samples
• ND
© 40-99|iig/kg
O 100-150f.ig/kg
Minnesota Slip
n
A
Toxaphene (jjg/kg dry wt.)
Mean = 78
Median = 70
Minimum = 44
Maximum = 140
Duluth, MN
Lake Superior
Kimbali's Bay
Superior
Figure 7. Distribution of surficial toxaphene ooncaitrations (ng'kg dry wt) in the Duluth/Superior Haibor.
XXIll
-------
p,p'-DDDando,p'-DDT:
Surficial Sample
• ND
© 0.005 - 7.9 ug/kg
O 8.0-50
Minnesota Slip
SlipC
Miller Creek
p.p'-DDD and o,p'-DDT (ng/kg dry wt.)
Mean = 6.3
Median = 2.43
Minimum = 0.005
Maximum = 48
Duluth, MN
Lake Superior
Grassy Point
Hearding Island
City of Superior VWVTT
Clough
v\ %lancl,
Superior, Wl
Notes:
Ontario LEL = 8ng/kg (for o,p' + p,p'-DDT)
Ontario SEL = 2,600u g/kg at 3.6% OC (for o.p1 + p,p'-DDT)
Figure 8 Distribution of surficial p,p'-DDD and o,p'-DDT concaitrations (jig'kg dry wt) in the Duluth/Supaior Harbor.
x\i\
-------
Arsenic: Surficial Samples
• NO
© 0.4-5.9 mg/kg
O 6.0-32.9 mg/kg
• 33.0-34.0 mg/kg
Arsenic (mg/kg dry wt.)
Mean = 9.6
Median = 6.8
Minimum = 0.4
Maximum = 33.5
Duluth, MN
Lake Superior
Grassy Poi
Heard ng Island
' ,
dough'
Island
Hog Island
Superior, Wl
Burlington Northern
Taconite Facility
USX Superfund Site
Notes:
Ontario LEL= 6 mg/kg
Ontario SEL = 33 mg/kg
Mmejcta Pciufta-vCyrd Agency
Kilometers
Figure 9. Distribution of surficial arsenic concentrations (mg/kg dry wt.) in the Duluth/Superior Harbor.
XXV
-------
Cadmium: Surficial Samples
• ND
© 0,50-0.59 mg/kg
O 0.60-10 mg/kg
Cadmium (mg/kg dry wt.)
Mean = 2.35
Median = 2.03
Minimum = 0.52
Maximum = 7.43
Duluth, MN
C. Reiss Coal Dock
N
Notes:
Ontario LEL = 0.6 mg/kg
Ontario SEL = 10 mg/kg
1
2
h
Kilometers
3
H
Lake Superior
Figure 10 Distribution of surficial cadmium concentrations (mg/kg dry wt) in the Duluth/Superior Harbor
\\\T
-------
Chromium: Surficial Samples
• ND
• 5.0-25.9 mg/kg
O 26.0-109 mg/kg
Chromium (mg/kg dry wt.)
Mean = 35.8
Median = 38.0
Minimum = 5.48
Maximum = 93.8
Duluth, MN
Grassy Point
n
A
Lake Superior
Notes:
Ontario LEL = 26 mg/kg
Ontario SEL = 110 mg/kg
101234
i—i i— i i • ^i i
Kilometers
Figure 11. Distribution of surficial chromium concentrations (mglcg dry wt) in the Duluth/Superior Harbor.
XXVII
-------
Copper: Surficial Samples
• NO
O 4,0-15.9 mg/kg
O 16.0-109 mg/kg
• 110-500 mg/kg
Copper {mg/kg dy wt.)
Mean = 42.3
Median = 29.7
Minimum = 4.11
Maximum = 496
Lake Superior
Mnnfisota Slip
Heard ng Island
Duluth, MN
Dough
island
KJirballs Bay
Superior, Wl
Allouez Bay
O
USX Superfund Site
Notes;
Ontario LEL = 16 mg/kg
Ontario SEL = 110 mg/kg
F-'itajre 12 Distrtbirii
nceritrabons (iiis/kB dry wt ) in the Duluth/Superior Harbor.
-------
Lead: Surficial Samples
• ND
9 1.5-31.0 mg/kg
O 31.1 -249 mg/kg
• 250-550 mg/kg
Mnnesota Slip
Lead (mg/kg dry wt.)
Mean = 58.2
Median = 15.5
Minimum = 1.5
Maximum = 548
Duluth, MN
Lake Superior
Kimball s Bay
Superior, Wl
Notes:
Ontario LEL= 31 mg/kg
Ontario SEL = 250 mg/kg
1
Kilometers
OHM Ag«*y
Figure 13. Distribution of surficial lead concentrations (mg/kg dry wt.) in the Duluth/Superior Harbor.
xxix
-------
Nickel: Surftcial Samples
• ND
© 3.0-15.9 mg/kg
O 16,0-74.9 mg/kg
• 75.0-120 mg/kg
Nickel (mg/kg dry wt.)
Mean =21.4
Median = 22.7
Minimum = 3.01
Maximum = 118
Hearing Island
Duluth, MN
Grassy Point
IT
A
Notes:
Ontario LEL= 16 mg/kg
Ontario SEL = 75 mg/kg
1
Kilometers
Lake Superior
KJrrtall s Bay
Superior, Wl
Figure 14, Distribution of surficial nickel concentrations (mg/kg dry wi) in the Duluth/Superior Harbor.
XXX
-------
Zinc (mg/kg dry wt)
Mean = 240
Median = 93.1
Minimum = 11.4
Maximum = 3,780
Zinc: Surficial Samples
• ND
O 10-119 mg/kg
O 120-819 mg/kg
• 820 - 3,800 mg/kg
Heard ng Island
Duluth, MN
Lake Superior
Barker's Island
Clougn ,
Island
* *JMfj/
AllouezBay
O
Superior, Wl
USX Superfund Site
Notes:
Ontario LEL = 120 mg/kg
Ontario SEL = 820 mg/kg
Figure 15. Distribution of surficial zinc concentrations (mg/kg dry wt.) in the Duluth/Superior Haitwr.
xxxi
-------
Nickel: Surficial Samples
• ND
© 3.0-15.9 mg/kg
O 16,0-74.9 mg/kg
• 75.0-120 mg/kg
Nickel (mg/kg dry wt.)
Mean =21.4
Median = 22.7
Minimum = 3.01
Maximum = 118
Hearing Island
Duluth, MN
Grassy Point
i-t
A
Notes:
Ontario LEL= 16 mg/kg
Ontario SEL = 75 mg/kg
1
Kilometers
Lake Superior
Kimball s Bay
Superior, Wl
Figure 14, Distribution of surficial nickel concentrations (mg/kg dry wi) in the Duluth/Superior Harbor.
XXX
-------
Table 2. Continued.
Site
DSH36
DSH 17
DSH 12
DSH 35
DSH 19
DSH 29
DSH 10
Total
RCF Value
35
30
30
25
23
22
22
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, p.p'-DDE,
p,p'-DDD & o,p'-DDT, Phe, Fla,
Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PAHs, Fie, Phe, Ant, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, p.p'-DDE,
p,p'-DDD & o.p'-DDT, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp
Hg, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Fie, Phe,
Fla, Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, Cd, Cu, Pb, Zn, total
PCBs, total PAHs, Fie, Phe, Ant,
Fla, Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Fla, Pyr,
Baa, Cry, Bfa, Bap
Exceed SEL?
Significant Toxicity Text Results?
H. azteca2
Incon.
Incon.
Incon.
Incon.
Incon.
C. tentans
-
Microtox
X
X
X
X
X
X
Mutatox
X
X
X
X
Priority for Further Study/Comments
High; high Hg in 122-216 cm core segment,
high PCBs in most deeper core segments
High; surficial PCB sample lost for this site
and could not be included in total RCF
calculation
High; high Hg in 163-180 cm core segment,
PCBs elevated in other core segments but
less than surface
Medium; high Hg in 31-61 cm core segment
Medium; high Hg in 31-61 cm core segment
Medium; high Hg and PCBs in all deeper
core segments
Medium
-------
Table 2. Continued.
Site
DSH03
DSH32
DSH37
DSH 13
DSH 18
DSH 16
DSH 26
DSH 01
DSH 28
Total
RCF Value
21
20
19
18
18
18
17
16
14
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Phe, Fla,
Pyr, Baa, Cry, Bfa, Bap, Idp
Hg, Cd, Cu, Pb, total PCBs,
total PAHs, Fie, Phe, Ant, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
Cry, Bfa
As, Cd, Cr, Cu, Ni
As, Cd, Cr, Cu, Ni,
total PCBs, p,p'-DDD & o.p'-DDT
Hg, As, Cd, Cr, Cu, Ni, Zn,
total PAHs, Phe, Pyr, Bfa, Bap, Bgp
As, Cd, Cr, Cu, Ni
As, Cd, Cr, Cu, Ni, Pyr, Bfa
Exceed SEL?
Significant Toxicity Text Results?
H. azteca2
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
C. tentans
-
Microtox
X
X
Mutatox
X
X
X
X
X
X
Priority for Further Study /Comments
Medium; higher PCBs than surface in
61-91 cm core segment
Medium; higher Hg than surface in 31-61 cm
core segment
Medium; higher Hg than surface in 31-61 cm
and 61-91 cm core segments
Medium
Medium
Medium; higher Hg than surface in 81-122
cm core segment, higher PCBs than surface
in 51-81 cm core segment
Low
Low; higher PCBs than surface in 61-91 cm
core segment
Low
XXXIV
-------
Table 2. Continued.
Site
DSH33
DSH23
DSH30
DSH38
DSH22
DSH21
DSH 15
DSH 14
DSH 06
DSH 20
DSH 04
DSH 09
DSH 02
DSH 27
DSH 07
DSH 39
DSH 05
DSH 08
Total
RCF Value
13
12
11
10
9.4
8.6
8.3
8.2
7.3
6.3
5.9
5.6
5.2
5.1
4.6
3.5
3.4
-
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, As, Cd, Cr, Cu, Ni
Hg, Cd, total PCBs, total
PAHs, Fie, Phe, Ant, Fla, Pyr, Baa,
Cry, Bfa, Bap, Idp, Bgp
Hg, Cd, Cr, Cu, Ni
Cd, Pb, total PCBs,
total PAHs, Phe, Pyr, Baa, Cry, Bfa
As, Cd, Cr, Cu, Ni
Cd, Cr, Ni, Bpg
Hg, Cd, Cr
Cd, Cr, Cu, Ni, Bfa
Cd, Cr, Ni
Cd
Cd
Cd, Bfa, Bgp
Cd, total PCBs
Cd
Cd
Cd
No vibracore sediment sample collected
Exceed SEL?
Significant Toxicity Text Results?
H. azteca2
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
C, tentans
-
X
Microtox
X
X
X
X
Mutatox
X
X
X
X
X
X
X
Priority for Further Study/Comments
Low
Low
Low
Medium; higher Hg and PCBs than surface
in 31-61 cm core segment
Very Low
High; high PAHs (RCF = 22) observed at
this site when it was resampled in 1994
Very Low
Very Low
Very Low
Very Low
Very Low
Very Low
Low; high surficial PCBs, other core
segments not analyzed for PCBs
Very Low
Very Low
Very Low
Very Low
Insufficient information to evaluate
'Codes: Fle = Fluorene; Phe = Phenanthrene; Ant=Anthracene; Fla=Fluoranthene; Pyr=Pyrene;
Baa=Benz(a)anthracene; Cry=Chrysene; Bfa=Benzofluoranthene; Bap=Benzo(a)pyrene;
Idp = Indeno( 123-cd)pyrene; Dba=Dibenz(a,h)anthracene; Bgp=Benzo(g,h,i)perylene
2Incon. = Inconclusive test results due to control failure
-------
CHAPTER 1
INTRODUCTION
1.1 BACKGROUND
The Duluth/Superior Harbor has been designated as part of the St. Louis River Area of
Concern (AOC) by the International Joint Commission (IJC) (Figure 1-1). This designation
resulted from the 1978 Great Lakes Water Quality Agreement between the United States and
Canada. The Stage I Remedial Action Plan (RAP), prepared jointly by Minnesota and
Wisconsin state agencies, identified sediment contamination within the estuary as a primary
factor impairing many beneficial uses, including: fish consumption, dredging activities,
aesthetics, and fish, wildlife, and benthic populations and habitat [Minnesota Pollution
Control Agency/Wisconsin Department of Natural Resources (MPCA/WDNR), 1992].
Contaminants of concern in the sediments include: mercury (Hg), polychlorinated biphenyls
(PCBs), 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), polycyclic aromatic hydrocarbons
(PAHs), and a variety of other metals and organic compounds. The following areas of the
AOC have been identified as having elevated levels of sediment contaminants
(MPCA/WDNR, 1992):
• Embayment that receives discharge from the Western Lake Superior Sanitary District
(WLSSD) in Duluth, MN, and historically received discharge from a previous sewage
treatment plant
• Interlake/Duluth Tar Superfund site in Duluth, MN
• U.S. Steel (USX) Superfund site in Duluth, MN
• Newton Creek and Hog Island Inlet of Superior Bay in Superior, WI
• Crawford Creek Wetland/Koppers Co. hi Superior, WI.
During the past four years, the MPCA has been actively involved in delineating the extent of
sediment contamination hi the St. Louis River AOC. These studies include:
• Preliminary assessment of contaminated sediments and fish in the Thomson, Forbay,
and Fond du Lac Reservoirs (Schubauer-Berigan and Crane, 1996)
• Survey of sediment quality in the Duluth/Superior Harbor: 1993 sampling results of
contaminants in depositional areas outside the shipping channels
-------
• Survey of sediment quality in the Duluth/Superior Harbor: 1994 sampling results of
contaminants in hotspot areas
• Regional Environmental Monitoring and Assessment Program (R-EMAP) surveying,
sampling, and testing: 1995 and 1996 sampling results.
The above investigations have been conducted with the cooperation and financial support of
either the U.S. Environmental Protection Agency (EPA) or the Great Lakes National
Program Office (GLNPO). These studies will support the assessment goals of the Phase I
sediment strategy for the RAP. In this report, the results of the 1993 survey of sediment
quality in the Duluth/Superior Harbor will be presented. Reports for the 1994 sediment
survey and R-EMAP project are in the process of being prepared. The status and
distribution of these reports can be determined by contacting Judy Crane at the MPCA office
in St. Paul, MN. The raw data from most of these investigations are being entered into two
similar, but separate, GIS-based databases for the Duluth/Superior Harbor. The databases
are funded by U.S. Army Corps of Engineers and GLNPO. The GLNPO database contains
more quality assurance/quality control (QA/QC) information, and an electronic copy of this
database is included in Appendix A. ,
1.2 PROJECT DESCRIPTION
Sediment contamination in the Duluth/Superior Harbor is of concern, not only for the
impairment of beneficial uses identified in the RAP (MPCA/WDNR, 1992), but also because
of the close proximity to Lake Superior. Sediments in this AOC are likely to be a source of
contaminants to Lake Superior through mechanisms such as resuspension, partitioning to the
water column, advective transport, volatilization, and biotic uptake. Thus, it is important to
reduce the loading of contaminants to Lake Superior to protect this natural resource.
Previous to this investigation, sediments in the Duluth/Superior Harbor had not been well
characterized for either contaminants or toxic effects. In addition, historical sources of
contaminants have not been characterized for the entire St. Louis River AOC. Over time,
sections of the harbor have been filled hi with material that may have been obtained from
unknown, contaminated sites. Therefore, it may be difficult to determine potentially
responsible parties at some sites.
The Stage I RAP report (MPCA/WDNR, 1992) identified a critical need for an estuary-wide
sediment survey measuring horizontal and vertical chemical concentrations, as well as
toxicity to benthic organisms. This project, by simultaneously analyzing areas known to be
contaminated, as well as unknown sites, was intended to provide a consistent framework for
-------
prioritizing remedial sediment activities at contaminated sites, as well as suggesting
contaminants and endpoints of concern for each site for any future investigations.
The MPCA surveyed 40 sites in depositional areas of the Duluth/Superior Harbor during the
fall of 1993 and summer of 1994. Most of the sites were selected for sediment analysis
based on known proximity to current or former source discharges. Two sites were selected
as indicators of ambient sediment conditions in areas not known to be affected by point
sources, although effects from nonpoint sources could not be determined. Six sites were
selected for the assessment of site variability within a spatially large depositional area (the
WLSSD/Miller Creek Bay), and four sites for a spatially small depositional area (Slip C).
1.3 PROJECT OBJECTIVES
The primary objectives of this investigation were to:
• Quantify the level of sediment contamination in selected sections of cores from the
Duluth/Superior Harbor. Contaminants of concern included: mercury, tributyltin and
other priority metals [i.e., arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu),
lead (Pb), nickel (Ni), and zinc (Zn)], thirteen pesticides, PCBs, 2,3,7,8-TCDD and
2,3,7,8-tetrachlorodibenzofuran (TCDF), PAHs, ammonia (NH3+), and total organic
carbon (TOC).
• Compare the utility of two screening-level analytical techniques (i.e., PCB
immunoassay and PAH fluorometry) with detailed methods for the semi-quantitation of
PCBs and PAHs.
• Measure vertical distributions of PCBs, mercury, TOC, and PAHs (using a PAH
fluorescence screening method) at up to five strata at all sites.
• Assess the toxic potential of surficial sediments to two benthic macroinvertebrates (i.e.,
Hyalella ayteca and Chironomus tentans).
• Assess the acute toxicity and genotoxicity of surficial sediments to two different
microbes.
• Date the presence of identified chemicals by 137Cs on a subset of sediment cores.
• Prioritize areas for more intensive site surveys in the future.
-------
St. Louis River Area of Concern
Lake Superior
St.Louis River
Cloquet\
Nemadji River
Figure 1-1. Site map of the St. Louis River AOC.
-------
CHAPTER 2
METHODS
2.1 FIELD METHODS
2.1.1 Preliminary Site Selection
A "worst-case" sampling design (U.S. EPA, 1992a) was used to select preliminary sites for
this investigation. Final site selection occurred while in the field as described in Section
2.1.2. The "worst-case" sampling design incorporated available historical information on
contamination, sources, bathymetry, currents, and other factors (U.S. EPA, 1992a). This
sampling design was appropriate since one of the goals of this study was to identify the most
heavily contaminated areas downstream of the Fond du Lac dam, rather than to provide data
on the overall quality of the sediments in the Duluth/Superior Harbor. Thus, this study
could be used to determine the potential for a contamination problem, which could be
followed up with more complete sampling at a later date.
Suspected contaminant hotspots were identified either from sediments determined to be
contaminated in previous studies (MPCA/WDNR, 1992; Glass et al., 1993) or by evaluation
of likely sources of contamination due to past or continuing point sources. The USX and
Interlake Steel/Duluth Tar Superfund sites were selected for evaluation of sediment
contamination within the St. Louis River outside of the boundaries initially established during
the remedial investigations (Barr Engineering, 1985; Malcolm Pirnie, 1991). Navigational
maps of the St. Louis River and Duluth/Superior Harbor were evaluated to identify areas of
high deposition for sampling at other sites in the study area.
2.1.2 Sediment Collection
Sediments for chemical analyses and toxicity testing were collected on board the U.S. EPA's
R/V Mudpuppy, a monohull aluminum barge with an overall length of 9.2m, a 2.4m beam,
and a draft of 0.5 m (Smith and Rood, 1994). This vessel was designed for collecting deep
cores in depositional areas, and can be operated in shallow, confined areas. The Mudpuppy
was equipped with Loran positioning capabilities, an electric generator, two electric winches
(110-volt AC and 12-volt DC), a vibracoring system, and a horizontal, bow-mounted boom
with 746 kg lifting capacity for lifting cores (Smith and Rood, 1994). In addition, a GPS
unit was employed with post-survey correction to locate coring positions.
-------
Actual coring locations were selected by first determining the extent of soft, depositional
sediments within each sampling area. This was achieved using one of two methods. One
method involved informally surveying the area with a shallow draft, 7.3 m boat prior to
sampling. The bottom substrate was examined with a small modified Hongve gravity corer,
to determine suitability for sampling with the vibracorer, and the selected location was then
flagged using a small buoy. A second method of locating sampling positions was to sample
with the small gravity corer, while on the Mudpuppy, at randomly selected locations until a
suitable substrate was obtained. The number of attempts required to locate depositional
sediments was noted in the field notebook. Table 2-1 and Figures 2-1 and 2-2 indicate the
sites examined in this study.
Sediment chemistry analyses, with the exception of tributyltin, were performed on 30-cm
sections of sediment obtained from a 3-m vibracore sample. As decided prior to the survey,
the cores were sectioned hi 30 cm intervals, beginning with the surface sediment layer.
Samples for tributyltin analyses were collected using only the top 10 cm of the small gravity
corer in order to collect a more intact surface layer. The vibracoring system may not always
collect intact surface layers. However, vibracoring is a versatile and efficient method for
collecting long sediment cores (Smith and Rood, 1994).
Vibracore samples were collected as described in Smith and Rood (1994). The vibracorer
head was attached to a stainless steel 3-m core tube containing a 2-mm (wall thickness), clear
polyethylene core tube liner. In brief, cores were collected by lowering the vibracorer into
the water column, using an electric winch, until the nose cone contacted the sediment
surface. The vibracoring head was then powered up while slowly releasing the tension on
the cable supporting the vibracorer. The sampler was maintained upright by releasing
tension on the cable while the vibracorer penetrated the sediment surface. Sediment refusal
depth was defined as the point at which cable tension could not be further released (i.e., the
point at which the vibracorer could penetrate no further into the sediment).
A Ponar grab sampler was used to collect sediment samples within 2 m of the vibracore
sample. These sediments were used for the MicrotoxR, MutatoxR, and sediment toxicity
tests.
2.2 LABORATORY METHODS
Standard operating procedures (SOPs) for the chemical analyses and toxicity assays are
appended to the Quality Assurance Project Plan (QAPP) for this project (Schubauer-Berigan,
1993). The methods and relevant QA/QC parameters are cited here for reference purposes.
-------
2.2.1 Chemical Analyses
2.2.1.1 Established Methods
Established methods were used to measure the following analytes: 2,3,7,8-TCDD and
2,3,7,8-TCDF; Aroclor and congener PCBs; PAHs; thirteen pesticides; arsenic (As) copper
(Cu), chromium (Cr), cadmium (Cd), lead (Pb), mercury (Hg), nickel (Ni), tributyltin, and
zinc (Zn); ammonia; total organic carbon (TOC); and 137Cs. These analytical methods are
summarized in Tables 2-2 and 2-3. In summary, sediment measurements of 2,3,7,8-TCDD
and TCDF were performed by high resolution gas chromatography/low resolution mass
spectroscopy (GC/MS) using acid/base, silver nitrate/silica gel, copper, alumina, and carbon
columns for cleanup. EPA SW 846 method 8081 (capillary column GC) was used for the
PCS Aroclors/congeners in sediments, using Florisil for cleanup. Individual PAHs were
analyzed using Method 8270 (with Soxhlet extraction); pesticides were measured using the
same method and GC/electron capture detection (ECD). Mercury was measured via method
EPA 245.5 by cold-vapor atomic absorption spectroscopy (AAS), using high-temperature
acid digestion cleanup. Most of the remaining metals (As, Cd, Cr, Cu, Ni, Pb, and Zn)
were measured using U.S. EPA/ACOE method 81-1. Metals were also measured using X-
ray metals analysis. Tributyltin was measured using GC/flame photometric detection (FID).
TOC was measured by the sample ignition method using U.S. EPA/Army Corp of Engineers
(ACOE) method 81-1. Ammonia was measured using Agronomy Soils Method 33-3 (KC1
extraction). Selected sediment cores were analyzed for 137Cs as detailed in the QAPP
(Schubauer-Berigan, 1993). 137Cs concentrations corresponding to the dates 1954 and 1964,
based on the initiation and peak, respectively, hi analyte concentrations were determined.
2.2.1.2 Screening Methods
Two screening methods, the PAH fluorometric screen and PCB immunoassay, were used in
this investigation (Tables 2-2 and 2-3). Method modifications were made where necessary.
For example, in the PCB immunoassay, sediments were dried prior to analysis in order to
improve the method quantitation limit and facilitate comparison with the GC/ECD PCB
analysis (in which sediments were also dried). Several methodological alterations were made
in the PAH fluorescence screen. These changes necessitated the preparation of a new SOP
from that initially included in the QAPP.
-------
2.2.2 Toxicity Tests
2.2.2.1 Benthic Invertebrate Tests
The parameters for the toxicity tests are described in Tables 2-4 and 2-5. The use of
Hyalella azteca and Chironomus tentans as sensitive species for determining toxicity of
freshwater sediments followed modified procedures described in ASTM (1993). However,
the specific test system to be used for these assays is not indicated in the methods. The
toxicity tests were conducted by the MFC A in accordance with ASTM methods, and used a
portable mini-diluter system described in Benoit et al. (1993). Three replicates of each
sample were tested. Sediment from West Bearskin Lake (Gunflint Trail, MN) was used as
the control sediment. The acute (mortality) and chronic (growth) tests were conducted for 10
days, with an assigned overly ing water renewal schedule of 2 volume additions per day.
Overlying water for the tests was nonchlorinated well water. The overlying water was
monitored daily for pH, dissolved oxygen, and temperature. Methods for preparing
glassware, food, reconstituted water, and for performing reference toxicant tests and
acute/chronic toxicity tests are described in the QAPP for this survey.
The Hyalella azteca and Chironomus tentans tests were required to meet QA requirements
such as acceptable control sediment survival (mean survival of 80% for H. azteca and 70%
for C. tentans), and acceptable performance on reference toxicant tests (i.e., test results
within 2 standard deviations of the running mean for all monthly tests). Reference toxicant
tests were not performed with C. tentans, because they do not survive well hi water-only
tests.
2.2.2.2 MicrotoxR and MutatoxR Tests
The procedures for the MicrotoxR and MutatoxR tests with Photobacterium phosphoreum and
Vibrio fischeri, respectively, are described in the product manual (Microbics Inc., 1993).
Sediment interstitial porewater was used as the test phase, because it is less expensive than
the whole sediment assay and also allows dilution of the test medium so that relative toxicity
can be ascertained. The porewater was prepared by centrifugation and was tested unfiltered
within 48 hours of preparation. In the MicrotoxR test, all sediments were initially screened
for toxicity using the 90% whole porewater assay. Those sediments that were toxic were
subjected to the porewater EC50 dilution test (i.e., the effective concentration at which
luminescence was reduced to 50% of the control luminescence), beginning with 100%
porewater concentrations and diluting up to four-fold. The EC50 was calculated graphically
using system software.
8
-------
1993 Sediment
Sampling Sites
8
20
N
A
Duluth, MN
Hearding Island
7 Lake Superior
Kilometers
Figure 2-1. Location of sediment sampling sites in the Duluth/Superior Harbor.
-------
Figure 2-2. Detailed map of site locations in the vicinity of WLSSD and Slip C
-------
Table 2-1. Summary of site codes, descriptions, and reasons for inclusion in the 1993 Duluth/Superior Harbor sediment
assessment. Sites in Wisconsin are bold and italicized, whereas sites in Minnesota are in normal typeface.
Site
Number
Site Description
Reason for Inclusion in this Study
DSH 01 Burlington Northern Taconite facility (Superior)
DSH 02 Barkers Island Channel, East End (Superior)
DSH 03 Off Superior POTW
DSH 04 Public launch area, Minnesota Point
DSH 05 Off Superior Fiber Products former discharge
DSH 06 Base of East Gate Basin, Superior
DSH 07 Hoarding Island deep hole
DSH 08 Corps of Engineers vessel yard
DSH 09 Near Globe Elevators (Superior)
DSH 10 Interstate Island deep hole
DSH 11 WLSSD, just west of outfall
DSH 12 Old 21st Ave. W. Channel
DSH 13 DM&IR taconite storage facility
DSH 14 East of Erie Pier (Scrap yard at International
Welders & Machinists)
high usage as a taconite loading facility
represent conditions in Barker's Island Marina; heavy use by
recreational boaters
represent conditions off the POTW outfall
represent conditions along Minnesota Point, near an area
receiving relatively heavy recreational boating use
proximity to a former discharger in the harbor
previous investigation found relatively high concentrations of
copper and other heavy metals in dredged sediments from the
East Gate Basin
contaminant/toxicity information is needed to determine whether
this site can be used as a demonstration project for habitat
creation in and around Hearding Island
high usage marina along Minnesota Point
represent conditions in the large bay south of Howard's Bay
area is being considered for various habitat creation projects
proximity to a current discharger
assess contaminant profile of sediments filling in this channel
evaluate potential contamination associated with ore loading at a
site just outside the limestone dock of this facility
evaluate the effect of runoff from the scrapyard and Erie Pier
11
-------
Table 2-1. Continued,
Site
Number
Site Description
DSH 15 West of Incan Superior dock
DSH 16 North of M.L. Hibbard plant/DuIuth Steam District
(DSD) No. 2
DSH 17 South of M.L. Hibbard plant/DSD No. 2
DSH 18 Loon's Foot Landing Inlet (Superior)
DSH 19 C. Reiss coal dock
DSH 20 Channel between Hearding Island and Park Point
DSH 21 Mouth of Stryker Embayment
DSH 22
Near Stryker Embayment, just west of current channel
DSH 23 Across channel from Tallas Island, east of buoy
DSH 24 Off Un-named Creek (USX Superfund site)
DSH 25 Near Wire Mill Settling Pond (USX Superfund site)
DSH 26 Mud Lake (near ME International)
DSH 27 Kimballs Bay (no known contaminant source)
Reason for Inclusion in this Study
represent sediment conditions in St. Louis Bay, along the
Wisconsin shoreline
Glass et al. (1993) found high mercury concentrations in this area
same reason as for DSH 16
determine if contamination from Hog Island Inlet could be
affecting this area
determine contamination resulting from this coal loading facility
address citizen and RAP Committee concerns about elevated
mercury concentrations in sediments behind Hearding Island
address the extent of contamination outside the bay to resolve a data
gap in the Remedial Investigation/Feasibility Study (RI/FS) for the
Interlake Steel/Duluth Tar Superfund site
concern over the potential transport of contaminated sediment from
Stryker Bay to the ship channel; this area has been considered in
the past for possible channel extension
evaluate sediment quality downstream of the USX Superfund site
RI/FS suggests the site is contaminated with heavy metals and PAHs
same reason as for DSH 24
proximity to two industrial dischargers, ME International and USX
reference site to evaluate "background" concentrations of
contaminants
-------
Table 2-1. Continued.
Site
Number
Site Description
Reason for Inclusion in this Study
DSH 28 Allouez Bay, Superior
DSH 29 Slip C (near end)
DSH 30 New Duluth (site of old paint factory)
DSH 31 Fraser Shipyards, first slip west of drydocks # / and 2
DSH 32 Across Howard's Bay Channel from Fraser Shipyards Slip
DSH 33 305 m S-SW of WLSSD outfall
DSH 34 91 m SE of WLSSD outfall
DSH 35 24 m W of Rice's Point, E of 21st Ave. W. Channel
DSH 36 61 m S of Coffee Creek outfall and near Miller Creek Outfall
sewers
DSH 37 Slip C, in front of Superwood plant
DSH 38 Slip C, near Great Lakes Towing Co,
DSH 39 Slip C, just up from Cutler Magner Co.
DSH 40 Minnesota Slip, near William Irvin ore boat
assess potential contamination from the former City of Superior
landfill on Wisconsin Point
assess intra-site variability of potential contamination at this site
assess sediment contamination downstream of an old paint factory
WDNR suggested sediment contamination existed in this area,
primarily from heavy metals
same reason as for DSH 31
proximity to a current discharger; assess intra-site variability
same reason as for DSH 33
same reason as for DSH 33
assess contamination from the Miller and Coffee Creek storm
same reason as for DSH 29
same reason as for DSH 29
same reason as for DSH 29
historical industrial and shipping operations in the vicinity of this
slip
13
-------
Table 2-2. Summary of sediment analytical methods.
Analyte
Method
(description)
Sample cleanup
Precision
Accuracy
2,3,7,8-TCDD
& 2,3,7,8-TCDF
PCBs
PAHs
Pesticides
Hg
As
Cd, Cu, Pb
Zn, Ni, Cr
SW846
(GC/MS)
EPA SW846--8081
(capillary column GC)
Method 8270
(capillary column GC)
Method 8270
(capillary column GC)
EPA 245.5
(cold vapor AAS)
EPA 206.5
(hydride generation)
Nitric acid/hydrogen peroxide
digestion. Flame/furnace AAS
acid/base, AgNO3/silica gel, 50% RPD
Cu, alumina, carbon
Florisil 50% RPD
GPC 50% RPD
Soxhlet extraction 50% RPD
N/A 50% RPD
N/A 50% RPD
N/A 50% RPD
+50%
50-120%
18-137%
50-120%
80-120%
80-120%
80-120%
-------
Table 2-2. Continued.
Analyte
Tributyltin
Ammonia
TOC
137Cs
PCB Immunoassay
X-ray metal analysis
PAH fluorometric
analysis
Method
(description)
N/A
KC1 extraction (Soils method
33.3: exchangeable ammonia)
Total organic carbon
Sample ignition method 1
Radioisotope counting
N/A
N/A
N/A
Sample cleanup
None
N/A
N/A x v
N/A
Drying
None
None
Precision
30% RPD
50% RPD
50% RPD
N/A
50% RPD
50% RPD
50% RPD
Accuracy
75-125%
80-120%
80-120%
85-115%
60-140%
60-140%
60-140%
15
-------
Table 2-3. Summary of quality assurance parameters for sediment analytical methods.
Analyte
2,3,7,8-TCDD
& 2,3,7,8-TCDF
PCBs
PAHs
Pesticides
Hg
As
Cd, Cu, Pb
Zn, Ni, Cr
Calibration
initial ongoing
5
3
5
3
4
4
4
pt. curve
pt. curve
pt. curve
pt. curve
pt. curve
pt. curve
pt. curve
Every
Every
Every
Every
Every
Every
Every
7 samples
12 samples
12 samples
12 samples
20 samples
20 samples
20 samples
Blanks
Every
Every
Every
Every
Every
Every
Every
7 samples
7 samples
20 samples^ v
7 samples
20 samples
20 samples
20 samples
IDL1
1 pg/g
10 ng/g
33 ng/g
4 ng/g
2.6 ng/g
10 ng/g
100 ng/g
100 ng/g
MDL1
1.1
10
Pg/g
ng/g
330 ng/g
20
13
ng/g
ng/g
100 ng/g
Cd
All
: 0.5
rest:
mg/kg
1 mg/kg
1 IDL, Instrument Detection Limit: the concentration equivalent of the analyte signal which is equal to three times the standard
deviation of a series of ten replicate measurements of a reagent blank signal at the same wavelength.
2 MDL, Method Detection Limit: the minimum concentration of a substance that can be measured and reported with 99%
confidence that the analyte concentration is greater than zero.
-------
Table 2-3. Continued.
Analyte
Calibration
initial ongoing
Blanks
IDL
MDL
Tributyltin
Ammonia
TOC
137Cs
3 pt. curve Every 12 samples Every 12 samples
3 pt. curve Every 20 samples Every 20 samples
% of SRM Every 20 samples Every 20 samples
4 pt. curve Every run
Every 10 samples
PCB Immunoassay 4 pt. curve Every 20 samples Every 20 samples
X-ray metal analysis 4 pt. curve Every 20 samples Every 20 samples
PAH fluorometric 4 pt. curve Every 20 samples Every 16 samples
analysis
2.5 ng/g (as Sn) 5 ng/g (as Sn)
500 ng/g
0.1%
N/A
8.3 ng/g
see SOP
N/A
1000 ng/g
N/A
60 ng/g
N/A
17
-------
Table 2-4. Summary of toxicology methods.
Analyte
Method #
(description)
Sample cleanup
Precision
Accuracy
Photobacteriumphosphoreum Microbics Inc., 1993
MicrotoxR (Porewater 90% screen/
100% dilution EC50 assay)
None
30% RPD
Acceptable control
performance
Vibrio fischeri
MutatoxR
Hyalella azteca
toxicity tests
Chironomus tentans
toxicity tests
Microbics Inc., 1993 None
(100% genotoxicity assay)
ASTM E 1383 None
(10-day test)
ASTM E 1383 None
(10-day test)
N/A
50% RSD
50% RSD
NaCl Reference
toxicity test
N/A
-------
Table 2-5. Summary of quality assurance parameters for sediment toxicology methods.
Analyte
Calibration
initial ongoing
Blanks
IDL
ng/g
MDL
ng/g
Photobacterium phosphoreum N/A
MicrotoxR
N/A
Diluent water
N/A
Vibrio fischeri
MutatoxR
N/A
N/A
Diluent water
N/A
Hyalella azteca
toxicity tests
Chironomus tentans
toxicity tests
N/A
N/A
N/A
N/A
West Bearskin L.
control sediment
West Bearskin L.
control sediment
N/A
N/A
19
-------
CHAPTERS
RESULTS AND DISCUSSION
3.1 SITE LOCATIONS AND FIELD OBSERVATIONS
3.1.1 Site Locations, Water Depth, and Core Sections Analyzed
Sediment sampling was conducted during September 13-28, 1993. As discussed in Section
3.2.8.1, it was also necessary to collect five additional sediment samples on May 11, 1994
for PAH analyses. The rest of this section will pertain to the 1993 field sampling effort.
Site coordinates for this survey were to be identified using a Loran and Global Positioning
System (GPS). However, the 1993 GPS coordinates were not usable due to operator error.
The Loran coordinates were recorded in the field notebook; subsequent mapping of the Loran
coordinates using GIS showed most of the positions to be far off the actual locations
sampled. Therefore, because most of the locations were sampled in fairly well-defined slips,
bays or channels, it was decided to use field information to locate the sites as precisely as
possible on the National Oceanographic and Atmospheric Administration (NOAA) chart for
the Duluth/Superior Harbor; this was done while in the field as a backup to the Loran and
GPS methods. The geographic positions of the coordinates were determined to within 1/2
second by interpolation of the sites on the NOAA chart. The resulting positions are indicated
in Table 3-1.
The Corps of Engineers vessel yard (DSH 08) was highly unsuitable for contaminant
assessment due to a stone and sand substrate. No vibracore sample could be collected here;
a Ponar grab sample was collected for toxicity testing and butyltin analysis. Similarly, the
substrate was too sandy to take a vibracore sample at the east end of Barkers Island Channel
(DSH 02); two Ponar samples were taken from this site for sediment chemistry and toxicity
testing. A problem was also encountered with collecting the vibracore sample off the
Superior Fiber Products former discharge (DSH 05). A full core could not be collected at
DSH 05 due to water washing through the core; approximately 30 cm of the core length was
retrieved. A Ponar grab sample was collected at DSH 05 for additional sediment chemistry
and toxicity testing.
20
-------
One site was initially intended to assess contamination within Hog Island Inlet, in the context
of comparison to contamination in the rest of the Duluth/Superior Harbor. Hog Island Inlet
and its tributary, Newton Creek, have been under intensive monitoring by the WDNR due to
elevated levels of ammonia, certain PAHs, and heavy metals. Sampling the inlet proved
impossible, as the R/V Mudpuppy could not pass through its extremely shallow mouth from
the harbor. Therefore, in consultation with researchers at the WDNR (who were present on
the boat), it was decided to analyze contaminants present at a site in Loon's Foot Landing
Inlet (DSH 18). This area was not analyzed intensively during the WDNR survey, and it
was unknown to what extent contamination from Hog Island Inlet could be affecting this area
(Scott Redman, WDNR, personal communication, 1993).
The water depth at the point of core collection is shown in Table 3-2. The shallowest site
sampled with the R/V Mudpuppy was DSH 05 (off the Superior Fiber Products former
discharge) at less than 30 cm. The deepest site at which sediment was collected was DSH 07
(Hearding Island deep hole) at 8.4 m. The majority of sites at which sediment cores were
collected were less than 3 m deep. The median water depth at the sites sampled was 2.3 m.
>
The median core length collected from the Duluth/Superior Harbor was 122 cm. If the core
was longer than 120 cm, the fifth core section comprised the bottom 30 cm of the core
length. Table 3-1 shows the depth of the core sections collected at each site. Twenty-one
core sites were less than or equal to 120 cm in length, probably due to refusal by stiff clay,
sand, wood chips, or bedrock. The longest cores were approximately 230 cm in length and
were obtained at the following sites: DSH 13 (DM&IR taconite storage facility), DSH 19 (C.
Reiss coal dock), and DSH 27 (Kimballs Bay).
3.1.2 Sediment Core Depths
Sediment depth measurements given hi this study should be considered as approximate,
especially those cores in deep water sites. These qualifications should be considered for any
future sediment assessments to be conducted, especially if different sampling equipment is
used.
During vibracore sampling, the depth of penetration (i.e., displacement) through the sediment
was measured using 30-cm markings on the head cable. The core length was measured after
extrusion of the core liner on the deck of the R/V Mudpuppy. The retrieved length of core
was calculated as:
21
-------
Retrieved Length (%) = Core Length (cm) x 100
Core Displacement (cm)
Core Compaction (%) = 100 - Retrieved Length (%)
Sites with compaction of the core exceeding 50% are noted in Table 3-2. It should be noted,
however, that there are a number of independent events which can reduce (compress) the
length of the recovered core. Reduction can occur in a core from compression of the
sediments. It can also be caused by the partially filled core tube acting as a solid and
displacing deeper soft sediment layers, from the core catching head assembly displacing soft
surficial sediments, or by vibrations causing liquefaction of unconsolidated surface sediments
inside the core tube. Cores with missing sediments are referred to as discontinuous cores.
In addition, depth of penetration can be overestimated if not taken vertically. The greater the
coring angle from vertical, the longer the length of the recovered core is relative to the actual
sediment depth sampled. In water depths approaching or greater than 3 m, visual
verification of vertical penetration was,-difficult or impossible due to the highly colored
waters. With an unknown combination of these events taking place, it is relatively rare to
recover a continuous core equal to the penetration depth.
3.1.3 Sediment Physical Description
The field descriptions of the Ponar grab samples and vibracore sediment core sections are
given in Tables 3-3 and 3-4, respectively. A wide variety of sediment types were observed
in the Duluth/Superior Harbor. The sediments varied from mostly sand (e.g., DSH 04, DSH
05, DSH 07, DSH 14, DSH 20) to mostly clay (e.g., DSH 03, DSH 06). In general,
sediments from sites near Minnesota Point were predominantly sand, whereas sediments near
the Wisconsin shoreline of Superior Bay were mostly clay. Many cores displayed noticeable
contamination from visual inspections. Sediments from the slips hi Superior Bay, the
WLSSD/Miller and Coffee Creek embayment, and near the USX Superfund site contained
visible oil. Sediment from sites near the M.L. Hibbard/Duluth Steam District (DSD) No. 2
plant contained material which appeared to be gritty fly ash and coal residue. The native
substrate for most of the sediments appeared to be an extremely stiff gray or red clay, which
was reached in most cores by 1 m. Many of the sediment cores contained a band of woody
debris, at variable depth and thickness (Table 3-4), which corresponded to the historical
activities of sawmills adjacent to the harbor near the turn of the century.
22
-------
3.2 CHEMICAL ANALYSES
Chemical results are presented in graphical format in the following sections. In addition,
maps of the surficial contaminant distributions are given in the Executive Summary for
selected contaminants. The analytical data is provided in electronic format in Appendix A.
All chemical concentrations given in this section are reported on a dry weight basis.
In order to interpret the chemical data, it is useful to compare the data to some kind of
benchmark such as a criteria or guideline value. The U.S. EPA has developed draft
sediment quality criteria for five nonionic organic compounds: acenaphthene, dieldrin,
endrin, fluoranthene, and phenanthrene (U.S. EPA, 1994). Additional sediment quality
criteria will be developed by the EPA for nonionic organic compounds and for metals once
the methodology has been approved. The Great Lakes States and EPA Regions will use the
EPA's sediment criteria to assist in the ranking of contaminated sediment sites needing
further assessment, to target hot spots within an area for remediation, and to serve as a
partial basis for the development of State sediment quality standards. These criteria will also
be used to assist in selecting methods yfor contaminated sediment remediation and for
determining whether a contaminated site should be added or removed from its list of
designated Areas of Concern (U.S. EPA, 1994).
The State of Minnesota has not developed sediment quality criteria, or guidelines, for
contaminants. However, other jurisdictions from Canada, the Netherlands, and the United
States (e.g., New York) have developed sediment quality values (Crane et al., 1993) which
may be useful to compare to the results of this investigation. The Ontario Ministry of
Environment and Energy (OMOEE) guidelines may be the most useful to compare to the
results of this survey, because their guidelines are based on freshwater toxicity data. Many
other jurisdictions incorporate marine data into their derivation of guidelines or criteria. The
OMOEE currently uses a three-tiered approach in applying sediment quality guidelines
(Persaud etal., 1993):
• No Effect Level (NEL): the level at which contaminants in sediments do not present a
threat to water quality, biota, wildlife, and human health. This is the level at which no
biomagnification through the food chain is expected.
• Lowest Effect Level (LEL): the level of sediment contamination that can be tolerated
by the majority of benthic organisms, and at which actual ecotoxic effects become
apparent.
23
-------
• Severe Effect Level (SEL): the level at which pronounced disturbance of the sediment
dwelling community can be expected. This is the concentration of a compound that
would be detrimental to the majority of the benthic species in the sediment.
The NEL, LEL, and/or SEL values (given as dry weight) have been included on the graphs
for many of the contaminants listed in the following sections. In some cases, background
levels of contaminants may exceed the LEL value. In this case, the background level should
be used in place of the LEL value. For northeastern Minnesota, there is insufficient data for
most contaminants to determine background concentrations. The OMOEE guidelines are
only used in this report as general benchmark values since they have no regulatory impact in
Minnesota.
3.2.1 Ammonia
Ammonia was measured in two ways in the samples. In the first method, whole sediment
ammonia concentrations were measured using potassium chloride (KC1) extraction. In the
second method, interstitial water was ^extracted using high-speed centrifugation in glass rubes,
and porewater concentrations were measured directly using an ammonium-ion analyzer.
Both measurements were performed in order to properly evaluate the concentrations affecting
biota. While the U.S. Army Corps of Engineers and EPA Region 5 have historically used
whole sediment ammonia concentrations for evaluating potential hazards, the research
community has tended to evaluate ammonia toxicity to benthic organisms based on porewater
concentrations (Schubauer-Berigan et al., 1995).
Table 3-5 shows the whole sediment and porewater ammonia concentrations for the surficial
Duluth/Superior Harbor sediments. The median whole sediment ammonia concentration was
37.8 mg/kg, and the median porewater concentration was 2.8 mg/L. The distribution of
whole sediment ammonia in the Duluth/Superior Harbor sites is shown in Figure 3-1.
The sites with the highest whole sediment ammonia concentrations tended to be associated
with slips in the northern section of the Duluth Harbor basin (DSH 29, DSH 40), the sites
near the two area waste water treatment plants (DSH 11, DSH 12, DSH 34), and the area
near Loon's Foot Landing Inlet (DSH 18). All of these sites exceeded 100 mg/kg which is
the cutoff for Ontario Open Water Disposal Guidelines (Persaud et al., 1993).
Although KCl-extractable concentrations were high for some sediments, the porewater
concentrations were not always correspondingly high hi these sediments. Three of the sites
with high whole sediment concentrations had the highest levels of porewater ammonia
(DSH 40, DSH 34, DSH 29). However, other sites with very low levels of whole sediment
24
-------
ammonia (e.g., DSH 07, the Hoarding Island deep hole, 14.6 mg/kg) had relatively high
levels of porewater ammonia (8.5 mg/L at this site). The reason for this is not known.
None of the porewater concentrations appear to be sufficient to cause toxicity to the benthic
species tested. Chironomus tentans, Hyalella azteca, and Photobacteriwn phosphoreum are
all likely to tolerate ammonia concentrations as high as 16 mg/L at the pH ranges present in
the Duluth/Superior Harbor (Ankley et al. 1990; Schubauer-Berigan et al., 1995).
3.2.2 Total Organic Carbon
TOC was measured in most depth segments of the sediment cores (Figure 3-2, Table 3-6).
Hydrophobic organic contaminants, such as PCBs, preferentially associate with TOC. Thus,
it is useful to normalize PCB concentrations for TOC when comparing the distribution of
PCBs in an area. TOC levels varied widely throughout the survey area. The median,
surficial TOC concentration was 3.4% (n=39) with a range of 0.10 - 39.8% TOC. The
lowest surficial levels (0.1 - 0.5%) were found at very sandy sites, such as the mouth of Slip
C (DSH 39) and the deep hole at Hearding Island (DSH 07). Approximately 82% of the
surficial TOC values were less than 5^6%. In comparison, the OMOEE LEL value is 1%
TOC, and the SEL value is 10% TOC (Persaud et al., 1993). The OMOEE values are
probably too restrictive to compare to TOC concentrations in the Duluth/Superior Harbor as
the median TOC measurement in the deepest core sections was 2.1% (n=19) with a range of
0.14 - 7.3% TOC. Thus, the background concentration of surficial TOC in the harbor is
probably around 2% TOC.
High surficial TOC levels (10-40%) were observed at the area north of the Hibbard/DSH
No. 2 coal storage facility (DSH 16), at Allouez Bay (DSH 28), at the C. Reiss coal dock
(DSH 19), and near Stryker Embayment (DSH 22). The elevated levels in Allouez Bay were
most likely due to the predominance of semi-decomposed plant material (Table 3-4). The
core from DSH 16 was composed of a gritty substance which appeared to be coal. Any coal
in this material would most likely be responsible for the high TOC levels in the upper three
sections of this core. The lower two sections of the DSH 16 core had TOC levels less than
10%. The core from DSH 19 was a dark brown sandy silt which may have contained coal.
For DSH 22, this core was composed of soft brown silt underlain by sand and wood chips.
The elevated levels of TOC in this core may be due to wood chips and other organic
material.
25
-------
3.2.3 Mercury
Mercury was measured in most depth segments of the sediment cores. Surficial mercury
concentrations ranged from 0.005 - 2.3 mg/kg throughout the estuary (Figure 3-3, Table 3-
7). The modal (i.e., most frequent) concentration in the surficial sediments was in the range
of 0.16 - 0.32 mg/kg. The median surficial concentration was 0.22 mg/kg, just above the
OMOEE LEL value of 0.2 mg/kg (Persaud et al., 1993). Surficial concentrations were
highest at the site nearest the discharge from WLSSD (DSH 34; 2.3 mg/kg). Levels at this
site were more than 2.5 times greater than at the next most contaminated site, which was
also near the WLSSD discharge (DSH 11; 0.84 mg/kg).
The mercury core profiles for some of the more contaminated sites are shown in Figures 3-4
to 3-6. The core profiles include three sites hi the vicinity of WLSSD (DSH 12, DSH 34,
and DSH 36), two sites at USX (DSH 24 and DSH 25), and Minnesota Slip (DSH 40).
Although the mercury concentrations at some of these sites (e.g., DSH 24 and DSH 34)
rapidly decreased below the surficial layer, the other sites showed both declines and increases
in mercury concentrations at depth (F4gures 3-4 to 3-6). For these sites, mercury
concentrations dropped to less than 0.10 mg/kg at depths deeper than 30 cm.
The highest mercury concentrations hi the sediment cores were associated with areas with
known industrial discharges and waste production. For example, the 1990 mercury discharge
from WLSSD, the largest waste water treatment plant hi the Lake Superior basin, was
estimated as 22 kg/yr (Tetra Tech, 1996). Some sediment mercury is also probably due to
the atmospheric deposition of mercury resulting from natural degassing of the earths crust
(WHO, 1996) and from combustion of incinerators and coal (Glass et al., 1990), as well as
mining and industrial uses (Tetra Tech, 1996). The Duluth/Superior Harbor used to be a
major port for the storage and transport of coal from the late 1800s to early 1900s; at that
time, coal-powered ships were used to transport the coal. For example, the amount of coal
received by ship at the docks of Superior hi 1883 was 13,430 tons, and it steadily increased
to 6,577,356 tons by 1918 [Ron Peterson, Fraser Shipyards, personal communication
(supported by unpublished shipping information), 1996]. At one time, Superior held the
record of being the greatest coal port hi the world. A coal gasification plant and storage
facility used to be located hi Canal Park, adjacent to Minnesota Slip, and this facility could
have contributed to the historical input of mercury at site DSH 40.
Mercury has also been used as a slimicide hi the pulp and paper industry, and as an
antifouling and mildew-proofing agent hi paints (Friberg and Vostal, 1972 as cited in U.S.
EPA, 1993). Mercury can volatilize from surfaces painted with mercury-containing paints,
26
-------
and it can also be retained as a component of paint chips that have been scraped or
sandblasted from ships. The deposition of paint chips in the sediments of some boat slips
and ship repair areas (e.g., Fraser Shipyards) may have contributed to the mercury load in
the sediments. In addition, upstream sources of mercury hi the St. Louis River have
contributed to the sediment load of mercury in the Duluth portion of the harbor.
Mercury is a contaminant of concern in the Thomson, Forbay, and Fond du Lac Reservoirs,
of which Thomson Reservoir appears to serve as the primary catchment basin for sediment-
associated contaminants (Schubauer-Berigan and Crane, 1996). These reservoirs represent
impoundments of the St. Louis River which drain into the Duluth portion of the harbor. The
greatest concentrations of mercury (up to 2 mg/kg in Thomson Reservoir) correspond to the
period from 1950-1960 (Schubauer-Berigan and Crane, 1996). The surficial levels of
mercury in the reservoirs are now approaching background levels. Thus, historical loadings
of mercury from these reservoirs may have contributed to the historical profile of mercury in
the lower St. Louis River and Duluth Harbor sediments.
Generally, lower mercury concentratipns (i.e., <0.16 mg/kg) were present hi cores taken
from the Superior Harbor basin, except for the Superior POTW. The Nemadji River flows
into this basin. For most of the Superior sites, the concentrations of mercury hi the cores
appears to correspond to background levels for sediments affected only by watershed or
atmospheric inputs of mercury. This statement is supported by data from eighty remote lakes
in Minnesota which exhibited sediment mercury concentrations of 0.034 to 0.33 mg/kg, with
an average of 0.16 mg/kg (Sorensen et al., 1990).
3.2.4 Other Heavy Metals
3.2.4.1 Atomic Absorption Spectroscopy
Arsenic, chromium, copper, cadmium, lead, nickel, and zinc were measured by atomic
absorption spectroscopy hi the surficial core sections of all the study sites except DSH 08
(Table 3-8). All heavy metal concentrations referred to in the following subsections are
expressed as mg/kg (ppm) dry weight. Site DSH 05 has two samples shown; one is a
surficial core sample, and the other (DSH 05—P) is a Ponar sample collected from the same
site.
27
-------
Arsenic
Arsenic concentrations ranged from not detectable to 33.5 mg/kg in the Duluth/Superior
Harbor (Figure 3-7, Table 3-8). The median arsenic concentration among the sites was 6.8
mg/kg with a mean value of 9.6 mg/kg. Arsenic was not detected at eight sites, including
Kimball's Bay (DSH 27). The area of greatest arsenic contamination (33.5 mg/kg) was near
the USX Superfund site off the Un-named Creek discharge (DSH 24). In comparison, the
OMOEE LEL value is 6 mg/kg, whereas the SEL value is 33 mg/kg. Seventeen sites
bracketed this range, with the DSH 24 site slightly exceeding the SEL. Since arsenic was
not detected at several sites, it appears that the other sites were contaminated with arsenic
from anthropogenic sources.
Arsenic is a by-product of nonferrous metal (lead, zinc, and copper) mining and smelting
operations (NAS, 1977 as cited in U.S. EPA, 1993). Thus, arsenic appears to have been
produced as a by-product of operations at USX. The USX Superfund site was utilized by
U.S. Steel from 1915-1979 for the purposes of coke production, steel production, and
materials storage (MPCA/WDNR, 19,92). All effluents from operations in the vicinity of the
Coke Plant were discharged into the St. Louis River via the Un-named Creek. Discharges
from the mill's hot rolling process, pickling, cold rolling, and galvanizing operations were
channeled into the Wire Mill Settling Basin (MPCA/WDNR, 1992).
High arsenic concentrations were also observed at the Burlington Northern Taconite facility
(DSH 01), hi the vicinity of the M.L. Hibbard Plant/DSD No. 2 (DSH 16-17), at the Loon's
Foot Landing Inlet (DSH 18), at the Interstate Island deep hole (DSH 10), and in the vicinity
of WLSSD (DSH 11-12). The sources of arsenic at these sites can not be determined. The
other major anthropogenic sources of arsenic to waterways include the importation of arsenic
compounds for use in rodenticide and other pesticide formulations. Although rodenticides
are frequently applied in harbor areas to control rat populations, it is unknown how much of
this material may have been used in the vicinity of the harbor.
Cadmium
Cadmium concentrations ranged from 0.52-7.4 mg/kg at the sample sites (Figure 3-8, Table
3-8). The median concentration was 2.0 mg/kg, whereas the mean was 2.4 mg/kg. In
comparison, the mean background concentration of surficial cadmium in three northern
Minnesota lakes was not detectable at a detection limit of 0.5 mg/kg (Heiskary, 1996). The
OMOEE LEL value for cadmium is 0.6 mg/kg, whereas the OMOEE SEL value is 10 mg/kg
(Persaud et al., 1993). The SEL value was not exceeded at any of the study sites.
28
-------
The highest cadmium concentrations were observed at the USX Superfund sites (DSH 24-25).
Cadmium is commonly found in zinc, lead, and copper deposits (May and McKinney, 1981
as cited in U.S. EPA, 1993), and is released to the environment during the smelting and
refining of ores. Thus, cadmium would be expected to be found at this site. As described in
the following section, the DSH 25 sample site at USX was extremely contaminated with
copper.
Other anthropogenic sources of cadmium include the following: electroplating, application of
phosphate fertilizers, surface mine drainage, waste disposal operations, as well as the
manufacture of paints, alloys, batteries, and plastics (U.S. EPA, 1993). The contribution of
these sources to the loading of cadmium to the sediments is unknown.
Chromium
Chromium concentrations ranged from 5.5-93.8 mg/kg at the study sites (Figure 3-9, Table
3-8). The median concentration was 38 mg/kg, whereas the mean was 35.8 mg/kg. The
mean and median exceeded the mean^surficial background concentration of 22 mg/kg
chromium observed at three northern Minnesota reference lakes (Heiskary, 1996). The
OMOEE LEL value for chromium is 26 mg/kg, whereas the SEL value is 110 mg/kg. As
with cadmium, the mean level of chromium at the study sites exceeded the LEL value. The
OMOEE has published background levels of some metals for Great Lakes pre-colonial
sediment Horizons, of which chromium was 31 mg/kg (Persaud et al., 1993). Thus, the
OMOEE background value for chromium also exceeded the LEL value.
The relative pattern of chromium contamination at the study sites was similar to that of
nickel, and to a lesser extent, to zinc. The Wire Mill Pond at USX (DSH 25) had the
highest chromium contamination of 93.8 mg/kg. Twenty-seven sites had chromium
concentrations ranging between 30 - 63 mg/kg.
Some of the industrial uses of chromium which may have contributed to contamination in the
Duluth/Superior Harbor include the following: electroplating, steehnaking, and photographic
industries; other industries that use chromium salts; and industries that add chromate
compounds to cooling water for corrosion control (APHA/AWWA/WEF, 1995). The
contribution of any of these sources to contamination in the Duluth/Superior Harbor is
unknown.
29
-------
Copper concentrations ranged from 4.1 - 496 mg/kg at the sample sites (Figure 3-10, Table
3-8). The median concentration was 29.7 mg/kg, whereas the mean was 42.3 mg/kg copper.
In comparison, the mean copper concentration at three northern Minnesota reference lakes
was 16 mg/kg (Heiskary, 1996), and the background copper level in Great Lakes pre-
colonial sediments was 25 mg/kg (Persaud et al., 1993). The OMOEE LEL value for copper
is 16 mg/kg (Persaud et al., 1993) which was less than the median copper concentration
measured at the study sites. The OMOEE SEL value of 110 mg/kg copper was grossly
exceeded at the USX Wire Mill Pond (DSH 25). This exceedance reflects the visage of
copper for the production of wire at USX. Twenty-five sites had copper concentrations
ranging between 16 - 83 mg/kg, of which Minnesota Slip (DSH 40), Fraser Shipyards (DSH
31), and the area around WLSSD (DSH 12, DSH 34, and DSH 36) had the highest copper
concentrations in this range.
Other anthropogenic sources for coppei may be derived from electrical industries, as well as
from water supply systems and lake managers that use copper salts to control algal growth.
The contribution of the sources to the Duluth/Superior Harbor has not been determined.
Lead
Lead concentrations ranged from 1.5 - 548 mg/kg at the sample sites (Figure 3-11, Table 3-
8). The median concentration was 15.5 mg/kg, whereas the mean was 58.2 mg/kg. The
mean was skewed by four high lead concentrations at the USX Superfund sites (DSH 24-25),
Fraser Shipyards (DSH 31), and Minnesota Slip (DSH 40). The lead concentrations at the
other sites were all less than 107 mg/kg lead.
In comparison, the mean lead concentration at three northern Minnesota reference lakes was
32 mg/kg (Heiskary, 1996), and the background lead level hi Great Lakes pre-colonial
sediments was 23 mg/kg (Persaud et al., 1993). Anthropogenic sources of lead were thought
to have contributed to the lead levels in some of Heiskary's study lakes (Heiskary, 1996).
The OMOEE LEL value for lead is 31 mg/kg, whereas the SEL value is 250 mg/kg (Persaud
et al., 1993). The lead concentration was less than the LEL at 22 sites, whereas three sites
exceeded the SEL hi the Duluth/Superior Harbor.
Lead is derived primarily from the mining and processing of limestone and dolomite
deposits, which are often sources of copper and zinc, too (May and McKinney, 1981 as cited
in U.S. EPA, 1993). Lead is also a minor component of coal and is found in fly ash
30
-------
resulting from coal combustion. Historically, lead was used in paints, in solder used in
plumbing and food cans, and as a gasoline additive (U.S. EPA, 1993). At present, lead is
used primarily in batteries, electric cable coverings, some exterior paints, ammunition, and
sound barriers (U.S. EPA, 1993).
The processing of mineral ore at USX (DSH 24-25) was probably the major contributor of
lead at this site. Lead was also very high at Eraser Shipyards (DSH 31) which was the site
for much transport of coal, as well as for building, repairing, and repainting ships. Lead
was also high at Minnesota Slip; a historical coal gasification plant and coal storage area near
this slip may have contributed to a portion of the lead load in the sediments. The relative
importance of other anthropogenic sources of lead to the harbor was not determined.
Nickel
Nickel concentrations ranged from 3.0 - 118 mg/kg at the study sites (Figure 3-12, Table 3-
8). The median concentration was 22.? mg/kg, whereas the mean was 21.4 mg/kg nickel.
The OMOEE LEL value for nickel is 16 mg/kg, whereas the SEL value is 75 mg/kg
(Persaud et al., 1993). Although the LEL value was exceeded at 25 sites hi the harbor, most
site values were below the background level of nickel observed in Great Lakes pre-colonial
sediment horizons (i.e., 31 mg/kg). The USX Wire Mill Pond site (DSH 25) was the only
site that exceeded the OMOEE SEL value.
The most important anthropogenic sources of nickel include fossil fuel combustion, nickel
ore mining, smelting and refining activities, and the electroplating industries [Canadian
Council of Resource and Environment Ministers (CCREM), 1987]. The high sediment
nickel concentration observed at DSH 25 is consistent with past industrial activities at the
USX Wire Mill site.
Zinc
Zinc concentrations ranged from 11.4 - 3780 mg/kg at the study sites (Figure 3-13, Table 3-
8). The median concentration was 93.1 mg/kg, whereas the mean was 240 mg/kg. The
mean value was skewed by two exceedingly high zinc values at USX (DSH 24-25). Values
at all other sites were less than 300 mg/kg zinc. Twenty-three sites had surficial zinc
concentrations less than the OMOEE LEL value of 120 mg/kg zinc. Other sites showing
high levels of zinc included the area around WLSSD (several sites), south of the M.L.
Hibbard/DSD No. 2 plant (DSH 17), Fraser Shipyards (DSH 31-32), and Minnesota Slip
(DSH 40).
31
-------
Zinc is used in coatings to protect iron and steel, in alloys for die casting, in brass, in dry
batteries, in roofing and exterior fittings for buildings, and in some printing processes. The
principal sources of zinc to aquatic systems include municipal wastewater effluents, zinc
mining, smelting, and refining activities, wood combustion, waste incineration, iron and steel
production, and other atmospheric emissions (CCREM, 1987). The high sediment zinc
values observed at DSH 24 and DSH 25 are consistent with past industrial uses of zinc at the
USX site.
3.2.4.2 X-ray Fluorimetry
X-ray fluorimetry (XRF) was performed on a subset of samples to ascertain its utility as a
low-cost, rapid analytical alternative to the traditional method of atomic absorption
spectroscopy (AAS) (Table 3-9). Table 3-10 shows the comparison of metal determinations
by the two methods. The accuracy of the XRF method was determined by calculating the
relative percent difference (RPD) between the two methods, using the AAS determinations as
the "true" value. A negative RPD indicates a fluorimetry method measurement less than the
"true" AAS determination, whereas a,, positive RPD indicates the opposite.
Examining the RPDs indicates the methods showed mediocre comparability; of the 28
measurements for which both methods obtained quantifiable levels, only 20 (71%) were
within allowable QC limits for metal determinations (50% RPD). The vast majority of the
RPDs were positive, indicating that the XRF method tended to overestimate the metal
concentrations, as measured by atomic absorption spectroscopy. When non-detectable
measurements (for either method) were added to the comparison, the comparability was
unchanged: of 48 measurements, 33 (69%) were either within 50% RPD of the AAS
determination, or were consistent with the AAS determination.
The x-ray metal determination was most accurate for nickel, copper, lead, and zinc, and was
least accurate for arsenic, cadmium, and mercury. In the case of mercury, the metal was
never detected by the XRF method, making its utility in the Duluth/Superior Harbor
sediment assessment very low. Because of the tendency of the method to overestimate metal
concentrations in these sediments, XRF may be useful as a screening tool when accompanied
by more traditional metal measurement methods. However, because of the high proportion
of non-detectable arsenic and mercury determinations, XRF is not useful for measuring these
two metals in sediments.
32
-------
3.2.5 PCBs
PCBs were measured in most sediment sections obtained from the Duluth/Superior Harbor
cores. PCBs were determined by both GC/ECD (Aroclor and congener-specific analyses)
and using the PCB immunoassay method. The following section is a discussion of the results
of both analytical methods.
3.2.5.1 GC/ECD Method
PCBs were quantitated on a congener-specific basis, as well as by Aroclor mixtures. A
software program, COMSTAR, was used to estimate PCBs as Aroclors 1242, 1248, 1254,
1260, and total PCBs. However, this program does not fully take into account the
weathering or enrichment of PCB congeners hi the environment that make-up an Aroclor
mixture. Thus, there may be some error associated with dividing up the total PCB
concentration into Aroclor components. Only total PCB concentrations will be discussed in
this section. It was beyond the scope of this project to provide a detailed assessment of the
congener data. A database of congener-specific sediment data is being accumulated for the
Duluth/Superior Harbor from three different MPCA investigations. The MPCA would like
to evaluate the congener data at a future date. These data can be assessed to evaluate trends
in the distribution and fate of PCB congeners in the Duluth/Superior Harbor. For example,
information on the enrichment and depletion of PCB congeners, determination of congeners
which have the highest potential for toxicity and bioaccumulation, and evaluation of congener
trends which may be associated with particular watershed sources of congeners can be
determined from this data set.
The total PCB concentrations for the core sections are given in Table 3-11. The distribution
of surficial PCB concentrations is shown hi Figure 3-14. Surficial PCB concentrations
ranged from 4.3 - 439 /tg/kg with a mean of 99.7 jig/kg and a median value of 68 /ng/kg
PCBs. In comparison, the OMOEE No Effect Level (NEL) is 10 /*g/kg, and the LEL is 70
Mg/kg (Persaud et al., 1993). Nineteen sites exceeded the LEL for the suficial sediments.
The most contaminated surficial sites were located in the vicinity of WLSSD and
Miller/Coffee Creeks. Bahnick and Markee (1985) reported an average concentration of 175
ng/L PCBs in effluent from WLSSD; they estimated that WLSSD effluent was a major
source of PCBs to the Duluth/Superior Harbor. Another possible source of PCBs in the
WLSSD/Miller and Coffee Creek embayment may have been a series of PCB-contaminated
electrical transformers that were buried on the WLSSD property many years ago. Some of
these transformers were discovered in 1994 during the construction of a recycling facility
near Miller and Coffee Creeks (J. Stollenwerk, MPCA Division of Water Quality, personal
33
-------
communication). While adequate steps were taken to contain and properly remove these
transformers once found, it is unknown what impact they may have had on sediments or
groundwater during the period of their burial.
PCBs have also been detected upstream in the Thomson, Forbay, and Fond du Lac
Reservoirs. From a limited sampling effort in 1992, total PCBs were highest in Thomson
Reservoir sediments; PCBs were detected at 108 /xg/kg in the 0-4 cm core section up to a
peak of 299 /ig/kg in the 136-144 cm section (Schubauer-Berigan and Crane, 1996).
Thomson Reservoir appears to serve as the primary catchment basin for sediment-associated
contaminants. Forbay and Fond du Lac Reservoirs appear to receive PCB inputs principally
from Thomson Reservoir (Schubauer-Berigan and Crane, 1996). A MPCA sediment survey
conducted hi 1980 along the Cloquet portion of the St. Louis River found the highest PCB
concentrations hi Scanlon and Thomson Reservoirs (240 and 120 fAg/kg, respectively). The
potential sources of PCBs to the reservoirs could not be determined, in part, due to a lack of
PCB effluent data for the two largest industries upstream of the Thomson Reservoir. If
PCBs were discharged in industrial effluent hi the St. Louis River AOC, this effluent would
have been diverted to WLSSD in the ^ate 1970s for treatment. A portion of the existing
PCB-contaminated sediments in the reservoirs could have been resuspended and transported
downstream to the Duluth/Superior Harbor. The suspended solids load of the St. Louis
River consists of eroded soil, resuspended material, and biological material; most of this load
settles within the harbor (Bahnick and Markee, 1985). Stortz and Sydor (1980) determined
that resuspension of bottom sediments by ship traffic is an important secondary source of
turbidity in the harbor. However, most of the material resuspended by ship traffic is rapidly
redistributed to the low turbulence areas within the shipping channels (Stortz and Sydor,
1980). Thus, PCB-contaminated sediments can be resuspended and re-worked in the
Duluth/Superior Harbor.
Other sources of PCBs to the St. Louis River AOC could have arisen from landfills,
atmospheric deposition, leaking PCB-contaminated equipment, and shipping activities.
Minnesota Power has taken steps to reduce the use of PCB capacitors and PCB-contaminated
substation equipment at its electrical power operations hi the upstream portion of the St.
Louis River AOC (Lake Superior Buiational Program, 1996). PCBs were never
manufactured in the Lake Superior basin, and their presence in Lake Superior is attributed
mostly to atmospheric deposition (Jeremiason et al., 1994). Thus, some of the PCB load in
the St. Louis River AOC watershed has arisen from atmospheric deposition in addition to
other sources.
34
-------
Sediment core profiles of normalized, total PCB concentrations for six selected sites are
given in Figures 3-15 to 3-17. None of these sites exceeded the OMOEE SEL of 530, (XX)
/tg/kg organic carbon (oc) of PCBs. The sediment profiles for sites DSH 03 (off Superior
POTW), DSH 20 (channel between Bearding Island and Park Point), DSH 31 (Eraser
Shipyards), and DSH 40 (Minnesota Slip) indicate PCB peaks below the surface. Sites DSH
12 (old 21st Ave. West Channel) and DSH 34 (91 m southeast of WLSSD outfall) had the
greatest PCB concentrations in the surficial sediments.
As discussed in Section 3.4, cesium dating was conducted on a core from DSH 20; the
cesium profile for this core indicated there was a great deal of sediment mixing. Since DSH
20 was located in the channel between Bearding Island and Park Point, both dredging and
ship traffic operations could have contributed to sediment mixing at this site. The highest
level of PCBs observed in any core segment occurred in the 36-66 cm section of the DSH 40
core. Historical sources of PCBs appeared to have contributed to this contaminant profile.
The total PCB concentrations measured in this study are low in comparison to some other
Great Lakes AOCs. For example, PCB levels in whole sediment samples from the Indiana
Harbor and Saginaw River AOCs ranged up to two orders of magnitude higher than the
worst level of contamination observed in this survey (Ingersoll et al., 1993). However, since
PCBs are bioaccumulative compounds, they have the potential to cause adverse effects to
biota and humans at sufficiently high exposure concentrations. For the St. Louis River, PCB
contamination has resulted in a do not eat advisory for carp (15-20 inches) near Cloquet and
Scanlon; an advisory for 20-25 inch carp exists from Fond du Lac Reservoir to Lake
Superior (Minnesota Department of Health, 19%). Fish have been found to spend a
disproportionately large amount of time in the WLSSD/MUler and Coffee Creek Embayment
during the winter months due to increased water temperatures resulting from WLSSD
effluent (Kutka and Richards, 1993). Thus, these fish will have a longer exposure period to
sediment and effluent-derived contaminants such as PCBs and mercury. Whether these fish
would be exposed to contaminant levels sufficient to cause harm to them or other fish eaters
has not been determined.
3.2.5.2 Immunoassay
The PCB immunoassay was assessed in this survey for use as a screening tool, compared to
the more traditional GC/ECD method for analyzing total PCB levels. The results of the PCB
immunoassay are given in Table 3-12. Method modifications were necessary in order to
improve quantitation limits (e.g., sediments were dried prior to analysis). The method
detection limit (MDL) for this assay (40-67 ng/kg) was still much higher than that obtained
35
-------
by the GC/ECD method (1.7 Mg/kg). The method quantitation limit (MQL) (i.e., two to ten
times the MDL) for the immunoassay method was 120 jig/kg. Only 17 of the 195 samples
analyzed by immunoassay were found at levels above the MQLs (Table 3-12).
Figure 3-18 shows the relationship between the two analytical methods. While the two
methods had fairly good comparability (e.g., a chi-square test of matched-site data
compatibility found the two methods hi agreement in a significant percentage of cases), the
low ratio of "hits" using the immunoassay data, even in a hotspot assessment, suggests this
method is not suited to routine monitoring of sediment contamination for PCBs in the
Duluth/Superior Harbor. That is, the majority of sites will probably be below the
immunoassay's method detection and quantitation limits.
3.2.6 2,3,7,8-TCDD/TCDF
Surficial sediment concentrations of 2,3,7,8-TCDD (hereafter referred to as dioxin) and
2,3,7,8-TCDF (hereafter referred to a» furan) are given in Table 3-13 and Figures 3-19 and
3-20, respectively. Due to difficulties associated with extracting the samples, dioxin was
detected at very few sites. Dioxin concentrations ranged from 0.9 - 13 ng/kg at four sites.
The highest concentrations were observed at the two USX sites (DSH 24-25) followed by the
DM&IR taconite storage facility (DSH 13), and the Superior Fiber Products former
discharge (DSH 05-ponar sample). Because of matrix interference, 11 samples could not be
analyzed at a satisfactory detection limit of 5.0 ng/kg. The interferents were likely to be
PAH compounds; most of the samples with unsatisfactory quantitation limits tended to have
high levels of PAHs or other contaminants (e.g., DSH 11: WLSSD outfall; DSH 23: across
channel from Tallas Island; DSH 29, DSH 37, DSH 39: Superwood Slip; DSH 31, DSH 32:
Fraser Shipyards; and especially DSH 36: near Miller/Coffee Creek outfall). In these
samples, no amount of sample preparation or cleanup could remove these interferences (Irene
Moser, UMD-NRRI Trace Organics Lab analyst, personal communication, 1994).
Furan was detected and quantified more frequently in the Duluth/Superior Harbor sediments
(Figure 3-20, Table 3-13). 2,3,7,8-TCDF could only be quantified at twelve sites. Samples
that could not be quantified tended to show the presence of other contaminants like PAHs
(e.g., DSH 29, DSH 31, DSH 33, DSH 37, DSH 40), which may have caused matrix
interferences during sample analysis. The highest furan concentrations were found at DSH
23 (across channel from Tallas Island) and DSH 25 (USX Wire Mill Settling Pond outfall)
followed by DSH 19 (C. Reiss coal dock), DSH 12 (old 21st Ave. West Channel), DSH 11
(west of WLSSD outfall), DSH 35 (near Rice's Point), and DSH 03 (off Superior POTW).
36
-------
The sources of dioxin to the Duluth/Superior Harbor mty be partly attributable to upstream
sources. The MFC A collected sediment cores from the Thomson, Forbay, and Fond du Lac
Reservoirs for dioxin analysis in 1992. Dioxin was not detected in the surface and bottom
sections of the cores from all three reservoirs (Schubauer-Berigan and Crane, 1996). Dioxin
concentrations, up to a maximum of 14.9 pg/g (in Fond du Lac Reservoir), were detected in
the middle sections of the cores; based on cesium-137 dating, maximum concentrations were
reached in either the mid-1940s (Thomson Reservoir) or the mid-1950s (Forbay and Fond du
Lac Reservoirs) (Schubauer-Berigan and Crane, 1996).
Other sources of dioxin to the Lake Superior basin have been discussed in the Lake Superior
Lakewide Management Plan (Lake Superior Binational Program, 1996). Anthropogenic
sources of dioxins may be released into the environment during: industrial processes, fuel
combustion, incineration, and the production or use of contaminated chemicals such as
pesticides. Three pulp and paper mills that discharge effluent to WLSSD have been
identified to have the potential to emit dioxins based on chlorine use by the mill itself, or hi
the pulp or recycled material used by the mill (Lake Superior Binational Program, 1996). In
1990, dioxins were detected hi the effluent from the primary clarifiers at one of the paper
mills discharging to WLSSD; furan has been detected in WLSSD sludge, but it could not be
attributed to any particular source (Lake Superior Binational Program, 1996). Dioxin has
also been detected in effluent from Murphy Oil in Superior, WI (Lake Superior Binational
Program, 1996). Sediment samples from the vicinity of Murphy Oil were not collected for
this investigation due to ongoing sediment work by the WDNR.
Dioxin can also be released to the atmosphere through the smelting and refining of
nonferrous metals such as aluminum, copper, nickel, and magnesium (Lake Superior
Binational Program, 1996). Many fuels, including wood, coal, natural gas, oil, gasoline,
and diesel can also potentially release dioxins when burned (Lake Superior Binational
Program, 1996). Dioxins observed at DSH 25 may be due, in part, to the coke operations
and metallic slags produced in the Wire Mill operations at USX. Cutting oils, including
petroleum, were used in the vicinity of Un-named Creek (DSH 24) and may have contributed
to dioxins at this site. Dioxin can also be emitted from incineration activities. The only
municipal solid waste incinerator in the U.S. Lake Superior basin occurs at WLSSD;
WLSSD also incinerates wastewater treatment plant sludge (Lake Superior Binational
Program, 1996). Other sources of dioxin include its inclusion in other compounds as an
impurity, such as PCBs and pentachlorphenol (PCP). PCP was used to treat railroad ties
from 1955 to 1979 at Kopper, Inc. in Superior, WI; WDNR is monitoring dioxins in
groundwater, waste disposal ponds, and a drainage ditch leaving this site ((Lake Superior
37
-------
Binational Program, 1996). The Koppers site was not included in this investigation due to
existing work being carried out by WDNR.
No detectable concentrations of dioxin were found in fish tissue collected from the Thomson
and Fond du Lac Reservoirs (Schubauer-Berigan and Crane, 1993). According to the U.S.
EPA's Ecological Risk Assessment for Dioxin document (Cook et al. 1993), areas with
sediment concentrations as low as 2.0 ng/kg dioxin, with a TOC of 5%, can cause harmful
effects in fish-eating biota. Since the dioxin measurements in this study were based on the
upper 30 cm of sediment, it can not be assumed that this reflects the concentration of dioxin
in the biologically active zone (i.e., upper 10-15 cm). In addition, better analytical
capabilities would be needed to lower the detection limit to 2.0 ng/kg and to resolve
analytical problems with interferences. Thus, future monitoring efforts would be useful to
determine if dioxins are accumulating in fish tissue to an extent that may present an
ecological or human health risk hi the St. Louis River AOC.
The source of 2,3,7,8-TCDF to the Duluth/Superior Harbor is unknown. Two possibilities
are the discharges of historical and current WLSSD effluent into the harbor, and the
transport of resuspended dioxin-like compounds from the upper St. Louis River reservoirs.
Other sources, as previously mentioned for dioxins, may be sources of furans as well.
3.2.7 Pesticides
A total of 13 pesticides were analyzed in surficial sediments at the study sites (Table 3-14).
Included in this list were some of the critical pollutants targeted by the Zero Discharge
Demonstration Program and identified in the Stage 1 LaMP for Lake Superior in 1990 (Lake
Superior Binational Program, 1996). These critical pollutants included the pesticides
chlordane, DDT (and its metabolites of DDD and DDE), dieldrin, hexachlorobenzene
(HCB), toxaphene, and the organochlorine octachlorostyrene. The other pesticides analyzed
for this project included lindane, aldrin, endrin, and other metabolites of DDT. All uses of
DDT, dieldrin, endrin, HCB, and toxaphene were banned hi the 1980s; chlordane and
lindane have only been allowed for restrictive uses since the mid-to-late 1980s (U.S. EPA,
1993). Many of these organochlorine pesticides were historically used in large amounts, and
they are not easily degraded or metabolized. Thus, these pesticides persist in the
environment, and they can bioaccumulate through aquatic and piscivorous food chains (U.S.
EPA, 1993).
Of the pesticides analyzed in this study, chlordane was not detected at any sites, and most of
the other pesticides were detected at low levels (Table 3-14). The pesticide analyses were
38
-------
confounded, in some cases, by the presence of interferences, primarily in samples with high-
to-moderate levels of PAHs (e.g., DSH 24, DSH 40, DSH 25, DSH 29, and DSH 17). For
DSH 17, this sample could not be analyzed for any pesticides due to interferences in the
sample. The detection limits of all samples varied, depending on the amount of analytical
interferences present in the samples. Dieldrin and endrin could not be quantitated in 12
samples because they were destroyed in the cleanup process.
The pesticide values in Table 3-14 were compared to available background sediment
concentrations and the OMOEE LEL values (Persaud et al., 1993). The background values
were based on the highest of the Lake Huron or Lake Superior mean surficial sediment
concentrations (Persaud et al., 1993). The greatest exceedances were for p,p-DDD + o,p-
DDT and p,p'-DDE. The sites with the greatest exceedances for pesticides included the
vicinity of WLSSD/Miller and Coffee Creeks (DSH 11, DSH 12, DSH 34, DSH 36), Eraser
Shipyards (DSH 31), Minnesota Slip (DSH 40), and Slip C (DSH 29 and DSH 37).
Octachlorostyrene was present at low levels, but no information was found concerning its
biological effects or distribution elsewhere.
>
Toxaphene was detected at 10 sites, with the highest concentrations occurring at DSH 40
(Minnesota Slip) and DSH 11 (just west of the WLSSD outfall). The extracts of these
samples were re-run on a more sensitive instrument [i.e., gas chromatography selective ion
methodology (GC/SIM)] at Dr. Deborah Swackhamer's laboratory at the University of
Minnesota-Minneapolis (Table 3-15). In general, the toxaphene values were on the same
order of magnitude as those analyzed by a GC using electron capture detector. Toxaphene
was higher in the Duluth/Superior Harbor sediments than in Great Lakes sediments which
run around 15 ng/g (Deborah Swackhamer, University of Minnesota, personal
communication, 1996). Additional surficial sediment samples were collected in the vicinity
of WLSSD during June 1996 for toxaphene analysis; the analytical results are not yet
available to include in this report. The sources of toxaphene to the Duluth/Superior Harbor
are not known. Toxaphene was the most heavily used pesticide in the United States between
1966 and the mid-1970s; it was used primarily on cotton fields in the southern United States.
Toxaphene was banned in the United States during 1982.
Detectable pesticide concentrations were normalized to the sediment organic carbon levels
observed in this study (Table 3-16). The U.S. EPA has proposed draft sediment quality
criteria for dieldrin and endrin, and these criteria were not exceeded in this study. The
OMOEE SEL values for eight pesticides were also not exceeded at the study sites.
39
-------
The particular sources of pesticides to the Duluth/Superior Harbor have not been determined,
but potential sources will be discussed here. Anthropogenic sources of HCB to the Lake
Superior basin are discussed in the Lake Superior LaMP (Lake Superior Binational Program,
1996). However, source identification for HCB is difficult due to potential contamination in
other organochlorine chemicals that may be used in the basin. The pesticide contamination
observed in the vicinity of WLSSD/Miller and Coffee Creeks may be mostly due to
discharges of effluent and stormwater. Pesticide contamination was also observed in several
boat slips. Some pesticide sources may have been due to accidental spills or releases from
ship traffic; in addition, the ship propellers may stir up sediments at these sites, thus delaying
the deposition of cleaner sediments over more contaminated sediments. Other potential
sources of pesticide contamination in the harbor include: atmospheric transport and
deposition resulting from aerial drift of pesticides, volatilization from applications in
terrestrial environments, and wind erosion of treated soil (U.S. EPA, 1993).
3.2.8 PAHs
j
3.2.8.1 Gas Chromatography/Mass Spectrometry (GC/MS)
GC/MS PAH analyses were conducted on September 9, 1993 and October 13, 1993 for
samples collected during September 1993. However, the detection levels were higher than
the original data quality objectives and there was blank contamination at very low levels.
This was caused, in part, by the presence of analytical interferents and high water content in
several of the sediment matrices (letter from Deneen Walker, Project Manager at Twin City
Testing to Luke Charpentier, MPCA analytical coordinator), as well as the fact that the
dilution series for the standard curves were set too high (thus leading to elevated quantitation
limits). Because of these analytical difficulties, it was decided by MPCA Water Quality staff
(in conjunction with the GLNPO Project Manager) to send archived sediment samples from
half of the sites to the contract laboratory for the extraction and analysis of PAH compounds.
In addition, five of the sites were re-sampled during June 1994, as close to the original site
as possible. These samples were extracted and analyzed at the same time as the archived
sediment samples in order to give another measure of sediment contamination.
September 1993 Samples (analyzed September and October 1993)
The original PAH results of surficial sediments (i.e., approximately 0-30 cm) are given in
Figure 3-21 and Table 3-17. In some samples, PAHs were detected at low levels and were
estimated below the detection limit established for each compound. A total of 17 PAH
compounds were quantitated. Due to the high detection limits, PAH compounds that were
40
-------
not detected were excluded from the tabulation of total PAHs. Eighteen sites had total PAH
concentrations above the OMOEE LEL value of 4000 pg/kg (Persaud et al., 1993).
The most PAH contaminated site was at DSH 24 (off Un-named Creek at USX) which was
3.5 times more contaminated than the next highest site at DSH 40 (Minnesota Slip). Sites
DSH 25 (near USX Wire Mill Settling Pond), DSH 29 (near end of Slip C), and DSH 17
(south of M.L. Hibbard Plant/DSD No. 2) had less than one-half the amount of PAH
contamination at DSH 40. The level of contamination observed at these sites was most likely
due to industrial activities and the shipment of coal. Industrial activities that produce PAHs
include coal coking (which took place at USX), production of coal tar (which took place at
Duluth Tar), and historic coal gasification plants (one such plant was located hi Canal Park,
close to Minnesota Slip). Coal was used historically at the M.L. Hibbard Plant/DSD No. 2
and many coal storage piles and loading/unloading facilities were historically present in many
areas of the Duluth/Superior Harbor (e.g., Howard's Pocket).
Individual PAHs that contributed most significantly to the total PAH levels varied according
to the site (Table 3-17). However, certain compounds emerged as most prevalent:
phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene,
benzofluoranthenes, benzo(a)pyrene, and naphthalene. OMOEE LEL values are available for
12 PAH compounds. Detected PAH compound concentrations that exceeded the LEL are
shown in bold typeface hi Table 3-17.
PAH compounds are best evaluated individually by normalizing the concentrations to TOC.
Table 3-18 shows TOC-normalized PAH concentrations for those sites and compounds with
detectable surficial concentrations. Normalized PAH concentrations were highest, in
descending order, at: DSH 24 (off Un-named Creek at USX), DSH 40 (Minnesota Slip),
DSH 25 (near the Wire Mill Settling Pond), DSH 36 (near Miller Creek outfall), and at DSH
29 and DSH 37 (Slip C sites). The normalized PAH concentrations were compared to the
OMOEE SEL values for 12 PAH compounds; no exceedances were found. In addition, the
U.S. EPA has proposed sediment quality criteria (SQC) for three PAH compounds:
fluoranthene, acenaphthene, and phenanthrene as 620, 130, and 180 mg/kg oc, respectively.
The SQC value for phenanthrene was exceeded at DSH 24 (off Un-named Creek at USX)
(Table 3-18). No other exceedances of the EPA SQC were observed in this study.
The presence of PAHs hi some samples was easily detected by field observations. A
comparison of the presence/absence of an oil sheen or petroleum odor (Table 3-4) and
analytical determination of these compound shows that for sampling locations near the USX
Superfund site (DSH 24-25), Minnesota Slip (DSH 40), WLSSD/Miller and Coffee Creek
41
-------
Embayment (DSH 34-36), and Slip C (DSH 37), high levels of PAHs were associated with
field observations. However, other locations with PAH concentrations exceeding the
OMOEE LEL did not give visible evidence of their presence, including Fraser Shipyards
(DSH 31) and the region south of the M.L. Hibbard plant/DSD No, 2 (DSH 17), In the
latter case, however, other visual cues (i.e., fly ash and coal residues) suggested the presence
of complex organic compounds.
September 1993 Samples (analyzed July 1994)
In order to achieve lower detection limits, archived split samples from the September 1993
field collection were extracted and quantitated during July 1994, The results are presented in
Table 3-19. The results of the initial analyses (in which extrapolation beyond the standard
curve was used to estimate low levels of PAHs) were compared to those of the later analyses
(which had lower detection limits) for total PAHs (Table 3-20). The relative percent
difference (RPD) and coefficient of variation (CV) was determined for samples from the
same site. Samples that had nondetectable total PAH concentrations were counted as 0 ^tg/kg
to yield a conservative comparison. The data quality objectives for this study specified a
RPD of ^50% for total PAHs. Six of 14 sample sites had RPDs «£50%. The RPD
measures the precision of duplicate chemical analyses. Since these measurements were of
split samples with a nine month lag in the analysis time, there may have been some loss of
PAHs through volatilization during sample storage or else difference in the analytical
extraction efficiency. In addition, the lower detections limits of the samples quantitated
during July 1994 resulted in the detection of several previously undetected samples (DSH 05,
DSH 06, DSH 30). Thus, the aforementioned reasons probably contributed to the higher
RPD values at eight sites. The CV is the sample standard deviation expressed as a
percentage of the sample mean. The CV values ranged from 0 to 141 %. As with the RPD
calculation, the difference in detection limits probably contributed the greatest amount of
variation between samples from the same site. A few samples (DSH 21, DSH 26, DSH 40)
appeared to lose PAHs following sample storage.
June 1994 Samples (analyzed July 1994)
Sediments from five sites sampled during the 1993 survey (DSH 21, DSH 22, DSH 23, DSH
26, DSH 27) were collected again on June 11, 1994 and analyzed during July 1994 in
conjunction with the re-analyses described above. The coordinates of these sampling
locations are shown in Table 3-21.
42
-------
The samples were not collected in the same manner as the 1993 samples. Short gravity
corers were used to collect the top 15 cm of sediments. In addition, corresponding samples
for TOC were not collected. Cores were collected from DSH sites thought to be relatively
uncontaminated, in order to obtain "background" concentrations of PAHs adjacent to the
Interlake/Duluth Tar and USX Superfund sites. While in the field, attempts were made to
obtain sediments from sites as close as possible to those sampled in 1993. In the case of site
DSH 21 (a shallow area just outside Stryker Embayment at the Interlake/Duluth Tar
Superfund site), it was obvious during collection that this sample was contaminated with
PAHs (there was a strong petroleum odor as well as a black oil sheen during sampling). The
sample collected in September 1993 did not show this level of visual contamination.
The PAH analyses of the 1994 samples are given to Table 3-22. The results are not directly
comparable to the 1993 samples due to differences in the core depths (i.e., 15 cm versus 30
cm) and slight differences in sample locations contributing to sediment heterogeneity. Total
PAH concentrations ranged from 208 - 90,300 Mg/kg for the five sites sampled in 1994
(Table 3-22). There was an insufficient number of samples collected to determine
background levels of PAHs in the harbor. The R-EMAP investigation the MPCA and
Natural Resources Research Institute are currently conducting in the St. Louis River AOC
will more adequately identify background levels of contaminants in this AOC.
Total PAH concentrations exceeded the OMOEE LEL of 4,000 jig/kg at DSH 21 (mouth of
Stryker Embayment) and DSH 23 (across channel from Tallas Island). An estimate of the
organic carbon normalized total PAH concentration was made by using the 1993 TOC values
for DSH 22 (10% TOC) and DSH 23 (5.3% TOC) for sites DSH 21 and DSH 23,
respectively. The 1993 TOC value at DSH 21 appeared to be too low based on the amount
of PAH contamination measured in the 1994 sample. Thus, the TOC measurement from a
nearby, more contaminated site (DSH 22) was used. The estimated TOC-normalized values
for DSH 21 and DSH 23 were 903 and 158 mg/kg oc, respectively. Both of these values
were less than the OMOEE SEL value of 10,000 mg/kg oc (Persaud et al., 1993).
3.2.8.2 Fluorescence Screen
In addition to the GC/MS PAH analyses, the 1993 core sections were analyzed using a PAH
fluorescence screening method. This method has been under development for several years,
and it has been adapted for use in Great Lakes harbors (Smith and Filkins, 1992; Smith and
Rood, 1994). The fluorescence screen is rapid and relatively inexpensive compared to the
GC/MS method. However, this method has not been used previously in the Duluth/Superior
43
-------
Harbor, and it was not known how well it would compare to the GC/MS results from this
study.
The results of the fluorescence screen method are shown in Table 3-23. A statistical
comparison between the PAH fluorescence screen and GC/MS results could not be made due
to the following reasons:
• The initial GC/MS analyses were not sufficiently sensitive (i.e., the quantitation limits
were too high); this could lead to underprediction of the true sample concentration by
GC/MS analysis.
* The samples were not analyzed during the same time period (the GC/MS method was
performed approximately 6 months to 1 year prior to the fluorescence method on the
split samples).
• The GC/MS method identified a discrete number of PAH compounds, whereas the
fluorescence method is functionally defined, and measures the sum total of all
compounds that fluoresce underAhe given conditions. Thus, this could lead to
overprediction of the total PAH concentrations.
The surficial PAH fluorescence screening results tended to overpredict the GC/MS results by
zero to three orders of magnitude. On a qualitative basis, the ranking of the most
contaminated sites differed from using the GC/MS results. The surficial screening results
indicated that the most contaminated sites, in descending order, were: DSH 09 (near Globe
Elevators), DSH 37 (Slip C in front of Superwood plant), DSH 36 (near Miller Creek
outfall), DSH 38 (Slip C, near Great Lakes Towing Co.), DSH 24 (off Un-named Creek at
USX), and DSH 32 (across channel from Fraser Shipyards). In comparison, the most
contaminated surficial sediments, as determined by GC/MS, were DSH 24, DSH 40, DSH
25, DSH 29, DSH 17, and DSH 23. Although DSH 24 was by far the most PAH
contaminated site when using the GC/MS data, it was ranked fifth in contamination using the
PAH screening results. DSH 09 had the most contaminated surficial sediments, as
determined by the PAH screening method, whereas it was one of the lesser contaminated
sediments, as determined by GC/MS. Thus, the relative ranking of contaminated sites was
not consistent between the two methods, and the screening method appeared to have limited
utility for this study. As discussed in Owen et al. (1995), the accuracy of this screening
technique will be improved by calibrating the screening method against a wide range of
directly measured PAHs (by GC/MS) that have low detection limits and good precision.
The PAH screen showed some trends hi concentrations with sediment depth throughout the
harbor (Table 3-23). While some sites showed a tendency for total PAH levels to decrease
44
-------
to low levels with depth (e.g., DSH 04, DSH 07, DSH 09, DSH 10, DSH 11, DSH 13,
DSH 20, DSH 35), at many other sites, PAHs either remained high or increased downcore
(e.g., DSH 01, DSH 03, DSH 14, DSH 16, DSH 18, DSH 19, DSH 22, DSH 24, DSH 25,
DSH 26, DSH 28, DSH 29, DSH 30, DSH 36, DSH 38, DSH 40). Several of these results
were supported by the field book physical descriptions which gave visual or olfactory
evidence of PAH-like compounds below the sediment surface. Sites DSH 01, DSH 12, DSH
16, DSH 18, DSH 24, DSH 25, DSH 34, DSH 36, DSH 37, DSH 38, and DSH 40 all gave
physical indications of the presence of PAH-like compounds below the surficial sediment
layer (Table 3-4). Therefore, field observations may be sufficient for determining the worst
sites in the Duluth/Superior Harbor to have quantitated by GC/MS for PAHs.
3.2.9 Tributyltin
Tributyltin is an antifouling agent in marine paint that is used to paint ship hulls, boat docks,
and buoys. Tributyltin and three other butylated forms of tin (i.e., mono, di, and tetra-)
were measured in six samples, selected by their proximity to commercial, private or public
shipyards, boat docks, or loading facilities. The sites selected for butyltin analyses were
DSH 01 (near the Burlington Northern Taconite Loading Facility), DSH 02 (Barkers Island
boatyard), DSH 08 (U.S. Army Corps of Engineers Shipyard), DSH 20 (behind Hoarding
Island), DSH 31 (Fraser Shipyards), DSH 40 (Minnesota Slip). Results of the butyltin
analysis [reported as tin (Sn)] are given hi Table 3-24; the results for tributyltin are also
converted from tin to tributyltin (TBT) by multiplying the results by 2.5. Concentrations of
tributyltin were greatest in sediment from Fraser Shipyards (DSH 31), at 178 ng/kg TBT,
and were lowest at DSH 01, at 3.3 /*g/kg TBT. The remainder of the samples had
intermediate tributyltin concentrations. Overall, the mean concentration of tributyltin at the
six sites was 74 ± 63 (SD) /tg/kg TBT. Monobutyltin and dibutyltin were present at the six
sites in concentrations ranging from 1.7 jtg/kg Sn to 54.1 ^g/kg Sn. Tetrabutyltin was not
detected in any of the samples.
Tributyltin is designed to slowly leach from marine paints after it is applied. Tributyltin can
be released to the water column through leaching from paint on boats or from paint chips or
dust from maintenance facilities (e.g., dry docks, sandblasting residues). Nontarget water
column and benthic organisms are subject to exposure and potential toxicity from butyltins;
this is primarily a concern in marine environments. Tributyltin is highly toxic to aquatic
organisms with the toxicity of butyltin compounds decreasing with decreasing number of
butyl groups. Mono- and dibutyltin compounds are at least one to two orders of magnitude
less toxic than tributyltin. In addition, the organotin compounds are bioaccumulated through
45
-------
the food chain, causing potential harm to fish, as well as (potentially) human fish consumers
(Krone etal., 1989).
Due to the demonstrated toxicity of tributyltin to aquatic organisms, especially marine oyster
and mussel beds, restrictions were placed on the use of tributyltin in marine paints by the
State of Wisconsin, U.S. EPA, and several European countries during the late 1980s (Tom
Janisch, WDNR, personal communication, 1996). Some recent data on tributyltin in
sediments from the Superior Harbor, and past water column monitoring by WDNR
statewide, indicates that tributyltin is present in sediments and water of Wisconsin marinas
(Tom Janisch, WDNR, personal communication, 1996). In addition, tributyltin appears to be
very persistent in the sediments and can desorp back to the water column, dependent on its
partitioning coefficient.
The WDNR has used two different partitioning models to derive sediment quality objective
concentrations (SQOCs) for tributyltin found in Wisconsin sediments. The first model uses
an equilibrium partitioning water quality criteria approach to estimate environmentally safe
concentrations of tributyltin in sediments. This approach assumes that: 1) the partitioning of
tributyltin between the sediment solids and porewater is controlled in a predictable manner by
a continuous equilibrium between the two phases, 2) sediment organic carbon determines the
bioavailability of tributyltin hi the sediment porewater, 3) the toxicity of tributyltin to benthic
organisms is governed by their exposure to tributyltin dissolved in sediment porewater and
does not include other exposure pathways such as ingestion of contaminated sediment or
food, and 4) benthic organisms are as sensitive to tributyltin levels as water quality
organisms upon which water quality criteria are generally based. Recent literature indicates
that organic carbon is not a good predictor for tributyltin sorption and release in the
sediments (Tom Janisch, WDNR, personal communication, 1996). For this study, there
appeared to be no positive correlation between tributyltin and TOC for the limited data set
available. Depending on the water chemistry, tributyltin may be a neutral or nonpolar
compound at higher pHs and may otherwise exist in the cationic form. Thus, sole use of the
equilibrium partitioning model may not be appropriate to predict its chemical behavior, and
the tributyltin results from this study were not compared to the Wisconsin SQOCs. This
model also does not take into account the higher partition coefficient that is probably
associated with tributyltin in paint chips; thus, tributyltin in sediment deposited paint chips
may be less bioavailable.
The second partitioning model used by the WDNR is based on the ratio of tributyltin in the
overlying water column to the concentration in the sediment. Based on partitioning
coefficient values, the water column tributyltin concentration can be predicted based on the
46
-------
measured sediment concentrations. These water column concentrations can then be compared
to U.S. EPA acute and chronic water quality criteria for tributyltin. The WDNR used
literature-derived partitioning coefficients to estimate water column concentrations of
tributyltin at some ship building sites in Wisconsin (Tom Janisch, WDNR, personal
communication, 1996). WDNR extrapolated partition coefficients from some marine
sediments, and they made the assumption that the partitioning of tributyltin between the
sediment and overlying water had reached an equilibrium. This partitioning model was not
used for the data set from this study because: 1) site-specific field derived partitioning values
would be more appropriate to use and 2) inadequate information is available about the
chemical behavior of tributyltin.
3.3 TOXICITY TESTS
Four organisms were included hi the suite of toxicity tests conducted in this sediment survey:
the amphipod Hyalella azteca (10-d lethality), the midge Chironomus tentans (10-d lethality
and growth), the bacterium Photobacterium phosphoreum (MicrotoxR), and the bacterium
Vibrio fischeri (MutatoxR). Whole-sediment tests were conducted with H. azteca and C.
tentans, whereas porewater was used in the MicrotoxR and MutatoxR tests. The toxicity test
results are shown in Table 3-25, and are described hi the following sections for each
organism and endpoint.
In attempting to explain toxicity for any of the species, it is important to note that the
chemical analyses are not synoptic with the toxicity test results. The surficial analytical
chemistry was performed on the 0-30 cm section of the vibracore for each site, whereas the
toxicity tests were conducted using the Ponar grab sample (0-20 cm) from each site.
Therefore, caution should be used hi interpreting toxicity based on particular contaminant
profiles.
3.3.1 10-day Sediment Toxicity Tests
The 10-day toxicity tests were conducted on seven batches of samples, all of which were ran
within two months of sample collection. Detailed information on the sample collection and
handling, methods, water quality and survival results, data analysis, and H. azteca reference
toxicant test results are provided in MFC A laboratory reports given in Appendix B. In
general, the pH ranges of all the toxicity tests were acceptable. However, dissolved oxygen
occasionally fell below 40% saturation in the C, tentans tests. Temperature was slightly less
than the recommended range of 23 ± 1°C (U.S. EPA, 1994) for most tests (i.e., down to
20°C). Sediments for DSH 18 and DSH 19 were accidently frozen prior to testing. The
47
-------
samples were thawed out and used in the sediment toxicity tests. Changes in the sediment
matrix may have resulted from freezing, and it is not known whether similar survival data
would have resulted from using unfrozen sediments.
In order for the test to pass, the mean control survival for H. azteca had to be greater or
equal to 80%. For C. tentans, a mean control survival of 70% or greater was required for
the test to pass. Survival data from acceptable tests were analyzed statistically using
TOXSTAT (Gulley and WEST, Inc., 1994), a statistical software package obtained from the
University of Wyoming. All survival data were expressed as a proportion and were
transformed using an arc sine-square root transformation prior to analysis. Zero variance
survival data from the C. tentans tests were excluded from the statistical analysis because
nonparametric statistics could not be run on the three replicates. A minimum of four
replicates is needed to run nonparametric statistics. In most cases, the survival data of
excluded tests was greater or equal to the mean control survival. For site DSH 24, there was
0% mean survival (and thus zero variance) in the C. tentans tests; this result was obviously
statistically less than the control and was excluded from the statistical analysis. The Shapiro-
Wilk's test for normality and Bartlett's test for homogeneity of variance were run on the
transformed data. Next, an Analysis of Variance (ANOVA) was conducted, and the data
were analyzed statistically using a one-tailed Dunnett's test (ex = 0.05). A sample was
considered toxic when mean percent survival was significantly lower than mean control
survival.
3.3.1.1 Acute Toxicity to Hyalella azteca
Table 3-25 shows the mean percent survival of H, azteca resulting from the 40 toxicity tests.
A problem was encountered with 28 of the sediments in that the survival of the control
organisms did not meet quality control requirements (i.e., 80% mean survival after 10 days).
Of the 12 tests that passed, none of the samples were statistically less than the control. The
health of the organisms was suspect, as they also performed poorly hi the sodium chloride
reference toxicant test over that period (refer to the laboratory reports in Appendix B).
Unfortunately, sufficient sediment volume was not available to retest these sediments.
Therefore, the potential toxicity of 28 sites to the amphipod is not known.
3.3.1.2 Acute Toxicity to Chironomus tentans
The survival of C. tentans in the 10-day sediment toxicity tests is given in Table 3-25.
Control survival was acceptable for all of the C. tentans tests. Of the 40 sites tested, three
sites were acutely toxic to the midge: DSH 14 (the bay east of Erie Pier), DSH 24 (the USX
48
-------
Un-named Creek outfall), and DSH 34 (the WLSSD discharge). DSH 24 was extremely
toxic; no survival was observed in any of the replicates. This site was one of the most
contaminated in the survey with respect to heavy metals (Pb, Cr, Ni, Cd, and Zn), mercury,
and PAHs.
3.3.1,3 Chronic Toxicity to Chironomus tentans
Growth (weight) was measured at the end of the C. tentans test to assess chronic effects.
Although the dried C. tentans were weighed, the balance on which they were weighed was
not calibrated with standard weights. Therefore, the data are suspect since the internal
calibration of the balance may have drifted with time. Due to this quality assurance
problem, the growth data could not be analyzed statistically.
3.3.4 Acute Toxicity to Photobacterium phosphoreum (Mierotox*)
The MicrotoxR and MutatoxR tests were conducted using sediment porewater instead of whole
sediment. Porewater was used for M£crotoxR and MutatoxR because this procedure is
technically more-developed than the bulk sediment tests. In addition, the use of porewater
minimized test expenses and enhanced comparability with other studies. The porewater was
isolated by centrifuging whole sediment at 10,000 g in glass tubes. Of the 40 sites tested in
an initial screen for acute toxicity to P. phosphoreum (MicrotoxR), 16 sites were toxic.
These toxic sediment porewaters were then subjected to a dilution series test in order to
establish an EC50 (i.e., effective porewater concentration at which luminescence is reduced
by 50%). This was done to evaluate relative toxicity of the various sediments. Decreasing
ECSOs signify increasing toxicity. Of the 16 toxic samples evaluated for ECSOs, 9 were not
toxic in the EC50 screen. Therefore, these samples were considered marginally toxic. The
sites showing the lowest ECSOs (therefore the highest toxicity) were DSH 24 (USX Un-
named Creek outfall), DSH 02 (east end of Barkers Island), DSH 10 (Interstate Island deep
hole), DSH 11 (west of WLSSD outfall), DSH 08 (U.S. Army Corps of Engineers vessel
yard), DSH 13 (DM&IR taconite storage facility), and DSH 33 (south/southwest of WLSSD
outfall).
3.3.5 Genotoxicity to Vibrio fischeri (Mutatox*)
Like the MicrotoxR test, the MutatoxR test was conducted using porewater rather than whole
sediment. It was developed to provide a rapid alternative to the Ames assay for mutagenicity
(Microbics, Inc., 1993). The MutatoxR test system is designed to detect potential genotoxins.
Genotoxins are chemical or physical agents which, in addition to being mutagens (i.e., affect
49
-------
a cell's DNA by altering its base sequence), change chromosome structure, number, shape,
or position (Azur Environmental, 1996). The test uses a strain of Vibrio flscheri that has
been genetically altered to suppress natural luminescence. Certain genotoxins present in
some sediments may cause back-mutation of these altered organisms to the "wild type" (i.e.,
back to the light-producing strain). Therefore, this assay tests for the opposite endpoint of
the MicrotoxR test. Increased light emission over that of the controls suggests the presence
of genotoxic agents in the sediment porewater. One problem in interpreting the results of
this test is that mutagenic sediments that are also acutely toxic in the MicrotoxR test may
suppress the light output of bacteria they have mutated back to the wild strain. Thus, the
potential exists to obtain false negative results for the MutatoxR assay. Because the
MicrotoxR assay was conducted synoptically, the potential for this result was evaluated.
Some compounds become mutagenic only following activation by enzymes in the mammalian
liver. In addition to direct mutagenicity, the MutatoxR test also determines the mutagenicity
of sites following activation with the S9 enzyme, which emulates hepatic (i.e., liver) function
during exposure. In this way, sites that are not directly mutagenic can be evaluated for their
potential to be activated to mutagenicity hi the mammalian liver.
/
Of the 40 sites tested for potential genotoxins, 21 sites detected genotoxic agents. These
included DSH sites 01-03, 7, 12, 18-20, 23-29, 31, 34, 36-38, and 40. One site (DSH 15)
was mutagenic following enzyme activation. Many of the genotoxic sediments were
contaminated by heavy metals, mercury, PAHs, and pesticides (e.g., DSH sites 12, 19, 23-
25, 29, 31, 34, 36-38, and 40), any of which could account for genotoxic agents. However,
other sites showed much lower levels of these contaminants; thus, the source of their
genotoxic agents is unknown (e.g., DSH sites 01, 02, 07, 18, 20, 27, and 28). Therefore,
caution should be used in interpreting the results of the MutatoxR test. Use of this test for
evaluating contaminated sediments is hi the early stages, and the effects of naturally-
occurring sediment compounds on this test is not known.
3.4 CESIUM DATING OF SEDIMENT CORES
Five sediment cores were dated by measuring the presence of the radioactive element 137Cs.
The measurements were performed by Dr. Daniel Steck of St. John's University's Schaefer
Environmental Radiation Laboratory. The cores selected for cesium dating were collected in
the inner and outer Duluth/Superior Harbor areas: DSH 36 (near Miller/Coffee Creek
outfalls), DSH 38 (Superwood Slip near Great Lakes Towing Co.), DSH 11 (just west of
WLSSD outfall), DSH 20 (channel between Hearding Island and Park Point), and DSH 28
(Allouez Bay). Cores were sectioned in 2.5 cm increments, beginning with the surficial
sediments. Twenty of these sections were analyzed for the presence of 137Cs. Dating was
50
-------
achieved by noting the initiation of cesium in the sediment profile (i.e., the lowest depth at
which it was detected). This depth corresponds to the year 1954, when surface testing of
atomic weapons in the western U.S. led to widespread deposition of airborne 137Cs on surface
waters of the eastern U.S. Testing peaked in the year 1964; therefore, this year
corresponded to the highest concentrations of 137Cs in the sediment profile. Yearly
sedimentation rates may be calculated for the period between 1954 and 1964 by subtracting
the core depth of the 137Cs peak (1964) from the core depth of 137Cs initiation (1954) and
dividing by 10 (the number of years elapsed). Similarly, yearly deposition rates can be
calculated for 1964 to present by dividing the depth of the 1964 peak by the number of years
elapsed.
The sedimentation rates for the five cores evaluated are shown in Table 3-26. Dr. Steck's
laboratory noted that two of the cores, DSH 36 and DSH 38, showed "classic" 137Cs profiles,
with easily distinguishable peaks and edges. The cores also appeared to have similar
sedimentation rates over the entire period of 1954-1993 (1.14 and 0.94 cm/yr, respectively).
Two of the cores (DSH 11 and DSH 20) showed unusual results. DSH 11 appeared to have
the entire period 1954-1964 crowded into the top 7.5 cm (i.e., the 137Cs initiation and peak
were within 7.5 cm of the core surface), and core DSH 20 showed a uniformly decreasing
cesium profile toward the bottom of the core. According to Dr. Steck, this suggests that
there was a great deal of sediment mixing at DSH 20. He did not know what could account
for the profile observed in core DSH 11. The fifth core, DSH 28 showed no 137Cs content in
any of the four sections analyzed. This suggests that insufficient sediment depth was
sampled.
The findings of the cesium dating suggest either a very slow sediment deposition rate at sites
DSH 11 and DSH 20 during the past 37 years, or else indicate that a great deal of mixing
has occurred. Both of these areas are subject to high circulation patterns from water
movement due both to flow from the St. Louis River and the Lake Superior seiche. It is
possible that the apparent shallow depth of the cesium peak in the DSH 11 core is caused by
scouring of more recent surficial sediments due to storms, effluent discharges, or other
random events.
In contrast to DSH 11 and DSH 20, relatively higher deposition rates were calculated for
sites DSH 36 and DSH 38. Both of these locations are near flow sources with the potential
for heavy sedimentation. DSH 36, which showed the highest sedimentation rates of all the
cores, is near the outfalls of Miller and Coffee Creeks. These creeks drain the majority of
the area of the west end of Duluth, as well as the Miller Hill watershed. Runoff of both
contaminants and sediment is likely to be high from these watershed sources (John Thomas,
51
-------
MPCA, personal communication). In 1993, staff from the U.S. Soil and Water Conservation
Service conducted a sediment sounding of the bay near the old 21st Ave. W. ship channel,
and they found that a great deal of sedimentation had filled hi the channel since the late
1970s. A likely source of the additional sediment is probably from Miller and Coffee
Creeks, according to the Natural Resources Conservation Service (formerly the U.S. Soil and
Water Conservation Service) (Paul Sandstrom, personal communication). Similarly, site
DSH 38 very likely has had much sedimentation occurring hi recent years; it is near a
stormwater overflow outlet for the City of Duluth which is in the nearby Cutler-Magner Slip.
During high rainstorm events and spring run-off events, high loads of sediment may have
been deposited to this area. The fact that identifiable peaks and edges were obtained in these
cores suggests that not much mixing has occurred in these sediments in recent years.
The observation that no cesium was found in the core sections from DSH 28 in Allouez Bay
suggests that inadequate depth was sampled from this site. Field observations indicated that
most of the shallow core collected from this site was composed of peaty organic material
deposited from the surrounding wetlands. Unfortunately, the vibracorer was not able to
penetrate this peaty layer to obtain underlying sediments.
In summary, it is likely that cesium dating will not be very useful for identifying recent
sedimentation rates in the exposed areas of the Duluth/Superior Harbor. This is due
primarily to the high mixing rates caused by the fluctuating seiche of Lake Superior, the flow
of the St. Louis River, ship traffic, and storm events. However, in more isolated bays and
slips, cesium dating could provide a useful date marker for recent contamination events.
52
-------
o
O
OJ
eg
is
Surficial Section
Open Water
Disposal Guidelines
09
••••• i
i.h
i,
i
T- w n •# >o
a R a a
DSH Site
Figure 3-1. Distribution of surficial KCL-extractable ammonia at the sample sites.
53
-------
o _
o
•7- CO
"O
c
o
JQ
(0
O
o
'c
E?
O
15
LlL
1
WJ U) h-
DSH Site
Surficial Section
•SEL(10%)
•LEL(1%)
1
1
Figure 3-2. Distribution of surficial TOC at the sample sites.
54
-------
in
04
CM --
o>
<
0)
o
Surficial Section
-SEL(2mg/kg)
• LEL (0.2 mg/kg)
1
*- Pi r* •"« «>
I.III.I. I ll .Mill
I
DSH Site
Figure 3-3. Distribution of surficial mercury at the sample sites.
55
-------
DSH12
Hg Concentration (mg/kg dry wt.)
0.3
0.4
0.5
0.6
o
a.
a>
a
0.1
0.2
DSH24
Hg Concentration (mg/kg dry wt.)
0.3 0.4 0.5
Figure 3-4. Depth profile of mercury at sites DSH 12 and DSH 24.
0.6
0.7
0.8
56
-------
0.1
DSH25
Hg Concentration (rug/kg dry wt)
0.2 0.3 0.4
0.5
0.6
O.S
DSH34
Hg Concentration (mg/kg dry wt)
1 1.5
2.5
109
Figure 3-5. Depth profile of mercury at sites DSH 25 and DSH 34.
57
-------
216
0.2
DSH36
Hg Concentration (mg/kg dry wt)
0.4
0.6
0.8
1.2
1.4
0.2
0.4
DSH40
Hg Concentration (mg/kg dry wt.)
06 0.8
Figure 3-6. Depth profile of mercury at sites DSH 36 and DSH 40.
1.2
1.4
1.6
58
-------
8
o
CO
10
CM
T3 O
o 10
0)
o
IO
Surficial Section
1
L
i
? 8 S 8 S3 3 8
DSH Site
-SEL(33mg/kg)
•LEL(6mg/kg)
1
Figure 3-7. Distribution of surficial arsenic at the sample sites.
-------
a> --
CD --
.
I
O
co - -
o
1
DSH Site
Surficial Section
•SEL(10mg/kg)
• LEL (0.6 mg/kg)
II
Figure 3-8. Distribution of surficial cadmium at the sample sites.
60
-------
o
CM -
0 .
-o
CO
^>
&
-------
o
in -r
o
o
O>
^
O)
L»
CD
Q.
Q.
O
O o
in
496
Surficial Section
-SEL(110mg/kg)
•LEL(16mg/kg)
I
DSH Site
Figure 3-10. Distribution of surficial copper at the sample sites.
62
-------
o
o
CD
O
o
10
o
o
o>
•a
CO
0)
Surficial Section
—SEL (250 mg/kg)
- - LEL (31 mg/kg)
o
o
CM
o
o
I
DSH Site
Figure 3-11. Distribution of surficial lead at the sample sites.
-------
o
O) •*"
o
CD
T3
O)
ID
z o
CO
118
DSH Site
Surficial Section
-SEL(75mg/kg)
•LEL(16mg/kg)
m n
Figure 3-12. Distribution of surficial nickel at the sample sites.
64
-------
o
8
0
in
h-
O>
o
N
O
IO
CM
3785
.i
X1647
! ? 8 S 13 R 8 §
DSH Site
Surficial Section
-SEL
•LEL(120mg/kg)
Hu
Figure 3-13. Distribution of surficial zinc at the sample sites.
-------
o
O -r
in
o
o
0>
QQ
O
Q_
"ro
"5
o --
CM
O
O
Surficial Section
•~ ---LEL(70ug/kg)
l
h
DSH Site
Figure 3-14. Distribution of surficial, total PCBs at the sample sites.
66
-------
DSH3
91
2000
Normalized PCB Concentration (pg/kg oc dry wt)
4000 6000 8000 10000
12000
14000
2000
DSH12
Normalized PCB Concentration (pg/kg oc dry wt)
4000 6000
8000
10000
Figure 3-15. Depth profile of normalized, total PCBs at sites DSH 03 and DSH 12.
67
-------
DSH20
5000
Normalized PCB Concentration (M9/kg oc dry wt.)
10000 15000 20000 25000
35000
117
DSH31
Normalized PCB Concentration (ng/kg oc dry wt.)
0 2000 4000 6000 8000 10000 12000 14000 16000 18000
Figure 3-16. Depth profile of normalized, total PCBs at sites DSH 20 and DSH 31.
68
-------
DSH34
31
Q 91
109
2000
Normalized PCS Concentration (pg/kg oc dry wL)
4000 6000 8000 10000
12000
14000
2000
DSH40
Normalized PCB Concentration (M9/kg oc dry wt.)
4000 6000 8000
10000
12000
Figure 3-17. Depth profile of normalized, total PCBs at sites DSH 34 and DSH 40.
69
-------
ouu
700
600
"Q- 500
tx
400
OS
0
c
| 300
200
100
A
' * /
/
1
1
1
1
1
1:1 ratio /
X. 1
^^v\ '
;
*
^
i
i
. i
i '
Overestlmatlon /
n-20 . /
'/
1
/
• * / *
/ . n-24
^undoresllmatlon
'• '-— *• '....»'
10
100
1000
10
100
1000
GC/ECD (total Aroclors, ppb)
GC/ECD (total Aroclors, ppb)
Figure 3-18. Relationship between PCB immunoassay and GC/ECD method. Chart on left shows screening veracity of the
immunoassay method, showing number of false positive, true positive, false negative and true negative results; vertical " + " bars
indicate the two detection limits of the immunoassay method. Chart on right shows the quantitation accuracy of the
immunoassay method; the dashed line indicates perfect concordance between the methods.
70
-------
? -
CM .
O
TJ
j?00 "
"Si
•S
Q
go -
CO
K
CM"
CM
, 1
DSH Site
In
r
Surficial Section
Figure 3-19. Distribution of surficial 2,3,7,8-TCDD at the sample sites.
71
-------
in _
t
O)
C
Q
O
oo
tv: in
co
ol
Surficial Section
o* o *•
DSH Site
Figure 3-20. Distribution of surficial 2,3,7,8-TCDF at the sample sites.
72
-------
O)
Q.
1 10
185
tllY*
K
1
? s ?3 a a s s
DSH Site
Surficial Section
- ..... LEL(4ug/g)
Figure 3-21. Distribution of surficial, total PAHs at the sample sites.
73
-------
Table 3-1. Approximate location of sites and depth of vibracore sections analyzed.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
Date
9/21/93
9/21/93
9/22/93
9/22/93
9/22/93
9/22/93
9/21/93
9/13/93
9/24/93
9/24/93
9/24/93
9/13/93
9/23/93
9/14/93
9/24/93
9/14/93
9/23/93
9/21/93
9/23/93
9/27/93
Latitude
46°41.618'N
46°42.870'N
46°43.545'N
46°44.041'N
46°44.081'N
46°44.447'N
46°45.451'N
46°46.467'N
46°44.431'N
46°44.870'N
46°45.427'N
46°45.545'N
46°45.028'N
46°44.675'N
46°44.228'N
46°44.228'N
46°44.041'N
46°42.240'N
46°43.415'N
46°45.650'N
Core
Longitude Depth (cm)
92°01.130'W
92°03.225'W
92°03.982'W
92°03.456'W
92°04.562'W
92°05.130'W
92°05.296'W
92°05.574'W
92°06.142'W
92°06.882'W
92°07.189'W
92°07.041'W
92°07.669'W
92°08.178'W
92°07.651'W
92°09.024'W
92°09.089'W
92°01.864'W
92°09.473'W
92°04.970'W
170
0
155
244
31
102
91
0
71
183
112
206
234
152
211
163
102
173
231
137
1
0-31
NC1
0-31
0-31
0-31
0-31
0-31
NC
0-31
0-31
0-31
0-41
0-31
0-30
0-31
0-20
0-31
0-31
0-31
0-31
Sections Analyzed (in cm)
2345
31-61
NC
31-61
31-61
NC
31-61
31-61
NC
31-61
31-61
31-61
41-81
31-61
30-61
31-61
20-51
31-61
31-61
31-61
31-61
61-91
NC
61-91
61-91
NC
61-90
NC
NC
NC
61-91
61-91
81-122
61-91
61-91
61-91
51-81
61-91
61-91
61-91
61-91
91-122
NC
NC
91-122
NC
NC
NC
NC
NC
91-122
91-112
122-163
91-122
91-122
91-122
81-122
NC
91-122
91-122
91-117
122-152
NC
NC
169-198
NC
NC
NC
NC
NC
122-152
NC
163-180
203-234
122-152
167-183
122-152
NC
122-152
198-229
NC
'NC: not able to be collected due to unsuitable substrate
74
-------
Table 3-1. Continued.
Site
DSH21
DSH22
DSH23
DSH24
DSH25
DSH26
DSH27
DSH28
DSH29
DSH 30
DSH31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
Date
9/17/93
9/17/93
9/17/93
9/23/93
9/23/93
9/20/93
9/23/93
9/27/93
9/14/93
9/20/93
9/24/93
9/24/93
9/27/93
9/27/93
9/27/93
9/27/93
9/28/93
9/28/93
9/28/93
9/14/93
Latitude
46°43.106'N
46°43.016'N
46°42.626'N
46°41.285'N
46°40.659'N
46°39.764'N
46°42.415'N
46°41.081'N
46°46.285'N
46°39.024'N
46°44.191'N
46°44.289'N
46°45.309'N
46°45.443'N
46°45.524'N
46°45.809'N
46°46.301'N
46°46.362'N
46°46.402'N
46°47.008'N
Core
Longitude Depth (cm)
92°10.367'W
92°10.237'W
92°11.663'W
92°12.166'W
92°12.059'W
92°12.459'W
92°09.450'W
91°59.781'W
92°06.592'W
92°13.176'W
92°05.450'W
92°05.361'W
92°07.254'W
92°07.112'W
92°06.822'W
92°07.225'W
92°06.556'W
92°06.444'W
92°06.379'W
92°05.840'W
76
191
163
147
145
122
244
74
168
170
56
137
178
125
152
231
94
117
137
198
1
0-31
0-31
0-31
0-31
0-31
0-31
0-31
0-31
5-36
0-31
0-31
0-31
0-31
0-31
0-31
0-31
0-31
0-31
0-31
5-36
Sections Analyzed (in cm)
2345
31-61
31-61
31-61
31-61
31-61
31-61
31-61
31-64
36-66
31-61
31-51
31-61
31-61
31-61
31-61
31-61
31-61
31-61
31-61
36-66
61-76
61-76
61-91
61-91
61-91
61-91
61-91
NC
66-96
61-91
NC
61-91
61-91
61-91
61-91
61-91
61-74
61-91
61-91
66-96
NC
91-122
91-122
91-122
91-122
NC
91-122
NC
96-127
91-122
NC
91-122
91-122
91-109
91-122
91-122
NC
NC
91-122
96-127
NC
145-175
122-152
NC
NC
NC
198-229
NC
127-157
122-152
NC
NC
122-152
NC
122-137
185-216
NC
NC
NC
140-170
'NC: not able to be collected due to unsuitable substrate
75
-------
Table 3-2. Water depth sampled and sediment core length.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
DSH 31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
Water depth
(m)
5.49
3.33
3.81
2.93
0
0.22
8.53
N/A
1.07
2.13
2.44
7.92
2.29
1.52
1.22
1.83
2.59
7.01
2.13
2.03
2.74
1.83
2.90
1.37
1.68
2.74
1.98
1.98
6.10
1.68
3.51
1.98
2.29
3.96
2.29
1.52
5.49
5.79
7.62
4.88
Core displacement
(cm)
244
18
244
305
61
152
189
0
198
244
152
335
351
333
305
305
213
274
231
229
292
257
351
244
168
244
274
152
213
213
107
259
305
274
213
305
305
259
244
305
Core length Retrieved Length
(cm) (% of penetration depth)
170
0
155
244
30
102
91
0
71
183
112
206
234
152
211
175
102
173
0
137
76
191
163
147
145
122
244
74
168
170
56
137
178
124
152
231
94
117
137
198
70
0
64
80
49
67
48*
.
36*
75
74
61
67
46*
69
57
48*
63
0
60
26*
74
46*
60
86
50
89
49*
79
80
52
53
58
45*
71
76
31*
45*
56
65
Sites with core compaction of >50% of penetration depth.
76
-------
Table 3-3. Physical description of Ponar grab samples.
Site Description of Ponar grab samples
DSH 01 Silty clay with detritus, oil sheen
DSH 02 Light brown silt/sand mixture, oil sheen
DSH 03 Brown silty clay
DSH 04 Fine brown silty clay
DSH 05 Loose, silty, fibrous sand; slight sheen
DSH 06 Brown, fine sand
DSH 07 Loose, unconsolidated silt
DSH 08 Reddish sand
DSH 09 Light brown sand; some algae growth
DSH 10 Uniform, soft clayey silt
DSH 11 Odorous, mucky silt
DSH 12 Grayish-brown silt/clay; oil sheen
DSH 13 Dark brown silty clay; taconite pellets
DSH 14 Medium brown sand
DSH 15 Reddish sand with fine silt
DSH 16 Sand mixed with gritty ash particles
DSH 17 Dark brown fibrous silty sand
DSH 18 Soft, loose dark brown clay mixture
DSH 19 Dark brown sandy silt
DSH 20 Soft brown silt, slight oil sheen
DSH 21 Mostly sand
DSH 22 Soft brown silt
DSH 23 Soft brown silt/sand
DSH 24 Dark brown silt, oil sheen
DSH 25 Silt and oil mixture
DSH 26 Reddish sand, silt clay mixture
DSH 27 Medium brown soft, silty clay
DSH 28 Plant detritus with silt
DSH 29 Soft brown silt, slight oil sheen
DSH 30 Oxidized iron, very soft silt; Sulfide odor
DSH 31 Medium brown fibrous sand and gravel
DSH 32 Light brown floccy silt (2 cm) atop coarse sand
DSH 33 Clean silt overlaying thick black oil
DSH 34 Clean silt (1 cm) over thick black oil
DSH 35 Clean silt over moderate black oil
DSH 36 Silt with slight oil sheen
DSH 37 Brown silty sand with oil sheen
DSH 38 Brown sandy silt with oil
DSH 39 Reddish brown sand with oil
DSH 40 Dark brown, oily silt
77
-------
Table 3-4, Physical description of sediment cores collected using the vibracorer.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
Depth of Visible Oil
0-45 cm
N/A
None
None
None
None
None
N/A
None
None
8-15 cm
0-45 cm
None
None
None
None
None
91-122 cm
None
0-5 cm
None
None
None
0-41 cm
Depth of Wood Chips
None
N/A
45-50 cm
45-91 cm
None
61-74 cm
None
N/A
51-61 cm
None
93-111 cm
163-180 cm
76-78 cm
81-91 cm
122-127 cm
122-127 cm
41-43 cm
None
95-105 cm
None
15-76 cm
10-86 cm
61-91 cm
None
Other Comments
Clay/sand
No vibracore collected
Mostly clay
Mostly sand
1-ft core; all sand
Mostly clay
Mostly sand
No vibracore collected
Sand to clay
Silt to clay
Silt to clay
Silt to clay
Silt/sand to clay
Mostly sand
Sand to clay
Fly ash and pulverized coal to 91 cm
Black, gritty ash to 41 cm
Soft, blackish clay/silt
All dark brown sandy silt
0-15 cm silt— remainder is sand
Mostly wood chips
Sand and wood chips
Silt/sand and wood chips
Heavy black oil on surface to clay
78
-------
Table 3-4. Continued.
Site
DSH25
DSH26
DSH27
DSH28
DSH29
DSH30
DSH31
DSH32
DSH33
DSH34
DSH35
DSH36
DSH 37
DSH38
DSH 39
DSH 40
Depth of Visible Oil
0-51, 91-104 cm
None
None
None
None
None
None
None
8-15 cm
0-38 cm
8-15 cm
0-21, 27-43 cm
0-41 cm
0-68 cm
0-2 cm
5-36, 96-127 cm
Depth of Wood Chips
51-91 cm
None
None
None
61-96 cm
41-91 cm
None
8-31 cm
None
76-91 cm
41-71 cm
185-215 cm
51-61 cm
31-45 cm
None
None
Other Comments
Heavy black oil through core
Silt to red clay
Mostly stiff gray clay
2-ft core; all plant detritus
Silt to clay to sand; Gas bubbles.
Silt to sandy clay
1.5-ft core; gravel to hard clay
Sand to clay
Silt to clay
Oily sand to clean clay
Oily silt/sand to brown clay
Oily silt/clay to sawdust to fibers
Oily silt to red sand
Heavy oil; sandy; coal chunks
Oil to reddish sand
Oil to clean silt to oil
79
-------
Table 3-5. KCl-extractable and porewater ammonia concentrations in surficial
(approximately 0-30 cm) sediments from the Duluth/Superior Harbor.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH 05-P
DSH06
DSH 07
DSH 08
DSH 09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
KCl-Extractable
Ammonia Concentration
mg/kg dry wt.
71.3
7.71
81.2
41.0
18.2
8.90
20.51
14.6
—
13.7
60.9
110
194
48.0
31.41
9.07
37.8
24.4
135
59.4
12.3
33.6
25.2
89.8
59.0
31.41
20.1
10.7
60.1
200
Porewater
Ammonia Concentration
mg/L
3.38
2.82
2.92
2.51
0.91
__
7.87
8.47
—
1.89
2.74
—
2.63
__
5.63
3.28
2.20
0.50
1.74
2.08
1.34
0.81
1.64
2.12
1.15
2.72
9.54
3.32
_
9.24
lMean of two replicates
80
-------
Table 3-5. Continued.
KCl-Extractable Porewater
Site Ammonia Concentration Ammonia Concentration
mg/kg dry wt. mg/L
DSH30
DSH31
DSH32
DSH33
DSH34
DSH35
DSH36
DSH37
DSH38
DSH39
DSH40
22.6
57.2
46.2
36.7
190
62. 41
83.1
56.0
32.9
6.83
116
3.59
6.87
5.99
5.94
11.4
4.72
5.54
7.52
2.55
0.79
15.6
'Mean of two replicates
81
-------
Table 3-6. TOC concentrations in sediment cores from the Duluth/Superior Harbor. Core
sections are listed in order from the surface to bottom. Table 3-1 gives the sampling depths
associated with each numbered core section.
Site
DSHOl
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
DSH 31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
1
5.36
1.09
3.961
4.21
1.04
2.55
0.40'
NO
1.05
4.08
5.02
3.29
3.16
2.40
0.49
39.80
8.86
1.98
16.10
7.89
1.531
10.15
5.27
5.56
5.23
3.49'
1.29
22.68
5.26
2.98
7.13
2.91
3.15'
3.38
4.03
2.84
5.08
1.65
0.10
3.581
TOC (percent
2
4.15
0.63
9.371
Ponar-1.271
1.23
0.07
NO
1.42
1.19
4.78'
2.67
3.09
1.00
1.27
25.77
1.11
1.92
26.30
0.08
1.60
20.201
6.57
3.25
7.88
3.33'
3.01
33.73
8.96
2.49
0.46
3.93
3.02
5.47'
3.43
4.16
2.73
3.20
0.12
5.72'
dry wt.) in
3
8.37
0.19
5.23
NO
1.55
NO
NO
NO
1.07
5.00
3. 49'
1.64
0.33
1.04
19.16
2.17
1.72
13.76
0.09
NO
1.89
3.70
2.42
10.37'
2.34'
2.84
NO
7.66
1.65
NO
1.66
3.48
4.97
2.28
5.42
2.06
1.01
0.18'
8.29'
each Core Section
4
8.56
NO2
0.08
NO
NO
NO
NO
NO
0.95
11.16
4.00'
1.86
0.90
1.68
9.42'
NO
2.17
8.54
0.08
NO
0.28
4.13
1.091
8.61
NO
3.78
NO
3.79
1.57
NO
1.731
2.59
4.94
4.73
4.02
NO
NO
0.09
6.841
5
5.86
NO
0.14
NO
NO
NO
NO
NO
1.37
NO
5.06
1.35
0.58
1.39
2.09
NO
2.03'
0.89
NO
NO
0.64
5.90
NO
NO
NO
2.16
NO
4.87
1.29
NO
NO
2.261
NO
3.83
7.31
NO
NO
NO
2. 96'
'Mean of at least 2 replicate analyses; 2NO = section not obtained
82
-------
Table 3-7. Mercury concentrations in sediment cores from the Duluth/Superior Harbor.
Core sections are listed in order from the surface to bottom. Table 3-1 gives the sampling
depths associated with each numbered core section.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
Mercury
1
0.102
0.129
0.513
0.162
0.045
0.045
0.054
NO
0.117
0.331
0.838
0.544
0.375
0.080
0.217
0.152
0.457
0.102
0.260
0.124
0.028
0.039
0.414
0.706
0.427
0.274
0.012
0.054
Concentration
2
0.091
NO1
0.176
LOST
0.040
0.022
0.004
NO
0.009
0.031
0.068
0.270
0.092
0.016
0.020
0.237
0.043
0.214
0.373
0.020
0.020
0.045
0.190
0.125
0.652
0.192
0.152
0.063
(mg/kg dry wt.)
3
0.164
NO
<0.001
0.017
NO
0.019
NO
NO
NO
0.019
0.060
0.307
0.026
0.083
0.020
0.159
0.014
0.160
0.164
0.001
NO
0.007
0.121
0.040
0.041
0.049
0.041
NO
in each Core
4
0.131
NO
NO
0.005
NO
NO
NO
NO
NO
NO
0.060
0.232
0.032
0.012
0.020
0.316
NO
0.131
0.091
0.005
NO
0.016
0.071
0.024
0.043
NO
0.051
NO
Section
5
0.110
NO
NO
0.002
NO
NO
NO
NO
NO
NO
NO
0.592
0.014
0.017
0.018
0.034
NO
0.168
0.006
NO
NO
0.010
0.062
NO
NO
NO
0.045
NO
'NO: Section not obtained during coring
83
-------
Table 3-7. Continued
Site
DSH29
DSH30
DSH31
DSH32
DSH33
DSH 34
DSH35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
Mercury
1
0.227
0.231
0.327
0.286
0.198
2.267
0.720
0.410
0.449
0.086
0.005
0.219
Concentration
2
0.393
0.036
0.047
0.516
0.053
0.419
0.115
0.170
0.444
0.436
0.003
0.532
(mg/kg dry wt.)
3
0.298
0.017
NO
0.049
0.065
0.098
0.038
0.164
0.456
0.112
0.007
1.330
in each Core
4
0.219
0.015
NO
0.013
0.033
0.048
0.054
0.215
NO
NO
0.003
1.600
Section
5
0.354
0.014
NO
NO
0.028
NO
0.038
1.333
NO
NO
NO
0.809
'NO: Section not obtained during coring
84
-------
Table 3-8. Heavy metal concentrations in surficial sections (0-30 cm) of sediment cores
from the Duluth/Superior Harbor, measured by cold vapor atomic absorption spectroscopy.
All concentrations are expressed as dry weight, in mg/kg (ppm).
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH 05--P
DSH06
DSH 07
DSH 08
DSH 09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
As
23,7
ND1
10.6
ND
0.7
ND
3.3
ND
NO
ND
17.22
16.8
11.8
11.4
2.5
0.7
14.1
23.3
21.3
6.8
ND2
4.8
7.3
ND
33.5
20.2
8.7
ND
11.9
1.4
4.2
Pb
13.7
3.65
46.1
4.89
5.88
11.4
6.41
5.53
NO
4.28
39.62
49.2
93.3
34.9
9.23
4.84
6.81
73.8
18.6
41.7
12.3
2.47
5.11
19.2
548
289
13.3
4.11
5.26
51.1
9.372
Cu
37.6
4.11
41.6
7.11
6.92
5.31
14.8
6.45
NO
4.76
32.22
48.7
61.4
29.7
18.3
12.1
31.1
52.5
34.2
36.9
11.9
15.3
25.1
7.31
63.9
495
25.7
11.6
45.0
37.3
24.9s
Cr
49.9
5.48
51.5
13.8
14.4
8.17
29.6
12.4
NO
5.71
S3.72
58.4
54.0
49.9
30.4
30.5
30.6
62.8
55.2
43.7
15.0
34.6
37.2
8.46
53.5
93.8
42.9
25.0
40.9
20.9
40.72
Cd
1.84
0.68
2.18
1.24
0.52
1.31
1.48
1.11
NO
1.09
2.862
3.80
2.62
2.41
1.12
2.03
3.02
3.66
2.95
4.56
1.50
1.93
1.49
0.92
7.43
5.53
2.92
1.12
2.16
2.39
1.792
Ni
27.9
3.01
27.1
7.51
8.19
6.37
16.7
7.05
NO
3.90
27. 12
29.6
28.1
25.0
16.5
15.6
27.0
42.0
28.4
26.4
7.90
16.8
24.2
3.77
21.6
118
24.3
12.0
15.9
11.8
25. 32
Zn
91.9
13.7
172
28.4
32.3
18.8
51.8
26.7
NO
11.4
1832
192
193
164
70.3
41.6
45.5
260
102
180
40.1
55.3
76.2
27.7
3780
1650
124
40.7
70.8
123
99.42
'ND; Not detected
2Mean of at least 2 replicate analyses
85
-------
Table 3-8. Continued.
Site
DSH31
DSH32
DSH33
DSH34
DSH35
DSH36
DSH37
DSH38
DSH39
DSH40
Mean
SD
Median
Minimum
Maximum
As
6.0
11.5
6.2
0.4
5.2
5.8
1.0
0.8
ND
3.42
9.6
8.3
6.8
0.4
33.5
Pb
286
47.1
15.5
94.2
37.6
107
54.1
48.9
1.50
205
58.2
105
15.5
1.5
548
Cu
75.2
34.1
25.6
70.4
38.8
63.7
32.4
12.9
5.78
83. 22
42.3
76.6
29.7
4.1
496
Cr
53.3
41.8
38.0
45.3
43.4
43.0
19.0
9.68
15.0
49. 82
35.8
19.4
38.0
5.5
93.8
Cd
3.05
2.07
1.74
4.09
3.59
3.09
1.94
0.92
1.04
2.652
2.4
1.4
2.0
0.52
7.4 "
Ni
26.1
25.4
24.5
25.5
22.7
25.9
10.5
6.23
5.66
30.72
21.4
18.3
22.7
3.0
118
Zn
285
243
93.1
294
153
155
99.4
58.8
20.8
2142
240
629
93.1
11.4
3780
'ND; Not detected
2Mean of at least 2 replicate analyses
86
-------
Table 3-9. X-Ray fluorescence determination of metals concentrations (mg/kg dry wt.) from
selected sites and core depths.
SAMPLE #
DSH 05-01
DSH 05-P
DSH 11-01
DSH 11-02
DSH 11-03
DSH 11-04
DSH 17-01
DSH 17-02
DSH 17-03
DSH 22-02
DSH 22-03
DSH 22-04
DSH 22-05
DSH 24-01
DSH 24-02
DSH 24-03
DSH 24-04
DSH 27-01
DSH 27-02
DSH 27-03
DSH 27-04
DSH 27-05
DSH 32-02
DSH 32-03
DSH 36-01
DSH 36-02
DSH 36-03
DSH 36-04
Cd
ND
<2
2.91
<2
ND
ND
ND
ND
4.07
<2
ND
ND
<2
<2
2.06
<2
<2
<2
ND
ND
<2
ND
<2
ND
4.02
4.59
ND
<2
Ni
<15
16.9
37.4
32.4
36.3
32.6
41.7
<15
22.3
31.9
<15
17.5
19.0
ND
ND
15.0
17.9
<15
<15
36.5
33.1
30.2
34.8
21.2
41.2
32.0
18.6
<15
Cu
15.9
19.1
53.9
30.2
33.7
24.9
66.5
16.3
19.3
34.2
20.0
20.9
18.8
74.8
25.0
35.6
18.0
16.5
31.1
25.6
25.3
19.3
55.7
22.3
81.8
52.2
42.9
42.0
Pb
17.0
12.0
59.0
<5
12.5
<5
82.7
12.1
13.3
17.4
15.1
9.17
9.92
446
59.3
9.38
6.63
<5
27.1
8.04
15.3
9.76
94.1
17.7
119
54.9
22.6
24.9
Hg
ND
<4
<4
ND
ND
ND
ND
ND
ND
ND
<4
ND
ND
ND
ND
<4
ND
ND
ND
<4
ND
ND
<4
<4
<4
ND
ND
ND
Zn
39.9
52.9
242
90.5
94.3
107
326
34.5
24.1
67.2
30.0
26.8
28.2
1630
220
71.6
47.3
38.6
130
75.9
93.4
89.0
192
41.1
190
125
115
101
As
<3.43
4.53
<5.47
9.54
<3.62
5.39
12.6
ND
ND
<3.54
ND
ND
3.66
109
<5.44
4.52
5.62
6.12
<4.05
<3.28
<4.67
5.02
ND
3.80
ND
<5.07
4.39
5.73
87
-------
Table 3-10. Comparison of metal determinations made by atomic absorption spectroscopy
(AAS) vs. x-ray fluorimetry (XRF), in surficial (<30 cm) sediments of the Duluth/Superior
Harbor. The relative percent difference (RPD) of the measurements is given for each sample
and metal. All concentrations are in mg/kg dry wt.
Site
DSH 05-1
(AAS)
(XRF)
RPD
As
0.7
<3.43
Con.1
Cd
0.52
ND (2.0)
Con.
Ni
8.19
<15
Con.
Cu
6.92
15.9
130%
Pb
5.88
17.0
189%
Hg
0.045
N.D. (4)
Con.
Zn
32.3
39.9
23.5%
DSH 05-Ponar
(AAS)
(XRF)
RPD
DSH 11-01
(AAS)
(XRF)
RPD
DSH 17-1
(AAS)
(XRF)
RPD
DSH 24-1
(AAS)
(XRF)
RPD
DSH 27-1
(AAS)
(XRF)
RPD
DSH 36-1
(AAS)
(XRF)
RPD
ND
4.53
Incon.2
16.8
<5.47
Incon.
23.3
12.6
-45.2%
33.5
109
225%
ND
6.12
Incon.
5.8
ND (5.47)
Con.
1.31
<2.0
Con.
3.80
2.91
-23.4%
3.66
ND (2.0)
Incon.
7.43
<2
Incon.
1.12
<2
Con.
3.09
4.02
30.1%
6.37
16.9
165%
29.6
37.4
26.2%
42.0
41.7
-0.69%
21.6
ND (15)
Incon.
12.0
<15
Con.
25.9
41.2
59.0%
5.31
19.1
260%
48.7
53.9
10.7%
52.5
66.5
26.7%
63.9
74.8
17.0%
11.6
16.5
42.4%
63.7
81.8
28.5%
11.4
12.0
5.0%
49.2
59.0
20.0%
73.8
82.7
12.0%
548
446
-18.6%
4.11
<5
Con.
107.18
119
11.0%
—
<4
—
0.838
. <4
Con.
0.457
N.D.
Con.
0.706
N.D.
Con.
0.012
ND
Con.
0.410
<4
Con.
18.8
52.9
181%
192
242
26.3%
260
326
25.1%
3780
1630
-56.9%
40.7
38.6
-5.25%
155
190
22.5%
'Con.; XRF measurement was consistent with AAS measurement
2Incon.; XRF measurement was inconsistent with AAS measurement
-------
Table 3-11. Total PCB concentrations in sediment cores from the Duluth/Superior Harbor.
Core sections are listed in order from the surface to bottom. Table 3-1 gives the sampling
depths associated with each numbered core section.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
1
34,0
140
105
17.0
13.0
10.0
32.52
NO
60.0
95.0
315
296
57.0
29.0
12.0
88.52
lost
68.0
102
16.0
8.8
11.0
105
190
116
68.0
8.3
27.0
154
31.0
Total PCBs
2
45.0
NO1
17.0
7.8
-Ponar: 16.0
7.9
6.6
NO
10.6
10.0
5.4
100
17.0
18.0
2.6
54.0
15.0
73.0
83.0
27.0
30.0
35.0
11.0
7.0
109
49.0
37.0
47.0
470
17.0
Oig/kg dry wt.)
3
78.0
NO
27.0
12.0
NO
11.0
NO
NO
NO
12.0
6.3
125
12.0
17.0
8.2
105
8.7
32.0
43.0
5.8
NO
9.4
8.8
5.9
19.0
37.0
20.0
NO
284
11.0
in each Core Section
4
49.0
NO
NO
2.5
NO
NO
NO
NO
NO
11.0
44.0
75.0
22.0
7.5
17.0
29.0
NO
33.0
9.8
8.3
NO
3.3
15.0
5.4
18.0
NO
11.0
NO
106
14.0
5
17.0
NO
NO
3.7
NO
NO
NO
NO
NO
11.0
NO
158
3.2
8.6
14.0
14.0
NO
19.0
6.0
NO
NO
7.5
27.0
NO
NO
NO
4.0
NO
99.0
15.0
'NO: Section not obtained during coring
2Mean of duplicate values
89
-------
Table 3-11. Continued.
Site
Total PCBs Gig/kg dry wt.) in each Core Section
234
DSH31
DSH32
DSH33
DSH34
DSH35
DSH36
DSH37
DSH38
DSH39
DSH40
156
73.0
56.0
439
203
243
142
132
4.3
131
79.0
26.0
20.0
20.0
14.0
242
36.0
185
11.0
612
NO
13.0
18.0
24.0
12.0
46.0
48.0
20.0
6.0
157
NO
16.0
21.0
21.0
10.0
69.0
NO
NO
7.0
31.0
NO
NO
13.0
NO
10.0
234
NO
NO
NO
7.8
1NO: Section not obtained during coring
2Mean of duplicate values
90
-------
Table 3-12. PCB immunoassay determinations in sediment cores from the Duluth/Superior
Harbor. Core sections are listed in order from the surface to bottom. Table 3-1 gives the
sampling depths associated with each numbered core section.
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
DSH 31
1
<67
<67
170
<67
412
<40
1802
NO
742
1022
<40
<67
962
<67
<40
<67
<40
<67
782
<67
<67
<67
170
<40
<67
<40
130
<67
<67
Total PCBs Gtg/kg
2
<67
NO1
HO2
<67
-Ponar: 442
<40
<67
NO
<40
<40
<40
<67
<40
<67
<40
<67
<40
<67
<40
<40
<67
<67
<67
562
<40
<67
<40
170
330
<67
dry wt.)
3
<67
NO
<40
<67
NO
<40
NO
NO
NO
<40
<40
<67
<40
<67
<40
<67
<40
<67
<40
<40
NO
<67
<67
<40
160
<67
<40
NO
<67
<67
NO
in each Core Section
4
<67
NO
NO
<67
NO
NO
NO
NO
NO
<40
<40
<67
<40
<67
<40
<67
NO
<67
<40
<40
NO
<67
<67
<40
160
NO
<40
NO
<67
<67
NO
5
<67
NO
NO
<67
NO
NO
NO
NO
NO
<40
NO
<67
<40
<67
<40
<67
NO
<67
<40
NO
NO
<67
NO
NO
NO
<40
NO
<67
<67
NO
'NO: Section not obtained during coring
2Less than method quantitation limit (estimated)
91
-------
Table 3-12. Continued.
Total PCBs (/tg/kg dry wt.) in each Core Section
Site 1234
DSH 32
DSH33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
<40
970
150
680
532
270
<40
<67
<40
<40
502
120
260
592
650
<40
190
<40
<40
<40
<40
982
HO2
412
<40
<67
<40
<40
822
<40
210
NO
NO
<40
<67
NO
<40
NO
<40
340
NO
NO
NO
<67
NO: Section not obtained during coring
:Less than method quantitation limit (estimated)
92
-------
Table 3-13. 2,3,7,8-TCDD/TCDF concentrations in surficial sediment core samples from
the Duluth/Superior Harbor.
TCDD
Site (ng/kg dry wt.
DSH01
DSH02
DSH03
DSH04
DSH05
DSH OS-P
DSH06
DSH 07
DSH 08
DSH 09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
ND1
ND
NQ
ND
NQ
0.9
ND
ND2
NO
ND
NQ
ND
ND
2.6
ND
ND2
ND
._
NQ
ND
ND
ND2
ND
ND
8.9
13
NQ
ND
ND
ND
ND
Detection
) Limit
1.6
0.9
2.3
1.5
2.6
—
0.9
1.8
NO
1.6
2.5
11
1.7
—
0.8
0.6
1.6
—
17
3.8
2.3
2.0
2.2
11
—
—
4.0
1.3
1.8
14
6.2
TCDF
(ng/kg dry wt.;
NQ
3.9
9.1
ND
NQ
1.8
ND
4.02
NO
ND
7.9
10
11
NQ
ND
ND2
ND
._
NQ
11
ND
ND2
ND
15
NQ
13
NQ
ND
ND
NQ
NQ
Detection
( Limit
1.6
—
—
1.5
2.1
—
1.4
_
NO
1.4
—
_
—
17
1.9
0.35
3.0
--
5.6
—
4.7
0.45
1.1
__
2.1
—
7.8
1.6
4.8
29
9.0
'Codes: NO = Section not obtained during coring; ND
Quantified
2Mean of duplicate values
= Not Detected; NQ = Not
93
-------
Table 3-13. Continued.
TCDD
Site (ng/kg dry wt.
DSH 31
DSH32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
ND
ND2
ND
ND
ND
NQ
ND
ND
ND
NQ2
Detection
.) Limit
6.8
5.3
2.6
3.5
6.1
62
7.4
2.4
5.5
4.4
TCDF
(ng/kg dry wt.)
NQ
NQ2
ND
3.1
9.5
ND
NQ
ND
ND
NQ2
Detection
I Limit
20
2.6
7.6
_.
__
8.8
31
2.0
1.2
7.3
'Codes: NO = Section not obtained during coring; ND = Not Detected; NQ = Not
Quantified
2Mean of duplicate values
94
-------
Table 3-14. Pesticide concentrations (/Jg/kg dry wt.) in surficial sediment core samples from the Duluth/Superior Harbor. Detection
limits are given in parentheses. Any associated blank concentrations have been deducted from reported concentrations. Boldface
concentrations exceed Lake Huron/Lake Superior background (Persaud et al., 1993). Italicized concentrations exceed OMOEE LEL
guidelines (Persaud et al., 1993).
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH 05-P
DSH06
DSH 072
DSH 08
DSH 09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 162
DSH 17
HCB1
0.04
0
0.13
0
0.03
0
0
0.01
Core
0.15
0.35
0.16
0.17
0.32
0.12
0.12
0.71
Sample
Core section 1
Lindane Aldrin OCS1 o,p'-DDE Dieldrin p,p'-DDE o,p'-DDD
0.07 0.13 0.07
0.01 0.05 0.02
0.21 ND (2.2) ND (0.40)
0.09 0.16 0.02
0.01 ND(1.3) 0.05
0.06 0.06 0.04
0.09 ND (0.24) 0.06
0.03 0.17 0.04
sample could not be collected
ND(1.5) 0.10 0.20
ND (1.5) ND (0.55) ND (0.06)
ND (2.2) ND (0.20) ND (0.01)
ND (3.4) ND (10.1) ND (0.57)
ND(2.1) ND (0.01) ND (0.02)
ND(1.4) 0.15 ND(0.02)
ND(1.6) 0 ND(O.Ol)
ND(1.8) 1.1 ND(0.01)
0.11
0.06
0.56
0.02
0.08
0.07
0.06
0.11
0.41
0.29
1.1
0.73
0.31
0.50
0.08
0.16
NQ
NQ
NQ
NQ
NQ
NQ
NQ
NQ
0.06
ND(1.2)
3.5
0.42
ND (0.53)
0.14
0.06
1,0
0.84
0.63
4.46
0.51
0.21
0.27
0.04
0.63
1.06
1.7
8.5
6.26
1.8
0.19
0.09
1.4
0.32
0.34
ND(l.l)
0.53
0.16
0.13
0.03
0.27
0.78
0.97
3.0
3.6
1.0
0.21
ND (0.01)
1.5
p,p'-DDD
Endrin & o,p'-DDT p,p'-DDT
NQ
NQ
NQ
NQ
NQ
NQ
NQ
NQ
ND (0.30)
0.28
ND (0.46)
ND (0.06)
0.33
0.10
0.07
0.33
1.90
1.42
10.0
2.43
0.45
0.46
0.21
0.75
4.9
5.6
12
10.2
5.7
1.3
0.25
8.1
0.17
0.20
0.51
0.21
0.04
0.07
0.22
0.16
ND(0.13)
ND(0.19)
0.78
0.91
ND (0.03)
ND (0.01)
ND (0.01)
0.57
Chlordane
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND(1.3)
ND (2.7)
ND (9.4)
ND (7.7)
ND (3.2)
ND (3.5)
ND (2.0)
ND (10)
Toxaphene
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (20)
ND (9.3)
ND (19)
113
ND (62.3)
ND (16)
ND (19)
ND (4.8)
ND (9.7)
could not be analyzed due to interferences
'HCB = Hexachlorobenzene; OCS = Octachlorostyrene
2Mean of duplicate values
ND = Not Detected; NQ = Not Quantified, dieldrin and endrin were destroyed during clean-up; N/A = Not Available
95
-------
Table 3-14. Continued. See previous page for a description of footnotes and codes.
Core section
Site
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 272
DSH 28
DSH 29
DSH 30
DSH 31
DSH 32
DSH 33
DSH 342
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 402
Bkgd
LEL
HCB1
0
0.23
0.53
0
0
0.21
0.11
0.99
0.07
0
0.23
0.21
0.10
0.40
0.21
0.17
0.19
0.24
0.28
0.38
0.56
0.03
2.0
1
20
Lindane Aldrin OCS1
ND(0.09) ND(0.44) 0.173
ND (0.80) ND (2.6) ND (0.59)
ND (0.91) ND (0.78) ND (0.49)
ND(2.1) ND(0.78) 0.073
ND(5.6) ND(1.2) 0.153
ND(0.16) ND(1.7) 0.60
ND (5.0) ND (0.06) 8.5
ND(4.8) ND (0.21) ND (0.10)
ND(0.98) ND(5.1) ND (3.6)
ND (0.54) 0.228 0.093
ND(5.1) ND (0.03) ND (0.14)
ND(4.3) ND(0.83) 2.7
ND(2.4) ND(0.12) ND (0.21)
ND (2.3) 3.4 0.21
ND(2.1) 0.89 0.22
ND(1.9) ND (0.75) ND (0.02)
ND(5.2) ND(0.14) ND(0.10)
ND (2.0) ND (0.05) ND (0.05)
ND (2.5) ND (0.08) ND (0.10)
ND(3.3) ND(0.03) 0.19
ND(2.9) ND(0.02) 0.11
ND (2.0) 0.09 ND (0.01)
ND(3.4) ND(0.02) 3.1
1 1
3 2
o,p'-DDE
0.10
0.15
0.14
0.05
ND (0.60)
0.07
0.88
ND (0.5)
0.06
0.025
ND (0.04)
0.63
0.02
0.80
0.38
0.28
2.6
0.69
1.2
0.49
0.58
0.01
0.69
Dieidrin
ND (0.09)
ND (2.0)
ND (0.34)
ND(0.17)
ND (0.95)
ND (1.08)
NQ
NQ
ND (0.33)
ND (0.03)
1.4
1.3
ND (0.24)
3.9
ND (0.74)
0.44
2.5
0.07
NQ
0.02
0
0.01
NQ
1
2
J.
p,p'-DDE
1.08
1.96
0.74
ND (0.58)
0.06
2.6
3.3
12
1.1
0.09
0.49
3.2
0.75
6.7
1.8
0.80
24
4.8
7.6
3.2
1.8
ND (0.004)
4.5
3
5
o,p'-DDD
0.62
1.5
0.52
ND (0.31)
0.07
1.0
0.76
3.0
0.35
ND (0.79)
0.23
2.0
0.12
5.4
1.3
0.23
7.2
2.0
7.3
1.8
0.80
0.02
2.0
Endrin
ND (0.15)
ND (2.6)
ND (0.70)
ND (0.38)
ND (0.57)
ND(O.ll)
NQ
NQ
ND (0.20)
ND (0.03)
ND (0.51)
ND (0.91)
0.20
ND (0.35)
ND (0.06)
0.26
ND (0.52)
0.01
NQ
0.08
0.19
0.02
NQ
1
3
p,p'-DDD
& o,p'-DDT
2.49
2.75
2.25
0.00
0.19
3.09
1.7
1.4
2.09
0.105
0.22
9.3
0,95
36
6.5
2.0
31
8.2
48
8.4
3.6
0.15
JO
• 5
8
p.p'-DDT
0.00
0.95
ND (2.9)
ND (0.34)
ND(1.8)
ND (3.0)
3.0
0.56
ND(1.5)
ND(l.O)
0.18
1.2
ND (0.03)
20
ND (0.37)
ND (0.25)
2.3
0.26
5.7
0.86
0.01
0.10
1.9
Chlordane
ND (3.3)
ND (3.0)
ND (3.4)
ND (3.8)
ND (7.3)
ND (9.6)
-
--
ND (12)
ND (3.6)
ND(2.1)
ND (3.6)
ND (3.2)
ND (7.6)
ND (3.5)
ND (4.8)
ND (15)
ND (3.5)
ND (7.9)
ND (2.3)
ND (2.0)
ND (2.5)
ND (5.2)
1
7
Toxaphcne
ND(ll)
ND (27)
ND (19)
NDtlS)
ND(ll)
ND (18)
-
-
ND(9)
ND (6.8)
ND (14)
64
ND (18)
70
76
ND (18)
81
74
62
60
44
ND (2.9)
140
96
-------
Table 3-15. Comparison of toxaphene extracts analyzed by GC/ECD and GC/SIM.
Toxaphene Concentration (ng/g)
Site GC/ECD GC/SIM
DSH 11 113 85
DSH 32 76 100
DSH 34 69 109
DSH 36 62 60
DSH 37 60 133
DSH 40 147 204
97
-------
Table 3-16. TOC-normalized pesticide analyses of Duluth/Superior Harbor sediments.
indicate samples lacking a detected pesticide value. Chlordane was excluded from table
All concentrations are in /ig/kg oc dry weight. Dashes
due to nondetectable values.
Station
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 79
HCB
0.75
0
3.3
0
2.9
0
2.5
Not
14.3
8.6
3.2
5.2
10.1
5.0
24.5
1.8
0
1.4
6.7
0
q
Lindane
1.3
0.92
5.3
2.1
1.0
3.5
7.5
Collected
—
—
_~
—
—
—
Sample
Aldrin
2.4
4.6
3.8
—
__
42.5
9.5
__
—
—
6,3
0
2.8
could
ocs
1.3
1.8
„_
0.48
4.8
2.4
10.0
19.1
__
_- .
__
—
not
8.7
—
4.8
1 5
Dieldrin
—
__
—
_»
5.7
-._
69.7
12.8
—
5.8
12.2
2.5
be
—
—
Endrin
—
__
__
_,
__
6.9
—
_
10.4
4.2
14.3
0.83
anal.
„
__
o,p'-
DDE
2.1
5.5
14.1
0.48
7.7
2.4
27.5
39.1
7.1
21.9
22.2
9.8
20.8
16.3
0.40
5.1
0.93
1.8
3.3
P,P'-
DDE
15.7
57.8
112
12.1
20.2
1.6
158
101
41.7
169
190
57.0
7.9
18.4
3.5
54.6
12.2
9.4
„
0 59
Total
DDE
17.7
63.3
126.8
12.6
27.9
3.9
185
140
48.8
191
212
66.8
28.8
34.7
3.9
59.6
13.1
11.2
3.3
0 59
o,p'-
DDD
6.0
31.2
.„
12.6
15.4
1.2
67.5
74.3
23.8
59.8
109
31.7
8.8
3.8
31.3
9.3
6.6
__
0 69
p,p'-DDD
&
o,p'-DDT
35.5
130
254
57.7
43.3
8.2
188
467
137
239
312
180
54.2
51.0
20.4
126
17.1
28.5
0
I q
P.P'-
DDT
3.2
18.4
12.9
5.0
3.9
8.6
38.8
—
__
15.5
27.7
—
1.4
0
5.9
—
—
Toxa-
phene
:
|£ _-
--
—
—
2250
: „
—
_-
—
„-
_-
98
-------
Table 3-16. Continued.
Station
DSH23
DSH 24
DSH25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 3O
DSH 31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
OMOEE SEL
EPA SQC
HCB
4.0
2.0
18.9
2.0
0
1.0
4.0
3.4
5.6
7.2
5.4
5.6
6.0
9.9
7.5
33.9
30.0
55.9
24,000
Lindane
—
—
—
—
—
—
—
—
—
--
—
—
--
—
—
—
—
—
1,000
Aldrin
—
—
--
--
17.7
—
—
—
47.7
30.6
—
—
~
—
—
--
90.0
—
8,000
DCS
11.4
1540
—
--
7.2
—
51.3
—
3.0
7.6
--
—
— -
~
3.7
6.7
—
86.6
Dieldrin
—
—
—
—
—
6.2
24.7
—
54.7
—
14.0
74.0
1.7
—
0.39
—
10.0
—
91,000
9,000
Endrin
—
--
-- •
—
--
—
—
6.7
—
—
8.3
~
0.25
"-
1.6
11.5
20.0
—
130,000
4,100
o,p'-
DDE
1.3
15.8
--
1.7
1.9
—
12.0
0.67
11.2
13.1
8.9
76.9
17.1
42.3
9.7
35.2
10.0
19.3
P.P'-
DDE
49.3
59.4
229
31.5
7.0
2.2
60.8
25.2
94.0
61.9
25.4
710
119
268
63.0
109
—
126
19,000
Total
DDE
50.7
75.2
229
33.2
8.9
2.2
72.8
25.8
105
74.9
34.3
787
136
310
72
144
10.0
145
o,p'-
DDD
19.0
13.7
57.4
10.0
—
1.0
38.0
4.0
75.7
44.7
7.3
213
49.6
257
35.4
48.5
20.0
55.9
p.p'-DDD
&
o,p'-DDT
58.6
3d.6
26.8
59.9
8.1
0.97
177
31.9
505
223
63.5
917
203
1690
165
218
150
279
7,100
P,P'-
DDT
—
54.0.
10.7
—
—
0.79
22.8
—
281
—
—
68.1
6.5
201
17.0
0.61
100
53.1
Toxa-
phcne
—
—
—
--
—
—
1220
"
982
2610
~
2400
1840
2180
1180
2670
—
3910
-------
Table 3-17. PAH analyses, conducted October 1993, for samples collected during September 1993. All measurements are reported as
dry weight and are corrected for associated blank concentration. Samples exceeding the OMOEE LEL are given in bold print.
Station
DSHOl
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH09
DSH 10
DSH It
DSH 12
DSH 13
DSH 14
DSH IS
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
Acy
<1900
<1600
<1900
<1900
-------
Table 3-17. Continued.
Station
DSH23
DSH24
DSH25
DSH26
DSH 27
DSH28
DSH 29
DSH 30
DSH 31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
OMOEE
LEL
Acy
<2200
1800
260
<2000
-------
Table 3-18. TOC-normalized PAH results for samples collected during September 1993, analyzed during October 1993. All measurements are
reported as mg/kg oc dry weight. Concentrations exceeding the U.S. EPA SQC are given in italics.
Station
DSH01
DSH02
DSH03
DSH04
DSH 05
DSH06
DSH 07
DSH 09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
Acy
..
-
--
-
--
-
-
..
_
—
-
..
_
..
--
--
-
„
-
_
-
--
Ace
-
-
-
-
-
_
-
—
-
-
-
--
-
—
--
7.68
—
—
—
—
—
11.6
Fie
-
-
-
—
_
--
_
_
_
..
-
~
-
—
_
7.79
-
1.37
-
„
10.8
Phe
1.12
-
—
10.2
—
-
-
14.3
6.86
12.0
16.4
4.75
7.50
_
--
23.4
-
4.16
—
10.5
„
27.9
Am
_
-
—
-
--
—
-
—
—
-
-
„
..
—
-
6.87
-
1.30
-
--
_
6.64
Car
-
-
—
-
-
-.
_
-
—
-
—
_
—
—
„
2.71
-
—
-
_
..
--
Fla
2.80
7.34
3.03
7.84
-
-
0
24.8
23.0
21.9
33.7
14.2
13.8
—
_
22.7
2.53
6.89
..
20.3
__
38.0
Pyr
0.75
19.3
1.77
10.9
-
_
0
5.71
27.0
35.9
28.9
10.4
10.8
„
-
19.8
0
5.28
—
24.8
„_
35.1
Baa
-
_
-
2.66
_
-
-
16.2
15.2
14.7
16.2
8.61
10.1
_
-
12.6
—
4.92
—
11.9
„
23.0
Cry
2.56
9.82
3.46
-
—
—
..
22.9
16.7
15.9
21.2
11.6
11.5
—
-
12.5
—
5.39
_
13.5
~
22.9
Bfa
1.51
9.27
3.06
3.59
—
-
7.75
23.8
29.4
25.5
34.4
17.4
13.4
„
-
19.2
4.09
8.14
—
9.22
_„
35.7
Bap
—
13.8
_
2.14
„
-
-
17.1
13.2
13.0
12.8
4.11
4.17
_
—
8.58
—
3.79
—
13.1
..
17.6
Idp
—
-
-
-
-
„
-
-
—
9.16
9.94
3.39
6.13
—
-
4.59
_
2.78
_
—
__
8.86
Dba
-
-
-
--
_
-
_
_
—
—
_
—
-
.-
„
-
—
—
—
_
—
-
Bgp
—
27.5
-
3.09
—
--
-
18.1
—
9.96
3.04
—
_
—
—
6.21
_
0.68
-
20.9
—
10.4
Nap
-
--
~
-
-
-
—
-
6.37
—
-
7.91
—
_
1.81
37.2
-
2.92
_
..
—
38.0
2Mn
-
-
--
-
-
—
-
-
—
—
„
„
_
_
„
11.3
_
4.16
—
-
—
12.0
TPAH
8.73
87.0
11.3
40.4
-
0
7.75
183
138
158
176
82.5
77.4
—
1.81
208
6.62
51.8
-
124
—
299
102
-------
Table 3-18. Continued.
Station
DSH24
DSH25
DSH26
DSH27
DSH28
DSH29
DSH 30
DSH31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
DSH 37
DSH 38
DSH 39
DSH 40
OMOEE
SEL
EPA
SQC
Aey
32.4
4.97
—
-
-
-
-
-
-
„
-
-
_
..
_
—
-
Ace
10.1
16.2
8.60
—
_
9.70
-
—
-
-
-
—
-
4.92
--
_
26.0
130
Re
95.3
15.9
—
_
—
10.8
--
3.23
-
--
-
—
-
5.71
9.09
--
20.1
160
Phe
450
62.5
27.8
—
1.06
71.7
--
23.8
19.2
—
21.0
10.4
42.2
41.3
43.6
130
164
950
180
Ant
119
15.5
4.84
_
—
13.1
--
5.33
-
-
-
-
6.69
7.48
-
—
42.4
370
Car
15.6
..
„
-
-
5.70
--
-
-
-
-
_
—
—
—
..
20.7
Ra
540
55.6
18.9
—
1.90
81.9
--
21.0
27.5
9.52
32.5
27.3
66.9
35.4
37.0
—
226
1020
620
Pyr
540
75.5
27.2
—
2.43
71.3
_
37.9
48.1
12.1
47.3
29.8
91.6
76.8
54.6
140
225
850
Baa
234
42.3
8.65
-
1.24
36.4
--
15.4
17.9
—
20.4
13.2
38.7
27.6
21.2
_
12.1
1480
Cry
234
53.7
7.36
-
1.41
38.2
-
19.6
18.9
5.71
26.9
14.9
49.3
27.6
21.8
-
123
460
Bfa
362
42.8
8.05
-
1.90
56.5
-
27.1
29.6
8.89
47.0
29.0
86.6
38.2
23.6
—
172
1340
Bap
173
31.2
11.2
—
1.24
25.3
_
13.5
14.4
6.67
21.9
12.9
42.2
18.9
15.2
—
101
1440
Idp
144
27.5
5.65
-
—
17.8
-
12.6
10.3
_
_
—
30.6
14.6
—
-
79.2
320
Dba
36.0
„
-
—
_
-
-
_
—
..
_
_
-
—
..
_
22.4
130
Bgp
101
22.0
17.8
-
-
-
--
10.8
—
-
--
9.93
33.8
-
..
-
74.0
320
Nap
180
19.1
1.15
-
„
4.18
--
„
-
--
8.88
-
-
5.51
15.2
—
67.0
2Mn
23.4
9.94
-
-
.
..
-
2.53
—
-
6.81
-
—
4.72
12.1
..
14.5
TPAH
3330
502
147
-
11.2
442
--
193
186
42.9
233
147
489
309
253
270
1490
10000
Code for PAHs: Acy=Acenaphthylene; Ace=Acenaphthene; Fle=Fluorene; Phe=Phenanthrene; Ant=Anthracene; Car=Carbazole;
Fla=Fluoranthene; Pyr=Pyrene; Baa=Benz(a)anthracene; Cry=Chrysene; Bfa=Benzofluoranthene; Bap=Benzo(a)pyrene; Idp=Indeno(123-
cd)pyrene; Dba=Dibenz(a,h)anthracene; Bgp=Benzo(g,h,i)perylene; Nap=Naphthalene; 2Mn=2-methylnaphthalene; TPAH=Total PAHs.
-------
Table 3-19. PAH analysis on stored surficial (0-30 cm) Vibracore samples (collected September 1993 and analyzed July 1994). All PAHs are in
j*g/kg (ppb) dry weight. Samples exceeding the OMOEE LEL are given in bold print.
PAH
Acy
Ace
Fie
Dbt
Phe
Ant
Car
Fla
Pyr
Baa
Cry
5 me
Bfa
Bep
Bap
Per
Idp
Dba
DSH02
9.6
ND
9.6
ND
59
16
ND
130
110
74
67
ND
150
68
93
130
46
ND
DSH03
51
24
65
41
330
99
30
740
618
440
390
ND
740
290
440
520
200
47
DSH05
27
ND
14
ND
83
15
ND
110
98
54
57
ND
110
42
52
110
26
ND
DSH06
ND
ND
ND
ND
49
12
ND
97
73
51
46
ND
92
33
49
170
25
ND
DSH 14
22
10
29
10
120
40
ND
300
230
150
120
ND
220
78
120
210
63
17
DSH 16
46
ND
37
12
110
17
12
150
94
20
22
ND
17
ND
ND
ND
ND
ND
DSH 18
15
ND
17
ND
84
25
ND
190
180
110
130
ND
250
91
110
180
58
15
DSH 21
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
380
ND
ND
DSH 22
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4200
ND
ND
DSH 23
150
26
120
44
410
270
26
2400
1600
1400
1200
ND
1800
780
1200
480
550
170
DSH 26
ND
ND
ND
ND
53
ND
ND
110
120
45
74
ND
100
47
47
390
24
ND
DSH 29
110
420
500
220
3100
830
390
4900
3400
2000
2000
30
2400
930
1500
400
620
ND
DSH 30
ND
ND
, ND
ND
32
ND
ND
66
72
29
35
ND
64
37
28
290
14
ND
DSH 40
240
660
830
370
6800
1300
840
1300
910
ND
ND
71
7300
2800
4200
1000
2100
460
104
-------
Table 3-19. Continued.
PAH
Bgp
Dip
Dtp
Dip
23bf
23di
Ine
Nap
Bbt
Qnl
Ino
2mn
Imn
Bph
TPAH
DSH02
71
11
32
12
ND
ND
ND
28
ND
ND
ND
35
21
ND
898
DSH03
150
37
63
64
ND
33
33
190
16
ND
ND
230
120
29
4780
DSH05
34
ND
ND
ND
ND
ND
ND
45
ND
ND
ND
63
39
ND
788
DSH06
24
ND
ND
ND
ND
ND
ND
16
ND
ND
ND
22
14
ND
556
DSH 14
50
14
14
ND
ND
25
29
160
11
ND
ND
90
48
13
1740
DSH 16
ND
ND
ND
ND
57
14
96
460
64
68
ND
150
72
19
1140
DSH 18
58
17
27
ND
ND
ND
ND
46
ND
ND
ND
38
19
ND
1330
DSH 21
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DSH 22
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DSH 23
480
160
150
ND
ND
22
48
200
ND
ND
ND
100
46
28
12102
DSH 26
36
ND
ND
ND
ND
ND
ND
21
ND
ND
ND
29
14
ND
659
DSH 29
600
ND
ND
ND
ND
15
29
220
ND
ND
ND
240
150
37
23200
DSH 30
27
ND
ND
ND
ND
ND
ND
16
ND
ND
ND
22
ND
ND
405
DSH 40
2100
56
48
41
ND
16
67
550
17
20
23
620
400
96
30200
ND = Not Detected
Code for PAHs: Acy = Acenaphthylene; Ace = Acenaphthene; Fie = Fluorene; Dbt = Dibenzothiophene; Phe = Phenanthrene; Ant = Anthracene;
Car = Carbazole; Fla = Fluoranthene; Pyr = Pyrene; Baa = Benz(a)anthracene; Cry = Chrysene; 5mc = 5-methylchrysene; Bfa =
Benzofluoranthenes; Bep = Benzo(e)pyrene; Bap = Benzo(a)pyrene; Per = Perylene; Idp = Indeno(l,2,3-cd)pyrene; Dba = Dibenz(a,h)anthracene;
Bgp = Benzo(ghi)perylene; Dip = Dibenzo(a,l)pyrene; Dep = Dibenzo(a,e)pyrene; Dip = Dibenzo(a,i)pyrene; 23bf = 2,3-benzofuran; 23di = 2,3-
dihydroindene; Ine = Indene; Nap = Naphthalene; Bbt = Benzo(b)thiophene; Qnl = Quinoline; Ino = Indole; 2mn = 2-methylnaphthalene; Imn =
1-methylnaphthalene; Bph = Biphenyl; TPAH = total of 17 PAH compounds (i.e., same list as quantitated in the October 1993 analysis).
1O5
-------
Table 3-20. Comparison of split analyses of sediment samples collected during June 1993
and analyzed during either October 1993 or July 1994. Total PAHs include the sum of 17
PAH compounds.
Site
DSH02
DSH03
DSH05
DSH06
DSH 14
DSH 16
DSH 18
DSH 21
DSH 22
DSH 23
DSH 26
DSH 29
DSH 30
DSH 40
Total PAHs
Oct. 1993
948
448
ND
ND
1860
720
131
1900
ND
15,700
5140
23,300
ND
53,400
(j«g/kg dry wt.)
July 1994
898
4780
788
556
1740
1140
1330
ND
ND
12,100
659
23,200
405
30,200
RPD(%)
5.4
150
200
200
6.7
45
160
200
0
26
150
0.43
200
56
CV(%)
3.8
120
140
140
4.7
32
120
140
0
18
110
0.30
140
39
106
-------
Table 3-21. Location and description of surficial sediment samples (0-15 cm) collected on
June 11, 1994.
Site Latitude Longitude Description
DSH21 46°43'10.9"N 92°10'25.4"W Silt mixed with heavy oil
DSH 22 46°43'01,6"N 92°10'17.5"W Fibrous silt/sand mixture
DSH23 46°42'37.8"N 92°11'41.8"W Sandy silt
DSH 26 46°39'48.3"N 92°12'22.4"W Mucky silt (plant material)
DSH 27 46°42'31.0"N 92°09'35.0"W Sandy silt
107
-------
Table 3-22. PAHs in surficial sediments (0-15 cm) from the Duluth/Superior Harbor
collected during June 1994 and analyzed during July 1994. Concentrations are in ng/kg dry
wt. Values exceeding the OMOEE LEL values for 12 PAH compounds are given in bold
print.
PAH Compound
Acenaphthylene
Acenaphthene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
Carbazole
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
5-methylchrysene
Benzofluoranthenes
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 23-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
Dibenzo(a, l)pyrene
Dibenzo(a,e)pyrene
Dibenzo(a, i)pyrene
2,3-benzofuran
2 , 3-dihydroindene
DSH21
2400
650
1900
520
6800
7800
1000
21000
14000
ND
ND
160
15000
5400
9800
2100
4900
1300
4000
1400
1200
ND
ND
110
DSH22
34
ND
24
ND
69
250
28
330
230
360
320
ND
420
140
250
180
110
37
96
34
29
ND
ND
ND
DSH23
84
16
80
28
220
190
16
1500
1200
730
580
96
1600
490
910
380
510
110
460
130
79
240
ND
25
DSH26
ND
ND
ND
ND
16
ND
ND
41
35
26
ND
22
42
33
37
90
11
ND
26
ND
ND
ND
ND
ND
DSH27
17
ND
16
ND
70
34
ND
230
180
150
170
18
250
97
140
380
65
19
72
29
17
ND
ND
ND
108
-------
Table 3-22. Continue^-
PAH Compound
Indene
Naphthalene
Benzo(b)thiophene
Quinoline
Indole
2-methylnaphthalene
1 -methylnaphthalene
Biphenyl
Total PAHs*
DSH21
,
590
750
63
17
24
480
210
110
90,300
DSH22
ND
42
ND
ND
ND
ND
ND
ND
2,570
DSH23
65
180
20
ND
ND
110
59
25
8,370
DSH26
ND
ND
ND
ND
ND
ND
ND
ND
208
DSH27
ND
110
ND
ND
ND
26
13
ND
1,520,'
"Total PAHs are based on the sum of: aeenaphthene, acenaphthylene, anthracene, fluoranthenes,
benzo(b)fluorene, benzo(a)anthracene, benzo(a)pyrene, benzo(g,h,i)perylene, chrysene,
dibenzo(a,h)anthracene, fluorene, indeno(l,2,3-cd)pyrene, naphthalene, phenanthrene, and pyrene.
109
-------
Table 3-23. PAH fluorescence screen results for Duluth/Superior Harbor sediments collected
in September 1993. Core sections are listed in order from surface to bottom. Table 3-1
gives the sampling depths associated with each numbered core section. All concentrations
expressed as /xg/kg dry wt.
Site 1
DSH 01 4600
DSH02 1150±71'
DSH 03 3100±141'
DSH 04 7100
DSH 05 1550±71'
DSH 06 700 ±0'
DSH 07 6200
DSH 08 19600 (Ponar)
DSH 09 577400
DSH 10 18700
DSH 11 28200
DSH 12 136700
DSH 13 30400
DSH 14 1100±141'
DSH 15 1000
DSH 16 900
DSH 17 61000
DSH 18 650
DSH 19 123800
DSH 20 22000
DSH 21 733 ±57'
DSH 22 600
DSH 23 18550 ±353'
DSH 24 286800
DSH 25 2800
DSH 26 2600
DSH 27 650
DSH 28 2400
DSH 291 14733 ±66 10'
DSH 30 800 ±0'
DSH 31 148600
DSH 32 279800
DSH 33 18900
DSH 34 153300
DSH 35 25700
DSH 36 399900
DSH 37 412300
DSH 38 360100
DSH 39 1500
DSH 40 21300±4700'
2
3200
NO2
32,900
800
8800 (Ponar)
600
600
NO
800
800
900
11900
8600
18500
700
2000
7500
8000
223100
700
700
89000
NO
5300
900
2500
900
13200
4300
15200
1900
49700
800
53900
12900
3900
332900
801800
1300
1700
Core section
3
10200
NO
700
1400
NO
600
NO
NO
NO
700
800
23600
800
18500
700
1600
500
24400
132400
700
NO
1000
NO
500
81300
6600
800
NO
2600
500
NO
1800
14200
1700
600
84000
148200
72400
700
2200
4
17100
NO
NO
600
NO
NO
NO
NO
NO
700
800
39000
600
NO
700
40700
NO
6200
55200
700
NO
500
NO
600
15500
NO
500
NO
557700
500
NO
900
700
800
NO
6800
NO
NO
700
2600
5
13500
NO
NO
600
NO
NO
NO
NO
NO
700
NO
38800
500
NO
700
1400
NO
6200
700
NO
NO
800
500
2400
14300
1600±0
301500
18900
'Mean (± standard deviation) of two or more values
2NO: Section not obtained during coring
110
-------
Table 3-24. Tributyltin (TBT), monobutyltin (1-BT), dibutyltin (2-BT), and tetrabutyltin (4-
BT) concentrations in Duluth/Superior Harbor sediments.
Site
DSH01
Mg/kg Sn
Hg/kg Sn OC
Mg/kg TBT
Mg/kg TBT OC
DSH02
Mg/kg Sn
Mg/kg Sn OC
Mg/kg TBT
Mg/kg TBT OC
DSH08
Mg/kg Sn
Mg/kg Sn OC
Mg/kg TBT
Mg/kg TBT OC
DSH20
Mg/kg Sn
Mg/kg Sn OC
Mg/kg TBT
Mg/kg TBT OC
DSH31
Mg/kg Sn
Mg/kg Sn OC
Mg/kg TBT
Mg/kg TBT OC
DSH40
Mg/kg Sn
Mg/kg Sn OC
Mg/kg TBT
Mg/kg TBT OC
TBT
1.3
24
3.3
60
34.3
3150
86
7900
16.3
8151
41
2000
42.8
542
110
1400
71.0
996
180
2500
12.1
338
30
850
1-BT
2.1
39
15.9
1460
18.6
9301
38.4
487
54.1
759
26.9
751
2-BT
1.7
32
20.4
1870
17.8
8901
5.4
68
50.3
705
23.0
642
4-BT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
'Total organic carbon not measured in this very sandy sample; TOC of 2% assumed.
Ill
-------
Table 3-25. Sediment toxicity to Hyalella azteca, Chironomus teutons, Photobacterium
phosphoreum (MicrotoxR), and Vibrio fischeri (MutatoxR).
Site
DSH01
DSH02
DSH03
DSH04
DSH05
DSH06
DSH07
DSH08
DSH09
DSH 10
DSH 11
DSH 12
DSH 13
DSH 14
DSH 15
DSH 16
DSH 17
DSH 18
DSH 19
DSH 20
DSH 21
DSH 22
DSH 23
DSH 24
DSH 25
DSH 26
DSH 27
DSH 28
DSH 29
DSH 30
DSH 31
DSH 32
DSH 33
DSH 34
DSH 35
DSH 36
Percent Survival (%)
Hyalella azteca C. tentans
63
70
77
63
87
57
63
33
83
93
93
27
70
87
90
60
80
50
40
70
23
77
30
60
90
60
100
97
37
53
90
93
77
77
77
63
100
93
90
87
90
97
87
100
87
90
87
90
93
43*
83
83
90
90
77
60
90
80
97
0*
97
83
83
93
93
97
73
77
53
47*
93
73
P. phosphoreum
EC501
NT
39.8%
NT
NT
NT
NT
NT
54.1%
NT
48.0%
52.6%
90%3
74.4%
NT
NT
NT
NT
NT
90%3
90%3
NT
NT
NT
23.7%
NT
NT
NT
NT
90%3
NT
NT
NT
95.9%
90%3
90%3
90 %3
F. fischeri
Genotoxicity2
D
D
D
N
N
N
D
N
N
N
N
D
N
N
S9
N
N
D
D
D
N
N
D
D
D
D
D
D
D
N
D
N
N
D
N
D
112
-------
Table 3-25. Continued.
Site
DSH37
DSH38
DSH39
DSH40
Percent Survival (%)
Hyalella azteca C. tentans
60
57
63
27
53
80
70
83
P. phosphoreum
EC501
90%3
N/A
NT
90%3
V. fischeri
Genotoxicity2
D
D
N
D
'EC50: the sediment porewater concentration at which 50% reduction in bacterial
luminescence was observed. NT = not toxic; N/A = sample not available for testing.
2In the MutatoxR test, N = sample not genotoxic; D = sample caused direct mutation back
to wild strain; S9 = S9 (hepatic-type) activation required for sample to be mutagenic.
Indicates sample was toxic in initial 90% screen, but not in EC50 test run.
113
-------
Table 3-26. Sedimentation rates for sediment cores collected from the Duluth/Superior
Harbor, in cm/year.
Sediment core
Period DSH 36 DSH 38 DSH 11 DSH 20 DSH 28
1954-1993 1.14 ± 0.131 0.94 ± 0.10 0.15 ± 0.05 0.30 ± 0.05 ?2
1954-1964 3.05 ± 0.51 2.03 ± 0.51 ~3 - ?
1964-1993 0.48 ± 0.13 0.56 ±0.15 - - ?
'Estimated uncertainty in the deposition rate
2Not known; no 137Cs was detected in any of the core sections
3Not known; no peak occurred in 137Cs
114
-------
CHAPTER 4
COMPOSITE DESCRIPTIONS
4.1 RELATIVE CONTAMINATION FACTORS
This section provides a comprehensive picture of the relative contamination among 39 of the
40 sites evaluated in this survey. DSH 08 was excluded from the data set because the
substrate was unsuitable for collecting a vibracore sample; butyltins were the only
contaminant measured in a surficial sample collected from this site. For each contaminant
measured that had a corresponding OMOEE LEL value, a relative contamination factor
(RCF) was calculated as follows:
RCF = Contaminant concentration (dry wt. units)
OMOEE LEL (dry wt. units)
This normalization allows comparison of the surficial contamination at a site to that at other
sites, with respect to a guideline that is biologically-based and widely utilized as a screening
tool throughout the Great Lakes. The Wisconsin DNR has used a similar approach in
evaluating relative contamination in Newton Creek and Hog Island Inlet in the Superior
Harbor (Redman, 1994). The same units were used for the contaminant concentration and
LEL value. Metals were given in mg/kg units, organic contaminants in fig/kg units, and
TOC was expressed as a percentage.
Eighteen individual RCFs were calculated for each site (Table 4-1), one for each of the
following contaminants: Hg, As, Cd, Cr, Cu, Pb, Ni, Zn, TOC, aldrin, hexachlorobenzene
(HCB), p,p'-DDD & o,p'-DDT, p,p'-DDE, dieldrin, endrin, lindane, total PCBs, and total
PAHs. OMOEE LEL values were not available for ammonia, toxaphene, octachlorostyrene,
some DDT metabolites, tributyltin, 2,3,7,8-TCDD, and 2,3,7,8-TCDD. Only total PAHs
were included hi the calculation of the total RCFs so as not to skew the results with
individual PAH compounds. Individual RCF values which exceeded 1.0 (i.e., sediment
concentration exceeded the OMOEE LEL value) are listed in bold typeface in Table 4.1.
This table also indicates total RCFs for each site, calculated by adding the unweighted RCFs
for each parameter. TOC was removed from the total RCF values because the LEL value
appeared to be too low for the background TOC in the harbor. Sites with a total RCF
(excluding TOC) value greater than 17 are given in bold typeface in Table 4-1 (i.e., this
signifies sites with an average per contaminant RCF exceeding 1.0).
115
-------
The sites evaluated in this survey showed a great degree of variability in overall level of
contamination (Figure 4-1, Table 4-1). Based on the surficial chemistry results, the least
contaminated site was DSH 05 (total RCF = 3.4), and the most contaminated site was DSH
25 (total RCF = 91). A number of sites exceeded the OMOEE LEL values for heavy
metals, PCBs, and PAHs. Sites in the Superior Harbor generally had relatively fewer
exceedances of the heavy metal, PCB, and PAH LELs than sites in the Duluth Harbor.
Some of this difference may be due to different watershed inputs as the Nemadji River drains
into the Superior Harbor and the St. Louis River drams into the Duluth Harbor. In addition,
the Duluth Harbor watershed has a greater industrial/commercial/residential base than the
Superior Harbor watershed. Thus, there is a greater probability of anthropogenic point and
nonpoint sources of contamination in the Duluth portion of the harbor. The Duluth portion
of the harbor is also impacted by two Superfund sites: USX and Interlake/Duluth Tar.
Two contaminated sediment deposits are located along the western shoreline of the USX
Superfund site. One sediment delta is situated at the mouth of Unnamed Creek, and the
other delta is located at the former outfall of the Wire Milling operation. As part of the
Record of Decision (ROD) for this site, a remedial approach was chosen to remove
contaminants and "cap" the contaminated material with clean material (Barr Engineering,
1985). This approach has not been successful because wave erosion along the shoreline of
the two delta areas is disturbing contaminated sediments. Thus, a clean sediment layer has
not been able to accumulate to naturally cap the sediments. The resuspension of
contaminated sediments from the USX site is a potentially important source of contaminants
to downstream portions of the St. Louis River and Duluth Harbor.
The Remedial Investigation/Feasibility Study (RI/FS) for the Interlake/Duluth Tar Superfund
site found extremely elevated concentrations of coal tars, PAHs, and heavy metals in
sediments near the eastern shore of Stryker Embayment (Malcolm Pirnie, 1991). Stryker
Embayment is encompassed by this Superfund site. The RI/FS indicated there were elevated
concentrations of contaminants within the bay near the mouth. From the sample (DSH 21)
collected in the mouth of Stryker Embayment for this study, the surficial sediment appeared
to be fairly "clean" (i.e., total RCF = 8.6). However, when the upper 15 cm of sediment
was sampled from this site during June 1994, the sediment was highly contaminated with
PAHs (i.e., 90,300 Mg/kg total PAHs). This demonstrates that sediment-associated PAHs
have been transported to the mouth of Stryker Embayment.
The consultants for Interlake have undertaken additional sediment sampling within the
boundaries of the Superfund site, including Stryker Embayment and Docks 6 and 7; the
results of sediment chemistry, toxicity, and benthos data have not been finalized yet. This
116
-------
more recent study will provide additional information as to the potential for resuspended
sediments to be transported and deposited downstream from the Interlake/Duluth Tar site.
Some sediment remediation was conducted during the summer to winter of 1996 that resulted
hi the removal and incineration/landfilling of PAH contaminated sediments from the inland
side of Dock 6. A number of other remediation options are being considered for containing
or treating contaminated sediments from this Superrand site.
As mentioned in Section 3.2.3, the Duluth/Superior Harbor used to be a major port for the
storage and transport of coal from the late 1800s to early 1900s. Several coal gasification
plants, coal storage facilities, and coal-powered ships were historically found in the vicinity
of the harbor. Today, coal is used to a lesser extent, and several technologies are employed
to reduce dust emissions from coal piles. For example, the use of coal for generating
electricity at the M.L. Hibbard/DSD No. 2 Plant ceased in 1973 (Lowell Neudahl,
Minnesota Power, personal communication, 1996). Fuel oil was used from 1973 to 1981,
and the plant was idle from 1981 to 1986. The plant currently burns a mixture of 85% wood
and 15% coal to produce steam instead of electricity; this results in much lower fuel usage at
the plant.
Contaminants associated with coal and coal combustion products include: PAHs, mercury,
lead, and nickel. This study only examined the surficial (0-30 cm) level of these
contaminants, except for the PAH screen. Since the PAH screen results did not correlate
well with the PAH results by GC/MS, it is not possible to quantitatively assess the PAH
contamination at depth. However, the general PAH screening results and field observations
indicated that PAH-like compounds were associated with depth in some cores. This could be
indicative of historical uses of coal in the harbor.
From Table 4-1, the RCFs for individual pesticides were fairly low except for DDT
metabolites in the ernbayment bounded by the Lakehead Material Storage Facility on the west
and Rices Point on the east. This bay has several suspected sources of contamination,
including the discharge of WLSSD and the outfalls of Miller and Coffee Creeks. The
WLSSD discharge encompasses the sum of the cities of Duluth, Proctor, and Cloquet's
treated municipal and industrial effluents, and thus represents a significant potential source of
current contamination. The bay also contains a shipping channel (the 21st Ave. W. Channel)
which has not been dredged in 20 years. Recent work by the Natural Resources
Conservation Service has shown that the channel has been fflled-in by sediments since
dredging was curtailed.
117
-------
4.2 FIELD DESIGN CONSIDERATIONS
In order to ascertain whether it was likely for a site to be misidentified as uncontaminated
(i.e., determine the likelihood of false negative results), sediment contamination was assessed
at several sites in a spatially large area (the bay near WLSSD/Coffee Creek/Miller Creek
outfalls) and several sites in a spatially small area (Slip C).
Six sites (DSH 11-12 and DSH 33-36) were selected in the bay to address the possibility of
false negative results. With the possible exception of site DSH 33, the analysis of any one of
the six sites would have pointed to the need for further assessment. Thus, while the sites
varied slightly among themselves in degree of contamination, the pattern and magnitude of
contamination throughout the area pointed to the need for further evaluation. This area
should be of high priority for future sediment assessments because it represents an area
where current point source loading of contaminants is occurring; thus, the status of the
sediments could provide a valuable indicator of the success of current pollution prevention
and control strategies in protecting sediment quality. The cesium-dating of the sediment
cores in this bay indicated that either sedimentation rates were very slow near the WLSSD
outfall (DSH 11), or that much scouring has occurred there. Therefore, it seems likely that
contaminated sediments from this bay may be moving out into other parts of the harbor.
Four sites were evaluated in Slip C along a line emanating from the terminus of the slip to its
outlet, with the sites approximately 50 m apart. The RCFs for DSH 29 and DSH 37-39,
respectively, were 22, 19, 10, and 3.5. Therefore, overall surficial contamination decreased
from the inland end to the outer end of the slip. The possibility of intrasite variability
affecting the assessment of site contamination hi Slip C was moderate. In two out of four
cores, the slip would have been identified as a medium priority site for further investigation.
The chances of successful identification can be unproved by well planned site selection; that
is, by selecting sites in the reconnaissance survey that are either closest to the suspected
source, or that preliminary, cursory inspections indicate are contaminated. Possible sources
of contaminants to this slip include the City of Duluth's stormwater overflow outfalls; at least
one of these outfalls exists in the Cutler-Magner Slip which drains into Slip C. Additional
historical sources include the industrial effluents that may have been released into this slip
from the Superwood plant, Cutler Magner, and other (now defunct) industries on the north
end of Rice's Point (including a coal gasification plant). It was fairly obvious in the field
that the core at DSH 39 was less-contaminated than those at DSH 29, DSH 37, and 38.
Thus, by carefully pre-selecting sites on a worst-case basis and using field observations to aid
in site selection, the possibility of false negative contamination identification can be avoided.
118
-------
4.3 COMPILATION OF RESULTS
Table 4-2 contains a compilation of the surficial sediment chemistry results for contaminants
that had comparable OMOEE LEL values. A summary of the sediment toxicity tests
resulting in significant toxicity is also given in Table 4-2. The sample sites are given in
descending order according to their total RCF value. It is important to note that correlations
cannot be made between the toxicity test results and sediment chemistry data; this is because
the sediment chemistry measurements were based on the upper 30 cm of the vibracore
samples, whereas the toxicity tests were run on approximately the top 0-20 cm of sediments
obtained using a Ponar dredge.
For the sediment toxicity test results, there was little comparability between the C. tentans
results and the MicrotoxR and MutatoxR results. Double "hits" with the MicrotoxR and
MutatoxR tests only corresponded to significant toxicity in the C. tentans test in two out of
ten occurrences. The results for the H. azteca tests were largely inconclusive due to control
failure of several test runs. However, the results of other sediment investigations the MPCA
is conducting in the harbor also indicate a low occurrence of significant toxicity to H. azteca
and C. tentans. Thus, it may be implied for this study that the H. a&eca results probably
would have shown a low degree of significant acute mortality based on the results of the C.
tentans tests.
Table 4-2 also lists the qualitative priority for conducting further sediment investigations at
the sample sites. This ranking was based on the total RCF value and presence of
bioaccumulative contaminants (e.g., mercury, PCBs) at depth in the core. In general, sites
were ranked as follows:
• Total RCF = 0-10, Very Low
• Total RCF = 11-17, Low
» Total RCF = 18-29, Medium
• Total RCF = 30 - 48, High
• Total RCF = 49-91, Very High
Although DSH 21 (mouth of Stryker Embayment) had a low RCF value of 8.6, this site was
highly contaminated with PAHs when it was resampled in 1994. Therefore, site DSH 21
was given high priority for further study.
The highest priority site for further study was the USX Superfund site. This site, along with
the Interlake/Duluth Tar Superfund site, have been undergoing additional investigations as
119
-------
part of the potentially responsible parties legal obligations. Other sites that were rated highly
for further study included the bay surrounding the WLSSD and Coffee/Miller Creek outfalls,
Fraser Shipyards, Minnesota Slip, area between the M.L. Hibbard Plant/DSD No. 2 and
Grassy Point, and in the old 21st Ave. West Channel. Other areas, such as Slip C and off
the Superior POTW outfall, were listed as medium priority. It is important to note that this
study was limited in scope and was not meant to characterize large areas as to the extent of
contamination.
The preliminary results of this investigation were used to select sites for a hotspot
investigation the MPCA carried put in 1994. The hotspot areas included:
• Minnesota Slip
• SlipC
• WLSSD, Miller Creek, and Coffee Creek Embayment
• Bay south of the DM&IR Taconite Storage Facility
• Bay east of Erie Pier
• Area north of Grassy Point
• Howard's Bay
• Superior POTW
• Kimball's Bay (reference site)
The hotspot investigation included sediment chemistry measurements of different core
segments, 10-day sediment toxicity tests with H. azteca and C. tentans, and an assessment of
the benthological community structure. The results of this hotspot investigation are currently
being evaluated by the MPCA Water Quality Division.
120
-------
Surficial Sediment (0-30 on):
Total RCF of 17 contaminants
O 3-17 O40-49
©18-29 *86-9i
Q3Q-39
Hoarding Island
Lake Superior
Total RCF< 17: ranges from clean sites to potential
to affect some sensitive water uses.
Total RCF > 18: will affect sediment use by some
benthic organisms.
Mmesoia PcfluSglConfrd Agency
1
Kilometers
Figure 4-1. Map of total relative contamination factors (RCFs) for surficial sediments collected in the Duluth/Superior Harbor.
121
-------
Table 4-1. Relative contamination factors (RCFs) for surficial sediments collected in the Duluth/Superior Harbor survey. Boldface RCFs are
greater than 1 (i.e., the surface sediment concentration exceeds the OMOEE LEL).
Chemical
Hg
As
Cd
Cr
Cu
Pb
Ni
Zn
TOC
Aldrin
HCB
p,p' -DDE
p,p'-DDD
& o,p'-DDT
Dieldrin
Endrin
Lindane
PCBs
PAJHs
OMOEE
LEL1
0.2
6
0.6
26
16
31
16
120
1
2
20
5
8
2
3
3
70
4000
Total RCF
Total RCF excluding TOC
Sampling Location (DSH #)
01
0.51
4
3.1
1.9
2.4
0.44
1.7
0.77
5.4
0.065
0.002
0.17
0.24
-
-
0.023
0.48
0.12
21
16
02
0.64
-
1.1
ijm
0.26
0.12
0.19
0.11
1.1
0.025
0
0.13
0.18
-
-
0.003
2
0.24
6.3
5
03
2.6
1.8
3.6
2.0
2.6
1.5
1.7
1.4
4
-
0.0065
0.89
1.3
-
-
0.07
1.5
1.2*
25
21
04
0.81
-
2.1
0.53
0.44
0.16
0.47
0.24
4.2
iO08_
0
0.10
0.30
-
i -
0.03
0.24
0.42
10
6
05
0.22
0.12
0.87
0.55
0.43
0.19
0.51
0.27
1
-
0.0015
0.042
0.056
-
-
0.0033
0.18
0.20*
4.4
3
06
0.22
0.55
2.5
1.1
0.92
0.21
1.0
0.43
2.6
-
0
0.008
0.026
-
-
0.03
0.14
0.14
10
7
07
0.27
-
^JL9_
0.48
|__0.40_
0.18
0.44
0.22
0.4
0.085
0.0005
0.13
0.094
-
-
0.01
0.46
0.0078
5.0
5
09
0.58
-
1.8
0.22
0.30
LJU4_
0.24
Ljy_
i
0.05
0.0075
0.21
0.61
0.03
-
-
0.86
0.48
6.6
6
10
1.6
2.9
4.8
2.1
2.0
1.3
1.7
1.5
4.1
-
0.018
0.34
0.7
-
0.093
-
1.4
1.4
26
22
11
4.2
2.8
6.3
2.2
3.0
1.6
1.9
1.6
5
-
0.008
1.7
1.5
1.8
-
-
4.5
2
40
35
12
2.7
2
4.4
2.1
3.8
3.0
1.8
1.6
3.3
-
0.0085
1.3
1.3
0.21
-
-
4.2
1.4
33
30
13
1.9
1.9
U^L
1.9
1.9
L_L1_
1.6
i_M_
3.2
-
0.016
0.36
0.71
-
0.11
-
0.81
0.65
21
18
14
0.4
0.42
1.9
1.2
1.1
0.3
1.0
0.59
2.4
0.075
0.006
0.038
0.16
0.07
0.033
-
0.41
0.46
11
8
15
l.l
0.12
3.4
LjyL
0.76
0.16
0.98
0.35
0.5
0
0.006
0.018
0.031
0.03
0.023
-
0.17
-
8.8
8
16
0.76
2.4
iJ^L^
1.2
^Ji?_
0.22
1.7
0.38
4
0.55
0.036
0.28
1.0
0.5
0.11
-
1.3
0.28
22
18
17
2.3
3.9
6.1
2.4
3.3
2.4
2.6
2.2
8.9
-
-
-
-
-
-
-
4.6
39
30
18
0.51
3.6,
[_ 4.9
2.1
2.1
0.6
1.8
0.85
2
-
0
0.22
0.31
-
-
-
0.97
0.33*
20
18
19
1.3
1.1
7.6
1.7
^JLJ^
1.4
1.7
,L5_
16
-
0.012
0.39
0.34
-
-
-
1.4
2.1
39
23
20
0.62
-
2.5
0.58
0.74
0.4
0.49
0.33
7.9
-
0.026
0.15
0.28
-
-
-
0.23
Lost
14
6
Concentration units: metals (mg/kg), organic contaminants (/tg/kg), TOC (%)
*PAH value taken from samples collected June 1993 and analyzed July 1994.
122
-------
Table 4-1. Continued.
Chemical
Hg
As
Cd
Cr
Cu
Pb
Ni
Zn
TOC
Aidrin
HCB
p,p'-DDE
p.p'-DDD
& o,p'-DDT
Dieldrin
Endrin
Linda ne
PCBs
PAHs
OMOEE
LEL1
0.2
6
0.6
26
16
31
16
120
1
2
20
5
8
2
3
3
70
4000
Total RCF
Total RCF excluding TOC
Sampling Location (DSH #)
21
0.14
0.8
3.2
1.3
0.96
0.08
1.1
0.46
1.5
-
-
0
0.12
OAS
10
9
22
0.2
1.2
2.5
"T4 ~
1.6
0.16
1.5
0.63
10
-
-
0.012
0.024
-
0.16
19
9
23
2.1
-
1.5
0.33
0.46
0.62
0.24
0.23
5.3
-
0.01
0.52
0.39
-
1.5
' ' 379"
17
12
24
3.5
5.6
12
~ 2.1
4.0
18
1.4
32
5.6
-
0.006
0.66
0.21
2.7
4.6
92
86
25
2.1
3.4
9.2
3.6
31
9.3
7.3
14
5.2
-
0.05
2.4
0.18
1.6
6.6
96
91
26
1.4
1.4
4.9
~~L7 "
1.6
0.43
1.5
1.0
3.5
-
0.004
0.22
0.26
-QJJJ
Ij
20
17
27
0.06
-
1.9
0.96
0.72
0.13
0.75
0.34
1.3
0.11
-
0.018
0.013
-
-
0.12
-
6.4
5
28
0.27
2
3.6
1.6
2.8
0.17
0.99
0.59
23
-
0.012
0.098
0.028
0.7
-
0.38
0.63
37
14
29
1.1
0.23
4.0
0.80
2.3
1.7
0.74
1.0
5.3
-
0.01
0.64
1.2
0.65
-
..___..-
5.8
28
22
30
1.2
0.7
3.0
--~-
1.6
0.3
1.6
0.83
3
-
0.005
0.15
0.12
-
0.067
0.44
0.10*
14
11
31
1.6
1
5.1
2.1
4.7
9.2
1.6
2.4
7.1
1.7
0.02
1.3
4.5
2
-
2J
3.4
50
43
32
1.4
1.9
3.5
1.6
2.1
1.5
1.6
2.0
2.9
0.45
0.01
0.36
0.81
-
-
-
1.0
1.4
23
20
33
0.99
1
2.9
"L5~"
1.6
0.5
"\'.s~
0.78
3.1
-
0.0085
0.16
0.25
0.22
0.087
-
0.8
0.34
16
13
34
11
0.067
6.8
L7
~4.4~"
3.0
1.6
2.5
3.4
-
0.0095
4.8
3.9
1.2
-
-
6.3
2.0
53
49
35
3.6
0.87
6.0
1.7
~~2~4~
1.2
1.4
1.3
4
-
0.012
0.96
1.0
0.035
0.0033
-
2.9
1.5
29
25
36
2
0.97
5.2
L7
__._..
3.5
1.6
1.3
2.8
-
0.01
1.5
6
-
-
~3L5
3.5
37
35
37
2.2
0.17
3.2
0.73
2.0
1.8
0.66
0.83
5.1
-
O.OJ9
0.64
1.1
0.01
0.027
2.0
3.9
24
19
38
0.43
0.13
1.5
0.37
Q.8Q
1.6
0.39
0.49
1.6
-
0.028
0.36
0.45
-
0.063
1.9
1.0
11
10
39
0.025
1.7
0.58
0.36
0.05
0.35
0.17
0.1
0.045
0.0015
0.019
0.005
0.0057
0.061
0.068
3.6
3
40
1.1
0.57
4.4
1.9
"5.2
6^6
1.9
1.8
3.6
O.'l
0.9
1.3
1.9
13
45
41
1 Concentration units: metals (mg/kg), organic contaminants (/tg/kg), TOC (%)
*PAH value taken from samples collected June 1993 and analyzed July 1994.
123
-------
Table 4-2. Summary of contaminant and toxicology data for 40 sites in the Duluth/Superior Harbor. Note that the sediment chemistry
results are not synoptic with the toxicity test results.
Site
DSH25
DSH24
DSH34
DSH31
DSH40
DSH 11
Total
RCF Value
91
86
49
43
41
35
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, p,p'-DDE,
Fie, Phe, Ant, Fla, Pyr, Baa, Cry,
Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn
total PCBs, total PAHs, Fie, Phe,
Ant, Fla, Pyr, Baa, Cry, Bfa,
Bap, Idp, Dba, Bgp
Hg, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Dieldrin,
p.p'-DDE, p.p'-DDD & o,p'-DDT,
Phe, Fla, Pyr, Baa, Cry, Bfa, Bap
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Aldrin,
Dieldrin, p.p'-DDE, Fie, Phe, Ant,
Fla, Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, p.p'-DDD
& o,p'-DDT, Fie, Phe, Ant, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp, Dba, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Dieldrin,
p.p'-DDE, p,p'-DDD&o,p'-DDT, Phe,
Fla, Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Exceed SEL?
Cu, Pb, Ni, Zn
As, Pb, Zn
Hg
Pb
Significant Toxicity Text Results?
H. azteca2
Incon.
Incon.
Incon.
C. tentans
X
X
Microtox
X
X
X
X
Mutatox
X
X
X
X
X
Priority for Further Study /Comments
Very High; high Hg and PCBs in 31-61 cm
core segment
Very High
Very High; high Hg in 31-61 cm core segment
High; higher PCBs than surface in 31-61 cm
core segment
High; high Hg in all deeper core segments,
higher PCBs than surface in 36-66 cm core
segment
High
124
-------
Table 4-2. Continued.
Site
DSH36
DSH 17
DSH 12
DSH 35
DSH 19
DSH 29
DSH 10
Total
RCF Value
35
30
30
25
23
22
22
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, p,p'-DDE,
p.p'-DDD & o.p'-DDT, Phe, Fla,
Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PAHs, Fie, Phe, Ant, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, p.p'-DDE,
p.p'-DDD & o.p'-DDT, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp
Hg, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Fie, Phe,
Fla, Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, Cd, Cu, Pb, Zn, total
PCBs, total PAHs, Fie, Phe, Ant,
Fla, Pyr, Baa, Cry, Bfa, Bap, Idp, Bgp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Fla, Pyr,
Baa, Cry, Bfa, Bap
Exceed SEL?
Significant Toxicity Text Results?
H. azteca
Incon.
Incon.
Incon.
Incon.
Incon.
C. tentans
Microtox
X
X
X
X
X
X
Mutatox
X
X
X
X
Priority for Further Study/Comments
High; high Hg in 122-216 cm core segment,
high PCBs in most deeper core segments
High; surficial PCB sample lost for this site
and could not be included in total RCF
calculation
High; high Hg in 163-180 cm core segment,
PCBs elevated in other core segments but
less than surface
Medium; high Hg in 31-61 cm core segment
Medium; high Hg in 31-61 cm core segment
Medium; high Hg and PCBs in all deeper
core segments
Medium
125
-------
Table 4-2. Continued.
Site
DSH03
DSH32
DSH37
DSH 13
DSH 18
DSH 16
DSH 26
DSH 01
DSH 28
Total
RCF Value
21
20
19
18
IB
18
17
16
14
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
total PCBs, total PAHs, Phe, Fla,
Pyr, Baa, Cry, Bfa, Bap, Idp
Hg, Cd, Cu, Pb, total PCBs,
total PAHs, Fie, Phe, Ant, Fla, Pyr,
Baa, Cry, Bfa, Bap, Idp
Hg, As, Cd, Cr, Cu, Pb, Ni, Zn,
Cry, Bfa
As, Cd, Cr, Cu, Ni
As, Cd, Cr, Cu, Ni,
total PCBs, p,p'-DDD & o.p'-DDT
Hg, As, Cd, Cr, Cu, Ni, Zn,
total PAHs, Phe, Pyr, Bfa, Bap, Bgp
As, Cd, Cr, Cu, Ni
As, Cd, Cr, Cu, Ni, Pyr, Bfa
Exceed SEL?
Significant Toxicity Text Results?
H. azteca2
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
C. tentans
Microtox
X
X
Mutatox
X
X
X
X
X
X
Priority for Further Study/Comments
Medium; higher PCBs than surface in
61-91 cm core segment
Medium; higher Hg than surface in 31-61 cm
core segment
Medium; higher Hg than surface in 31-61 cm
and 61-91 cm core segments
Medium
Medium
Medium; higher Hg man surface in 81-122
cm core segment, higher PCBs than surface
in 51-81 cm core segment
Low
Law; higher PCBs than surface in 61-91 cm
core segment
Low
126
-------
Table 4-2. Continued.
Site
DSH33
DSH23
DSH30
DSH38
DSH22
DSH21
DSH 15
DSH 14
DSH 06
DSH 20
DSH 04
DSH 09
DSH 02
DSH 27
DSH 07
DSH 39
DSH 05
DSH 08
Total
RCF Value
13
12
11
10
9.4
8.6
8.3
8.2
7.3
6.3
5.9
5.6
5.2
5.1
4.6
3.5
3.4
-
Surficial Chemical Contaminant Data1
Exceed LEL?
Hg, As, Cd, Cr, Cu, Ni
Hg, Cd, total PCBs, total
PAHs, Fie, Phe, Ant, Fla, Pyr, Baa,
Cry, Bfa, Bap, Idp, Bgp
Hg, Cd, Cr, Cu, Ni
Cd, Pb, total PCBs,
total PAHs, Phe, Pyr, Baa, Cry, Bfa
As, Cd, Cr, Cu, Ni
Cd, Cr, Ni, Bpg
Hg, Cd, Cr
Cd, Cr, Cu, Ni, Bfa
Cd, Cr, Ni
Cd
Cd
Cd, Bfa, Bgp
Cd, total PCBs
Cd
Cd
Cd
No vibracore sediment sample collected
Exceed SEL?
Significant Toxicity Text Results?
H. azteca2
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
Incon.
C. tentans
X
Microtox
X
X
X
X
Mutatox
X
X
X
X
X
X
X
Priority for Further Study /Comments
Low
Low
Low
Medium; higher Hg and PCBs than surface
in 31-61 cm core segment
Very Low
High; high PAHs (RCF = 22) observed at
this site when it was resampled in 1994
Very Low
Very Low
Very Low
Very Low
Very Low
Very Low
Low; high surficial PCBs, other core
segments not analyzed for PCBs
Very Low
Very Low
Very Low
Very Low
Insufficient information to evaluate
Codes: Fle = Fluorene; Phe = Phenanthrene; Ant=Anthracene; Fla=Fluoranthene; Pyr=Pyrene;
Baa=Benz(a)anthracene; Cry=Chrysene; Bfa=Benzofluoranthene; Bap=Benzo(a)pyrene;
Idp=Indeno( 123-cd)pyrene; Dba=Dibenz(a,h)anthracene; Bgp=Benzo(g,h,i)perylene
2Incon. = Inconclusive test results due to control failure
127
-------
CHAPTERS
RECOMMENDATIONS
This study filled a critical need for an estuary-wide sediment survey that assessed horizontal
and vertical chemical concentrations, as well as determined potential toxicity to benthic
organisms in the Duiuth/Superior Harbor. By supporting the assessment goals of the Phase I
sediment strategy for the RAP, this study formed the basis for three other sediment
investigations the MPCA has been conducting in the St. Louis River AOC. In lieu of listing
recommendations from this investigation that are already being carried out in ongoing MPCA
sediment surveys, some general recommendations for the management of contaminated
sediments in the harbor are given here.
• Determine background levels of contaminants in the St. Louis River AOC. The R-
EMAP project the MPCA is conducting in collaboration with NRRI and the U.S. EPA
will accomplish this for PAH compounds and mercury.
• Develop biologically-based sediment quality guidelines specific to the Duiuth/Superior
Harbor. A logistic modeling approach could be used to develop guideline values.
• Determine clean-up goals for remediation activities in the St. Louis River AOC.
• Implement proposed remediation options at the USX and Interlake/Duluth Tar
Superfund sites. The remediation would be carried out by the potentially responsible
parties in cooperation with the MPCA Site Response Section.
* Develop a GIS-based sediment database for the St. Louis River AOC that would
include sediment chemistry, toxicity, benthological, and tissue residue data. This
database could be expanded from the sediment database currently under development
by GLNPO.
* Conduct hydrodynamic and sediment transport modeling in the Duiuth/Superior
Harbor to determine how susceptible hotspot sediments are to resuspension.
128
-------
Assess the bioaccumulation of contaminants in the Duluth/Superior Harbor by
analyzing benthic fish tissue and conducting 28-day sediment bioaccumulation toxicity
tests with the oligochaete, Lumbriculus variegatus.
Develop sediment remediation options for non-Superfund sites in the Duluth/Superior
Harbor. This could be accomplished by screening previously sampled site data with
the MPCA's draft "Site Screening Evaluation Guidelines." Contaminated sites
identified by this screening step could then be evaluated to identify a set of remedial
options for each site.
Monitor concentrations of 2,3,7,8-TCDD/TCDF in fish tissue in order to ascertain the
risk to human and ecological health of fish consumers. In addition, it would be useful
to analyze sediments and fish tissue for all seventeen 2,3,7,8 substituted congeners of
dioxin and furans. Such assessment may also point out the need for continuing
diligence in controlling point and nonpoint sources of dioxins and furans.
Investigate the occurrence of toxaphene in the harbor.
Increase public education efforts to communicate the results of the MPCA's sediment
investigations hi the St. Louis River AOC and goals for remediation.
129
-------
REFERENCES
American Public Health Association (APHA)/American Water Works Association
(AWWA)/Water Environment Federation (WEF). 1995. Standard methods for the
examination of water and wastewater. 19th edition. American Public Health
Association, Washington, DC.
Ankley, G.T., A. Katko, and J.W. Arthur. 1990. Identification of ammonia as an
important sediment-associated toxicant in the lower Fox River and Green Bay, WI.
Environ. Toxicol. Chem. 9:313-322.
Ankley, G.T., D.A. Benoit, R.A. Hoke, E.N. Leonard, C.W. West, G.L. Phipps, V.R.
Mattson, and L.A. Anderson. 1993. Development and evaluation of test methods for
benthic invertebrates and sediments: Effects of flow rate and feeding on water quality
and exposure conditions. Arch. Environ. Contain. Toxicol. 25:12-19.
ASTM. 1993. Standard guide for conducting sediment toxicity tests with freshwater
invertebrates. E 1383-93. In Annual Book of ASTM Standards, Vol. 11.04. American
Society for Testing and Materials, Philadelphia, PA, pp. 1173-1199.
Azur Environmental. 1996. Mutatox: The Mutatox test system. Promotional literature
from Azur Environmental, Carlsbad, CA.
Bahnick, D.A. and T.P. Markee. 1985. Occurrence and transport of organic
microcontaminants in the Duluth-Superior Harbor. J. Great Lakes Res. 11:143-155.
Barr Engineering. 1985. Remedial Investigation/Feasibility Study for the USX Superfund
Site. Barr Engineering, Minneapolis, MN.
Benoit, D.A., G.L. Phipps, and G.T. Ankley. 1993. A sediment testing intermittent
renewal system for the automated renewal of overlying water in toxicity tests with
contaminated sediments. Water Research 27:1403-1412.
CCREM (Canadian Council of Resource and Environment Ministers). 1987. Canadian
Water Quality Guidelines. Task Force on Water Quality Guidelines. Ottawa, Canada.
130
-------
Cook, P.M., R.J. Erickson, R.L. Spehar, S.P. Bradbury, and G.T. Ankley. 1993. Interim
report on data and methods for assessment of 2,3,7,8-tetrachlorodibenzo-p-dioxin: Risks
to aquatic life and associated wildlife. EPA/600/R-93/OS5, March 1993. U.S. EPA,
Environmental Research Laboratory, Duluth, MN.
Crane, J.L., A.M. Crampton, and J.P. Stecko. 1993. Development of interim sediment
quality criteria for contaminated sites in British Columbia. Prepared for Industrial Waste
and Hazardous Contaminants Branch, Environmental Protection Division, Ministry of
Environment, Lands and Parks, BC. EVS Consultants, North Vancouver, BC. 45 pp.
+ appendices.
Glass, G.E., J.A. Sorensen, K.W. Schmidt, and G.R. Rapp. 1990. New source
identification of mercury contamination in the Great Lakes. Environ. Sci. Technol.
24:1059-1069.
Glass, G.E., J.A. Sorensen, K.W. Schmidt, J.K. Huber, and G.R. Rapp, Jr. 1992.
Mercury sources and distribution in Minnesota's aquatic resources: Surface water,
sediments, plants, plankton, fish, remediation, and methods. Chapter 3 in Mercury in
the St. Louis River, Mississippi River, Crane Lake and Sand Point Lake: Cycling,
Distribution and Sources. Report to the Legislative Commission on Minnesota
Resources, Minnesota Pollution Control Agency, Water Quality Division, St. Paul MN.
April 1992.
Glass, G.E., J.A. Sorensen, J.J. Austin, K.W. Schmidt, L.W. Kallemeyn, S.C. Hedman,
and G.R. Rapp, Jr. 1993. Mitigating mercury hi Minnesota lakes and streams. Report
to the Minnesota Pollution Control Agency and Legislative Commission on Minnesota
Resources.
Gulley, D.D. and West, Inc. 1994. TOXSTAT 3.4. WEST, Inc., Cheyenne, WY.
Heiskary, S. 1996. Lake sediment contaminant levels in Minnesota. Minnesota Pollution
Control Agency, Water Quality Division, St. Paul, MN. 45 pp.
Ingersoll, C.G., D.R. Buckler, E.A. Crecelius, and T.W. LaPoint. 1993. Biological and
chemical assessment of contaminated Great Lakes sediment. U.S. EPA Great Lakes
National Program Office, Chicago, IL. EPA 905-R93-006.
131
-------
Jeremiason, J.D., K.C. Hornbuckle, and S.J. Eisenreich. 1994. PCBs in Lake Superior,
1978-1992: Decreases in water concentrations reflect loss by volatilization. Environ.
Sci. Technol. 28:903-914.
Krone, C.A., D.G. Burrows, D.W. Brown, S.-L. Chan, and U. Varanasi. 1989. Butyltins
in fish from tributytin-contaminated sites. Society for Environmental Contamination and
Toxicology 1989 Annual Meeting Abstracts. Toronto, Ont., Canada.
Kutka, F., and C. Richards. 1993. Personal communication (Poster exhibited at University
of Minnesota Natural Resources Research Institute).
Lake Superior Binational Program. 1996 (draft). Estimates of mercury, PCBs, dioxins, and
HCB releases in the U.S. Lake Superior basin. Prepared by Superior Work Group,
Lake Superior Binational Program.
Malcolm Pirnie. 1991. Remedial Investigation/Feasibility Study for the Interlake
Steel/Duluth Tar Superfund site. Malcom Pirnie, Golden Valley, MN.
Microbics, Inc. 1993. Technical manual for conducting MicrotoxR and MutatoxR tests with
aqueous samples.
Minnesota Department of Health (MDH). 1996. Minnesota fish consumption advisory.
Minnesota Department of Health, Division of Environmental Health, Health Risk
Assessment Unit, St. Paul, MN.
Minnesota Pollution Control Agency (MPCA)/Wisconsin Department of Natural Resources
(WDNR). 1992. The St. Louis River System Remedial Action Plan, Stage One, April
1992.
Moore, D.R.J., R.C. Pierce, and M.P. Wong. 1990. Developing Canadian water quality
guidelines for tributyltin to protect freshwater and marine aquatic life. Society of
Environmental Toxicology and Chemistry Annual Meeting abstract. Arlington, VA.
Sept. 1990.
Owen, C.J., R.P. Axler, D.R. Nordman, M. Schubauer-Berigan, K.B. Lodge, and J.P.
Schubauer-Berigan. 1995. Screening for PAHs by fluorescence spectroscopy: A
comparison of calibrations. Chemosphere 31:3345-3356.
132
-------
Persaud, D., R. Jaagumagi, and A. Hayton. 1993. Guidelines for the protection and
management of aquatic sediment quality in Ontario (Revised). Report No. ISBN 0-7729-
9248-7. Ontario Ministry of Environment and Energy, Water Resources Branch,
Ottawa, Ontario.
Redman, S. 1994. Technical report on sediment contamination in Newton Creek and Hog
Island Inlet. Report of the Wisconsin DNR Sediment Management, Assessment and
Remediation Team, Madison, WI.
Schubauer-Berigan, M. 1993. Quality assurance project plan for a survey of sediment
quality in the Duluth/Superior Harbor. Minnesota Pollution Control Agency, Water
Quality Division, St. Paul, MN.
Schubauer-Berigan, M. and J.L. Crane. 1996. Preliminary contaminant assessment of the
Thomson, Forbay, and Fond du Lac Reservoirs. Minnesota Pollution Control Agency,
Water Quality Division, St. Paul, MN. 80 pp. + appendices.
Schubauer-Berigan, M.K., P.O. Monson, C.W, West, and G.T. Ankley. 1995. Influence
of pH on the toxicity of ammonia to Chironomus tentans and Lumbrieulus variegatus.
Environ. Toxicol. Chem. 14:713-717.
Smith, V.E. and J.C. Filkins. 1992. Method standard operating procedure for the analysis
of PAHs by the fluorescence screening method. U.S. EPA SOP; Large Lakes Research
Laboratory, Grosse He, MI.
Smith, V.E. and S.G. Rood. 1994. Sediment Sampling Surveys, pp. 33-56 hi ARCS
Assessment Guidance Document. Great Lakes National Program Office, Chicago, IL.
EPA-905-B94-002. 316pp.
Sorensen, J.A., G.E. Glass, K.W. Schmidt, J.K. Huber, and G.R. Rapp, Jr. 1990.
Airborne mercury deposition and watershed characteristics in relation to mercury
concentrations in water, sediments, plankton, and fish of eighty northern Minnesota
lakes. Environ. Sci. Technol. 24:1716-1727.
Stortz, K.R. and M. Sydor. 1980. Transports in the Duluth-Superior Harbor. J, Great
Lakes. Res. 6:223-231.
133
-------
Tetra Tech. 1996 (draft). Estimates of mercury, polychlorinated biphenyls, dioxins, and
hexachlorobenzene releases in the U.S. Lake Superior basin. Prepared by Tetra Tech,
Inc., Fairfax, VA for the U.S. Environmental Protection Agency, Washington, DC. 47
pp.
U.S. Corps of Engineers (USCOE). 1974. Duluth-Superior and adjoining areas urban
study. St. Paul District for the USCOE. 81 pp.
U.S. EPA. 1992a. Quality assurance/quality control, sampling, and analytical
considerations, pp. 2-1 to 2-21 in Sediment Classification Methods Compendium. U.S.
Environmental Protection Agency, Office of Water, Washington, DC. EPA 823-R-92-
006. 21 pp.
U.S. EPA. 1992b. Tiered testing issues for freshwater and marine sediments—Workshop
Proceedings Technical Report. U.S. EPA Science of Office and Technology,
Washington, DC.
U.S. EPA. 1993. Guidance for assessing chemical contaminant data for use in fish
advisories. Volume 1. Fish sampling and analysis. U.S. Environmental Protection
Agency, Office of Water, Washington, DC. EPA 823-R-93-002.
U.S. EPA. 1994. EPA's contaminated sediment maiiagement strategy. U.S. Environmental
Protection Agency, Office of Water, Washington, DC. EPA 823-R-94-001.
World Health Organization (WHO). 1990. Environmental health criteria 101:
Methylmercury. World Health Organization, Geneva, Switzerland.
134
-------
APPENDIX A
DATABASE OF SEDIMENT CHEMISTRY DATA
-------
APPENDIX A
DATABASE OF SEDIMENT CHEMISTRY DATA
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
GREAT LAKES NATIONAL PROGRAM OFFICE
77 WEST JACKSON BOULEVARD
CHICAGO, IL 60604-3590
Hw
January 16, 1997 JAN 21 1997
M P C A
Judy L.Crane, Ph. D, Water Quality
Minnesota Pollution Control Agency
Water Quality Division
520 Lafayette Rd. N.
St. Paul, MN 55155-4194
SUBJECT: Electronic data for 1993 Mudpuppy sampling - Duluth/Superior Harbor
VA^-"
DearfMsyCrane:
Please find enclosed a diskette with data from the 1993 Mudpuppy project. The data has been
formatted in MS Excel according to the GLNPO data reporting format, provided to you last
August, Ail the files, with the exception of one, adhere to this format. The one exception is the
station file (dsstatn.xls), which follows the Station Reporting Standard, a hard copy of which I
have enclosed.
The Mudpuppy data contains three types of files. The station file (dsstatn.xls) contains station
descriptions and location information. The field file (dsfield.xls) contains detailed sample
information, and all the remaining files contain analytical results. Each result file represents a
different analytical method (e.g., dspcb.xls and dspcbimrn.xls contain PCB and
PCB/immunoassay data, respectively).
Files containing the lists of allowable codes for the Station Reporting Standard are contained on
a second diskette. Each file contains codes for a single column within the Station Reporting
Standard.
A list containing short descriptions of file contents is enclosed. If you have any questions or
comments, please call me at (312) 353-3565.
Sincerely,
Brian Stage
Enclosures
cc: Callie Bolattino (letter only)
Printed on Recycled Paper
-------
File Name Description
93 Mudpuppy files
Note: 'ds' prefix stands for Duluth/Superior
dsdiox&f.xls dioxin & furan
dsfield.xls field file
dsmetais.xls metals other than As and Hg
dsmetas.xls arsenic (As)
dsmethg.xls mercury (Hg)
dsmetxrf.xls metals by x-ray fluorescence
dsnh3.xls ammonia
dspahall.xls PAH's
dspahflr.xls PAH, by fluorescence
dspcb.xls PCB's
dspcbimm.xls PCB's by immunoassay
dspest.xls pesticides
dsstatn.xls station file
dstoc.xls TOC
Station Reporting Standard files
(for use with dsstatn.xls)
alp_type.xls absolute location point type
country.xls country
county.xls F1PS county
datum_h.xls geopositioning horizontal datum
datum_v.xls geopositioning vertical datum
dist_shr.xls distance to shore
huc.xls FIPS hydrologic unit code
native.xls native american lands
poll_rel.xls pollutant spatial relation
poll.src.xls pollutant source
reln.shr.xls relation to shore
stn_shap.xls station shape
stn_typ.xls station type
-------
AUC-23-36 11 23 FROM AMS ID 7032276704 PACE 2/13
STATIC Reporting Standards
Station/Location Reporting Standard
This reporting standard includes two spreadsheet templates for entering station and location information.
When entering data, you first should enter all data into the station, spreadsheet template. Then, you wfll
enter the data in the absolute location point template. You also need to link the data in the two
spreadsheets by using the first column of both spreadsheets (Le., station GLNPO code).
Most importantly to submit data using this reporting standard, you should read through the following
directions carefully before entering any data into either spreadsheet template.
Template Layout
The template includes all the information about the data model that you need to know to enter data. For
example, the column headings denote the table and column names, the cardinality among the data in the
template, and additional information that may be useful. The presentation of the column headings also is
intended to provide you with useful information. For example, CAPITALIZATION denotes mandatory.
Underlined entries specify whether you need to indude a valid reference table code. These concepts are
described in more detail below. The following descriptions also can be used as reference material until you
become familiar with the general template layout
Column Headings
Each template has several column headings. Each row of the column heading has a different purpose as
described below.
1st row—Logical Data Unit * describes the group of columns that fall between the pair of dark black
lines.
2nd row—Cardinality Explanation * describes how many rows should be included for the logical
data unit (i.e., the columns mat faH between the pair of dark black lines).
3rd row—Entity Type/Table Name = references the entity type/table name where the data will be
stored in the target database.
-------
AUC-23-36 11 23 FROM AMS
ID 7832276704
PACE
The reference tables that are included in the station spreadsheet template include:
x (1) Absolute Location Boint Type
(1)- Map or Photo
./ (3) Geopositioning Map or Photo Scale
/* (4) Geopositioning Horizontal Method
45) Geopositioning Horizontal Datum
M6) Geopositioning Vertical Method
(7) Geopositioning Vertical Datum
/(8) FTPS County
\9) USDA District (to be determined)
/
,(10) HPSHUC
- (11) Native American Land
(12) EPA RF1 River Reach
(13) Unit of Measure
Reference tables with the valid code for data entry are attached to these instructions. Do not enter codes thai
do not exist in the attached tables. You also should not add entries and new codes to the attached reference ,
tables. (If you absolutely need a code that is not listed, contact the project manager. He will research your
request and provide an answer, usually within a few days.)
Linking Stations to Absolute Location Points
Although stations and absolute locations points are reported on separate spreadsheets, the data in both
spreadsheets are related. In other words, a row in the station spreadsheet is related to a row(s) in the
absolute location point spreadsheet Therefore, when you use this reporting standard, you need to makt
link between the two spreadsheets so that the data can be related in the database.
The logical connection between the rows in the two spreadsheets are as follows:
Station
Absolut**
Location Point
A STATION must have one or more ABSOLUTE LOCATION POINTS.
An ABSOLUTE LOCATION POINT must have one and only one STATION.
ST*Ti
Stsndarde
-------
AUC-23-96 11 21 FROM AMS
ID 7832275704
PACE
\ 3
For each logical unit, there is a pre-defined cardinality between station and the logical unit In other words,
each station could have many entries in a logical unit such as Station Pollutant Source information. For
example, a station may be polluted by more than one type of pollutant source (e.g., urban runoff, industrial
discharge).
These cardinalities are described in the second row of the template. When there is ONE Entry per Station,
the user should enter only one row of data for any given station. When this row states MANY Entries per
Station, the user may enter one or more rows of data.
The following table provides a high-level example of how the template should be used. To simplify the
explanation, this example does not include all me template columns.
Figure 3: Simplified Station Template
(In comparison to the r&ai template, some columns and rows of column headings have been deleted in £fc
-------
AUC-23-96 11 22 FROM AMS '° 7332276704 PAGE
Like the station template, the spreadsheets are divided into logical units of data entry as denoted by the
thick, solid black lines. For example in figure 6 above, the logical unit is standard location information.
Figure 5 includes the logjcaLunits called latitude/longitude and geopositioning explanation. In this
template, the cardinality among these logical units is one entry for every absolute location point
To enter data in the template, the user should begin in the left-most column (t'.e, station GLNPO code) a
continue to the right. On every row, you must not only enter a station GLNPO code in the first column,
the code must match a GLNPO code that was provided in the station template. If this GLNPO code dos
not correspond to an entry in the station template, there is no way to relate the absolute location
information to a station.
-------
APPENDIX B
SEDIMENT TOXICITY TEST REPORTS FOR HYALELLA AZTECA
AND CHIRONOMUS TENTANS
-------
ACUTE TOXICITY TESTS
WITH
HYALELLA AZTECA AND CHIRONOMUS TENTANS
ON SEDIMENTS FROM THE DULUTH/SUPERJOR HARBOR;
1993 Sampling Results - Batches # 1 and 2
Conducted by
Minnesota Pollution Control Agency
Monitoring and Assessment Section
520 Lafayette Road
St. Paul, Minnesota 55155-4194
February 1997
-------
TABLE OF CONTENTS
c
INTRODUCTION 1
SAMPLE COLLECTION AND HANDLING 1
METHODS 1
RESULTS 3
SUMMARY 5
REFERENCES 6
APPENDIX A - TOXSTAT Analysis
u
-------
LIST OF TABLES
*
TABLE 1. Daily Overlying Water pH Measurements 7
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L) 8
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius) 9
TABLE 4. Mean Percent Survival ofHyalella azteca and Chimnomus tentans 10
111
-------
INTRODUCTION
As part of the 1993 survey of Pediment quality in the Duluth/Superior Harbor, sediment toxicity
tests were conducted to assess acute (survival) and chronic (growth) toxicity to benthic
invertebrates. Acute effects were measured in separate 10-day toxicity tests to Hyalella azteca
(H. azteca) and Chironomus tentans (C. tentans). Growth was measured at the end of the
C. tentans test to assess chronic effects. Survival and growth endpoints were compared to
organisms similarly exposed to a reference control sediment collected from West Bearskin Lake
(Cook County, MM).
A total of 40 sediment samples were collected for toxicity testing. This report presents the
results of nine of these sediment samples run in two separate batches with separate controls.
SAMPLE COLLECTION AND HANDLING
Between September 13-23, 1993, Minnesota Pollution Control Agency (MPCA) staff collected
the nine sediments referred to in this report. The samples were collected from the harbor using a
Ponar sampler and were taken to the University of Minnesota-Duluth Chemical Toxicology
Research Laboratory. The samples were stored at 4°C until they were transported to the MPCA
Toxicology Laboratory in St. Paul, MN on October 4, 1993.
METHODS
Nine sediment samples and two control sediment samples were subjected to the 10-day sediment
toxicity tests using the modified procedures described in ASTM (1993). However, the specific
test system used for these assays is not indicated in the methods. The test organisms (H. azteca
and C. tentans) were exposed to sediment samples for ten days in a portable, mini-flow system
described in Benoit et al. (1993). The test apparatus consists of 300 mL, glass-beaker test
chambers held in a glass box supplied with water from an acrylic plastic headbox. The beakers
have two, 1.5 cm holes covered with stainless steel mesh, to allow for water exchange, while
containing the test organisms. The headbox has a pipette tip drain calibrated to deliver water at
an average rate of 32.5 mL/min. The glass box is fitted with a self-starting siphon to provide
exchange of overlying water.
The H. azteca used for this test were 1 to 3 mm long, and the C. tentans were approximately 14
days old. These organisms were supplied by Environmental Consulting and Testing in Superior,
WI. On the day of the Batch #1 test set up, MPCA personnel picked up the organisms from the
supplier and transported them to the MPCA Toxicology Laboratory. An insufficient number of
H. azteca were received to set up the toxicity tests. Thus, another batch of H. azteca was
received from the supplier the next day via Federal Express.
On October 4, 1993, four samples (DSH 08, DSH 12, DST" 21, and DSH 40) and the control
sediment were separately homogenized by hand, and 100 mL of each sediment was placed in a
test beaker (Batch #1). On October 5, 1993, five more samples (DSH 16, DSH 18, DSH 19,
-------
DSH 23, and DSH 29) and another control sediment were homogenized and placed in beakers
(Batch #2). Aerated, artesian well water was added to the beakers, and the sediments were
allowed to settle for approximately two hours before the organisms were added. The sediment
samples for DSH 18 and DSH 19 had accidentally frozen during storage. These sediment
samples were thawed in a water bath the morning of October 5 before homogenizing them.
Each sediment test was set up with three replicates of H. azteca and three replicates of C. tentans.
Ten organisms were placed in each of six beakers in a random fashion. The organisms were
exposed to 16 hours of light and eight hours of darkness for the duration of the ten-day test.
Each day, two liters of aerated water from the artesian well at Stroh Brewery in St. Paul were
exchanged in each test chamber. On weekdays, this was done in two equal aliquots. On
weekends, the two liters were passed through the chambers all at once. Water quality
measurements (i.e., pH, temperature, and dissolved oxygen) of the overlying water were taken in
one beaker of each of the triplicate sets of each of the sediments. The results, along with daily
observations involving the physical appearance of the sediments and organisms, were recorded in
a laboratory notebook.
The test was terminated on October 14, 1993 for Batch #1 and on October 15, 1993 for Batch #2.
The sediments were sieved through 40 mesh screens, and the sieved material was sorted for
organisms. The organisms found were counted, and the number of alive and dead organisms
were recorded. Organisms not found were recorded as missing and presumed dead. The
C. tentans that survived were placed hi aluminum weighing dishes, dried at approximately 90°C
for at least four hours, desiccated to room temperature, and weighed.
Growth (weight) of the C. tentans and survival of both organisms were used as the endpoints for
these tests. The resulting survival data were analyzed using TOXSTAT (Gulley and WEST, Inc.,
1994), a statistical software package obtained from the University of Wyoming; however, due to
a quality assurance problem, the growth data were not analyzed.
A 96-hour, reference toxicant test with H. azteca in sodium chloride (NaCl) was run in
conjunction with these toxicity tests to determine the acceptability of the H. azteca used. Four
concentrations of NaCl solution (i.e., 5, 2.5, 1.25, and 0.625 g/L) and a control (aerated, artesian
well water) were used in this test. Three replicates of five organisms each were set up per
concentration.
-------
RESULTS
Water Quality »
Measurements of pH, dissolved oxygen concentration, and temperature in the overlying water of
the test beakers were made daily. These measurements are summarized below and in Tables 1, 2,
and 3, respectively, for both batches of tests.
Batch # 1 Water Chemistry
In Batch #1, the range of pH values in the beakers containing H. azieca was 7.2 to 7.7 (Table 1).
The water in the C tentans beakers had a pH range of 7.0 to 7.5 (Table 1). The pH fluctuations
during these tests were acceptable since it did not vary more than 50% within each treatment
(U.S. EPA, 1994).
The dissolved oxygen concentration ranged from 3.8 to 7.6 mg/L in the H. azteca beakers and
from 1.6 to 7.2 mg/L in the C. tentans beakers (Table 2). It should be noted that on days 2, 3, 5,
6, and 9, the dissolved oxygen concentration in the DSH 40 sediment beaker containing C.
tentans was less than 40% saturated, which is out of the acceptable test range for dissolved
oxygen.
The temperature of the overlying water in each glass box was measured and ranged from 20.0°C
to 22.5°C (Table 3). The recommended temperature for this test is 23 ± 1°C (U.S. EPA, 1994).
Batch # 2 Water Chemistry
In Batch #2, the range of pH values in the beakers containing H. azteca was 6.9 to 7.7 (Table 1).
The water in the C. tentans beakers had a pH range of 6.8 to 7.7 (Table 1). These pH ranges
were acceptable for these tests.
The dissolved oxygen concentration ranged from 4.4 to 6.9 mg/L in the H. azteca beakers and
from 3.2 to 6.7 mg/L in the C. tentans beakers (Table 2). It should be noted that on day 5, the
dissolved oxygen concentration in the DSH 19 sediment beaker containing C. tentans was less
than 40% saturated. On day 9, sample DSH 29 and Control #2 also had low dissolved oxygen
concentrations in the C. tentans tests.
The range of temperature values in the beakers was measured and ranged from 20.0°C to 22.5°C
(Table 3). The recommended temperature for this test is 23 ± 1°C (U.S. EPA, 1994).
-------
Test Endpoints
The mean percent survival of the test organisms is summarized below and in Table 4. The
sediments for DSH 18 and DSH 19 had frozen during sample storage. Changes in the sample
matrix that may have taken place during the freezing and thawing of these sediments could not
be determined. Thus, it is not known whether similar survival data would have resulted from
using unfrozen sediments for these toxicity tests.
The mean percent survival of H. azteca in Control #1 was 13% with a range of 0% to 30%. For
Control #2, the mean percent survival was 33% with a range of 10% to 50%. Survival for both
of these controls was less than 80% and, therefore, unacceptable. Thus, both test batches for H.
azteca failed.
For the control sediment containing C. tentans, percent survival ranged from 90% to 100% with
a mean of 93% for Control #1 and a range of 80% to 100% with a mean of 90% for Control #2.
Mean percent survival of C. tentans in Batch #1 in the test sediments ranged from 83% in the
DSH 40 sample to 100% in the DSH 08 sample. Mean percent survival of C. tentans in Batch #2
ranged from 77% in the DSH 19 sample to 97% in the DSH 23 sample.
Although the dried C. tentans were weighed, the balance on which they were weighed was not
calibrated with standard weights; therefore, the data are suspect since the internal calibration of
the balance may have drifted with time.
Data Analysis
Survival data for both batches of test sediments containing C. tentans, except DSH 08 (100%
survival) and DSH 21 (90% survival), were transformed using an arc sine-square root
transformation before being analyzed statistically using Dunnett's test. A one-tailed test was
used to test the alternative hypothesis that sample survival was less than control survival. Thus,
it was not necessary to include the sample survival data which exceeded the control survival in
the Dunnett's test (e.g., survival data for DSH 08). For DSH 21, survival (90%) was within the
variability of 30-50% necessary to see any significant difference between the control and any
given sediment (T. Norberg-King, U.S. EPA, Duluth, MN, personal communication). Thus, it is
reasonable to assume that the effect that DSH 21 had on the test organisms was not significantly
less than that of the control.
For both batches of test, none of the test sediment survivals were statistically less than the control
at p=0.05 (Appendix A). For test batch #2, all of the survival results were included in the
Dunnett's test even though the survival in DSH 23 and DSH 29 exceeded the control survival.
This was because the statistical analysis had been run prior to implementing a policy at the
MPCA Toxicology Laboratory to exclude results exceeding the control survival.
4
-------
Reference Toxicant Test with Hvalella azteca in Sodium Chloride Solution
The pH of the overlying water in the reference toxicant test ranged from 7.1 to 8.0. The
dissolved oxygen ranged from 7.4 to 8.4 mg/L and the temperature was 21°C on the first day of
the test (temperature was not measured during the remainder of the test). Mean percent survival
of the organisms in the control was less than 90% (i.e., 40%) which was unacceptable. Thus, the
health of the test organisms was suspect, and the test failed.
SUMMARY
Survival of H. azteca in the control sediments was unacceptable (i.e., less than 80%), and the
reference toxicant test with H. azteca failed. Therefore, no conclusions can be drawn about the
effect that the sediments had on H. azteca.
Control survival was acceptable in both batches of C. tentans tests, and the survival of organisms
in the test sediments was not statistically less than the control sediments.
-------
REFERENCES
ASTM. 1993. Standard guide for conducting sediment toxicity tests with freshwater
invertebrates. El 383-93. In Annual Book of ASTM Standards, Vol. 11.04, American
Society for Testing and Materials, Philadelphia, PA. pp. 1173-1199.
Benoit, D.A., G. Phipps, and G.T. Ankley. 1993. A sediment testing intermittent renewal
system for the automated renewal of overlying water in toxicity tests with contaminated
sediments. Water Research 27:1403-1412.
Gulley, D.D. and WEST, Inc. 1994. TOXSTAT3.4. WEST, Inc., Cheyenne, WY.
U.S. EPA. 1994. Methods for Measuring the Toxicity and Bioaccumulation of Sediment-
associated Contaminants with Freshwater Invertebrates. Office of Research and
Development, U.S. Environmental Protection Agency, Duluth, MM. EPA/6QO/R-94/024.
-------
TABLE 1. Daily Overlying Water pH Measurements
Batch tt 1
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control I
C. tentans H. azteca
7.1 7.2
7.2 7.3
7.1 7.2
7.3 7.4
7.3 7.3
7.3 7.3
7.2 7.2
7.2 7.4
7.2 7.4
7.0 7.5
7.2 7.3
7.0-7.3 7.2 - 7.5
DSH08
C, tentans H. azteca
7.5 7.4
7.4 7.5
7.4 7.4
7.5 7.6
7.4 7.5
7.5 7.5
7.3 7.3
7.5 7.7
7.5 7.7
7.3 7.5
7.4 7.5
7.3 - 7.5 7.3 - 7.7
DSH 12
C. tentaiu H azteca
7.3 7.3
7.2 7.2
7.3 7.3
7.3 7.3
7.3 7.4
7.3 7.3
7.4 7.4
7.4 7.4
7.3 7.4
7.3 7.3
7.3 7.3
7.2 - 7.4 7.2 - 7.4
DSH 21
C. tentans H. azteca
7.5 7.5
7.4 7.5
7.3 7.3
7.5 7.5
7.4 7.5
7.3 7.3
7.3 7.2
7.5 7.5
7.4 7.7
7.3 7.6
7.4 7.5
7.3-7.5 7.2-7.7
DSH 40
C. tentans H. azteca
7.2 7.2
7.3 7.2
7.3 7.2
7.2 7.4
7.3 7.3
7.4 7.4
7.3 7.4
7.2 7.4
7.3 7.3
7.1 7.2
7.3 7.3
7.1-7.4 7.2-7.4
Batch « 2
0
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 2
C. tentans //. azteca
7.3 7.3
7.0 6.9
7.4 7.6
7.5 7.6
7.4 7.4
7.4 7.4
7.4 7.6
7.5 7.6
7.2 7.4
7.2 7.3
7.3 7.4
7.0-7.5 6.9-7.6
DSH 16
C. tentans H. azteca
7.4 7.4
7.2 7.2
7.5 7.7
7.5 7.7
7.4 7.4
7.4 7.4
7.4 7.7
7.7 7.7
7.4 7.6
7.3 7,4
7.4 7.5
7.2-7.7 7.2-7.7
DSH 18
C. tentans H. azteca
7.2 7.1
7.3 7.3
7.4 7.5
7.4 7.5
7.4 7.5
7.5 7.5
7.5 7.6
7.5 7.5
7.2 7.3
7.4 7.4
7.4 7.4
7.2-7.5 7.1-7.6
DSH 19
C. tentans H, azteca
7.3 7.2
7.3 7.3
7.5 7.5
7.5 7.6
7.4 7.4
7.5 7.4
7.5 7.6
7.4 7.6
7.2 7.5
7.4 7.4
7.4 7.5
7.2-7.5 7.2-7.6
DSH 23
C. tentans H. azteca
7.4 7.4
7.3 7.3
7.5 7.5
7.5 7.6
7.5 7.5
7.5 7.5
7.6 7.6
7.5 7.5
7.2 7.3
7.4 7.4
7.4 7.5
7.2-7.6 7.3-7.6
DSH 29
C. tentans H. azteca
6& 7.0
7.1 7.2
7.3 7.3
7.3 7.3
7.4 7.4
7.5 7.4
7.3 7.4
7.3 7.4
7.1 7.4
7.1 7.2
7.2 7.3
6.8-7.5 7.0-7.4
-------
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L)
Batch tt I
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control I
C. lentans H. azleca
6.9 6.8
5.9 6.7
5.0 6.3
6.1 64
5.3 6.8
4.2 6.1
4.0 5.8
5.7 6.7
5.7 6.6
4.4 6.5
5.3 6.5
4.0-6.9 5.8-6.8
DSH08
C. lenlans H. azleca
7.2 7,0
5.3 6.3
5.5 6.5
5.5 6.5
5.2 6.4
5.1 6.2
4.9 6.0
6.0 7.5
6.4 7.1
4.7 6.5
5.6 6.6
4.7-7.2 6.0-7.5
DSHI2
C. lentans H. azleca
6.7 6.7
6.0 5.7
4.3 5.7
4.4 5.7
5.1 6.1
4.5 5.2
4.2 5.1
5.7 6.0
5.5 5.8
4.1 5.1
5.1 5.7
4.1-6.7 5.1-6.7
DSH21
C. lentans H. azteca
7.2 7.3
6.4 7.0
5.8 6.4
5.5 5,9
5.8 6.8
4.1 5.9
4.0 6.0
6.5 7.0
6.1 7.6
4.8 6.8
5.6 6.7
4.0-7.2 5.9-7.6
DSH 40
C. lentans H. azleca
6.6 6.2
4.6 5.1
3.3 3.8
3.2 5.3
4.3 4.6
1.7 5.0
1.6 4.8
3.6 5.3
4.2 4.6
3.0 3.8
3.6 4.9
1.6-6.6 38-6.2
Batch # 2
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 2
C. lentans H. azteca
6.7 5.8
5.2 6.0
5.3 6.4
5.8 6.9
5.5 6.4
5.3 6.2
5.5 6.7
5.6 6.7
3.7 6.2
3.4 5.5
5.2 6.3
3.4-6.7 5.5-6.9
DSH 16
C. lentans H. azteca
6.6 6.9
5.3 5.8
4.9 6.0
5.2 6.5
51 6.3
5.0 5.8
4.5 6.6
6.2 6.7
4.5 6.1
4.1 5.8
5.1 6.3
4.1-6.6 5.8-6.9
DSH 18
C. tentans H. azleca
5.0 5.2
5.3 5.7
5.2 5.8
4.9 6.4
4.5 6.3
4.2 6.0
6.0 6.9
6.5 6.0
4.3 5.8
4.2 5.5
5.0 6.0
4.2-6.5 5.2-6.9
DSH 19
C. lentans H. azleca
4.7 4.4
4.2 5.0
5.1 5.4
6.0 6.4
3.5 6.1
3.2 5.7
5.3 6.8
5.0 6.6
3.9 6.0
3.5 5.6
4.4 5.8
3.2-6.0 4.4-6.8
DSH 23
C. tentans H. azteca
5.7 5.4
5.4 5.9
5.5 5.9
5.9 6.6
4.4 5.8
4.0 5.3
6.4 6.7
5.8 6.3
4.1 5.4
4.3 5.6
5.2 5.9
4.0-6.4 5.3-6.7
DSH 29
C. tentans H. azleca
6.7 6.9
5.0 5.4
5.0 5.4
4.8 6.1
4.5 6.0
4.3 6.1
4.7 6.3
5.1 5.9
3.8 6.0
3.4 5.4
4.7 6.0
3.4-6.7 5.4-6.9
3
tf
-L
U
-------
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius)
Batch # I
Day
0
I
2
3
4
5
6
7
8
9
Mean
Range
Control 1
C. tentans H. azteca
22.0 22,0
21.5 21.5
22.0 22.0
22.5 22.5
20.5 20.5
22.0 22.0
22.0 22.0
22.0 22.0
21.0 21.0
20.5 20.5
2!. 6 21.6
20.5-22.5 20.5-22.5
DSH08
C. tentans H. azteca
22.0 22.0
21.5 21.5
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
21.5 21.5
20.5 20.5
20.5 *
21.5 21.6
20.0-22.5 20.0-22.5
DSHI2
C. tentans H, azteca
22.0 22.0
20.5 21.0
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
21.5 21.5
20.5 20.5
* 20.5
21.4 21.4
20.0-22.5 20.0-22.5
DSH21
C. tentans H. azteca
22.0 22.0
21.5 21.5
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
22.0 22.0
20.5 20.5
20.5 20.5
21.5 21.5
20.0-22.5 20.0-22.5
DSH 40
C. tentans H. azteca
22.0 22.0
21.0 21.0
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
21.5 21.5
20.5 20.5
20.5 20.5
21.4 21.4
20.0-22.5 20.0-22.5
Temperature was not recorded.
Batch # 2
-a
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 2
C. tentans H. azteca
22.0 22.0
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
22.0 22.0
21.0 21.0
20.5 20.5
21.0 21.0
21.5 21.5
20.0-22.5 20.0-22.5
DSH 16
C. tentans H. azteca
21.5 21.5
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
22.0 220
21.0 21.0
20.5 20.5
21.0 21.0
21.5 21.5
20.0-22.5 20.0-22.5
DSH IS
C. tentans H. azteca
21.5 21.5
22.0 22.0
22.5 22.5
20.5 20.5
22.0 22.0
22.0 22.0
22.0 22.0
21.0 21.0
21.0 21.0
21.5 21.5
21.6 21.6
20.5-22.5 20.5-22.5
DSH 19
C. tentans H. azteca
21.5 21.5
22.0 22.0
22.5 22.5
20.5 20.5
22.0 22.0
22.0 22.0
22.0 22.0
21.0 21.0
20.5 20.5
21.5 21.5
21.6 21.6
20.5-22.5 20.5-22.5
DSH 23
C. tentans H. azteca
21.0 21.0
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
22.0 22.0
21.0 21.0
21.0 21.0
21.5 21.5
21.5 21.5
20.0-22.5 20.0-22.5
DSH 29
C. tentans H. azteca
21.5 21.5
22.0 22.0
22.5 22.5
20.0 20.0
22.0 22.0
22.0 22.0
21.5 22.0
21.0 21.0
20.5 20.5
21.0 21.0
21.4 21.5
20.0-22.5 20.0-22.5
-------
TABLE 4. Mean Percent Survival of Hyalella azteca and Chironomus tentans
*
Mean
Hyalella azteca l
Percent Survival
Chironomus tentans
Batch # 1
CONTROL #1
DSH08
DSH12
DSH21
DSH40
13%
33%
27%
23%
27%
93%
100%
90%
90%
83%
Batch # 2
CONTROL #2
DSH16
DSH18
DSH19
DSH23
DSH29
33%
60%
50%
40%
30%
37%
90%
83%
90%
77%
97%
93%
1 Controls were unacceptable (< 80% survival). Thus, the Hyalella azteca tests failed for both batches of samples.
10
-------
APPENDIX A
TOXSTAT Analysis
-------
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
4
3
3
3
3
CONTROL
1.00000000
0.90000000
0.90000000
DSH12
0.80000000
1.00000000
0.90000000
DSH40
0.80000000
0.70000000
1.00000000
a ft Ate
A-l
-------
TITLE: 93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
FILE: 93mpr2CA.DAT
TRANSFORM: ARC SINE(SQUARE ROOT(Y)) NUMBER OF GROUPS: 3
GRP IDENTIFICATION REP VALUE TRANS VALUE
1
1
1
2
2
2
3
3
3
CONTROL
CONTROL
CONTROL
DSH 12
DSH 12
DSH 12
DSH 40
DSH 40
DSH 40
1
2
3
1
2
3
1
2
3
1.0000
0.9000
0.9000
0.8000
1.0000
0.9000
0.8000
0.7000
1.0000
1.4120
1.2490
1.2490
1.1071
1.4120
1.2490 •
1.1071
0.9912
1.4120
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
File: 93mpr2CA.DAT Transform: ARC SINECSQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION N MIN MAX MEAN
1
2
3
CONTROL
DSH 12
DSH 40
3
3
3
1.249
1.107
0.991
1.412
1.412
1.412
1.303
1.256
1.170
A-2
-------
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
File: 93mpr2CA.DAT Transform: ARC SINE(SQUARE ROOKY))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
GRP IDENTIFICATION VARIANCE SD SEM C.V. *
1 CONTROL 0.009 0.094 0.054 7.22
2 DSH 12 0.023 0.153 0.088 12.15
3 DSH 40 0.047 0.217 0.126 18.58
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
File: 93mpr2CA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
ANOVA TABLE
SOURCE DF SS MS F
Between 2 0.027 0.014 0.517
Within (Error) 6 0.159 0.026
Total 8 0.186
Critical F value - 5.14 (0.05,2.6)
Since F < Critical F FAIL TO REJECT Ho: All equal
l^C-
A-3
-------
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
File: 93mpr2CA.DAT Transform: ARC SINECSQUARE ROOT(Y))
Shapiro - Wilk's test for normality
D = 0.159
W - 0.934
Critical W (P - 0.05) (n - 9) - 0.829
Critical W (P - 0.01) (n - 9) - 0.764
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
File: 93mpr2CA.DAT Transform: ARC SINECSQUARE ROOT(Y}}
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 1.05
Table Chi-square value = 9.21 (alpha - 0.01. df - 2)
Table Chi-square value = 5.99 (alpha - 0.05, df - 2)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
A-4
-------
93 MUDPUPPY RUN #2A CHIRONOMIDS 10/4/93
File: 93mpr2CA.DAT
DUNNETT'S TEST
Transform: ARC SINECSQUARE ROOT(Y))
«
TABLE 1 OF 2 Ho:Control
-------
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
6
3
3
3
3
3
3
CONTROL
0.8
1.0
0.9
DSH 16
0.8
0.8
0.9
DSH 18
1.0
0.8
0.9
DSH 19
0.6
0.8
0.9
DSH 23
0.9
1.0
1.0
DSH 29
0.9
1.0
0.9
A-6
-------
TITLE:
FILE:
TRANSFORM:
93 MUDPUPPY RUN
#2B CHIRONOMIDS
S : \MA\CHUBBAR\TSD\93MUD\93MPR2CB
ARC SINECSQUARE
GRP IDENTIFICATION REP
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
CONTROL 1
CONTROL 2
CONTROL 3
DSH 16 1
DSH 16 2
DSH 16 3
DSH 18 1
DSH 18 2
DSH 18 3
DSH 19 1
DSH 19 2
DSH 19 3
DSH 23 1
DSH 23 2
DSH 23 3
DSH 29 1
DSH 29 2
DSH 29 3
ROOT(Y))
*
VALUE
0.8000
1.0000
0.9000
0.8000
0.8000
0.9000
1.0000
0.8000
0.9000
0.6000
0.8000
0.9000
0.9000
1.0000
1.0000
0.9000
1.0000
0.9000
10/5/93
.DAT
NUMBER OF GROUPS: 6
TRANS VALUE
1.1071
1.4120
1.2490
1.1071
1.1071
1.2490
1.4120
1.1071
1.2490
0.8861
1.1071
1.2490
1.2490
1.4120
1.4120
1.2490
1.4120
1.2490
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR2CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
3RP IDENTIFICATION
1
2
3
4
5
6
CONTROL
DSH 16
DSH 18
DSH 19
DSH 23
DSH 29
N
3
3
3
3
3
3
MIN
1.107
1.107
1.107
0.886
1.249
1.249
MAX
1.412
1.249
1.412
1.249
1.412
1.412
MEAN
1.256
1.154
1.256
1.081
1.358
1.303
A-7
-------
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR2CB.DAT Transform: ARC SINE(SQUARE R(X)T(Y))
m-
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
6RP IDENTIFICATION VARIANCE SD SEM C.V. *
1
2
3
4
5
6
CONTROL
DSH 16
DSH 18
DSH 19
DSH 23
DSH 29
0.023
0.007
0.023
0.033
0.009
0.009
0.153
0.082
0.153
0.183
0.094
0.094
0.088
0.047
0.088
0.106
0.054
0.054
12.15
7.10
12.15
16.92
6.93
7.22
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR2CB.DAT Transform: ARC SINECSQUARE ROOT(Y))
ANOVA TABLE
SOURCE
Between
Within (Error)
Total
OF
5
12
17
SS
0.153
0.209
0.362
MS
0.031
0.017
F
1.755
Critical F value - 3.11 (0.05.5.12)
Since F < Critical F FAIL TO REJECT Ho: All equal
A-8
-------
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR2CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
Shapiro - Wilk's test for'normality
D = 0.209
W - 0.958
Critical W (P - 0.05) (n - 18) - 0.897
Critical W (P - 0.01) (n = 18) - 0.858
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR2CB.DAT Transform: ARC SINECSQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated Bl statistic = 1.79
Table Chi-square value = 15.09 (alpha - 0.01, df » 5)
Table Chi-square value - 11.07 (alpha = 0.05, df - 5)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
A-9
-------
93 MUDPUPPY RUN #2B CHIRONOMIDS 10/5/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR2CB.DAT
OUNNETT'S TEST
TABLE 1 OF 2
Transform: ARC SINECSQUARE ROOT(Y))
Ho:Control
-------
ACUTE TOXICITY TESTS
WITH
HYALELLA AZTECA AND CHIRONOMUS TENTANS
ON SEDIMENTS FROM THE DULUTH/SUPERIOR HARBOR:
1993 Sampling Results - Batches # 3 and 4
Conducted by
Minnesota Pollution Control Agency
Monitoring and Assessment Section
520 Lafayette Road
St. Paul, Minnesota 55155-4194
February 1997
-------
TABLE OF CONTENTS
*
INTRODUCTION 1
SAMPLE COLLECTION AND HANDLING 1
METHODS 1
RESULTS 3
SUMMARY .5
REFERENCES 6
APPENDIX A - TOXSTAT Analysis
11
-------
LIST OF TABLES
s
TABLE 1. Daily Overlying Water pH Measurements 7
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L) 8
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius) 9
TABLE 4. Mean Percent Survival ofHyalella azteca and Chironomus tentans 10
in
-------
INTRODUCTION
As part of the 1993 survey of sediment quality in the Duluth/Superior Harbor, sediment toxicity
tests were conducted to assess acute (survival) and chronic (growth) toxicity to benthic
invertebrates. Acute effects were measured in separate 10-day toxicity tests to Hyalella azteca
(H. azteca) and Chironomus tentans (C. tentans). Growth was measured at the end of the C
tentans test to assess chronic effects. Survival and growth endpoints were compared to
organisms similarly exposed to a reference control sediment collected from West Bearskin Lake
(Cook County, MN).
A total of 40 sediment samples were collected for toxicity testing. This report presents the
results of thirteen of these sediment samples ran in two separate batches with separate controls.
SAMPLE COLLECTION AND HANDLING
During September 14-23, 1993, Minnesota Pollution Control Agency (MFCA) staff collected the
thirteen sediments referred to in this report. The samples were collected from the harbor using a
Ponar sampler and were taken to the University of Minnesota-Duluth Chemical Toxicology
Research Laboratory. The samples were stored at 4°C until they were transported to the MPCA
Toxicology Laboratory in St. Paul, MN.
METHODS
Thirteen sediment samples and two control sediment samples were subjected to the 10-day
sediment toxicity tests using the modified procedures described in ASTM (1993). However, the
specific test system used for these assays is not indicated in the methods. The test organisms
(H. azteca and C. tentans) were exposed to sediment samples for ten days in a portable, mini-
flow system described in Benoit et al. (1993). The test apparatus consists of 300 mL, glass-
beaker test chambers held in a glass box supplied with water from an acrylic plastic headbox.
The beakers have two, 1.5 cm holes covered with stainless steel mesh, to allow for water
exchange, while containing the test organisms. The headbox has a pipette tip drain calibrated to
deliver water at an average rate of 32.5 mL/min. The glass box is fitted with a self-starting
siphon to provide exchange of overlying water.
The H. azteca used for this test were 1 to 3 mm long, and the C. tentans were approximately 14
days old. These organisms were supplied by Environmental Consulting and Testing, Superior,
WI and were shipped to St. Paul the night before the test was set up. The organisms arrived at 10
p.m. and were stored at the St. Paul bus depot until 9 a.m. the next morning. The organisms were
then transported to the MPCA Toxicology Laboratory. The majority of the organisms were then
placed in glass vessels and transferred to the test beakers by 1:30 p.m. The remaining organisms
were aerated in these vessels until they were placed in the test beakers the following day.
-------
On October 18, 1993, eight samples (DSH 01, DSH 02, DSH 06, DSH 07, DSH 14, DSH 22,
DSH 26, and DSH 30) and the control sediment were separately homogenized by hand, and 100
mL of each sediment was^placed in a test beaker (Batch #3). On October 19, 1993, five more
samples (DSH 03, DSH 04, DSH 13, DSH 17, and DSH 24) and another control sediment were
homogenized and placed in beakers (Batch #4). Each sediment test was set up with three
replicates of H. azteca and three replicates of C. tentans. Aerated, artesian well water was added
to the beakers, and the sediments were allowed to settle for approximately two hours before the
organisms were added. For each toxicity test, ten organisms were placed in each beaker in a
random fashion.
The organisms were exposed to 16 hours of light and eight hours of darkness for the duration of
the ten-day test. Each day, two liters of aerated water from the artesian well at Stroh Brewery in
St. Paul, MN were exchanged in each test chamber. On weekdays, 1-L was exchanged in the
morning and 1-L in the afternoon. On weekends, the two liters were passed through the
chambers all at once. Water quality measurements (i.e., pH, temperature, and dissolved oxygen)
of the overlying water were taken in one beaker of each of the triplicate sets of each of the
sediments. The results, along with daily observations involving the physical appearance of the
sediments and organisms, were recorded in a laboratory notebook. This notebook is retained on
file at the MPCA.
The test was terminated on October 28, 1993 for Batch #3 and on October 29, 1993 for Batch #4.
The sediments were sieved through 40 mesh screens, and the sieved material was sorted for
organisms. The organisms found were counted, and the number of alive and dead organisms
were recorded. Organisms not found were recorded as missing and presumed dead. The
C. tentans that survived were placed in aluminum weighing dishes, dried at approximately 90°C
for at least four hours, desiccated to room temperature, and weighed.
Growth (weight) of the C. tentans and survival of both organisms were used as the endpoints for
these tests. The resulting survival data were analyzed using TOXSTAT (Gulley and WEST, Inc.,
1994), a statistical software package obtained from the University of Wyoming; however, due to
a quality assurance problem, the growth data were not analyzed.
A 96-hour, reference toxicant test with H. azteca in sodium chloride (NaCl) was run in
conjunction with these toxicity tests to determine the acceptability of the H. azteca used. Four
concentrations of NaCl solution (i.e., 5, 2.5, 1.25, and 0.625 g/L) and a control (aerated, artesian
well water) were used in this test. Three replicates of five organisms each were set up per
concentration.
-------
RESULTS
«
Water Quality
Measurements of pH, dissolved oxygen, and temperature in the overlying water of the test
beakers were made daily. These measurements are summarized below and in Tables 1, 2, and 3,
respectively, for both batches of tests.
Batch # 3 Water Chemistry
In Batch #3, the range of pH values in the beakers containing H. azteca was 6.0 to 7.9 (Table 1).
The water in the C. tentans beakers had a pH range of 6.8 to 7.7 (Table 1). The pH fluctuation
during this test was acceptable since it did not vary more than 50% within each treatment (U.S.
EPA, 1994).
The dissolved oxygen concentration ranged from 4.3 to 7.8 mg/L in the H. azteca beakers and
from 3.3 to 8.1 mg/L in the C. tentans beakers (Table 2).
The temperature of the overlying water in each glass box was measured and ranged from 19.5°C
to 22.0°C (Table 3). The recommended temperature for this test is 23 ± 1°C (U.S. EPA, 1994).
Batch # 4 Water Chemistry
In Batch #4, the range of pH values in the beakers containing H. azteca was 7.2 to 8.0 (Table 1).
The water in the C. tentans beakers had a pH range of 7.0 to 8.0 (Table 1). These pH ranges are
acceptable for this test.
The dissolved oxygen concentration ranged from 3.6 to 6.9 mg/L in the H. azteca beakers and
from 3.4 to 7.0 mg/L in the C. tentans beakers (Table 2).
The temperature of the overlying water in each glass box was measured and ranged from 20.5°C
to 22.5°C (Table 3). The recommended temperature for this test is 23 ± 1°C (U.S. EPA, 1994).
-------
Test Endpoints
The mean percent survival of test organisms is summarized below and in Table 4.
Batch #3 Survival Data
The mean percent survival of//, azteca in Control #3 was 73% with a range of 70% to 80%. For
this test, the mean percent survival must be at least 80% in the controls for the test to pass. For
the control sediment containing C, tentans, percent survival ranged from 80% to 100% with a
mean of 90%. Survival for these controls was greater than 70% and, therefore, acceptable.
Mean percent survival of H. azteca in the test sediments of Batch #3 ranged from 53% in the
DSH 30 sample to 87% in the DSH 14 sample. Mean percent survival of C. tentans in Batch #3
test sediments ranged from 43% in the DSH 14 sample to 100% in the DSH 01 sample.
Batch #4 Survival Data
For Control #4 containing H. azteca, the mean percent survival was 73% with a range of 60% to
90%. The control survival for this test was unacceptable (<80% survival). Therefore, all of the
H. azteca tests for Batch #4 failed. Survival hi the control sediment containing C. tentans ranged
from 80% to 100% with a mean of 90%; this was acceptable, and the test passed.
Mean percent survival of H. azteca in Batch #4 ranged from 60% in the DSH 24 sample to 80%
in the DSH 17 sample. Mean percent survival of C. tentans in Batch #4 ranged from 0% in the
DSH 24 sample to 93% in the DSH 13 sample.
C. tentans Growth Data
Although the dried C, tentans were weighed, the balance on which they were weighed was not
calibrated with standard weights; therefore, the data are suspect since the internal calibration of
the balance may have drifted with time.
Data Analysis
Survival data for both batches of test sediments containing C. tentans, except DSH 01, 03, and
24, were transformed using an arc sine-square root transformation before being analyzed
statistically using Dunnett's test. The aforementioned data were eliminated from the analysis
because there was zero variance between replicates. Although nonparametric statistics can be
used to analyze zero variance data, a minimum of four replicates per sediment is needed. Only
three replicates per sediment were run in this toxicity test.
-------
A one-tailed test was used to test the alternative hypothesis that sample survival was significantly
less than control survival. Thus, it was not necessary to include the sample survival data which
exceeded the control survival in the Dunnett's test [e.g., survival data for DSH 01 (100%) and
DSH 03 (90%)]. Since it is assumed that variability of 30-50% is necessary to see any
significant difference between the control and any given sediment (T. Norberg-King, U.S. EPA,
Duluth, MN, personal communication), and since DSH 24 had 0% survival, it is reasonable to
assume that survival in DSH 24 was significantly less than the control. The only other sample
survival that was significantly less than the control was site DSH 14. Results of the statistical
analysis of the data are included in Appendix A.
Reference Toxicant Test with Hyalella azteca in Sodium Chloride Solution
The pH of the overlying water in the reference toxicant test ranged from 7.1 to 8.2. The
dissolved oxygen ranged from 7.8 to 8.7 mg/L, and the temperature ranged between 19.5°C and
22.0°C. Mean percent survival of the organisms in the control was less than 90% (i.e., 67%)
which was unacceptable. Thus, the health of the test organisms was suspect, and the test failed.
SUMMARY
Survival of H. azteca in both of the control sediments was unacceptable (i.e., less than 80%
survival), and the reference toxicant test failed. Therefore, no conclusions can be drawn about
the effect that the sediments had on H. azteca.
Control survival was acceptable in both batches of samples containing C. tentans. The mean
percent survival of C. tentans in the DSH 14 and DSH 24 samples was significantly less than
their respective test controls. Survival of C. tentans in all other samples analyzed was not
significantly different from the respective test controls
-------
REFERENCES
ASTM. 1993. Standard guifie for conducting sediment toxicity tests with freshwater
invertebrates. El 383-93. In Annual Book of ASTM Standards, Vol. 11.04. American
Society for Testing and Materials, Philadelphia, PA. pp. 1173-1199.
Benoit, D.A., G. Phipps, and G.T. Ankley. 1993. A Sediment Testing Intermittent Renewal
System for the Automated Renewal of Overlying Water in Toxicity Tests with
Contaminated Sediments. Water Research 27:1403-1412.
Gulley, D.D. and WEST, Inc. 1994. TOXSTAT3.4. WEST, Inc., Cheyenne, WY.
U.S. EPA. 1994. Methods for Measuring the Toxicity and Bioaccumulation of Sediment-
associated Contaminants with Freshwater Invertebrates. Office of Research and
Development, U.S. Environmental Protection Agency, Duluth, MR EPA/600/R-94/024.
-------
TABLE 1. Daily Overlying Water pH Measurements
Batch #3
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 3
C. tentans H. azteca
7.2 6.0
7.0 7.1
7.2 7.4
6.9 7.2
7.0 7.3
7.4 7.4
7.4 7.5
7.4 7.5
7.2 7.3
7.7 7.7
7.2 7.2
6.9-7.7 6.0-7.7
DSHOI
C. tentans H. azteca
6.9 6.8
7.2 7.3
7.3 7.4
7.2 7.3
7.3 7.4
7.5 7.5
7.3 7.3
7.5 7.6
7.3 7.4
7.2 7.4
7.3 7.3
6.9-7.5 6.8-7.6
DSH02
C. lenlans H. azteca
7.3 7.3
7.4 7.6
7.5 7.5
7.4 7.5
7.3 7.4
7.5 7.5
7.4 7.5
7.4 7.6
7.3 7.5
7.4 7.6
7.4 7.5
7.3-7.5 7.3-7.6
DSH06
C, tentans H. azteca
7.2 7.2
7.5 7.5
7.5 7.5
7.4 7.5
7.3 7.5
7.5 7.5
7.4 7.7
7.2 7.5
7.4 7.5
7.2 7.5
7.4 7.5
7.2-7.5 7.2-7.7
DSH07
C. tentans H. azteca
6.9 6.8
7.3 7.4
7.3 7.4
7.3 7.4
7.2 7.4
7.5 7.5
7.3 7.4
7.5 7.6
7.3 7.5
7.5 7.7
7.3 7.4
6.9-7.5 6.8-7.7
DSH 14
C. tenlans H. azteca
6,9 6.9
7.4 7.4
7.5 7.6
7.4 7.6
7.4 7.6
7.5 7.5
7.5 7.6
7.4 7.7
7.3 7.4
7.6 7.9
7.4 7.5
6.9-7.6 6.9-7.9
DSH 22
C. tenlans H. azteca
7.3 7.2
7.6 7.6
7.5 7.5
7.4 7.6
7.4 7.5
7.5 7.5
7.5 7.6
7.4 7.6
7.4 7.6
7.5 7.6
7.5 7.5
7.3-7.6 7.2-7.6
DSH 26
C. tenlans H. azteca
6.8 6.9
7.3 7.5
7.6 7.7
7.3 7.4
7.3 7.5
7.5 7.5
7.5 7.5
7.5 7.6
7.4 7.5
7.2 7.3
7.3 7.4
6.8-7.6 6.9-7.7
DSH 30
C. lenlans H. azteca
7.0 6.9
7.4 7.6
7.4 7.4
7.3 7.4
7.3 7.5
"7.5 7.5
7.3 7.6
7.4 7.6
7.3 7.4
7.4 7.6
7.3 7.5
7.0-7.5 6.9-7.6
>
Batch #4
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 4
C. lenlans H. azteca
7.4 7.3
7.0 7.4
7.3 7.5
7.3 7.4
7.4 7.4
7.1 7.4
7.4 7.5
7.4 7.4
7.7 7.9
7.2 7.3
7.3 7.5
7.0-7.7 7.3-7.9
DSH 03
C. tenlans H. azleca
7.3 7.2
7.3 7.3
7.3 7.3
7.3 7.3
7.4 7.4
7.3 7.4
7.4 7.6
7.3 7.5
7.7 7.9
7.3 7.4
7.4 7.4
7.3-7.7 7.2-7.9
DSH 04
C. tenlans H, azteca
7.5 7.4
7.5 7.6
7.5 7.5
7.4 7.5
7.5 7.5
7.3 7.5
7.5 7.7
7.3 7.5
7.9 8.0
7.8 7.9
7.5 7.6
7.3-7.9 7.4-7-8.0
DSH 13
C. tenlans H. azteca
7.5 7.3
7.5 7.5
7.5 7.6
7.5 7.6
7.5 7.5
7.5 7.6
7.5 7.7
7.5 7.6
7.9 8.0
7.8 7.9
7.6 7.6
7.5-7.9 7.3-8.0
DSH 17
C. tentans H, azleca
7.7 7.6
7.5 7.6
7.5 7.7
7.6 7.6
7.4 7.4
7.4 7.6
7.5 7.7
7.5 7.6
7.9 8.0
7.9 7.9
7.6 7.7
7.4-7.9 7.4-8.0
DSH 24
C. tenlans H. azleca
7.8 7.8
7.7 7.8
7.8 7.8
7.7 7.7
7.5 7.5
7.6 7.6
7.6 7.7
7.6 7.7
8.0 8.0
7.7 7.8
7.7 7.7
7.5-8.0 7.5-8.0
or
-------
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L)
Batch #3
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 3
C. tentans H. azteca
7.5 6.8
6.3 6.7
5.4 5.0
5.3 6.8
4.7 6.7
4.5 6.0
5.0 6.0
5.2 6.2
5.5 6.0
5.4 6.2
5.5 6.2
4.5-7.5 5.0-6.8
DSH01
C. tentans H, azteca
6.3 6.6
6.0 6.5
5.3 6.2
4.3 5.9
4.8 6.0
4.1 5.6
4.9 5.4
4.1 6.3
4.5 6.0
3.3 6.2
4.8 6.1
3.3-6.3 5.4-6.6
DSH 02
C. tentans H. azteca
6.9 6.8
6.2 6.9
5.2 6.3
5.2 6.2
4.7 6.2
4.5 5.9
3.7 5.7
4.0 6.8
3.9 5.6
5.0 6.0
4.9 6.2
3.7-6.9 5.6-6.9
DSH 06
C. tentans H. azteca
6.9 7.0
6.6 6.6
6.1 6.7
5.4 6.6
4.9 6.4
4.5 5.8
4.2 6.7
4.7 6.2
4.1 5.9
4.0 6.5
5.1 6.4
4.0-6.9 5.8-7.0
DSH 07
C. tentans H. azteca
6.7 6.1
6.1 6.5
5.1 5.7
4.1 5.5
4.4 5.9
3.8 5.1
3.5 4.4
4.7 6.3
4.0 6.3
4.5 6.4
4.7 5.8
3.5-6.7 4.4-6.5
DSH 14
C. tentans H. azleca
4.1 4.3
5.4 5.8
5.3 6.1
5.0 6.2
4.7 6.2
4.2 5.8
5.4 5.2
5.0 6.1
3.5 5.2
4.0 5.9
4.7 5.7
3.5-5.4 4.3-6.2
DSH 22
C. tentans H. azteca
7.0 6.9
6.6 6.2
5.8 6.4
5.4 6.7
4.8 6.5
4.3 5.0
5.0 6.0
4.2 6.6
4.0 6.1
5.3 6.7
5.2 6.3
4.0-7.0 5.0-6.9
DSH 26
C. tentans H. azteca
8.1 7.7
6.0 7.0
6.4 6.9
4.9 6.4
4.7 6.9
4.2 6.0
5.4 6.0
3.9 6.2
5.3 5.9
5.5 6.2
5.4 6.5
3.9-8.1 5.9-7.7
DSH 30
C. tentans H. azleca
6.2 7.8
6.2 7.0
5.8 6.3
. 4.6 6.5
4.6 6.4
4.0 5.0
4.4 5.9
4.5 6.3
4.4 5.7
4.0 64
4.9 6.3
4.0-6.2 5.0-7.8
Batch #4
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 4
C. lentans H. azteca
6.8 6.5
6.3 6.6
5.6 6.9
5.2 6.6
4.3 5.9
4.8 6.3
4.7 5.9
4.5 5.7
4.4 6.4
4.7 6.6
5.1 6.3
4.3-6.8 5.7-6.9
DSH 03
C. tentans H. azteca
6.6 5.7
5.8 5.9
4.9 5.4
5.1 5.6
3.7 5.5
4.9 5.8
4.6 6.4
4.8 6.2
3.5 6.0
3.6 5.5
4.8 5.8
3.5-6.6 5.4-6.4
DSH 04
C. tentans H. azteca
6.7 6.3
6.0 6.4
5.7 6.2
5.3 6.3
4.0 5.3
3.7 6.0
4.2 6.5
3.8 5.9
4.5 6.8
4.8 6.5
4.9 6.2
3.7-6.7 5.3-6.8
DSH 13
C. tentans H. azteca
6.7 6.0
6.2 6.3
6.3 6.3
6.1 6.7
5.0 5.2
6.0 5.0
4.9 5.6
5.1 6.7
4.5 6.9
5.5 5.9
5.6 6.1
4.5-6.7 5.0-6.9
DSH 17
C. tentans H. azteca
7.0 6.6
6.0 6.7
6.0 6.4
6.1 6.7
4.8 5.1
4.4 5.8
4.3 6.0
5.1 6.2
5.5 6.0
5.8 6.1
5.5 6.2
4.3-7.0 5.1-6.7
DSH 24
C. tentans H. azteca
6.4 6.3
5.7 6.2
5.4 6.1
5.1 5.7
4.8 3.6
4.3 4.3
3.4 5.0
4.3 5.1
4.5 4.5
3.6 4.3
4.8 5.1
3.4-6.4 3.6-6.3
-------
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius)
Batch #3
Day
0
1
2
3
^— 4
>-— 5
6
7
I 8
9
Mean
Range
Control 3
C. tentans H azteca
19.5 19.5
21.5 21.5
20.5 20.5
20.5 20.5
20.5 20.5
22.0 22.0
22.0 22.0
21.5 21.5
21.0 21.0
21.0 21.0
21.0 20.9
19.5-22.0 19.5-22.0
DSH 01
C. tentans H. azteca
19.5 19.5
21.5 21.5
20.5 20.5
20.0 20.0
20.5 20.5
22.0 NA
22.0 22.0
21.5 21.5
21.0 21.0
20.5 20.5
20.9 20.8
19.5-22.0 19.5-22.0
DSH 02
C. tenlans H. azteca
21.0 21.0
21.5 21.5
20.5 20.5
20.5 20.5
20.5 NA
22.0 NA
22.0 22.0
22.0 22.0
21.0 21.0
21.0 21.0
21.2 21.2
20.5-22.0 20.5-22.0
DSH 06
C. tenlans //. azleca
21.0 21.0
21.5 21.5
20.5 20.5
20.5 20.5
20.5 NA
22.0 22.0
22.0 22.0
21.5 21.5
21.0 21.0
21.0 21.0
21.2 21.1
20.5-22.0 20.5-22.0
DSH 07
C. tenlans H. azteca
20.0 20.0
21.0 21.0
20.5 20.5
20.0 20.0
20.5 20.5
NA 22.0
22.0 22.0
21.5 21.5
21.0 21.0
20.0 20.0
20.9 20.7
20.0-22.0 20.0-22.0
DSH 14
C. tentans H. azteca
20.0 20.0
21.5 21.5
20.5 20.5
20.0 20.0
20.5 NA
NA 22.0
22.0 22.0
21.5 21.5
21.0 21.0
20.0 20.0
20.9 20.8
20.0-22.0 20.0-22.0
DSH 22
C. tentans H. azteca
21.0 21.0
21.5 21.5
20.5 20.5
20.5 20.5
20.5 NA
22.0 NA
22.0 22.0
21.5 21.5
21.0 21.0
20.5 20.5
21 1 21.1
20.5-22.0 20.5-22.0
DSH 26
C. tentans H. azteca
19.5 19.5
21.5 21.5
20.5 20.5
20.0 20.0
20.5 20.5
22.0 NA
22.0 22.0
21.5 21.5
21.0 21.0
20.5 20.5
20.9 20J
19.5-22.0 19.5-22.0
DSH 30
C, lentans H. azleca
20.0 20.0
21.5 21,5
20.5 20.5
20.0 20.0
20.5 20.5
NA 22.0
22.0 22.0
21.5 21.5
21.0 21.0
20.0 20.0
20.9 20.8
20.0-22.0 20.0-22.0
Batch #4
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 4
C. tentans H. azleca
21.5 21.5
21.0 21.0
20.5 20.5
20.5 NA
NA 22.0
22.5 22.5
22.0 22.0
21.5 21.5
21.0 21.0
21.0 21.0
21.4 21.4
20.5-22.5 20.5-22.5
DSH 03
C. lentans H. azteca
21.5 21.5
21.0 21.0
20.5 20.5
20.5 NA
NA 22.0
22.5 22.5
22.0 22.0
21.0 21.0
21.0 21.0
21.0 21.0
21.3 21.3
20.5-22.5 20.5-22.5
DSH 04
C. tenlans H, azleca
21.5 21.5
21.0 21.0
20.5 20.5
20.5 NA
22.0 NA
22.0 22.0
22.0 22.0
21.0 21.0
21.5 21.5
21.0 21.5
21.3 21.4
20.5-22.0 20.5-22.0
DSH 13
C. tentant H. azleca
21.5 21.5
21.0 21.0
20.5 20.5
20.5 NA
22.0 NA
22.5 22.5
22.0 22.0
21.0 21.0
21.0 21.0
21.0 21.0
21.3 21.3
20.5-22.5 20.5-22.5
DSH 17
C. lentans H. azteca
21.5 21.5
21.0 21.0
20.5 20.5
20.5 NA
NA 22.0
22.5 22.5
22.0 22.0
21.5 21.5
21.0 21.0
21.0 21.0
21.4 21.4
20.5-22.5 20.5-22.5
DSH 24
C. tentans H. azteca
21.5 21.5
21.0 21.0
20.5 20.5
20.5 NA
NA 22.0
22.5 22.5
22.0 22.0
21.0 21.0
21.0 21.0
21.0 21.0
21.3 21.3
20.5-22.5 20.5-22.5
NA = Not applicable, no measurement taken.
-------
TABLE 4. Mean Percent Survival of Hyalella azteca and Chironomus tentans
Mean
Hyalella azteca1
Percent Survival
Chironomus tentans
Batch # 3
CONTROL #3
DSH01
DSH02
DSH06
DSH07
DSH14
DSH22
DSH26
DSH30
73%
63%
70%
57%
63%
87%
77%
60%
53%
90%
100%
93%
97%
87%
43% *
80%
83%
97%
Batch # 4
CONTROL #2
DSH03
DSH04
DSH13
DSH17
DSH24
73%
77%
63%
70%
80%
60%
90%
90%
87%
93%
90%
0% *
Controls were unacceptable (<80% survival). Thus, the Hyalella azteca tests failed for both
batches of samples.
* Significantly different from the control, p = 0.05.
\
10
-------
APPENDIX A
TOXSTAT Analysis
-------
93 MUDPUPPY RUN #3A CHIRONOMIDS 10/18/93
8
3
3
3
3
3
3
3
3
CONTROL
1.0
0.8
0.9
DSH 30
0.9
1.00000000
1.00000000
DSH 02
1.00000000
0.90000000
0.90000000
DSH 06
0.90000000
1.00000000
1.00000000
DSH 07
0.80000000
0.90000000
0.90000000
DSH 14
0.60000000
0.30000000
0.40000000
DSH 22
0.90000000
0.80000000
0.70000000
DSH 26
0.80000000
0.90000000
0.80000000
A-l
-------
TITLE: 93 MUDPUPPY RUN #3A CHIRONOMIDS 10/18/93
FILE: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CA.DAT
TRANSFORM: ARC SINECSQUARE ROOJ(Y)) NUMBER OF GROUPS: 8
GRP
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
IDENTIFICATION
CONTROL
CONTROL
CONTROL
DSH 30
DSH 30
DSH 30
DSH 02
DSH 02
DSH 02
DSH 06
DSH 06
DSH 06
DSH 07
DSH 07
DSH 07
DSH 14
DSH 14
DSH 14
DSH 22
DSH 22
DSH 22
DSH 26
DSH 26
DSH 26
REP
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
VALUE
1.0000
0.8000
0.9000
0.9000
1.0000
1.0000
1.0000
0.9000
0.9000
0.9000
1.0000
1.0000
0.8000
0.9000
0.9000
0.6000
0.3000
0.4000
0.9000
0.8000
0.7000
0.8000
0.9000
0.8000
TRANS VALUE
1.4120
1.1071
1.2490
1.2490
1.4120
1.4120
1.4120
1.2490
1.2490
1.2490
1.4120
1.4120
. 1.1071
1.2490
1.2490
0.8861
0.5796
0.6847
1.2490
1.1071
0.9912
1.1071
1.2490
1.1071
All*
A-2
-------
93 MUDPUPPY RUN #3A CHIRONOMIDS 10/18/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CA.DAT
Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION N
MIN
MAX
MEAN
1
2
3
4
5
6
7
8
CONTROL
DSH 30
DSH 02
DSH 06
DSH 07
DSH 14
DSH 22
DSH 26
3
3
3
3
3
3
3
3
1.107
1.249
1.249
1.249
1.107
0.580
0.991
1.107
1.412
1.412
1.412
1.412
1.249
0.886
1.249
1.249
1.256
1.358
1.303
1.358
1.202
0.717
1.116
1.154
93 MUDPUPPY RUN #3A CHIRONOMIDS 10/18/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CA.DAT
Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
GRP
I
2
3
4
5
6
7
8
IDENTIFICATION
CONTROL
DSH 30
DSH 02
DSH 06
DSH 07
DSH 14
DSH 22
DSH 26
VARIANCE
0.023
0.009
0.009
0.009
0.007
0.024
0.017
0.007
SO
0.153
0.094
0.094
0.094
0.082
0.156
0.129
0.082
SEM
0.088
0.054
0.054
0.054
0.047
0.090
0.075
0.047
C.V. %
12.15
6.93
7.22
6.93
6.82
21.72
11.58
7.10
A-3
-------
93 MUDPUPPY RUN f3A CHIRONOMIDS 10/18/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
Shapiro - Wilk's test for normality
D - 0.208
W - 0.952
Critical W (P - 0.05) (n = 24) - 0.916
Critical W (P = 0.01) (n - 24) = 0.884
Data PASS normality test at P-0.01 level. Continue analysis.
93 MUDPUPPY RUN |3A CHIRONOMIDS 10/18/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CA.DAT Transform: ARC SINE(SQUARE ROOT(Y)}
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 1.74
Table Chi-square value - 18.48 (alpha - 0.01, df = 7)
Table Chi-square value - 14.07 (alpha - 0.05. df - 7)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
A-4
-------
93 MUDPUPPY RUN #3A CHIRONOMIDS 10/18/93
File: S:\MA\CHUBBAR\TSO\93MUD\93MPR3CA.DAT
ANOVA TABLE
Transform: ARC SINECSQUARE ROOT(Y))
SOURCE
Between
Within (Error)
Total
DF
7
16
23
SS
0.912
0.208
1.120
MS
0.130
0.013
F
10.000
Critical F value = 2.66 (0.05,7.16)
Since F > Critical F REJECT Ho: All equal
93 MUDPUPPY RUN #3A CHIRONOMIDS 10/18/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CA.DAT
DUNNETTS TEST
TABLE 1 OF 2
Transform: ARC SINE(SQUARE ROOT(Y))
Ho:Control
-------
93 MUDPUPPY RUN f3A CHIRONOMIDS 10/18/93
File; S:\MA\CHUBBAR\TSD\93MUO\93MPR3CA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
it
DUNNETT'S TEST - TABLE 2 OF 2 Ho:Control
-------
93 MUDPUPPY RUN #3B CHIRONOMIDS 10/19/93
4
3
3
3
3
CONTROL
0.80000000
0,90000000
1.00000000
DSH 17
1.0
0.9
0.8
DSH 04
0.90000000
0.80000000
0.90000000
DSH 13
1.00000000
0.90000000
0.90000000
2
A-7
-------
TITLE: 93 MUDPUPPY RUN #3B CHIRONOHIDS 10/19/93
FILE: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT
TRANSFORM: ARC SINE(SQUARE ROOT(Y)) NUMBER OF GROUPS: 4
GRP IDENTIFICATION REP VALUE TRANS VALUE
1
1
1
2
2
2
3
3
3
4
4
4
CONTROL
CONTROL
CONTROL
DSH 17
DSH 17
DSH 17
DSH 04
DSH 04
DSH 04
DSH 13
DSH 13
DSH 13
1
2
3
1
2
3
1
2
3
1
2
3
0.8000
0.9000
1.0000
1.0000
0.9000
0.8000
0.9000
0.8000
0.9000
1.0000
0.9000
0.9000
1.1071
1.2490
1.4120
1.4120
1.2490
1.1071
1.2490
1.1071
1.2490
1.4120
1.2490
1.2490
93 MUDPUPPY RUN #3B CHIRONOMIDS 10/19/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT Transform: ARC SINECSQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION N MIN MAX MEAN
1
2
3
4
CONTROL
DSH 17
DSH 04
DSH 13
3
3
3
3
1.107
1.107
1.107
1.249
1.412
1.412
1.249
1.412
1.256
1.256
1.202
1.303
A-8
-------
93 MUDPUPPY RUN #3B CHIRONOM1DS 10/19/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
3RP IDENTIFICATION
1
2
3
4
CONTROL
DSH 17
DSH 04
DSH 13
VARIANCE
0.023
0.023
0.007
0.009
SD
0.153
0.153
0.082
0.094
SEM
0.088
0.088
0.047
0.054
C.V. X
12.15
12.15
6.82
7.22
93 MUDPUPPY RUN f3B CHIRONOMIDS 10/19/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT Transform: ARC SINECSQUARE ROOT(Y))
ANOVA TABLE
SOURCE
Between
Within (Error)
Total
DF
3
8
11
SS
0.016
0.124
0.140
MS
0.005
0.016
F
0.333
Critical F value = 4.07 (0.05,3,8)
Since F < Critical F FAIL TO REJECT Ho: All equal
A-9
-------
93 MUDPUPPY RUN #3B CHIRONOMIDS 10/19/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT Transform: ARC SINECSQUARE ROOT(Y))
Shapiro - Wilk's test for nofmality
D - 0.124
W = 0.939
Critical W (P - 0.05) (n = 12) - 0.859
Critical W (P = 0.01) (n - 12) - 0.805
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN #3B CHIRONOMIDS 10/19/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 0.98
Table Chi-square value = 11.34 (alpha - 0.01, df - 3)
Table Chi-square value = 7.81 (alpha - 0.05, df = 3)
Data PASS 81 homogeneity test at 0.01 level. Continue analysis.
A-10
-------
93 MUDPUPPY RUN #3B CHIRONOMIDS 10/19/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR3CB.DAT
DUNNETT'S TEST
•TABLE 1 OF 2
Transform: ARC SINECSQUARE ROOT(Y))
Ho:Control
-------
ACUTE TOXICITY TESTS
WITH
HYALELLA AZTECA AND CHIRONOMUS TENTANS
ON SEDIMENTS FROM THE DULUTH/SUPERIOR HARBOR:
1993 Sampling Results - Batches # 5 and 6
Conducted by
Minnesota Pollution Control Agency
Monitoring and Assessment Section
520 Lafayette Road
St. Paul, Minnesota 55155-4194
February 1997
-------
TABLE OF CONTENTS
INTRODUCTION 1
SAMPLE COLLECTION AND HANDLING 1
METHODS 1
RESULTS 2
SUMMARY 5
REFERENCES 6
APPENDIX A - TOXSTAT Analysis
n
-------
LIST OF TABLES
s
TABLE 1. Daily Overlying Water pH Measurements .7
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L) 8
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius) 9
TABLE 4. Mean Percent Survival ofHyalella azteca and Chironomus tentans 10
111
-------
INTRODUCTION
«
As part of the 1993 survey of sediment quality in the Duluth/Superior Harbor, sediment toxicity
tests were conducted to assess acute (survival) and chronic (growth) toxicity to benthic
invertebrates. Acute effects were measured in separate 10-day toxicity tests to Hyalella azteca
(H, azteca} and Chironomus tentans (C. tentans). Growth was measured at the end of the
C. tentans test to assess chronic effects. Survival and growth endpoints were compared to
organisms similarly exposed to a reference control sediment collected from West Bearskin Lake
(Cook County, MM).
A total of 40 sediment samples were collected for toxicity testing. This report presents the
results of twelve of these sediment samples run in two separate batches with separate controls.
SAMPLE COLLECTION AND HANDLING
During September 22-27, 1993, Minnesota Pollution Control Agency (MFCA) staff collected the
twelve sediments referred to in this report. The samples were collected from the harbor using a
Ponar sampler and were taken to the University of Minnesota-Duluth Chemical Toxicology
Research Laboratory. The samples were stored at 4°C until they were transported to the MPCA
Toxicology Laboratory in St. Paul, MN.
METHODS
Twelve sediment samples and two control sediment samples were subjected to the 10-day
sediment toxicity tests using the modified procedures described in ASTM (1993). However, the
specific test system used for these assays is not indicated in the methods. The test organisms (H.
azteca and C. tentans) were exposed to sediment samples for ten days in a portable, mini-flow
system described in Benoit et al. (1993). The test apparatus consists of 300 mL, glass-beaker test
chambers held in a glass box supplied with water from an acrylic plastic headbox. The beakers
have two, 1.5 cm holes covered with stainless steel mesh, to allow for water exchange, while
containing the test organisms. The headbox has a pipette tip drain calibrated to deliver water at
an average rate of 32.5 mL/min. The glass box is fitted with a self-starting siphon to provide
exchange of overlying water.
The H. azteca used for this test were 1 to 3 mm long, and the C, tentans were approximately 14
days old. These organisms were supplied by Environmental Consulting and Testing, Superior,
WI on the day of the test.
On November 1, 1993, eight samples (DSH 05, DSH 09, DSH 10, DSH 11, DSH 25, DSH 27,
DSH 31, and DSH 32) and the control sediment were separately homogenized by hand, and 100
mL of each sediment was placed in a test beaker (Batch #5). On November 2, 1993, four more
samples (DSH 15, DSH 28, DSH 34, and DSH 35) and another control sediment were
homogenized and placed in beakers (Batch #6). Each sediment test was set up with three
replicates of H. azteca and three replicates of C. tentans. Aerated, artesian well water was added
-------
to the beakers, and the sediments were allowed to settle for approximately two hours before the
organisms were added. For each toxicity test, ten organisms were placed in each beaker in a
random fashion. «
The organisms were exposed to 16 hours of light and eight hours of darkness for the duration of
the ten-day test. Each day, two liters of aerated water from the artesian well at Stroh Brewery in
St. Paul, MN were exchanged in each test chamber. On weekdays, 1-L was exchanged in the
morning and 1-L in the afternoon. On weekends, the two liters were passed through the
chambers all at once. Water quality measurements (i.e., pH, temperature, and dissolved oxygen)
of the overlying water were taken in one beaker of each of the triplicate sets of each of the
sediments. The results, along with daily observations involving the physical appearance of the
sediments and organisms, were recorded in a laboratory notebook. This notebook is retained on
file at the MPCA.
The test was terminated on November 11, 1993 for Batch #5 and on November 12, 1993 for
Batch #6. The sediments were sieved through 40 mesh screens, and the sieved material was
sorted for organisms. The organisms found were counted, and the number of alive and dead
organisms were recorded. Organisms not found were recorded as missing and presumed dead.
The C. tentans that survived were placed in aluminum weighing dishes, dried at approximately
90°C for at least four hours, desiccated to room temperature, and weighed.
Growth (weight) of the C. tentans and survival of both organisms were used as the endpoints for
these tests. The resulting survival data were analyzed using TOXSTAT (Gulley and WEST, Inc.,
1994), a statistical software package obtained from the University of Wyoming; however, due to
a quality assurance problem, the growth data were not analyzed.
A 96-hour, reference toxicant test with H. azteca in sodium chloride (NaCl) was run in
conjunction with these toxicity tests to determine the acceptability of the H. azteca used. Four
concentrations of NaCl solution (i.e., 5, 2.5, 1.25, and 0.625 g/L) and a control (aerated, artesian
well water) were used in this test. Three replicates of five organisms each were set up per
concentration.
RESULTS
Water Quality
Measurements of pH, dissolved oxygen, and temperature in the overlying water of the test
beakers were made daily. These measurements are summarized below and in Tables 1, 2, and 3,
respectively, for both batches of tests.
Batch # 5 Water Chemistry
In Batch #5, the range of pH values in the beakers containing H. azteca was 7.0 to 8.6 (Table 1). \
The water in the C tentans beakers had a pH range of 6.8 to 8.6 (Table 1). The pH fluctuation j
-------
during these tests was acceptable since it did not vary more than 50% within each treatment (U.S.
EPA, 1994).
s
The dissolved oxygen concentration ranged from 5.5 to 7.4 mg/L in the H. azteca beakers and
from 2.3 to 7.3 mg/L in the C. tentans beakers (Table 2). The recommended dissolved oxygen
concentration for these tests is greater than 40% saturation. The dissolved oxygen dipped below
40% saturation on day 6 in most of the C. tentans beakers (i.e., the control, DSH 9, 10, 11, 25,
27, 31, and 32) and in the control on days 8 and 9. Feeding of the organisms was suspended on
these days. The chambers were not aerated.
The range of temperature values in the H. azteca beakers was 19.0°C to 21.0°C, whereas the
range was 18.9°C to 21.0°C in the C. tentans beakers (Table 3). The recommended temperature
for this test is 23 ± 1°C (U.S. EPA, 1994).
Batch #6 Water Chemistry
In Batch #6, the range of pH values in the beakers containing H. azteca was 7.8 to 8.4 (Table 1).
The water in the C. tentans beakers had a pH range of 7.5 to 8.3 (Table 1). These pH ranges are
acceptable for these tests.
The dissolved oxygen concentration ranged from 5.0 to 7.9 mg/L in the H. azteca beakers and
from 2.2 to 8.0 mg/L in the C. tentans beakers (Table 2). The dissolved oxygen in some of the
C. tentans chambers dropped below 40% saturation. Levels were lower than acceptable on day 5
in chambers holding sediments DSH 15,28, and 35. On days 7, 8, and 9, levels were too low in
DSH 35. Dissolved oxygen levels were unacceptable in the control on days 8 and 9. Feeding of
the organisms was suspended on these days. The chambers were not aerated.
The range of temperature values in the H, azteca beakers was 18.9°C to 21.0°C, whereas the
range was 18.9°C to 21.0°C in the C. tentans beakers (Table 3). The recommended temperature
range for this test is 23 ± 1°C (U.S. EPA, 1994).
Test Endpoints
The mean percent survival of test organisms is summarized below and in Table 4.
Batch #5 Survival Data
The mean percent survival of H. azteca in Control #5 was 97% with a range of 90% to 100%.
For the control sediment containing C. tentans, percent survival ranged from 70% to 80% with a
mean of 77%. Survival for these controls was acceptable, and both tests passed.
Mean percent survival of H. azteca in the test sediments of Batch #5 ranged from 83% in the
DSH 09 sample to 100% in the DSH 27 sample. Mean percent survival of C. tentans in Batch
#5 test sediments ranged from 73% in the DSH 31 sample to 97% in the DSH 25 sample.
-------
Batch #6 Survival Data
*
For Control #6 containing H. azteca, the mean percent survival was 87% with a range of 80% to
90%. For the control sediment containing C. tentans, the range was 90% to 100% with a mean
of 97%. Both of these survival measurements were acceptable.
Mean percent survival of H. azteca in Batch #6 ranged from 77% in the DSH 34 and DSH 35
samples to 97% in the DSH 28 sample. Mean percent survival of C. tentans in Batch #6 ranged
from 47% in the DSH 34 sample to 93% in the DSH 35 sample.
C. tentans Growth Data
Although the dried C. tentans were weighed, the balance on which they were weighed was not
calibrated with standard weights; therefore, the data are suspect since the internal calibration of
the balance may have drifted with time and no conclusions regarding chronic toxicity (growth)
can be made.
Data Analysis
Survival data for all of the sediments tested, except DSH 05 containing C. tentans and DSH 15,
25 and 27 containing H. azteca, were transformed using an arc sine-square root transformation
before being analyzed statistically using Dunnett's test. The aforementioned samples were
eliminated from the analysis because there was zero variance between replicates. Although
nonparmetric statistics can be used to analyze zero variance data, a minimum of four replicates
per sediment is needed. Only three replicates per sediment were run in these toxicity tests. Since
it is assumed that variability of 30-50% is necessary to see any significant difference between the
control and any given sediment, and since survival of the organisms in the sediments in question
was equal to or greater than 90%, it is reasonable to assume that the effect these sediments had
on the organisms tested was not significantly less than that of their respective controls (T.
Norberg-King, USEPA, Duluth, MM, personal communication).
The mean percent survival of C. tentans in the DSH 34 sample was significantly less than the
control as determined by a 1-tailed Dunnett's test, p=0.05. The survival results of all other
organisms in all other samples run in these tests were not significantly less than their respective
controls. Results of the statistical analysis of the data are included in Appendix A.
Reference Toxicant Test with Hyalella azteca in Sodium Chloride Solution
The pH of the overlying water in the reference toxicant test ranged from 7.8 to 8.5. The dissolved
oxygen ranged from 7.8 to 8.5 mg/L, and the temperature ranged between 19.0°C and 20.0°C.
Mean percent survival of the organisms in the control was less than 90% (i.e., 73%) which was
unacceptable. Thus, the reference toxicant test failed. The cause of this failure could not be
determined. Since the control survivals in Batch #5 and Batch #6 were acceptable, the organisms
appeared to be healthy.
-------
SUMMARY
«
Survival of H. azteca in the control sediments was acceptable (greater than 80%), however, the
reference toxicant test failed, leaving the health of the organisms suspect and, therefore, no
conclusion can be drawn about the effect that the sediments had on H. azteca.
Control survival was acceptable in both batches of samples containing C. tentans. The mean
percent survival of C. tentans in the DSH 34 sample was significantly less than the control
(p=0.05). Survival of C. tentans in all other samples analyzed were not significantly different
than the control.
-------
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L)
Batch #5
Day
0
I
2
3
4
5
6
7
8
9
Mean
Range
Control 5
C. tentans H. azteca
7.0 6.5
6.1 6.8
5.2 6.3
4.3 6.9
4.6 6.8
4.5 6.9
2.9 6.3
3.6 6.8
3.1 6.4
2.9 6.3
4.4 6.6
2.9-7.0 6.3-6.9
DSH 05
C. tentans H. azteca
7.3 7.1
6.6 6.9
5.4 6.4
4.6 6.7
4.7 6.4
4.6 6.7
3.5 6.8
3.4 7.1
4.4 7.4
4.0 7.3
4.9 6.9
3.4-7.3 6.4-7.4
DSH 09
C. lentans H. azteca
7.3 6.9
6.6 6.8
4.3 6.7
4.9 6.9
4.4 7.0
3.9 7.0
2.4 6.6
3.4 7.1
3.4 7.0
5.7 7.0
4.6 6.9
2.4-7.3 6.6-7.1
DSH 10
C. tentans H. azteca
7.0 6.3
6.2 6.1
5.3 6.2
4.5 6.6
4.5 6.8
5.2 6.7
2.8 5.8
3.4 6.4
4.0 6.5
3.4 6.5
4.6 6.4
2.8-7.0 5.8-6.8
DSH 1 1
C. lentans H. azteca
6.9 6.5
6.0 6.5
4.6 6.1
4.5 6.6
4.3 6.8
4.3 6.5
2.9 6.5
3.4 7.0
4.0 7.0
4.5 6.9
4.5 6.6
2.9-6.9 6.1-7.0
DSH 25
C. tentans H. azleca
6.9 6.8
6.3 6.8
4.0 6.0
4.0 6.5
4.9 6.3
3.6 6.0
2.3 5.5
4.4 6.4
3.6 6.4
3.9 6.5
4.4 6.3
2.3-6.9 5.5-6.8
DSH 27
C. tentans H. azteca
7.3 6.7
6.9 6.6
5.7 6,1
5.4 6.4
5.8 6.6
4.9 6.9
3.1 6.6
4.3 6.7
4.5 7.0
4.0 7.0
5.2 6.7
3.1-7.3 6.1-7.0
DSH 31
C. tentans H. azteca
6.7 6.3
6.3 6.3
5.7 6.2
4.3 6.1
4.8 6.4
4.3 6.4
2.6 5.9
4.7 6.6
4.5 6.1
3.6 5.9
4.8 6.2
2.6-6.7 5.9-6.6
DSH 32
C. tentans H. azteca
6.7 6.2
6.4 6.5
4.6 6.9
4.2 6.1
5.2 6.4
4.5 6.3
2.9 5.9
4.0 6.7
4.6 6.8
4.8 6.6
4.8 64
2.9-6.7 5.9-6.9
Batch #6
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 6
C. tentans H. azteca
7.4 7.4
5.6 6.3
5.5 6.7
5.2 6.7
4.8 6.6
4.0 6.4
4.5 6.6
5.1 6.8
3.2 6.4
3.2 6.2
4.9 6.6
3.2-7.4 6.2-7.4
DSH 15
C. tentans H. azteca
8.0 7.9
5.8 6.3
6.0 6.8
6.0 7.1
4.6 6.7
2.8 6.6
4.4 7.2
4.8 7.0
6.0 6.8
4.6 6.5
5.3 6.9
2.8-8.0 6.3-7.9
DSH 28
C. lentans H. azteca
7.8 7.6
5.6 6.6
5.0 6.6
4.7 6.9
5.2 6.5
33 6.2
4.6 7.0
4.5 6.9
3.6 6.8
3.6 6.5
4.8 6.8
3.3-7.8 6.2-7.6
DSH 34
C. lentans H. azteca
7.6 7.5
5.5 5.9
5.8 6.4
5.7 6.4
4.9 6.4
4.8 5.9
5.3 6.4
5.7 6.1
3.8 5.0
4.3 5.6
5.3 6.2
3.8-7.6 5.0-7.5
DSH 35
C. tenlans H. azleca
7.5 7.6
5.3 6.1
5.2 6.4
4.3 6.3
4.1 6.6
2.2 5.4
3.6 6.7
3,2 7.1
3.0 64
2.6 6.0
4.1 6.5
2.2-7.5 5.4-7.6
i n c
->
-------
Table 3. Daily Overlying Water Temperatures (Degrees Celsius)
Batch #5
Day
0
I
2
3
4
5
6
7
8
9
Mean
Range
Control 5
C. tentans H. azteca
20.0 20.0
21.0 21.0
21.0 21.0
19.9 19.9
19.2 19.2
20.5 20.5
21.0 21.0
19.3 19.3
19.0 19.0
19.2 19.2
20.0 20.0
19.0-21.0 19.0-21.0
DSH 05
C. tenlans H. azteca
20.0 20.0
20.5 20.5
21.0 20.5
19.8 19.8
19.4 19.4
20.5 20.5
21.0 21.0
19.3 19.5
19.0 19.0
19.3 19.3
20.0 20.0
19.0-21.0 19.0-21.0
DSH 09
C. lenlans H azteca
20.0 20.0
20.5 20.5
20.5 20.5
20.1 20.1
19.5 19.6
21.0 21.0
21.0 21.0
19.5 19.5
19.1 19.3
19.3 19.6
20.1 20.1
I9.1-2I.O 19.3-21.0
DSH 10
C. tentans H. azteca
20.0 20.0
21.0 21.0
21.0 21.0
19.9 19.9
19.3 19.2
20.5 20.5
21.0 21.0
19.5 19.5
19.1 19.1
19.3 19.3
20.1 20.1
19.1-21.0 19.1-21.0
DSH 1 1
C. tentans H. azteca
20.0 20.0
21.0 21.0
21.0 21.0
20.1 20.1
19.8 19.2
20.5 20.5
21.0 21.0
19.7 19.7
19.3 19.3
19.5 19.5
20.2 20.1
19.3-21.0 19.2-21.0
DSH 25
C. tentans H. azteca
20.0 20.0
20.5 20.5
20.5 20.5
20.1 20.1
19.5 19.5
21.0 21.0
21.0 21.0
19.5 19.5
18.9 19.0
19.2 19.4
20.0 20.1
18.9-21.0 19.0-21.0
DSH 27
C. tentans H. azteca
20.0 20.0
20.5 20.5
21.0 21.0
19.9 19.9
19.4 19.4
20.5 20.5
21.0 21.0
19.5 19.5
19.1 19.1
19.1 19.3
20.0 20.0
19.1-21.0 19.1-21.0
DSH 31
C. tentans H. azteca
20.0 20.0
20.5 20.5
20.5 20.5
19.6 19.9
19.5 19.5
20.5 20.5
21.0 21.0
19.5 19.5
19.0 19.1
19.3 19.4
19.9 20.0
19.0-21.0 19.1-21.0
DSH 32
C. tentans H. azteca
20.0 20.0
20.5 20.5
20.5 20.5
20.4 20.4
19.5 19.5
20.5 20.5
214) 21.0
19.3 19.4
19.1 19.0
19.2 19.4
20.0 20.0
19.1-21.0 19.0-21.0
Batch #6
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control 6
C. tentans H. azteca
20.5 20.5
20.5 21.0
19.5 20.2
19.6 19.6
21.0 21.0
21.0 21.0
19.4 19.7
18.9 19.3
19.5 19.7
20.0 20.0
20.0 20.2
18.9-21.0 19.3-21.0
DSH 15
C. tentans H. azteca
21.0 21.0
21.0 21.0
20.5 20.5
19.8 19.9
21.0 21.0
21.0 21.0
19.6 20.1
19.5 19.6
19.6 19.6
19.7 20.0
20.3 20.4
19.5-21.0 19.6-21.0
DSH 28
C. tentans H. azteca
21.0 21.0
21.0 21.0
20.5 20.5
20.0 20.0
21.0 21.0
21.0 21.0
20.0 20.1
19.6 19.7
19.8 20.0
20.1 20.3
20.4 20.5
196-21.0 19.7-21.0
DSH 34
C. tentans H. azteca
21.0 21.0
21.0 21.0
20.2 20.6
19.8 19.7
21.0 21.0
21.0 21.0
19.7 19.8
19.5 19.5
19.6 19.8
20.0 20.0
20.2 20.3
19.5-21.0 19.5-21.0
DSH 35
C. tentans H. azteca
21.0 21.0
21.0 21.0
20.0 20.3
19.6 19.8
21.0 21.0
21.0 21.0
19.6 19.6
19.4 19.4
19.6 19.8
20.0 19.9
20.2 20.3
19.4-21.0 19.4-21.0
a
fl" ^s , H
•A> T)^ A
_,
-------
TABLE 4. Mean Percent Survival offfyalella azteca and Chironomus tentans
*
Hyalella azteca
Mean Percent Survival
Chironomus tentans
Batch # 5
CONTROL #5
DSH 05
DSH 09
DSH 10
DSH 11
DSH 25
DSH 27
DSH 31
DSH 32
97%
87%
83%
93%
93%
90%
100%
90%
93%
77%
90%
87%
90%
87%
97%
83%
73%
77%
Batch # 6
CONTROL #6
DSH 15
DSH 28
DSH 34
DSH 35
87%
90%
97%
77%
77%
97%
83%
93%
47% *
93%
Significantly different from the control, p=0.05.
/ .
10
-------
APPENDIX A
TOXSTAT Analysis
-------
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
8
3
3
3
3
3
3
3
3
CONTROL
0.8
0.7
0.8
DSH09
0.7
0.9
1.0
DSH10
0.9
1.0
0.8
DSH 11
0.8
1.0
0.8
DSH 25
0.9
1.0
1.0
DSH 27
0.9
0.7
0.9
DSH 31
0.8
0.6
0.8
DSH 32
0.7
0.8
0.8
A-l
-------
TITLE: 93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
FILE: 93MPR4CA.DAT
TRANSFORM: ARC SINECSQUARE ROOT(Y)) NUMBER OF GROUPS: 8
._ _ _ . *
GRP
1
1
I
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
IDENTIFICATION
CONTROL
CONTROL
CONTROL
DSH 09
DSH 09
DSH 09
DSH 10
DSH 10
DSH 10
DSH 11
DSH 11
DSH 11
DSH 25
DSH 25
DSH 25
DSH 27
DSH 27
DSH 27
DSH 31
DSH 31
DSH 31
DSH 32
DSH 32
DSH 32
REP
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
VALUE
0.8000
0.7000
0.8000
0.7000
0.9000
1.0000
0.9000
1.0000
0.8000
0.8000
1.0000
0.8000
0.9000
1.0000
1.0000
0.9000
0.7000
0.9000
0.8000
0.6000
0.8000
0.7000
0.8000
0.8000
TRANS VALUE
1.1071
0.9912
1.1071
0.9912
1.2490
1.4120
1.2490
1.4120
1,1071
1.1071
1.4120
1.1071
1.2490
1.4120
1.4120
1.2490
0.9912
1.2490
1.1071
0.8861
1.1071
0.9912
1.1071
1.1071
A-2
-------
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CA.DAT
Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION N
MIN
MAX
MEAN
1
2
3
4
5
6
7
8
CONTROL
DSH 09
DSH 10
DSH 11
DSH 25
DSH 27
DSH 31
DSH 32
3
3
3
3
3
3
3
3
0.991
0.991
1.107
1.107
1.249
0.991
0.886
0.991
1.107
1.412
1.412
1.412
1.412
1.249
1.107
1.107
1.068
1.217
1.256
1.209
1.358
1.163
1.033
1.068
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CA.DAT
Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
3RP IDENTIFICATION
1
2
3
4
5
6
7
8
CONTROL
DSH 09
DSH 10
DSH 11
DSH 25
DSH 27
DSH 31
DSH 32
VARIANCE
0.004
0.045
0.023
0.031
0.009
0.022
0.016
0.004
SD
0.067
0.212
0.153
0.176
0.094
0.149
0.128
0.067
SEM
0.039
0.123
0.088
0.102
0.054
0.086
0.074
0.039
C.V. %
6.27
17.43
12.15
14.56
6.93
12.80
12.35
6.27
A-3
-------
93 HUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINE(SQUARE ROOKY))
*
Shapiro - Milk's test for normality
0 - 0.311
W - 0.950
Critical W (P = 0.05) (n - 24) - 0.916
Critical W (P - 0.01) (n = 24) = 0.884
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINECSQUARE ROOKY))
Bartlett's test for homogeneity of variance
Calculated 81 statistic = 3.84
Table Chi-square value » 18.48 (alpha = 0.01, df - 7)
Table Chi-square value - 14.07 (alpha - 0.05. df =• 7)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
(\ fa?
A-4
-------
93 HUOPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINE(SQUAR£ ROOT(Y»
*
Shapiro • Milk's test for normality
0 - 0.311
W - 0.950
Critical W (P = 0.05) (n = 24) - 0.916
Critical W (P - 0.01) (n = 24) = 0.884
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINECSQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated 81 statistic - 3.84
Table Chi-square value = 18.48 (alpha - 0.01. df - 7)
Table Chi-square value - 14.07 (alpha = 0.05, df - 7)
Data PASS 81 homogeneity test at 0.01 level. Continue analysis.
(J
A-4
-------
93 MUDPUPPY RUN 34 CHIRONOMIOS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINECSQUARE ROOT(Y))
m
ANOVA TABLE
SOURCE
Between
Within (Error)
Total
DF
7
16
23
SS
0.257
0.311
0.568
MS
0.037
0.019
F
1.888
Critical F value - 2.66 (0.05.7,16)
Since F < Critical F FAIL TO REJECT Ho: All equal
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
DUNNETT'S TEST
TABLE 1 OF 2
Ho:Control
-------
93 MUDPUPPY RUN 34 CHIRONOMIDS 11/01/93
File: 93MPR4CA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
*
DUNNETT'S TEST - TABLE 2 OF 2 Ho:Controltreatment
GROUP
1
2
3
4
5
6
7
8
NUM OF
IDENTIFICATION REPS
CONTROL
DSH 09
DSH 10
DSH 11
DSH 25
DSH 27
DSH 31
DSH 32
3
3
3
3
3
3
3
3
Minimum Sig Diff X of DIFFERENCE
(IN ORIG. UNITS) CONTROL FROM CONTROL
0.277
0.277
0.277
0.277
0.277
0.277
0.277
36.1
36.1
36.1
36.1
36.1
36.1
36.1
-0.100
-0.133
-0.100
-0.200
-0.067
,0.033
0.000
A-6
-------
93 MUDPUPPY RUN #4B CHIRONOMIDS 11/02/93
5
*
3
3
3
3
control
1.0
0.9
1.0
dshlS
0.8
1.0
0.7
dsh28
1.0
0.9
0.9
dsh34
0.4
0.5
0,5
dsh35
0.9
0.9
1.0
A-7
-------
93 MUDPUPPY RUN #4B CHIRONOMIDS 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CB.DAT Transform: ARC SINE(SQUAR£ ROOT(Y))
Shapiro - Wilk's test for normality
D - 0.154
W = 0.942
Critical W (P - 0.05) (n - 15) = 0.881
Critical W (P = 0.01) (n = 15) - 0.835
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN *4B CHIRONOMIDS 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 3.45
Table Chi-square value - 13.28 (alpha - 0.01. df - 4)
Table Chi-square value - 9.49 (alpha - 0.05, df = 4)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
A-8
-------
TITLE:
FILE:
TRANSFORM:
93 MUDPUPPY RUN #4B CHIRONOMIDS
S : \MA\CHUBBAR\TSD\93MUD\93MPR4CB
ARC SINECSQUARE ROOT(Y))
m
11/02/93
.DAT
NUMBER
OF
GROUPS:
5
GRP IDENTIFICATION REP VALUE TRANS VALUE
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
control
control
control
dsh 15
dsh 15
dsh 15
dsh 28
dsh 28
dsh 28
dsh 34
dsh 34
dsh 34
dsh 35
dsh 35
dsh 35
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1.0000
0.9000
1.0000
0.8000
1.0000
0.7000
1.0000
0.9000
0.9000
0.4000
0.5000
0.5000
0.9000
0.9000
1.0000
1.4120
1.2490
1.4120
1.1071
1.4120
0.9912
1.4120
1.2490
1.2490
0.6847
0.7854
0.7854
1.2490
1.2490
1.4120
93 MUDPUPPY RUN #48 CHIRONOMIDS 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CB.DAT Transform: ARC SINECSQUARE ROOT(Y»
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION N MIN MAX MEAN
1
2
3
4
5
control
dsh 15
dsh 28
dsh 34
dsh 35
3
3
3
3
3
1.249
0.991
1.249
0.685
1.249
1.412
1.412
1.412
0.785
1.412
1.358
1.170
1.303
0.752
1.303
A-9
-------
93 MUDPUPPY RUN #48 CHIRONOMIDS 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
GRP IDENTIFICATION VARIANCE SD SEM C.V. *
1
2
3
4
5
control
dsh 15
dsh 28
dsh 34
dsh 35
0.009
0.047
0.009
0.003
0.009
0.094
0.217
0.094
0.058
0.094
0.054
0.126
0.054
0.034
0.054
6.93
18.58
6.93
7.73
7.22
93 MUDPUPPY RUN #4B CHIRONOMIDS 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
ANOVA TABLE
SOURCE
Between
Within (Error)
DF
4
10
ss
0.784
0.154
MS
0.196
0.015
F
12.701
Total 14 0.939
Critical F value - 3.48 (0.05.4,10)
Since F > Critical F REJECT Ho: All equal
A-10
-------
93 MUDPUPPY RUN #4B CHIRONOMIDS 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4CB.DAT
DUNNETT'S TEST
TABLE 1 OF 2
Transform: ARC SINECSQUARE ROOT(Y))
Ho:Control
-------
93 MUDPUPPY RUN #4A HYALELLA 11/01/93
7
3
">
3
3
3
3
3
control
1.0
0.9
1.0
DSH 05
1.0
0.8
0.8
DSH 09
0.9
0.9
0.7
DSH 10
1.0
0.9
0.9
DSH 11
0.9
0.9
1.0
DSH 31
0.8
0.9
1.0
DSH 32
0.8
1.0
1.0
-7
A-12
-------
TITLE: 93 MUDPUPPY RUN #4A HYALELLA 11/01/93
FILE: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HA.DAT
TRANSFORM: ARC SINE(SQUARE ROOT(Y)) NUMBER OF GROUPS: 7
GRP
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
IDENTIFICATION
control
control
control
DSH 05
DSH 05
DSH 05
DSH 09
DSH 09
DSH 09
DSH 10
DSH 10
DSH 10
DSH 11
DSH 11
DSH 11
DSH 31
DSH 31
DSH 31
DSH 32
DSH 32
DSH 32
REP
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
VALUE
1.0000
0.9000
1.0000
1.0000
0.8000
0.8000
0.9000
0.9000
0.7000
1.0000
0.9000
0.9000
0.9000
0.9000
1.0000
0.8000
0.9000
1.0000
0.8000
1.0000
1.0000
TRANS VALUE
1.4120
1.2490
1.4120
1.4120
1.1071
1.1071
1.2490
1.2490
0.9912
1.4120
1.2490
1.2490
1.2490
1.2490
1.4120
1.1071
1.2490
1.4120
1.1071
1.4120
1.4120
A-13
-------
93 MUDPUPPY RUN #4A HYALELLA 11/01/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HA.DAT
Transform: ARC SINECSQUARE ROOKY))
SUMMARY STATISTICS ONS TRANSFORMED DATA TABLE 1 of 2
3RP IDENTIFICATION
1
2
3
4
5
6
7
control
DSH 05
DSH 09
DSH 10
DSH 11
DSH 31
DSH 32
N
3
3
3
3
3
3
3
MIN
1.249
1.107
0.991
1.249
1.249
1.107
1.107
MAX
1.412
1.412
1.249
1.412
1.412
1.412
1.412
MEAN
1.358
1.209
1.163
1.303
1.303
1.256
1.310
93 MUDPUPPY RUN #4A HYALELLA 11/01/93
Fi1e: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HA.DAT
Transform: ARC SINE(SQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
3RP IDENTIFICATION
1
2
3
4
5
6
7
control
DSH 05
DSH 09
DSH 10
DSH 11
DSH 31
DSH 32
VARIANCE
0.009
0.031
0.022
0.009
0.009
0.023
0.031
SO
0.094
0.176
0.149
0.094
0.094
0.153
0.176
SEM
0.054
0.102
0.086
0.054
0.054
0.088
0.102
C.V. X
6.93
14.56
12.80
7.22
7.22
12.15
13.43
A/IT
A-14
-------
93 MUDPUPPY RUN |4A HYALELLA 11/01/93
File: S:\MA\CHUBBAR\TSO\93MUD\93MPR4HA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
m
Shapiro - Wilk's test for normality
D - 0.268
W - 0.950
Critical W (P - 0.05) (n - 21) - 0.908
Critical W (P - 0.01) (n = 21) = 0.873
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN #4A HYALELLA 11/01/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HA.DAT Transform: ARC SINECSQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 1.69
Table Chi-square value - 16.81 (alpha - 0.01, df - 6)
Table Chi-square value - 12.59 (alpha - 0.05. df = 6)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
(X i r *? /\
V\
A-15
-------
93 MUDPUPPY RUN #4A HYALELLA 11/01/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
«
ANOVA TABLE
SOURCE DF SS MS F
Between 6 0.081 0.013 0.703
Within (Error) 14 0.268 0.019
Total 20 0.349
Critical F value - 2.85 (0.05,6,14)
Since F < Critical F FAIL TO REJECT Ho: All equal
93 MUDPUPPY RUN |4A HYALELLA 11/01/93
File: S:\MA\CHU8BAR\TSD\93MUD\93MPR4HA.DAT Transform: ARC SINECSQUARE ROOT(Y))
DUNNETT'S TEST - TABLE 1 OF 2 Ho:Control treatment
TRANSFORMED MEAN CALCULATED IN
GROUP IDENTIFICATION MEAN ORIGINAL UNITS T STAT SIG
1 control 1.358 0.967
2 DSH 05 1.209 0.867 1.318
3 DSH 09 1.163 0.833 1.723
4 DSH 10 1.303 0.933 0.481
5 DSH 11 1.303 0.933 0.481
6 DSH 31 1.256 0.900 0.900
7 DSH 32 1.310 0.933 0.419
Dunnett table value - 2.53 (1 Tailed Value, P=0.05, df=14,6)
A-16
-------
93 MUDPUPPY RUN #4A HYALELLA 11/01/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HA.DAT Transform: ARC SINE(SQUARE ROOT(Y))
*
DUNNETT'S TEST - TABLE 2 OF 2 Ho:Control treatment
NUM OF Minimum Sig Diff % of DIFFERENCE
GROUP IDENTIFICATION REPS (IN ORIG. UNITS) CONTROL ROM CONTROL
1
2
3
4
5
6
7
control
DSH 05
DSH 09
DSH 10
DSH 11
DSH 31
DSH 32
3
3
3
3
3
3
3
0.184
0.184
0.184
0.184
0.184
0.184
19.1
19.1
19.1
19.1
19.1
19.1
0.100
0.133
0.033
0.033
0.067
0.033
A-17
-------
93 MUDPUPPY RUN #4B HYALELLA 11/02/93
4
3
3
3
3
control
0.9
0.9
0.8
DSH28
0.9
1.0
1.0
DSH34
0.9
0.7
0.7
DSH35
0.7
0.8
0.8
0
A-18
-------
TITLE: 93 MUDPUPPY RUN #4B HYALELLA 11/02/93
FILE: S:\MA\CHUBBAR\TSD\93HUD\93MPR4HB.DAT
TRANSFORM: ARC SINE(SQUAj*E ROOT(Y))
NUMBER OF GROUPS: 4
GRP IDENTIFICATION REP
VALUE
93 MUDPUPPY RUN #4B HYALELLA 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HB.DAT
TRANS VALUE
1
1
1
2
2
2
3
3
3
4
4
4
control
control
control
DSH 28
DSH 28
DSH 28
DSH 34
DSH 34
DSH 34
DSH 35
DSH 35
DSH 35
1
2
3
1
2
3
1
2
3
1
2
3
0.9000
0.9000
0.8000
0.9000
1.0000
1.0000
0.9000
0.7000
0.7000
0.7000
0.8000
0.8000
1.2490
1.2490
1.1071
1.2490
1.4120
1.4120
1.2490
0.9912
0.9912
0.9912
1.1071
1.1071
Transform: ARC SINECSQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION
MIN
MAX
MEAN
1
2
3
4
control
DSH 28
DSH 34
DSH 35
3
3
3
3
1.107
1.249
0.991
0.991
1.249
1.412
1.249
1.107
1.202
1.358
1.077
1.068
A-19
-------
93 MUDPUPPY RUN #4B HYALELLA 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HB.DAT Transform: ARC SINECSQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
GRP IDENTIFICATION VARIANCE SD SEM C.V. *
1 control 0.007 0.082 0.047 6.82
2 DSH 28 0.009 0.094 0.054 6.93
3 DSH 34 0.022 0.149 0.086 13,82
4 DSH 35 0.004 0.067 0.039 6.27
93 MUDPUPPY RUN #4B HYALELLA 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HB.DAT Transform: ARC SINECSQUARE ROOTCY))
ANOVA TABLE
SOURCE DF SS MS F
Between 3 0.165 0.055 5.212
Within (Error) 8 0.084 0.011
Total 11 0.249
Critical F value - 4.07 (0.05.3,8)
Since F > Critical F REJECT Ho: All equal
A-20
-------
93 MUOPUPPY RUN #4B HYALELLA 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HB.DAT Transform: ARC SINECSQUARE ROOT(Y))
m
Shapiro - Wilk's test for normality
D - 0.084
W - 0.855
Critical W (P - 0.05) (n - 12) = 0.859
Critical W (P = 0.01) (n - 12) - 0.805
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN #4B HYALELLA 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HB.DAT Transform: ARC SINE(SQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 1.23
Table Chi-square value - 11.34 (alpha - 0.01, df - 3)
Table Chi-square value - 7.81 (alpha - 0.05. df - 3)
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
A-21
-------
93 MUDPUPPY RUN #48 HYALELLA 11/02/93
File: S:\MA\CHU8BAR\TSD\93MUD\93MPR4HB.DAT Transform: ARC SINECSQUARE ROOKY))
DUNNETT'S TEST - TABLE* 1 OF 2 Ho: Control treatment
GROUP
1
2
3
4
IDENTIFICATION
control
DSH 28
DSH 34
DSH 35
TRANSFORMED
MEAN
1.202
1.358
1.077
1.068
MEAN CALCULATED
ORIGINAL UNITS
0.867
0.967
0.767
0.767
IN
T STAT
-1.859
1.486
1.589
SI6
Dunnett table value = 2.42 (1 Tailed Value. P-0.05. df-8,3)
93 MUDPUPPY RUN #48 HYALELLA 11/02/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR4HB.DAT Transform: ARC SINECSQUARE ROOT(Y))
DUNNETT'S TEST - TABLE 2 OF 2 Ho:Controltreatment
NUM OF Minimum Sig Diff % of DIFFERENCE
GROUP IDENTIFICATION REPS IN ORI6. UNITS) CONTROL FROM CONTROL
1
2
3
4
control
DSH 28
DSH 34
DSH 35
3
3
3
3
0.163
0.163
0.163
18.8
18.8
18.8
-0.100
0.100
0.100
Ofv^li ^c
A-22
-------
EPA 905-R97-005
, .,,„* National Program Office ,A_h 1997
ACUTE TOXICITY TESTS
WITH
HYALELLA AZTECA AND CHIRONOMUS TENTANS
ON SEDIMENTS FROM THE DULUTH/SUPERIOR HARBOR:
1993 Sampling Results - Batch # 7
Conducted by
Minnesota Pollution Control Agency
Monitoring and Assessment Section
520 Lafayette Road
St. Paul, Minnesota 55155-4194
February 1997
-------
TABLE OF CONTENTS
INTRODUCTION ". 1
SAMPLE COLLECTION AND HANDLING 1
METHODS 1
RESULTS 2
SUMMARY 4
REFERENCES 5
APPENDIX A - TOXSTAT Analysis
u
-------
. ,_«;»„„! Divwwora QfiiC®
EPA 905-R97-005
LIST OF TABLES
m
TABLE 1. Daily Overlying Water pH Measurements 6
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L) 7
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius) 8
TABLE 4. Mean Percent Survival ofHyalella azteca and Chironomus tentans 9
I
111
-------
INTRODUCTION
As part of the 1993 survey of sediment quality in the Duluth/Superior Harbor, sediment toxicity
tests were conducted to assess acute (survival) and chronic (growth) toxicity to benthic
invertebrates. Acute effects were measured in separate 10-day toxicity tests to Hyalella azteca
(H. azteca) and Chironomus tentans (C. tentans). Growth was measured at the end of the
C. tentans test to assess chronic effects. Survival and growth endpoints were compared to
organisms similarly exposed to a reference control sediment collected from West Bearskin Lake
(Cook County, MN).
A total of 40 sediment samples were collected for toxicity testing. This report presents the
results of six of these sediment samples.
SAMPLE COLLECTION AND HANDLING
During September 27-28,1993, Minnesota Pollution Control Agency (MPCA) staff collected the
six sediments referred to in this report. The samples were collected from the harbor using a
Ponar sampler and were taken to the University of Minnesota-Duluth Chemical Toxicology
Research Laboratory. The samples were stored at 4°C until they were transported to the MPCA
Toxicology Laboratory in St. Paul, MN.
METHODS
Six sediment samples and a control sediment sample were subjected to the 10-day sediment
toxicity tests using the modified procedures described in ASTM (1993). However, the specific
test system used for these assays is not indicated in the methods. The test organisms (H. azteca
and C. tentans) were exposed to sediment samples in a portable, mini-flow system described in
Benoit et al. (1993). The test apparatus consists of 300 mL, glass-beaker test chambers held in a
glass box supplied with water from an acrylic plastic headbox. The beakers have two, 1.5 cm
holes covered with stainless steel mesh, to allow for water exchange, while containing the test
organisms. The headbox has a pipette tip drain calibrated to deliver water at an average rate of
32.5 mL/min. The glass box is fitted with a self-starting siphon to provide exchange of overlying
water.
The H. azteca used for this test were 1 to 3 mm long, and the C. tentans were approximately 14
days old. These organisms were supplied by Environmental Consulting and Testing, Superior,
WI on the day of the test.
On November 12, 1993, six samples (DSH 20, DSH 33, DSH 36, DSH 37, DSH 38, and DSH
39) and the control sediment were separately homogenized by hand, and 100 mL of each
sediment was placed in a test beaker (Batch #7), Each sediment test was set up with three
replicates of H. azteca and three replicates of C. tentans. Aerated, artesian well water was added
to the beakers, and the sediments were allowed to settle for approximately two hours before the
-------
organisms were added. For each toxicity test, ten organisms were placed in each beaker in a
random fashion.
s
The organisms were exposed to 16 hours of light and eight hours of darkness for the duration of
the ten-day test. Each day, two liters of aerated water from the artesian well at Stroh Brewery in
St. Paul, MN were exchanged in each test chamber. On weekdays, 1-L was exchanged in the
morning and 1-L in the afternoon. On weekends, the two liters were passed through the
chambers all at once. Water quality measurements (i.e., pH, temperature, and dissolved oxygen)
of the overlying water were taken in one beaker of each of the triplicate sets of each of the
sediments. The results, along with daily observations involving the physical appearance of the
sediments and organisms, were recorded in a laboratory notebook. This notebook is retained on
file at the MFC A.
The test was terminated on November 22, 1993. The sediments were sieved through 40 mesh
screens, and the sieved material was sorted for organisms. The organisms found were counted,
and the number of alive and dead organisms was recorded. Organisms not found were recorded
as missing and presumed dead. The C. tentans that survived were placed in aluminum weighing
dishes, dried at approximately 90°C for at least four hours, desiccated to room temperature, and
weighed.
Growth (weight) of the C. tentans and survival of both organisms were used as the endpoints for
these tests. The resulting survival data were analyzed using TOXSTAT (Gulley and WEST, Inc.,
1994), a statistical software package obtained from the University of Wyoming; however, due to
a quality assurance problem, the growth data were not analyzed.
A 96-hour, reference toxicant test with H. azteca in sodium chloride (NaCl) was run in
conjunction with these toxicity tests to determine the acceptability of the H. azteca used. Four
concentrations of NaCl solution (i.e., 5, 2.5, 1.25, and 0.625 g/L) and a control (aerated, artesian
well water) were used in this test. Three replicates of five organisms each were set up pei
concentration.
RESULTS
Water Chemistry
Measurements of pH, dissolved oxygen, and temperature in the overlying water of the test
beakers were made daily. These measurements are summarized below and in Tables 1, 2, and 3,
respectively.
The range of pH values in the beakers containing H. azteca was 7.5 to 8.2 (Table 1). The water
in the C. tentans beakers had a pH range of 7.3 to 8.1 (Table 1). The pH fluctuation during these
tests was acceptable since it did not vary more than 50% within each treatment (U.S. EPA,
1994).
-------
The dissolved oxygen concentration ranged from 5.6 to 7.3 mg/L in the //. azteca beakers and
from 4.1 to 7.2 mg/L in the C. tentans beakers (Table 2). The recommended dissolved oxygen
concentration for these tests is greater* than 40% saturation; therefore, these dissolved oxygen
ranges were acceptable.
The range of temperature values in the beakers containing the H. azteca was 19.1°C to 22.0°C
(Table 3). For the C. tentans test, the water temperature ranged from 18.9°C to 22°C (Table 3).
The recommended temperature for this test is 23 ± 1°C (U.S. EPA, 1994).
Test Endpoints
The mean percent survival of H. azteca in the control was 37% which was unacceptable (Table
4). At least 80% survival in the control is necessary for the test to pass. Since the control
survival of H. azteca in the 4-day reference toxicant test was acceptable at 93%, this would
indicate that the culture was healthy. The reason for the poor control survival in the toxicity test
could not be determined. For C. tentans, the mean percent survival in the control was 87%
which was acceptable.
Mean percent survival of//, azteca in the test sediments ranged from 57% in the DSH 38 sample
to 77% in the DSH 33 sample. Mean percent survival of C. tentans in the test sediments ranged
from 53% in the DSH 33 and DSH 37 samples to 80% in the DSH 38 sample.
Although the dried C. tentans were weighed, the balance on which they were weighed was not
calibrated with standard weights; therefore, the data are suspect since the internal calibration of
the balance may have drifted with time.
Data Analysis
All C. tentans survival data were transformed using an arc sine-square root transformation before
being analyzed statistically using Dunnett's test. The mean percent survival of C. tentans in all
the samples was not significantly different from the control as determined by a 1-tailed Dunnett's
test, p=0.05. Results of the statistical analyses of the data are included in Appendix A.
Reference Toxicant Test with Hyaletta azteca in Sodium Chloride Solution
The pH of the overlying water in the reference toxicant test ranged from 8.2 to 8.7. The
dissolved oxygen ranged from 7.5 to 8.6 mg/L, and the temperature ranged between 18.0°C and
22.0°C. The mean percent survival of the control was 93% which met quality assurance
requirements (i.e., > 90% control survival). The LC50 value for this test was 3.2 g/L NaCl as
determined by the Trimmed Spearman-Karber method. A control chart will be developed for
this test once five data points are obtained.
-------
SUMMARY
Survival of H. azteca in the cpntrol sediment was unacceptable (less than 80%). Therefore, no
conclusions can be drawn about the effect that the sediments had on H. azteca. The reference
toxicant test for H. azteca was acceptable, and a LC50 value of 3.2 g/L NaCl was determined for
this test.
Control survival was acceptable in the control containing C. tentans. The mean percent survival
of C. tentans in the sediment samples was not significantly different from the control.
-------
REFERENCES
ASTM. 1993. Standard guide for conducting sediment toxicity tests with freshwater
invertebrates. El 383-93. In Annual Book of ASTM Standards, Vol. 11,04. American
Society for Testing and Materials, Philadelphia, PA. pp. 1173-1199.
Benoit, D.A., G. Phipps, and G.T. Ankley. 1993. A sediment testing intermittent renewal
system for the automated renewal of overlying water in toxicity tests with contaminated
sediments. Water Research 27:1403-1412.
Gulley, D.D. and WEST, Inc. 1994. TOXSTAT 3.4. WEST, Inc., Cheyenne, WY.
U.S. EPA. 1994. Methods for measuring the toxicity and bioaccumulation of sediment-
associated contaminants with freshwater invertebrates. Office of Research and
Development, U.S. Environmental Protection Agency, Duluth, MN. EPA/600/R-94/Q24.
-------
TABLE 1. Daily Overlying Water pH Measurements
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control #7
C. tentans H. azteca
7.7 7.7
7.6 7.8
7.3 7.5
7.8 7.9
8.1 8.1
7.8 8.0
7.9 8.0
7.8 7.9
7.7 8.0
7.8 7.9
7.8 7.9
7.3-8.1 7.5-8.1
DSH20
C. tentans H. azteca
7.7 7.8
7.5 7.6
7.6 7.6
7.7 7.7
7.9 7.8
7.8 7.9
7.8 7.9
8.0 8.0
8.0 8.0
8.0 8.0
7.8 7.8
7.5-8.0 7.6-8.0
DSH33
C. tentans H. azteca
7.9 7.8
7.5 7.6
7.6 7.7
7.7 7.8
7.8 7.8
7.9 7.9
7.8 7.9
7.8 7.9
7.8 8.0
7.9 8.0
7.8 7.8
7.5-7.9 7.6-8.0
DSH36
C. tentans H. azteca
7.9 7.8
7.4 7.5
7.5 7.6
7.7 7.7
7.8 7.9
7.8 7.8
7.7 7.8
7.7 7.8
7.7 7.9
7.8 7.9
7.7 7.8
7.4-7.9 7.5-7.9
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
DSH37
C. tentans H. azteca
7.8 7.7
7.5 7.5
7.4 7.5
7.7 7.7
7.8 7.8
7.8 7.8
7.8 7.8
7.8 7.8
7.7 7.8
7.8 7.9
7.7 7.7
7.4-7.8 7.5-7.9
DSH38
C. tentans H. azteca
7.8 7.9
7.6 7.7
7.6 7.7
7.7 7.8
7.8 7.8
7.8 7.9
7.9 8.0
7.8 7.9
7.8 8.0
8.0 8.0
7.8 7.9
7.6-8.0 7.7-8.0
DSH39
C. tentans H. azteca
8.0 7.7
8.1 8.0
7.7 7.7
7.8 8.0
7.8 7.9
7.9 8.1
7.9 8.2
7.7 8.0
7.8 8.2
8.0 8.1
7.9 8.0
7.7-8.1 7,7-8.2
-------
TABLE 2. Daily Overlying Water Dissolved Oxygen Concentrations (mg/L)
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control #7
C. tentans H. azteca
7.0 7.2
6.3 6.5
5.5 6.6
4.5 6.4
5.9 6.8
5.3 6.7
5.0 6.6
5.6 6.3
5.4 6.3
4.6 6.2
5.5 6.6
4.5-7.0 6.2-7.2
DSH20
C. tentans H. azteca
7.2 7,2
5.8 6.0
5.8 6.3
5.5 6.0
6.2 6.5
5.8 6.6
5.9 7.3
6.0 7.0
5.8 6.5
5.8 6.3
6.0 6.6
5.5-7.2 6.0-7.3
DSH33
C. tentans H. azteca
7.1 7.2
5.7 5.8
5.6 6.3
4.4 6.0
5.5 6.5
5.3 6.3
5.2 6.9
5.3 6.7
5.3 6.9
4.9 6.6
5.4 6.5
4.4-7.1 5.8-7.2
DSH36
C. tentans H. azteca
7.2 6.9
5.8 5.8
5.2 6.0
4.4 5.8
5.5 6.3
5.1 6.2
4.6 6.7
4.6 6.6
4.6 6.4
4.4 5.6
5.1 6.2
4.4-7.2 5.6-6.9
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
DSH37
C. tentans H. azteca
6.7 6.0
5.9 6.0
5.5 6.2
4.7 5.6
5.6 6.2
5.7 6.1
6.0 6.1
6.0 6.2
4.1 6.0
4.7 6.3
5.5 6.1
4.1-6.7 5.6-6.3
DSH38
C. tentans H. azteca
7.0 7.3
6.0 6.0
5.8 6.3
4.7 6.0
5.7 6.4
5.4 6.7
6.0 6.9
6.5 6.7
6.3 6.2
6.0 6.0
5.9 6.5
4.7-7.0 6.0-7.3
DSH39
C. tentans H. azteca
7.2 6.6
6.6 6.4
6.2 6.8
5.1 6.6
4.9 6.6
5.9 6.9
6.1 7.0
5.3 7.0
4.7 6.8
4.8 6.9
5.7 6.8
4.7-7.2 6.4-7.0
u^
J u
2
7
-------
TABLE 3. Daily Overlying Water Temperatures (Degrees Celsius)
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
Control # 7
*
C. tentans H. azteca
19.6 19.5
21,4 21.3
21.7 21.6
20.5 20.5
20.0 19.8
20.1 20.0
20.2 20.1
19.8 19.8
21.2 21.1
21.5 21.5
20.6 20.5
19.6-21.7 19.5-21.6
DSH20
C. tentans H. azteca
19.2 19.2
20.5 20.7
21.3 21.3
19.7 19.6
19.5 19.5
19.6 19.6
19.6 19.6
19.5 19.6
20.8 20.7
21.4 21.4
20.1 20.1
19.2-21.4 19.2-21.4
DSH33
C. tentans H. azteca
19.1 19.1
20.7 20.6
21.1 21.2
19.6 19.5
19.5 19.5
19.6 19.6
19.6 19.6
19.6 19.6
20.6 20.6
21.3 21.2
20.1 20.1
19.1-21.3 19.1-21.2
DSH36
C. tentans H. azteca
19.0 19.1
20.8 20.9
21.3 21.4
19.5 19.8
19.6 19.6
19.5 19.5
19.6 19.6
19.6 19.6
20.9 20.9
21.4 21.4
20.1 20.2
19.0-21.4 19.1-21.4
Day
0
1
2
3
4
5
6
7
8
9
Mean
Range
DSH37
C. tentans H. azteca
19.3 19,3
21.0 21.0
21.2 21.3
20.5 20.5
19.5 19.5
19.7 19.7
19.9 19.9
19.8 19.8
21.0 21.0
21.5 21.5
20.3 20.4
19.3-21.5 19.3-21.5
DSH38
C. tentans H. azteca
19.2 19.3
21.0 21.0
21.3 21.3
19.7 19.7
19.5 19.5
19.5 19.5
19.7 19.7
19.7 19.7
20.9 20.9
21.5 21.5
20.2 20.2
19.2-21.5 19.3-21.5
DSH39
C. tentans H. azteca
18.9 19.1
22.0 22.0
21.2 22.0
19.6 19.7
19.5 19,7
19.2 19.1
19.2 19.6
19.7 19.8
20.9 21.0
21.3 21.3
20.2 20.3
18.9-22.0 19.1-22.0
-------
TABLE 4. Mean Percent Survival of Hyalella azteca and Chironomus tentans
Batch #1
Sample
CONTROL #7
DSH20
DSH33
DSH36
DSH37
DSH38
DSH39
" Mean Percent Survival
Hyalella azteca1
37%
70%
77%
63%
60%
57%
63%
Chironomus tentans
87%
60%
53%
73%
53%
80%
70%
Control survival was unacceptable (<80% survival). Therefore, the test failed.
V_X
7-11
-------
APPENDIX A
TOXSTAT Analysis
-------
93 MUDPUPPY RUN #5 CHIRONOMIDS 11/12/93
7
3
m
3
3
3
3
3
3
control
0.9
0.7
1.0
dsh37
0.5
0.6
0.5
dsh36
0.7
0.7
0.8,
dsh33
0.8
0.3
0.5
dsh38
0.7
0.8
0.9
dsh20
0.3
0.9
0.6
dsh39
0.8
0.7
0,6
A-l
-------
TITLE: 93 MUDPUPPY RUN #5 CHIRONOMIDS 11/12/93
FI LE : S : \MA\CHUBBAR\TSD\93MUD\93MPR5C . DAT
TRANSFORM: ARC SINEtSQiARE ROOT(Y)) NUMBER OF GROUPS:
GRP
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
IDENTIFICATION
control
control
control
dsh 37
dsh 37
dsh 37
dsh 36
dsh 36
dsh 36
dsh 33
dsh 33
dsh 33
dsh 38
dsh 38
dsh 38
dsh 20
dsh 20
dsh 20
dsh 39
dsh 39
dsh 39
REP
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
VALUE
0.9000
0.7000
1.0000
0.5000
0.6000
0.5000
0.7000
0.7000
0.8000
0.8000
0.3000
0.5000
0.7000
0.8000
0.9000
0.3000
0.9000
0.6000
0.8000
0.7000
0.6000
TRANS VALUE
1.2490
0.9912
1.4120
0.7854
0.8861
0.7854
0.9912
0.9912
1.1071
1.1071
0.5796
0.7854
0.9912
1.1071
1.2490
0.5796
1.2490
0.8861
1.1071
0.9912
0.8861
93 MUDPUPPY RUN |5 CHIRONOMIDS 11/12/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR5C.DAT Transform: ARC SINECSQUARE ROOT(Y))
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 1 of 2
GRP IDENTIFICATION N MIN MAX MEAN
1
2
3
4
control
dsh 37
dsh 36
dsh 33
3
3
3
3
0.991
0.785
0.991
0.580
1.412
0.886
1.107
1.107
1.217
0.819
1.030
0.824
dsh 38 3 0.991 1.249 1.116
dsh 20 3 0.580 1.249 0.905
dsh 39 3 0.886 1.107 0.995
A-2
-------
CD A an£-RCi7-On5
93 MUDPUPPY RUN 15 CHIRONOMIDS 11^12/93
File: S:\MA\CHUB8AR\TSD\93MUD\93HPR5C.DAT Transform: ARC SINE(SQUARE RCX)T(Y»
SUMMARY STATISTICS ON TRANSFORMED DATA TABLE 2 of 2
GRP IDENTIFICATION VARIANCE SD SEM C.V. X
I
2
3
4
S
6
7
control
dsh 37
dsh 36
dsh 33
dsh 38
dsh 20
dsh 39
0.045
0.003
0.004
0.071
0.017
0.112
0.012
0.212
0.058
0.067
0.266
0.129
0.335
0.111
0.123
0.034
0.039
0.154
0.075
0.193
0.064
17.43
7.10
6.50
32.26
11.58
37.03
11.12
93 MUDPUPPY RUN |5 CHIRONOMIDS 11/12/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR5C.DAT Transform: ARC SINE(SQUARE ROOT(Y))
ANOVA TABLE
SOURCE
Between
Within (Error)
Total
DF
6
14
20
SS
0.399
0.530
0.929
MS
0.067
0.038
F
1.759
Critical F value - 2.85 (0.05,6,14)
Since F < Critical F FAIL TO REJECT Ho: All equal
A-3
-------
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR5C.DAT Transform: ARC SINE(SQUARE ROQT(Y))
ft
Shapiro - Wilk's test for normality
D - 0.530
W - 0.968
Critical W (P = 0.05) (n - 21) - 0.908
Critical W (P - 0.01) (n - 21) - 0.873
Data PASS normality test at P=0.01 level. Continue analysis.
93 MUDPUPPY RUN #5 CHIRONOMIDS 11/12/93
File: S:\MA\CHUBBAR\TSD\93MUD\93MPR5C.DAT Transform: ARC SINECSQUARE ROOT(Y))
Bartlett's test for homogeneity of variance
Calculated Bl statistic - 7.74
Table Chi-square value - 16.81 (alpha - 0.01. df - 6)
Table Chi-square value = 12.59 (alpha = 0.05, df - 65
Data PASS Bl homogeneity test at 0.01 level. Continue analysis.
A-4
-------
93 MUDPUPPY RUN #5 CHIRONOMIDS 11/12/93
File: S:\MA\CHUBBAR\TSD\93MUD\i3MPR5C.DAT
DUNNETT'S TEST
TABLE 1 OF 2
Transform: ARC SINECSQUARE ROOT(Y))
Ho:Control
-------
|